阅读说明：本技术 聚烯烃衍生的分散剂 (Polyolefin derived dispersants ) 是由 纳撒尼尔·凯恩 约翰·洛佩尔 劳伦斯·坎宁安 约瑟夫·W·鲁斯 于 2018-06-12 设计创作，主要内容包括：本文一般描述乙烯-C<Sub>3</Sub>-C<Sub>10</Sub>α-烯烃共聚物、分散剂和并入分散剂的润滑油/燃料组合物,以及相关方法。所述共聚物能够包含乙烯衍生单元和C<Sub>3</Sub>-C<Sub>10</Sub>α-烯烃衍生单元。所述C<Sub>3</Sub>-C<Sub>10</Sub>α-烯烃衍生单元能够具有三至十的碳数。举例来说,所述C<Sub>3</Sub>-C<Sub>10</Sub>α-烯烃衍生单元能够为丙烯衍生单元。所述分散剂能够由具有低金属和/或氟含量的共聚物制备。(ethylene-C is described generally herein 3 ‑C 10 α -olefin copolymer, dispersant, and lubricating oil/fuel composition incorporating dispersant, and related methods 3 ‑C 10 α -olefin derived units, the C 3 ‑C 10 α -olefin derived units can have a carbon number of three to ten, for example, the C 3 ‑C 10 α -olefin derived units can be propylene derived units the dispersant can be prepared from copolymers having low metal and/or fluorine content.)

1. A dispersant prepared by a process comprising: derived from ethylene and one or more C_3-10α -copolymer of olefin is functionalized,

wherein the copolymer has a number average molecular weight of less than 5,000g/mol as measured by GPC using polystyrene as a calibration reference;

wherein such as by¹The ethylene unit content of the copolymer is less than 80 mol% as measured by H-NMR spectroscopy;

wherein such as by¹³The terminal unsaturation of the copolymer is 70 mol% or more as measured by C-NMR spectroscopy, and¹(ii) at least 70 mol% of said terminal unsaturation is selected from the group consisting of terminal vinylidene groups, one or more trisubstituted isomers of said terminal vinylidene groups, and any combination thereof as measured by H-NMR spectroscopy;

wherein such as by¹³C NMR spectroscopy said copolymer having an average ethylene continuous chain length n of less than 2.6_{C2, practice}And wherein:

n_{c2, practice}<n_{C2, statistics}。

2. A dispersant as set forth in claim 1 wherein said copolymer has a crossover temperature of-25 ℃ or less.

3. A dispersant as claimed in claim 1 wherein the copolymer has a crossover temperature of-35 ℃ or less.

4. A dispersant as claimed in claim 1 wherein said ethylene unit content is less than 60 mol%.

5. A dispersant as claimed in claim 1 wherein said ethylene unit content is less than 50 mol%.

6. A dispersant as claimed in claim 1 wherein said ethylene unit content is at least 10% and less than 80%.

7. A dispersant as set forth in claim 1 wherein at least 85 mole percent of terminal unsaturation is selected from said terminal vinylidene group, one or more of said trisubstituted isomers of said terminal vinylidene group and any combination thereof.

8. The dispersant of claim 1, wherein at least 95 mol% of the terminal unsaturation is selected from one or more of the terminal vinylidene group, the trisubstituted isomer of the terminal vinylidene group, and any combination thereof.

9. A dispersant as claimed in claim 1 wherein said copolymer has an average ethylene continuous chain segment length of less than 2.4.

10. A dispersant as claimed in claim 1 wherein said copolymer has an average ethylene continuous chain segment length of less than 2.2.

11. A dispersant as set forth in claim 1 wherein said copolymer has a polydispersity index of less than or equal to 4.

12. A dispersant as set forth in claim 1 wherein said copolymer has a polydispersity index of less than or equal to 3.

13. The dispersant of claim 1 wherein the copolymer is an ethylene-propylene copolymer wherein the ethylene unit content is from 30 to less than 80 mol% and the propylene unit content is from 20 to 70 mol%.

14. The dispersant of claim 1 wherein the copolymer is an ethylene-propylene copolymer wherein the ethylene unit content is from 40 to 60 mol% and the propylene unit content is from 40 to 60 mol%.

15. The dispersant of claim 1 wherein the copolymer is an ethylene-propylene copolymer wherein the ethylene unit content is about 40 to 50 mol% and the propylene unit content is about 50 to 60 mol%.

16. A dispersant as set forth in claim 1 wherein said copolymer has a number average molecular weight of less than 3,500g/mol as measured by GPC.

17. A dispersant as claimed in claim 1 wherein the number average molecular weight of the copolymer is greater than 500g/mol and less than 3,000g/mol as measured by GPC.

18. A dispersant as claimed in claim 1 wherein the dispersant is post-treated.

19. The dispersant of claim 1 wherein the dispersant is post-treated with an anhydride, a boron compound, or a mixture thereof.

20. A dispersant as set forth in claim 1 wherein said dispersant has one of the following formulas:

wherein R is¹Being hydrocarbons derived from said copolymerA group; r²Is divalent C₁-C₆An alkylene group; r³Is divalent C₁-C₆An alkylene group; r⁴And R⁵Is independently H, C₁-C₆Alkyl, aryl, heteroaryl, and heteroaryl,Or with said R⁴And R⁵The attached N together form a 5 or 6 membered ring optionally fused to an aromatic or non-aromatic ring; r⁶Is H or C₁-C₆Alkyl, or-CH₂-(NH-R²)_n-NR⁴R⁵(ii) a Y is a covalent bond or C (O); and n is 0, 1, 2, 3, 4, 5, 6, 7 or 8.

21. The dispersant of claim 1 wherein the terminal vinylidene group of the copolymer and the trisubstituted isomer of the terminal vinylidene group have one or more of the following structural formulae (a) to (C):

and/or

Wherein R represents C₁-C₈Alkyl radical, andindicating the bond to the remainder of the copolymer.

22. The dispersant of claim 1 wherein said copolymer has a total Zr, Ti, Al, and B content of 25ppmw or less based on the total weight of said copolymer, wherein said Zr, Ti, Al, and B are derived from a single-site catalyst and optionally a cocatalyst.

23. The dispersant of claim 1 wherein the copolymer has a total Zr, Ti, Al, and B content of 10ppmw or less, 5ppmw or less, or 1ppmw or less, based on the total weight of the copolymer, wherein the Zr, Ti, Al, and B are derived from a single-site catalyst and an optional cocatalyst.

24. The dispersant of claim 1 wherein the copolymer has a fluorine content of less than 10ppmw, or less than 8ppmw, or less than 5ppmw, based on the total weight of the copolymer.

25. A lubricating oil, comprising:

at least 50 wt% of a base oil;

3 to 20 wt% of a viscosity index improver;

0 to 1 wt% of a pour point depressant; and

0.2 to 20 wt% of a dispersant as claimed in any one of claims 1 to 24.

26. The lubricating oil of claim 25, wherein the lubricating oil has a Mini Rotary Viscometer (MRV) value of 60,000cP or less at-30 ℃ as determined by ASTM D4684 testing.

27. The lubricating oil of claim 25, wherein the lubricating oil has a Mini Rotary Viscometer (MRV) value of 60,000cP or less at-40 ℃ as determined by the ASTM D4684 test.

28. The lubricating oil of claim 25, wherein the dispersant comprises less than 10 wt% of the lubricating oil.

29. A lubricant additive package comprising: 30 to 80 wt% of a dispersant as claimed in any one of claims 1 to 24.

30. A fuel composition or fuel additive composition comprising the dispersant of claim 20.

31. A fuel composition or fuel additive composition as claimed in claim 30, the dispersant having one of the following formulae:

wherein R is¹Is a hydrocarbyl group derived from the copolymer; r²Is divalent C₁-C₆An alkylene group; r³Is divalent C₁-C₆An alkylene group; r⁴And R⁵Is independently H, C₁-C₆Alkyl, aryl, heteroaryl, and heteroaryl,Or with said R⁴And R⁵The attached N together form a 5 or 6 membered ring optionally fused to an aromatic or non-aromatic ring; r⁶Is H or C₁-C₆Alkyl, or-CH₂-(NH-R²)_n-NR⁴R⁵(ii) a Y is a covalent bond or C (O); and n is 0, 1, 2, 3, 4, 5, 6, 7 or 8.

Background

Lubricating oils perform the following tasks under various operating conditions: (1) preventing wear and fatigue; (2) controlling friction; (3) maintaining a clean system; and (4) providing a suitable viscosity to form an oil film to protect the surface.

To achieve a particular SAE oil grade specification (e.g., SAE 5W-30), a lubricating oil needs to meet a set of criteria for a series of tests relating to its viscosity at different temperatures. The tests included KV100, cold start simulator (CCS), High Temperature High Shear (HTHS). A recently added additional test is the Micro Rotary Viscometer (MRV) test defined by ASTM D4684-14.

The MRV test was developed in response to a specific set of field problems seen in suforbes (sieux Falls, north dakota) in the mid 1990's, where a number of engine failures occurred after a specific cooling cycle of the day. Under these conditions, when a user starts a car, the engine rolls over as expected, but catastrophic damage occurs soon thereafter. The root cause for engine failure was determined to be the formation of a wax/gel structure in the oil sump and the oil pump was unable to overcome the high viscosity of the suction side of the pump where there was a low shear rate. As a result, no lubricant is fed to the engine components, eventually causing the engine to seize. MRV tests were then developed to address the possibility of this type of failure in lubricants that otherwise met the industry standards at the time.

Method of MRV testing is by ASTM D4684-14, which are incorporated herein by reference in their entirety and for all purposes. This test method includes measuring the yield stress and viscosity of the engine oil after cooling at a controlled rate to a final test temperature between-10 ℃ and-40 ℃ over a period of 45 hours. The accuracy of the test temperature was specified to be-40 ℃ to-15 ℃. Viscosity measurement was at 0.4 second^-1To 15 seconds^-1At a shear stress of 525 Pa. It was found that the viscosity as measured under this shear stress yields the best correlation between the temperature at which the viscosity reaches the critical value and the critical pumping failure temperature in the engine.

When engine oil is cooled, the rate and duration of cooling can affect its yield stress and viscosity. In this laboratory test, fresh engine oil is slowly cooled to a temperature range where wax crystallization is known to occur, and then relatively quickly cooled to the final test temperature. These laboratory test results have predicted that known engine oils that fail in the field due to lack of oil pumpability are failures. These reported field failure oils were all comprised of oils that were typically tested at-25 ℃. It is believed that these field failures are due to the oil forming a gel structure, which results in excessive yield stress or viscosity, or both, of the engine oil.

To perform the test, the engine oil sample was held at 80 ℃, and then cooled to the final test temperature at a programmed cooling rate and held for a specified period of time. At the end of this period, a series of increasing low torques are applied to the rotor shaft until rotation occurs to determine the yield stress (if any). A higher torque was then applied to determine the apparent viscosity of the sample.

The viscosity grade of the lubricating oil is determined by the Society of Automotive Engineers (SAE). Multi-grade lubricants must meet two viscosity specifications, the viscosity grades of which consist of two numbers, e.g. 10W-40: 10W (first number) refers to the low temperature viscosity ("winter grade") and 40 (second number) refers to the high temperature viscosity ("summer grade"). Table 1 shows the specified SAE winter grade and the corresponding temperature at which the viscosity of the lubricating oil was tested. To achieve a particular grade, the viscosity of the lubricating oil must be less than 60,000cP at the temperatures listed.

TABLE 1

Disclosure of Invention

The present invention relates generally to ethylene-C₃-C₁₀α -olefin copolymers, copolymer-derived dispersants, and lubricating oil or fuel compositions incorporating copolymer-derived dispersants, and related methods in some instances, the inventive subject matter relates to interrelated products, alternative solutions to particular problems, and/or a plurality of different uses of one or more systems and/or articles.

In one aspect, the present invention generally relates to a dispersant prepared by a process comprising: derived from ethylene and one or more C₃-C₁₀α -functionalization of copolymers of olefins, wherein the number average molecular weight of the copolymers is less than 5,000g/mol, as measured by GPC using polystyrene as calibration reference, wherein¹The ethylene unit content of the copolymer is less than 80 mol% as measured by H-NMR spectroscopy; wherein such as by¹³C NMR spectroscopy measurement of the copolymer having a terminal unsaturation of 70 mol% or more, and¹at least 70 mol% of the unsaturation being terminal vinylidene groups and/or trisubstituted isomers of terminal vinylidene groups, as measured by H-NMR spectroscopy; and wherein e.g. by¹³C NMR spectroscopy of the copolymer gives an average ethylene continuous chain length n of less than 2.6_{C2, practice}And wherein:

n_{c2, practice}<n_{C2, statistics}。

In another aspect, the present invention relates generally to a composition derived from ethylene and one or more C' s₃-C₁₀α -copolymers of olefins, wherein the number average molecular weight of the copolymer is less than 5,000g/mol, as measured by GPC, wherein the ethylene unit content of the copolymer is less than 80 mol%, wherein at least 70 mol% of the copolymer has a carbon-carbon double bond in the terminal monomer unit, and at least 70 mol% of the terminal monomer unit having a carbon-carbon double bond is terminal vinylidene and/or terminal vinylideneTrisubstituted isomers of the radicals; and wherein the copolymer has a crossover temperature of-20 ℃ or less.

In yet another set of embodiments, the present invention relates generally to fuel compositions comprising a derivatized copolymer of the following formula (III):

wherein R is¹Is a hydrocarbon radical derived from the copolymer according to claim 1, R⁴And R⁵Is independently H, C₁-C₆Alkyl, or with said R⁴And R⁵The attached N together form a5 or 6 membered ring optionally fused to an aromatic or non-aromatic ring; and R is⁶Is H or C₁-C₆An alkyl group.

In yet another embodiment, the present invention relates generally to a process comprising contacting ethylene and C with a coordination polymerization catalyst₃-C₁₀α -olefin reaction to produce a mixture comprising ethylene derived units and C₃-C₁₀α -a copolymer of olefin derived units, wherein the α -olefin derived units have a carbon number of from three to ten, wherein the number average molecular weight of the copolymer is less than 5,000g/mol, wherein at least 70 mol% of the copolymer has terminal monomer units that are terminal vinylidene groups and/or trisubstituted isomers of terminal vinylidene groups, wherein the average ethylene derived unit continuous chain length of the copolymer is less than 3 as determined by NMR spectroscopy, wherein less than 80% of the total number of units in the copolymer are ethylene derived units, and wherein the copolymer has a crossover temperature of-20 ℃ or less.

The additives described herein may be used as dispersants in lubricating oils to keep foreign insoluble particulates dispersed throughout the oil and prevent their deposition and accumulation. The choice and design of the dispersant can help improve performance. In various embodiments, the dispersants described herein can provide one or more of the following advantages: excellent dispersancy and/or viscosity, fuel economy and/or low temperature performance. When used in lubricating oils, dispersants may affect the performance of MRV tests as discussed herein.

Additionally, the dispersants described herein may also be used as deposit control additives (also referred to as fuel detergents) in fuels, including but not limited to gasoline, biodiesel, or diesel, to keep fuel injectors clean or to clean up contaminated injectors for spark and compression type engines.

The following are sentences describing additional embodiments of the present invention.

1. A dispersant prepared by a process comprising: derived from ethylene and one or more C_3-10α -copolymer functionalization of olefins, wherein the number average molecular weight of the copolymer is less than 5,000g/mol as measured by GPC using polystyrene as calibration reference, wherein¹The ethylene unit content of the copolymer is less than 80 mol% as measured by H-NMR spectroscopy; wherein such as by¹³The terminal unsaturation of the copolymer is 70 mol% or more as measured by C-NMR spectroscopy, and¹H-NMR spectroscopy measuring at least 70 mol% of said unsaturation being terminal vinylidene, a trisubstituted isomer of terminal vinylidene, or any combination thereof; and wherein e.g. by¹³C NMR spectroscopy said copolymer having an average ethylene continuous chain length n of less than 2.6_{C2, practice}And wherein:

n_{c2, practice}<n_{C2, statistics}。

2. The dispersant of sentence 1, wherein the copolymer has a crossover temperature of-25 ℃ or less, or-35 ℃ or less.

3. A dispersant as claimed in any one of the preceding sentences wherein said copolymer has a crossover temperature of-40 ℃ or less.

4. A dispersant as claimed in any one of the preceding sentences wherein said ethylene unit content is less than 60 mol%.

5. A dispersant as claimed in any one of the preceding sentences wherein said ethylene unit content is less than 50 mol%.

6. A dispersant according to any of the preceding sentences wherein the ethylene unit content is at least 10% and less than 80%.

7. A dispersant as in any one of the preceding sentences wherein at least 85 mol% of terminal unsaturation is one or more of terminal vinylidene, the trisubstituted isomer of the terminal vinylidene, or any combination thereof.

8. A dispersant as set forth in any one of the preceding sentences wherein at least 95 mol% of said terminal unsaturation is selected from said terminal vinylidene group, one or more of said trisubstituted isomers of said terminal vinylidene group, and any combination thereof.

9. A dispersant as set forth in any preceding sentence wherein said copolymer has an average ethylene continuous link length of less than 2.4.

10. A dispersant as set forth in any preceding sentence wherein said copolymer has an average ethylene continuous link length of less than 2.2.

11. A dispersant as in any preceding sentence, wherein the polydispersity index of the copolymer is less than or equal to 4.

12. A dispersant as in any preceding sentence, wherein the polydispersity index of the copolymer is less than or equal to 3.

13. A dispersant as claimed in any one of the preceding sentences wherein said copolymer is an ethylene-propylene copolymer wherein said ethylene unit content is from 30 to less than 80 mol% and propylene unit content is from 20 to 70 mol%.

14. A dispersant according to any of the previous sentences wherein said copolymer is an ethylene-propylene copolymer wherein the ethylene unit content is from 40 to 60 mol% and the propylene unit content is from 40 to 60 mol%.

15. A dispersant according to any of the previous sentences wherein said copolymer is an ethylene-propylene copolymer wherein the ethylene unit content is from about 40 to 50 mol% and the propylene unit content is from about 50 to 60 mol%.

16. A dispersant as in any one of the preceding sentences, wherein the number average molecular weight of the copolymer is less than 3,500g/mol as measured by GPC.

17. A dispersant as in any one of the preceding sentences, wherein the number average molecular weight of the copolymer is greater than 500 and less than 3,000g/mol as measured by GPC.

18. A dispersant as claimed in any one of the preceding sentences wherein said dispersant is post-treated.

19. A dispersant as set forth in any one of the preceding sentences wherein said dispersant is post-treated with an anhydride, a boron compound, or a mixture thereof.

20. A dispersant as set forth in any one of the preceding sentences wherein said dispersant has one of the following formulas:

wherein R is¹Is a hydrocarbyl group derived from the copolymer; r²Is divalent C₁-C₆An alkylene group; r³Is divalent C₁-C₆An alkylene group; r⁴And R⁵Is independently H, C₁-C₆Alkyl, aryl, heteroaryl, and heteroaryl,Or with said R⁴And R⁵The attached N together form a5 or 6 membered ring optionally fused to an aromatic or non-aromatic ring; r⁶Is H or C₁-C₆Alkyl, or-CH₂-(NH-R²)_n-NR⁴R⁵(ii) a Y is a covalent bond or C (O); and n is 0, 1,2, 3,4, 5,6, 7 or 8.

21. A dispersant according to any one of the preceding sentences wherein the terminal vinylidene group of the copolymer and the trisubstituted isomer of the terminal vinylidene group have one or more of the following structural formulae (A) to (C):

wherein R represents C₁-C₈Alkyl radical, andindicating the bond to the remainder of the copolymer.

22. A lubricating oil, comprising: a major amount of a base oil; 3 to 20 wt% of a viscosity index improver; 0 to 1 wt% of a pour point depressant; and 0.2 to 20 wt% of a dispersant according to any one of the preceding sentences.

23. The lubricating oil of sentence 22, wherein the lubricating oil has a Micro Rotary Viscometer (MRV) value of 60,000cP or less at-30 ℃ as determined by ASTM D4684 testing.

24. The lubricating oil of any one of sentences 22 or 23, wherein the lubricating oil has a Micro Rotary Viscometer (MRV) value at-40 ℃ of 60,000cP or less as determined by the ASTM D4684 test.

25. The lubricating oil according to any one of sentences 22 to 24, wherein the dispersant comprises less than 10 wt% of the lubricating oil.

26. A fuel composition or fuel additive composition comprising the dispersant of sentence 20.

27. The fuel composition or fuel additive composition of sentence 26, wherein the dispersant has one of the following formulas:

wherein R is¹Is a hydrocarbyl group derived from the copolymer; r²Is divalent C₁-C₆An alkylene group; r³Is divalent C₁-C₆An alkylene group; r⁴And R⁵Is independently H, C₁-C₆Alkyl, aryl, heteroaryl, and heteroaryl,Or with said R⁴And R⁵The attached N together form a5 or 6 membered ring optionally fused to an aromatic or non-aromatic ring; r⁶Is H or C₁-C₆Alkyl, or-CH₂-(NH-R²)_n-NR⁴R⁵(ii) a Y is a covalent bond or C (O); and n is 0, 1,2, 3,4, 5,6, 7 or 8.

28. A copolymer derived from ethylene and one or more C_3-10α -olefin, wherein the copolymer has a number average molecular weight of less than 5,000g/mol as measured by GPC, wherein the copolymer has an ethylene unit content of less than 80 mol%, wherein 70 mol% or more of the copolymer has a carbon-carbon double bond in a terminal monomer unit, and at least 70 mol% of the terminal monomer unit having a carbon-carbon double bond has a terminal vinylidene group, one or more of the trisubstituted isomers of the terminal vinylidene group, and any combination thereof, and wherein the copolymer has a storage modulus equal to the loss modulus of the copolymer at a temperature of-30 ℃ or less, the values of the storage modulus and the loss modulus of the copolymer being determined by oscillatory rheology.

29. The copolymer of sentence 28, wherein the terminal vinylidene group of the copolymer and the trisubstituted isomer of a terminal vinylidene group have one or more of the following structural formulae (a) through (C):

wherein R represents C₁-C₈Alkyl radical, andindicating the bond to the remainder of the copolymer.

30. The copolymer of clause 28, wherein the copolymer is prepared by¹³C NMR spectroscopy of the copolymer for average ethylene continuous chain length (n)_C2) Less than 2.6.

31. The copolymer of sentence 30, wherein

n_{C2, practice}<n_{C2, statistics}。

32. The copolymer of any of sentences 28 or 29, wherein the copolymer has a crossover temperature of-20 ℃ or less.

33. The copolymer of any of sentences 28 to 32, wherein the ethylene unit content is less than 70 mol%.

34. The copolymer of any of sentences 28 to 33 wherein less than 65% of the total number of units in the copolymer are ethylene-derived units.

35. The copolymer of any of sentences 28 to 34, wherein less than 60% of the total number of units in the copolymer are ethylene-derived units.

36. The copolymer of any of sentences 28 to 35, wherein less than 55% of the total number of units in the copolymer are ethylene-derived units.

37. The copolymer of any of sentences 28 to 36, wherein less than 50% of the total number of units in the copolymer are ethylene-derived units.

38. The copolymer of any of sentences 28 to 37, wherein less than 45% of the total number of units in the copolymer are ethylene-derived units.

39. The copolymer of any of sentences 28 to 38, wherein less than 40% of the total number of units in the copolymer are ethylene-derived units.

40. The copolymer of any of sentences 28 to 39, wherein at least 10% and less than 80% of the total number of units in the copolymer are ethylene-derived units.

41. The copolymer of any of sentences 28 to 40 wherein at least 20% and less than 70% of the total number of units in the copolymer are ethylene-derived units.

42. The copolymer of any of sentences 28 to 41, wherein at least 30% and less than 65% of the total number of units in the copolymer are ethylene-derived units.

43. The copolymer of any of sentences 28 to 42, wherein at least 40% and less than 60% of the total number of units in the copolymer are ethylene-derived units.

44. The copolymer of any of sentences 28 to 43, wherein at least 20% of the total of the copolymers is in the copolymerThe unit of the number is C₃-C₁₀α -olefin derived units.

45. The copolymer of any of sentences 28 to 44, wherein at least 30% of the total number of units in the copolymer is C₃-C₁₀α -olefin derived units.

46. The copolymer of any of sentences 28 to 45, wherein at least 35% of the total number of units in the copolymer is C₃-C₁₀α -olefin derived units.

47. The copolymer of any of sentences 28 to 46, wherein at least 40% of the total number of units in the copolymer is C₃-C₁₀α -olefin derived units.

48. The copolymer of any of sentences 28 to 47, wherein at least 45% of the total number of units in the copolymer is C₃-C₁₀α -olefin derived units.

49. The copolymer of any of sentences 28 to 48, wherein at least 50% of the total number of units in the copolymer is C₃-C₁₀α -olefin derived units.

50. The copolymer of any of sentences 28 to 49, wherein at least 55% of the total number of units in the copolymer is C₃-C₁₀α -olefin derived units.

51. The copolymer of any of sentences 28 to 50, wherein at least 60% of the total number of units in the copolymer is C₃-C₁₀α -olefin derived units.

52. The copolymer of any of sentences 28 to 51, wherein at least 75 mol% of the terminal monomer units having the carbon-carbon double bond have a terminal unsaturation selected from the terminal vinylidene group, one or more of the trisubstituted isomers of the terminal vinylidene group, and any combination thereof.

53. The copolymer of any of sentences 28-52 wherein at least 80 mol% of the terminal monomer units having the carbon-carbon double bond have a terminal unsaturation selected from the terminal vinylidene group, one or more of the trisubstituted isomers of the terminal vinylidene group, and any combination thereof.

54. The copolymer of any of sentences 28-53 wherein at least 85 mol% of the terminal monomer units having the carbon-carbon double bond have a terminal unsaturation selected from the terminal vinylidene group, one or more of the trisubstituted isomers of the terminal vinylidene group, and any combination thereof.

55. The copolymer of any of sentences 28 to 54 wherein at least 90 mol% of the terminal monomer units having the carbon-carbon double bond have a terminal unsaturation selected from the terminal vinylidene group, one or more of the trisubstituted isomers of the terminal vinylidene group, and any combination thereof.

56. The copolymer of any of sentences 28-55 wherein at least 95 mol% of the terminal monomer units having the carbon-carbon double bond have a terminal unsaturation selected from the terminal vinylidene group, one or more of the trisubstituted isomers of the terminal vinylidene group, and any combination thereof.

57. The copolymer of any of sentences 28 to 56, wherein the average ethylene-derived unit continuous link length of the copolymer is less than 2.8.

58. The copolymer of any of sentences 28 to 57, wherein the average ethylene-derived unit continuous link length of the copolymer is less than 2.6.

59. The copolymer of any of sentences 28 to 58, wherein the average ethylene-derived unit continuous link length of the copolymer is less than 2.4.

60. The copolymer of any of sentences 28 to 59, wherein the average ethylene-derived unit continuous link length of the copolymer is less than 2.2.

61. The copolymer of any of sentences 28 to 60, wherein the average ethylene-derived unit continuous link length of the copolymer is less than 2.

62. The copolymer of any of sentences 28 to 61, wherein the storage modulus of the copolymer is equal to the loss modulus of the copolymer at a temperature of-25 ℃ or less.

63. The copolymer of any of sentences 28-62, wherein the storage modulus of the copolymer is equal to the loss modulus of the copolymer at a temperature of-30 ℃ or less.

64. The copolymer of any of sentences 28 to 63, wherein the storage modulus of the copolymer is equal to the loss modulus of the copolymer at a temperature of-35 ℃ or less.

65. The copolymer of any of sentences 28-64, wherein the storage modulus of the copolymer is equal to the loss modulus of the copolymer at a temperature of-40 ℃ or less.

66. The copolymer of any of sentences 28 to 65, wherein the polydispersity index of the copolymer is less than or equal to 4.

67. The copolymer of any of sentences 28 to 66, wherein the polydispersity index of the copolymer is less than or equal to 3.

68. The copolymer of any of sentences 28 to 67, wherein the polydispersity index of the copolymer is less than or equal to 2.

69. The copolymer of any of sentences 28 to 68, wherein the C is₃-C₁₀α -olefin derived units comprise propylene derived units.

70. The copolymer of any of sentences 28-69, wherein the number average molecular weight of the copolymer is less than 5000 g/mol.

71. The copolymer of any of sentences 28 to 70, wherein the number average molecular weight of the copolymer is less than 4000 g/mol.

72. The copolymer of any of sentences 28 to 71 wherein the number average molecular weight of the copolymer is less than 3000 g/mol.

73. The copolymer of any of sentences 28-72, wherein the number average molecular weight of the copolymer is less than 2500 g/mol.

74. The copolymer of any of sentences 28 to 73, wherein the number average molecular weight of the copolymer is less than 2000 g/mol.

75. The copolymer of any of sentences 28 to 74, wherein the number average molecular weight of the copolymer is less than 1500 g/mol.

76. The copolymer of any of sentences 28 to 75, wherein the number average molecular weight of the copolymer is less than 1000 g/mol.

77. The copolymer of any of sentences 28 to 76, wherein the number average molecular weight of the copolymer is between 800 and 3000g/mol as measured by GPC.

78. The copolymer of any of sentences 28 to 77, having a total metal or ash content of 25ppmw or less, based on the total weight of the copolymer.

79. The copolymer of sentence 78, wherein the copolymer has a total Zr, Ti, Al, and B content of 25ppmw or less based on the total weight of the copolymer, wherein the Zr, Ti, Al, and B are derived from a single-site catalyst and an optional cocatalyst.

80. The copolymer of any of sentences 78 and 79, wherein the copolymer has a total Zr, Ti, Al, and B content of 10ppmw or less, or 5ppmw or less, or 1ppmw or less, based on the total weight of the copolymer, wherein the Zr, Ti, Al, and B are derived from a single-site catalyst and optionally a co-catalyst.

81. The copolymer of any of sentences 28 to 80 having a fluorine content of less than 10ppmw, or less than 8ppmw, or less than 5ppmw, based on the total weight of the copolymer.

82. A dispersant prepared by functionalizing the copolymer according to any one of sentences 28 to 81.

83. The dispersant of sentence 82, wherein the dispersant has one of the following formulas:

wherein R is¹Being hydrocarbon radicals derived from said copolymer, R²Is divalent C₁-C₆Alkylene radical, R³Is divalent C₁-C₆Alkylene radical, R⁴And R⁵Is independently H, C₁-C₆Alkyl, or with said R⁴And R⁵The attached N together form a5 or 6 membered ring optionally fused to an aromatic or non-aromatic ring; r⁶Is H or C₁-C₆Alkyl, Y is a covalent bond or c (o), and n is 0, 1,2, 3,4, 5,6, 7, or 8.

84. A lubricating oil, comprising: a base oil; and 0.2 to 20 wt% of a dispersant according to any one of sentences 82 or 83.

85. The lubricating oil of sentence 84, wherein the dispersant comprises less than 15 wt% of the lubricating oil based on the total weight of the lubricating oil.

86. The lubricating oil according to any one of sentences 84 or 85, wherein the dispersant comprises less than 10 wt% of the lubricating oil based on the total weight of the lubricating oil.

87. The lubricating oil of any one of sentences 84-86, wherein the dispersant comprises less than 5 wt% of the lubricating oil based on the total weight of the lubricating oil.

88. The lubricating oil of any one of sentences 84-87, wherein the lubricating oil has an MRV viscosity value at-25 ℃ of 60,000cP or less.

89. The lubricating oil according to any one of sentences 84 to 88, wherein the lubricating oil has an MRV viscosity value at-30 ℃ of 60,000cP or less.

90. The lubricating oil of any one of sentences 84-89, wherein the lubricating oil has an MRV viscosity value at-35 ℃ of 60,000cP or less.

91. The lubricating oil of any one of sentences 84-90, wherein the lubricating oil has an MRV viscosity value at-40 ℃ of 60,000cP or less.

92. A fuel or fuel additive composition comprising a derivatized copolymer of the formula:

wherein R is¹Being a hydrocarbon radical derived from the copolymer according to sentence 1, R⁴And R⁵Is independently H, C₁-C₆Alkyl, or with said R⁴And R⁵The attached N together form a5 or 6 membered ring optionally fused to an aromatic or non-aromatic ring; and R is⁶Is H or C₁-C₆An alkyl group.

93. The dispersant of sentence 82, wherein the dispersant is prepared by functionalizing the copolymer by one of the following chemical mechanisms: a succinimide-succinimide process, a Koch (Koch) process, a Mannich (Mannich) process, a hydroformylation-reduction-amination process, or a halogenation-amination process.

94. A dispersant prepared by a process comprising: derived from ethylene and one or more C_3-10α -a copolymer of an olefin, wherein the copolymer has a number average molecular weight of less than 5,000g/mol as measured by GPC, wherein the copolymer has an ethylene unit content of less than 80 mol%, wherein 70 mol% or more of the copolymer has a carbon-carbon double bond in a terminal monomer unit, and at least 70 mol% of the terminal monomer unit having a carbon-carbon double bond has a terminal unsaturation selected from a terminal vinylidene group, one or more trisubstituted isomers of the terminal vinylidene group, and any combination thereof, and wherein the copolymer has a molecular weight of less than 5,000g/mol as measured by GPC, and wherein the copolymer has a molecular weight of less than 80 mol% and wherein the copolymer has a molecular¹³C NMR spectroscopy said copolymer having an average ethylene continuous chain length n of less than 2.6_c2Average ethylene derived unit continuous chain length n_c2Is defined as the total number of ethylene derived units in the copolymer divided by the number of consecutive links of one or more sequential ethylene derived units in the copolymer, and wherein

n_{C2, practice}<n_{C2, statistics}。

95. The dispersant of sentence 94, wherein the terminal vinylidene group of the copolymer and the trisubstituted isomer of the terminal vinylidene group have one or more of the following structural formulae (a) through (C):

wherein R represents C₁-C₈Alkyl radical, andindicating the bond to the remainder of the copolymer.

96. The dispersant of clauses 94 or 95, wherein the copolymer has a crossover temperature of-25 ℃ or less.

97. A dispersant according to any of sentences 94 to 96 wherein the copolymer has a crossover temperature of-35 ℃ or less.

98. A dispersant according to any of sentences 94 to 97 wherein the ethylene unit content is less than 60 mol%.

99. A dispersant according to any of sentences 94 to 98 wherein the ethylene unit content is less than 50 mol%.

100. The dispersant of any of sentences 94 to 99 wherein at least 10% and less than 80% of the total number of units in the copolymer are ethylene derived units.

101. The dispersant of any of sentences 94 to 100 wherein at least 85 mol% of the terminal monomeric units having the carbon-carbon double bond have a terminal unsaturation selected from the terminal vinylidene group, one or more of the trisubstituted isomers of the terminal vinylidene group, and any combination thereof.

102. The dispersant of any of sentences 94 to 101 wherein at least 95 mol% of the terminal monomeric units having the carbon-carbon double bond have a terminal unsaturation selected from the terminal vinylidene group, one or more of the trisubstituted isomers of the terminal vinylidene group, and any combination thereof.

103. A dispersant according to any of sentences 94 to 102 wherein the average ethylene continuous link length of the copolymer is less than 2.4.

104. A dispersant according to any of sentences 94 to 103 wherein the average ethylene continuous link length of the copolymer is less than 2.2.

105. The dispersant of any of sentences 94 to 104 wherein the polydispersity index of the copolymer is less than or equal to 4.

106. The dispersant of any of sentences 94 to 105 wherein the polydispersity index of the copolymer is less than or equal to 3.

107. A dispersant according to any of the sentences 94 to 106 wherein said copolymer is an ethylene-propylene copolymer wherein the ethylene unit content is from 30 to 80 mol% and the propylene unit content is from 20 to 70 mol%.

108. A dispersant according to any of sentences 94 to 107 wherein said copolymer is an ethylene-propylene copolymer wherein the ethylene unit content is from 40 to 60 mol% and the propylene unit content is from 40 to 60 mol%.

109. A dispersant according to any of the sentences 94 to 108 wherein said copolymer is an ethylene-propylene copolymer wherein the ethylene unit content is about 40 to 50 mol% and the propylene unit content is about 50 to 60 mol%.

110. A dispersant according to any one of sentences 94 to 109 wherein the number average molecular weight of the copolymer is less than 3,500g/mol as measured by GPC.

111. A dispersant according to any one of sentences 94 to 110 wherein the number average molecular weight of the copolymer is less than 1,500g/mol as measured by GPC.

112. The dispersant of any of sentences 94-111 wherein the dispersant is post-processed.

113. The dispersant of any of clauses 94-112, wherein the dispersant is post-treated with an anhydride, a boron compound, or a mixture thereof.

114. The dispersant of any of sentences 94 to 113 wherein the dispersant has one of the following formulas:

wherein R is¹Is a hydrocarbyl group derived from the copolymer; r²Is divalent C₁-C₆An alkylene group; r³Is divalent C₁-C₆An alkylene group; r⁴And R⁵Is independently H, C₁-C₆Alkyl, aryl, heteroaryl, and heteroaryl,Or with said R⁴And R⁵The attached N together form a5 or 6 membered ring optionally fused to an aromatic or non-aromatic ring; r⁶Is H or C₁-C₆Alkyl, or-CH₂-(NH-R²)_n-NR⁴R⁵(ii) a Y is a covalent bond or C (O); and n is 0, 1,2, 3,4, 5,6, 7 or 8.

115. The dispersant of any of sentences 94 to 113 wherein the total metal or ash content of the copolymer is 25ppmw or less based on the total weight of the copolymer.

116. The dispersant of sentence 115, wherein the total metal or ash content is a total content of Zr, Ti, Al, and B derived from a single-site catalyst and an optional promoter.

117. The dispersant of any of sentences 115 and 116 wherein the total Zr, Ti, Al, and B content of the copolymer is 10ppmw or less, or 5ppmw or less, or 1ppmw or less, based on the total weight of the copolymer, wherein the Zr, Ti, Al, and B are derived from a single-site catalyst and an optional co-catalyst.

118. The dispersant of any of sentences 94 to 117 having a fluorine content of less than 10ppmw, or less than 8ppmw, or less than 5ppmw, based on the total weight of the copolymer.

119. A lubricating oil, comprising: at least 50 wt% of a base oil; 3 to 20 wt% of a viscosity index improver; 0 to 1 wt% of a pour point depressant; and 0.2 to 20 wt% of the dispersant according to any one of sentences 94 to 118.

120. The lubricating oil of sentence 119, wherein the lubricating oil has a Micro Rotary Viscometer (MRV) value at-30 ℃ of 60,000cP or less as determined by ASTM D4684 testing.

121. The lubricating oil of any one of sentences 119 or 120, wherein the lubricating oil has a Micro Rotary Viscometer (MRV) value at-40 ℃ of 60,000cP or less as determined by the ASTM D4684 test.

122. The lubricating oil according to any one of the sentences 119-121, wherein the dispersant comprises less than 10 wt% of the lubricating oil.

123. A lubricating additive package comprising 30 to 80 wt% of the dispersant of any one of sentences 94 to 118.

124. A fuel composition or fuel additive composition comprising the dispersant according to sentences 94 to 118.

125. The fuel composition or fuel additive composition of sentence 124, the dispersant having one of the following formulas:

wherein R is¹Is a hydrocarbyl group derived from the copolymer; r²Is divalent C₁-C₆An alkylene group; r³Is divalent C₁-C₆An alkylene group; r⁴And R⁵Is independently H, C₁-C₆Alkyl, aryl, heteroaryl, and heteroaryl,Or with said R⁴And R⁵The attached N together form a5 or 6 membered ring optionally fused to an aromatic or non-aromatic ring; r⁶Is H or C₁-C₆Alkyl, or-CH₂-(NH-R²)_n-NR⁴R⁵(ii) a Y is a covalent bond or C (O); and n is 0, 1,2, 3,4, 5,6, 7 or 8.

Additional details and advantages of the disclosure will be set forth in part in the description which follows and/or may be learned by practice of the disclosure. The details and advantages of the disclosure may be realized and obtained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure, as claimed.

In the event that the present specification and a document incorporated by reference include conflicting and/or inconsistent disclosure, the present specification controls. If two or more documents incorporated by reference include disclosures that conflict and/or are inconsistent with each other, then the document with the later effective date controls.

Drawings

Non-limiting embodiments of the present invention will be described by way of example with reference to the accompanying drawings, which are schematic and are not intended to be drawn to scale. In the drawings, each identical or nearly identical component that is illustrated is typically represented by a single numeral. For purposes of clarity, not every component may be labeled in every drawing, nor is every component of each embodiment of the invention shown where illustration is not necessary to allow those of ordinary skill in the art to understand the invention. In the drawings:

FIG. 1 is C in accordance with one or more embodiments₂/C₃A graphical representation of the average ethylene continuous chain segment length versus pure statistical and alternating microstructure of the copolymer at different ethylene incorporation levels;

FIG. 2 is a graphical representation of the effect of reactor temperature on microstructure in accordance with one or more embodiments;

FIG. 3 is a graphical representation of crossover temperature versus average ethylene continuous link length worse than statistical microstructure and better than statistical microstructure in accordance with one or more embodiments; and

FIG. 4 is a graphical representation of crossover temperature versus average ethylene continuous link length for copolymers only that are better than statistical microstructures in accordance with one or more embodiments.

FIG. 5 is a graphical representation of the temperature profile as a function of olefin flow rate into the reactor.

Fig. 6 is a graphical representation of the measured molecular weights and ethylene incorporation for the first six samples used in the low metal and/or fluorine content examples.

Detailed Description

ethylene-C is described generally herein₃-C₁₀α -olefin copolymer, dispersant, and lubricating oil/fuel composition incorporating dispersant (or detergent in fuel), and related methods₃-C₁₀α -olefin derived units C₃-C₁₀α -olefin derived units may have a carbon number of 3,4, 5,6, 7,8, 9, or 10, for example, C₃-C₁₀α the olefin derived units may be propylene derived units.

Ethylene derived units generally refer to the-CH within the copolymer chain₂CH₂Units derived from ethylene molecules during copolymerization, having the same meanings as apply to C₃-C₁₀α -similar definitions for olefin derived units or any other designated derived units the term "olefin" has its ordinary meaning in the art, e.g., refers to a compound of formula C_xH_2xThe term "α -olefin" has its ordinary meaning in the art and refers to an olefin having a double bond within its structure at the primary or α position.

In accordance with one or more embodiments, ethylene-C is generally disclosed₃-C₁₀α -olefin copolymer the copolymer may comprise ethylene derived units and C₃-C₁₀α -olefin derived units wherein C₃-C₁₀α -olefins have a carbon number of three to ten₃-C₁₀α -the number of carbons of the olefin may be 3,4, 5,6, 7,8, 9, or 10, for example, according to some embodiments, C₃-C₁₀α -the olefin derived units are propylene derived units in some embodiments, C₃-C₁₀α -olefin derived units may be 1-butene-, 1-pentene-, 1-hexene-, 1-heptene-, 1-octene-, 1-nonene-, or 1-decene-derived units.

Cross temperature

One characteristic of a copolymer that helps define its behavior at low temperatures is its crossover temperature or onset temperature. The copolymer may be generally viscoelastic; in other words, its mechanical properties are intermediate between those of a purely elastic solid and those of a purely viscous liquid. The viscoelastic behavior of a copolymer can be characterized as a combination of an elastic moiety (alternatively referred to as the elastic modulus or storage modulus) and a viscous moiety (alternatively referred to as the viscous modulus or loss modulus). These modulus values are used to characterize the viscoelasticity of the copolymer at a certain temperature. Copolymers having relatively more elastic and relatively less viscous portions will behave more like a purely elastic solid, while copolymers having relatively less elastic and relatively more viscous portions will behave more like a purely viscous liquid. Both the storage modulus and the loss modulus are functions of temperature, although they may change at different rates as a function of temperature. In other words, depending on the temperature, the copolymer may exhibit greater elasticity or greater viscosity. The maximum temperature at which the value of the storage modulus of the copolymer, determined by oscillatory rheometry, is equal to the value of the loss modulus is called the crossover temperature or onset temperature.

Oscillatory rheology is a technique that can be used to determine values of loss and storage modulus (typically expressed in units of pressure). The basic principle of an oscillating rheometer is to induce a sinusoidal shear deformation in a sample (e.g., a copolymer sample) and measure the resulting stress response. In a typical experiment, a sample is placed between two plates. While the top plate remains stationary, the motor rotates or oscillates the bottom plate, thereby applying a time-dependent strain to the sample. At the same time, the time-dependent stress was quantified by measuring the torque exerted by the sample on the top plate.

Measuring this time-dependent stress response reveals features about the material behavior. If the material is an ideal elastic solid, the sample stress is proportional to the strain deformation and the proportionality constant is the shear modulus of the material. The stress is always exactly in phase with the applied sinusoidal strain deformation. Conversely, if the material is a purely viscous fluid, the stress in the sample is proportional to the rate of strain deformation, where the proportionality constant is the viscosity of the fluid. The applied strain and the measured stress are out of phase.

Viscoelastic materials show a response containing both in-phase and out-of-phase contributions. These contributions reveal the extent of solid-like and liquid-like behavior. Viscoelastic materials will show a phase shift with respect to strain deformation applied between a solid and a liquid. These can be separated into an elastic component (storage modulus) and a viscosity component (loss modulus). Thus, the viscoelastic behavior of the system can be characterized by the storage modulus and loss modulus that characterize the solid-like and fluid-like contributions to the measured stress response, respectively.

As mentioned, the value of the modulus depends on the temperature. At warmer temperatures, the value of the loss modulus of the copolymer is greater than the value of the storage modulus. However, as the temperature decreases, the copolymer may behave more like an elastic solid, and the storage modulus contributes to a degree close to the loss modulus. As the temperature decreases, eventually, at a certain temperature, the storage modulus of the neat copolymer crosses the loss modulus and becomes a major contributor to the viscoelastic behavior of the neat copolymer. As mentioned above, the temperature at which the storage modulus of the neat copolymer equals the loss modulus is referred to as the crossover temperature or onset temperature. According to one or more embodiments, a lower crossover temperature of the copolymer correlates with better low temperature performance of the oil incorporating the copolymer.

Thus, according to one or more embodiments, the crossover temperature of the copolymer (that is, the temperature at which the storage modulus of the copolymer equals the loss modulus of the copolymer) can be-20 ℃ or less, -25 ℃ or less, -30 ℃ or less, -35 ℃ or less, or-40 ℃ or less, or-50 ℃ or less, -60 ℃ or less, -70 ℃ or less; for example, as determined by oscillatory rheology. Other values are also possible. As discussed herein, the advantageous crossover temperature of the copolymer can be achieved by controlling the characteristics of the copolymer during manufacture. One such feature is the average ethylene continuous link length.

Average ethylene continuous link length and triad distribution

According to one or more embodiments, the ethylene derived units and C in the copolymer₃-C₁₀α -the sequence of olefin derived units can be arranged in a manner that provides good low temperature performanceAs used herein, "average ethylene continuous mer length" refers to the average ethylene-derived unit continuous mer length incorporated into the copolymer.

In a copolymer molecule comprising chains of subunits of the first and second type (e.g., ethylene-derived and propylene-derived subunits), neither species will be uniformly distributed along the copolymer chain. Rather, some amount of random distribution of different types of monomer-derived units will occur. For example, in a representative copolymer comprising four species a monomer-derived units and four species B monomer-derived units, the monomer-derived units may be distributed as follows: A-A-B-A-B-B-A, or in any other manner. The average consecutive mer length of a species is the average number of sequential occurrences of the species, and the average consecutive mer length of a copolymer can be determined on average by dividing the number of total monomer derived units of a species by the number of consecutive mers of the species. For example, in the above example, there are a total of four a units and three separate a unit consecutive links. Thus, the average continuous link length of substance a is 1.33. For substance B, there are a total of four B units and two separate consecutive building blocks of B units. Thus, the average continuous link length of substance B was 2.0. The average ethylene-derived unit continuous mer length is defined as the total number of ethylene-derived units in the copolymer divided by the number of continuous mer of one or more sequential ethylene-derived units in the copolymer, and the average ethylene-derived unit continuous mer length n_c2。

Methods for determining ethylene sequence values are known in the art and include the use¹³Spectroscopic procedures established by C-NMR methods are described, for example, in "Carbon-13 NMR in Polymer science" in the American Society for chemistry, workshop 103 Series (ACS Symposium Series 103), the American Chemical Society of chemistry (American Chemical Society), Washington Columbia region (D.C.), 1978, p.97, and "Polymer sequencing Determination Carbon-13NMR method (Polymer sequencing diagnosis Carbon-13NM method"), J.C. Randall, Academic Press, N.Y. ", p.53.

For example, one can measure tris in a copolymerTuple distribution to calculate average ethylene continuous link length (n)_{C2, practice}). The "triad distribution" is the sequential arrangement of monomer units in the copolymer. The ternary distribution refers to the statistical distribution of the possible combinations of three consecutive subunits in the copolymer chain. Taking an ethylene-propylene copolymer as an example, where "E" represents ethylene derived units and "P" represents propylene derived units, a potential combination of triads of monomer units includes: E-E-E, E-E-P, P-E-E, P-E-P, E-P-E, P-P-E, E-P-P and P-P-P. According to one or more embodiments, the amount of E-E is less than 20%, less than 10%, or less than 5%, which indicates a relatively short n_{C2, practice}。

Methods for calculating the triad distribution of ethylene-propylene copolymers are described in J.C. Randall "JMS Review macromolecular chemical Physics (JMS-Review Macromolecules Chem Physics) C29, (1989) and E.W. Hansen, K.Redford" polymers (Polymer)' Vol 37, No. 1, pp 19-24 (1996). Collecting under quantitative conditions¹³After C NMR data, the eight regions (A-H) shown in Table 2 were integrated. The equations of table 3 are applied and the values are normalized. For the example described herein, the D, E and F regions are combined, k is a normalization constant, and T is the total intensity, due to peak overlap. The factor k is the NMR proportionality constant, which relates the observed resonance intensity to the number of contributing molecular species. Once a complete set of triplets is obtained, they can be removed later by normalization, as explained in j.c. randall "JMS-Review of polymer chemistry and Physics (JMS-Review Macromolecules Chem Physics) C29,201 (1989). Tables 2 and 3 are specifically used to calculate the molar fraction of the triads found in the ethylene-propylene copolymer. Those skilled in the art can modify C¹³NMR data collection to calculate the content of ethylene derived units and other C₄-C₁₀α -triad mole fraction of copolymer of olefin derived units.

The calculated mole fractions of the EEE, AEE, EEA and AEA triplets are input into equation 5 to obtain n_{C2, practice}. When in useWhen the measurements and calculations from the ethylene-propylene copolymer are used in equation 5, AEE is PEE, EEA is EEP, and AEA is PEP.

The copolymers herein must have n less than 2.6_{C2, practice}. When used in a finished fluid, contains n_{C2, practice}Dispersants of the copolymer less than 2.6 exhibit excellent cold weather performance as evidenced by the MRV test (ASTM D4684-14) and as shown in additional detail below.

However, the copolymers herein not only must have n less than 2.6_{C2, practice}And the following relationship must be satisfied:

n_{c2, practice}<n_{C2, statistics}

In the case where the arrangement of species a and B in the plurality of copolymer chains is purely random (i.e., each of a and B has a chance to occur somewhere in proportion to the amount of the species and whether the immediately preceding species is an a unit or a B unit), the expected average continuous mer length of species a can be statistically calculated as a function of the mole percent of species a in the copolymer, as understood by one of ordinary skill in the art. This value is referred to as the statistically expected random average consecutive link length (n)_{C2, statistics}) As will be discussed in additional detail below.

According to one or more embodiments, the copolymer may be synthesized by: by said method, n_{C2, practice}Less than n_{C2, statistics}. For example, the one or more catalysts may be selected such that during chain formation, propylene-derived units favor bonding with previous ethylene-derived units, while ethylene-derived units favor bonding with previous propylene-derived units, as discussed further below. As a result, n is obtained_{C2, practice}N of ethylene reduced and less than a given mole percent_{C2, statistics}. When n is_{C2, practice}Copolymers range between statistical and alternating when less than the average continuous segment length expected for random distribution. Instead ofWhen n is substituted_{C2, practice}Copolymers are between statistical and block when larger than the average continuous chain segment length expected for random distribution.

According to one or more embodiments, n_{C2, practice}At least in part as a function of the percentage of ethylene units in the copolymer and the catalyst selected. For example, a higher percentage of ethylene units will naturally result in a higher average continuous link length. The choice of catalyst affects the average continuous link length because the catalyst affects the relative insertion rates of the different units.

Thus, using an ethylene-propylene copolymer as an illustrative example, the reaction rate during formation of the copolymer chain, where an ethylene molecule is bonded to a previous ethylene unit at the end of the growing polymer chain, is referred to as the ethylene-ethylene propagation reaction rate constant ("k_pEE"). Wherein propylene (or other C)₃-C₁₀α -olefin comonomer) is referred to as the ethylene-propylene propagation reaction rate constant ("k ″) the reaction rate at which ethylene units are bonded to the ends of a growing polymer chain_pEP"). Reactivity ratio of ethylene (' r)_E") means the ratio k of the ethylene-ethylene propagation reaction rate constant to the ethylene-propylene propagation reaction rate constant_pEE/k_pEP。

Likewise, wherein propylene (or other C)₃-C₁₀α -olefin) molecules are bonded to propylene derived units at the ends of the growing polymer chain, referred to as the propylene-propylene reaction rate constant ("k_pPP"). The reaction rate at which ethylene molecules are bonded to propylene units at the ends of a growing polymer chain is referred to as the ethylene-propylene reaction rate constant ("k_pPE"). Reactivity ratio of propylene ("r)_P") means the ratio k of the propylene-propylene reaction rate constant to the propylene-ethylene reaction rate constant_pPP/k_pPE。

Each reactivity ratio (r)_EOr r_P) The lower, the more likely it is that a different unit will follow the preceding unit (e.g., ethylene follows propylene, or vice versa), and the resulting polymer chain will have alternating characteristics, where n_{C2, practice}Is lower thanThe continuous link lengths expected for a purely random distribution of units. In accordance with one or more embodiments, selection of an appropriate catalyst and control of other process parameters as discussed herein may reduce the reactivity ratio and thus n_{C2, practice}For example when used with propylene or other C as discussed herein₃-C₁₀α -copolymerization of olefins.

Lower n_{C2, practice}Certain advantages may be provided. For example, it can result in a lower crossover temperature of the copolymer, thereby improving the performance (e.g., cold weather performance) of dispersants comprising the copolymer and lubricating oils comprising the dispersant. In general, without wishing to be bound by any theory, it is believed that for a given ethylene unit content, n_{C2, practice}The shorter the cross-over temperature of the copolymer, the lower, which ultimately results in better low temperature performance of the lubricating oil incorporating the dispersant prepared from the copolymer.

According to one or more embodiments, comprising ethylene derived units and C₃-C₁₀α -copolymers of olefin derived units_{C2, practice}N of less than a given mole percent of ethylene derived units in the copolymer_{C2, statistics}. For example, as shown in FIG. 2, Cp comprising a coordinated metallocene is used under certain reaction conditions₂ZrCl₂The coordination polymerization catalyst and methylaluminoxane of (A) as a cocatalyst result in the production of n_{C2, practice}Less than n randomly distributed at a given percentage of ethylene units_{C2, statistics}The copolymer of (1).

According to one or more embodiments, n of the copolymer_{C2, practice}Can be less than 3.0, less than 2.9, less than 2.8, less than 2.7, less than 2.6, less than 2.5, less than 2.4, less than 2.3, less than 2.1, or less than 2.0. According to one or more embodiments, comprising ethylene and C₃-C₁₀α -copolymers of olefinic substances n_{C2, practice}N less than the mole percent of ethylene given in the copolymer_{C2, statistics}。

Statistical and alternating microstructures

Ethylene (C) produced from a fully alternating microstructure₂) And propylene (C)₃) Will not haveC₂The continuous chain link length distribution is because each ethylene sequence is exactly the same. The ethylene continuous link length of the fully alternating microstructure is calculated from equation (1).

However, a copolymer that does not have a fully alternating microstructure will have C₂Continuous link length distribution and prediction of pure statistical microstructure represents C₂Average C of continuous link length distribution₂Continuous link length (also referred to as "average ethylene continuous link length"). Average C of copolymers produced from a purely statistical microstructure₂The continuous link lengths may be statistically calculated from Bernoullian (Bernoullian). Mole fraction x of ethylene incorporated in the copolymer_C2By passing¹H-NMR spectroscopy was performed and used to calculate the fraction of the triplet EEE, AEE (or PEE), EEA (or EEP) and AEA (or PEP) (there are also EAE (or EPE), AAE (or PPE), EAA (or EPP) and AAA (or PPP)) in the pure statistical copolymer by equations (3) - (5).

EEE＝(x_C2)³(3)

(AEE+EEA)＝2(x_C2)²(1-x_C2) (4)

AEA＝x_C2(1-x_C2)²(5)

C in mol%₂Incorporation amount (x)_C2) Can be prepared using standard techniques known to those of ordinary skill in the art¹H-NMR or¹³C NMR measurement.

FIG. 1 shows n at different ethylene incorporation_{C2, practice}And comparison between alternans and calculation of statistical results. n is_{C2, practice}Comparison with the calculated statistical and alternation results gives whether the copolymer produced has less than n_{C2, statistics}Is indicative of the microstructure of (a). Without being bound by any theory, it is believed that the less-than-statistical microstructure hasWider C around the mean₂The continuous links are distributed in length.

Increasing the ethylene unit content of the copolymer increases the plasticizing efficiency, plasticizing durability, and oxidation stability of the plasticizer, but also reduces the amount of structure formation that can occur at lower temperatures. Unexpectedly, the specific combination of properties and microstructure of the copolymers of the present invention provide sufficient plasticizing efficiency, plasticizing durability, and oxidative stability, while providing good low temperature performance.

The results shown in figure 1 were produced from two different catalyst systems. The amount of ethylene incorporated during polymerization is controlled using standard techniques known in the art. Using Cp₂ZrCl₂Copolymerization of the catalyst System with Cp₂ZrMe₂The copolymerization of the/FAB/TEAL catalyst system is carried out at low temperatures and in a narrow temperature range, as shown in FIG. 2.

The copolymerization reaction can be controlled to provide the desired copolymer of the present invention. Parameters such as reaction temperature, pressure, mixing, reactor thermal management, feed rate of one or more of the reactants, type, ratio and concentration of catalyst and/or cocatalyst and/or scavenger, and phase of the feed components may be controlled to affect the structure of the copolymer obtained from the reaction. Thus, a combination of several different reaction conditions can be controlled to produce the desired copolymer.

For example, it is important to run the copolymerization reaction with proper heat management. Since the copolymerization reaction is exothermic, heat must be removed in order to maintain the desired set point temperature in the reactor. This can be done, for example, by two different methods commonly practiced in combination. Heat can be removed by cooling the feed stream entering the reactor to a temperature well below the reaction set point temperature (and sometimes even low), and thus allowing the feed stream to absorb some of the heat of reaction by increasing in temperature. In addition, heat can be removed from the reactor by external cooling (e.g., cooling coils and/or cooling jackets). The lower the set point temperature in the reactor, the greater the need for heat removal. The higher the reaction temperature, the less heat needs to be removed, or alternatively or in combination, the more concentrated the copolymer may be (higher productivity) and/or the shorter the residence time may be (smaller reactor). Figure 2 shows the results characterizing the deviation of the average ethylene continuous chain segment length from a purely statistical microstructure plotted against the reactor temperature for both catalyst systems during copolymerization.

When the reaction temperature is raised above 135 ℃, it appears that control of the microstructure may be lost and the copolymer generally becomes less than statistically bad. As a result, the low temperature characteristics of the copolymer may be impaired. Without being bound by theory, it is believed that the reduction in microstructure control of the copolymer produced at higher temperatures is due to a decrease in the reaction kinetics of comonomer incorporation relative to ethylene incorporation. The more difficult it is to incorporate the comonomer into the copolymer, the more irregularly the comonomer breaks up the continuous chain members of ethylene units in the chain during copolymerization. Some strategies to improve comonomer incorporation at higher reaction temperatures include increasing C in the reactor₃-C₁₀α -monomer ratio of olefin/ethylene, increasing Al/Zr ratio in the catalyst or by making changes to the catalyst architecture.

Thus, in some embodiments of the invention, the copolymerization reaction employs a reaction temperature of 60 to 135 ℃, or more preferably, the copolymerization reaction employs a reaction temperature of 62 to 130 ℃, or 65 to 125 ℃, or preferably 68 to 120 ℃ or 70 to 90 ℃.

Preferred Al/Zr ratios in the catalyst system may be less than 10,000:1, less than 1,000:1, less than 100:1, less than 10:1, less than 5:1, or less than 1: 1. For boron-containing technologies, preferred Al/Zr ratios in the catalyst are less than 100:1, less than 50:1, less than 10:1, less than 5:1, less than 1:1, less than 0.1:1, and preferred B/Zr ratios are less than 10:1, less than 5:1, less than 2:1, less than 1.5:1, less than 1.2:1, or less than 1: 1.

The low temperature properties of the copolymer may be related to the microstructure of the copolymer. The low temperature properties of the pure copolymers were measured by oscillatory rheology. The point where the storage modulus equals the loss modulus (i.e., the crossover or onset temperature) indicates the temperature where the copolymer will begin to exhibit unfavorable structure formation. The crossover temperature is the point where the structure formed in the copolymer exceeds the liquid-like character of the copolymer. This temperature has been shown to be predictive for determining the effect of copolymer structure on low temperature performance as a plasticizer for polyolefins.

FIG. 3 shows n_{C2, practice}Influence on crossover temperature. From Cp₂ZrCl₂The copolymers produced by the MAO catalyst system perform well and at crossover temperatures with n_{C2, practice}There is a strong correlation between them. Can control Cp₂ZrMe₂Copolymers produced by a/FAB/TEAL catalyst system to provide a desired combined crossover temperature and n_{C2, practice}. FIG. 3 shows for using Cp₂ZrMe₂The particularly broad range of crossover temperatures observed for copolymers produced by the/FAB/TEAL catalyst system. Specifically, n is about 2.6_{C2, practice}The crossover temperature of these copolymers varied from near-40 ℃ to about 5 ℃. This wide range of crossover temperatures is at the same n_{C2, practice}The various microstructures observed for these copolymers are also related. In fig. 4, only data showing better than statistical microstructure are included.

Molecular weight

The number average molecular weight of the copolymer can be determined by¹H-NMR or by Gel Permeation Chromatography (GPC) using polystyrene as a calibration reference, as described in U.S. Pat. No. 5,266,223. The GPC method additionally provides molecular weight distribution information; see, e.g., w.w.yau, j.j.kirkland, d.d.by ", Modern size exclusion Liquid Chromatography (Modern size exclusion Chromatography)", Wiley, inc (John Wiley and sons), New York (New York), 1979. According to some embodiments, the number average molecular weight of the copolymer can be less than 5,000g/mol, less than 4,500g/mol, less than 4,000g/mol, less than 3,500g/mol, less than 3,000g/mol, less than 2,800g/mol, less than 2,500g/mol, less than 2,000g/mol, less than 1,500g/mol, or less than 1,000g/mol, as determined by GPC using polystyrene standards. According to some embodiments, the number average molecular weight of the copolymer may be greater than 200g/mol, greater than 500g/mol, greater than 800g/mol, or greater than 1,000g/mol, as determined by GPC. Combinations of any of the above ranges are also possible (e.g., 200 and 1000g/mol, greater than 500 and less than 3,000g/mol, or greater than 500 and less than 1,500 g/mol). Other values are also possible.Additionally, in some cases NMR may be used in addition to and/or in place of GPC, for example, to determine the above values.

The polydispersity index (PDI) of a copolymer is a measure of the variation in the size of the individual chains of the copolymer. The polydispersity index is determined by dividing the weight average molecular weight of the copolymer by the number average molecular weight of the copolymer. The term number average molecular weight (by way of example)¹H-NMR or GPC determination) has its ordinary meaning in the art and is defined as the sum of the products of the weight of each polymer chain and the number of polymer chains having that weight divided by the total number of polymer chains. The weight average molecular weight of the copolymer has its ordinary meaning in the art and is defined as the sum of the product of the weight square of each polymer chain and the total number of polymer chains having that weight divided by the sum of the product of the weight of each polymer chain and the number of polymer chains having that weight. In accordance with one or more embodiments, the PDI of the copolymer may be less than or equal to 4, less than or equal to 3, less than or equal to 2, or less than or equal to 1.

Ethylene unit content

In some embodiments, the copolymer may comprise a mole percentage (mol%) of ethylene-derived units. According to some embodiments, the ethylene unit content of the copolymer is at least 10 mol%, at least 20 mol%, at least 30 mol%, at least 40 mol%, at least 45 mol%, at least 50 mol%, at least 55 mol%, at least 60 mol%, at least 65 mol%, at least 70 mol%, or at least 75 mol% relative to the total amount of units within the copolymer. According to some embodiments, the copolymer has an ethylene unit content of less than 80 mol%, less than 75 mol%, less than 70 mol%, less than 65 mol%, less than 60 mol%, less than 55 mol%, less than 50 mol%, less than 45 mol%, less than 40 mol%, less than 30 mol%, or less than 20 mol%, combinations of the above ranges also being possible (e.g., at least 10 mol% and less than 80 mol%, at least 20 mol% and less than 70 mol%, at least 30 mol% and less than 65 mol%, at least 40 mol% and less than 60 mol%). Other ranges are also possible, for example, by¹H-NMR or¹³C-NMR measurement.

Comonomer unit content

The copolymer may comprise a mole percentage of comonomer units, wherein the comonomer is selected from C having a carbon number of 3 and between 10₃-C₁₀α -an olefin, such as propylene, according to some embodiments, the copolymer has a comonomer unit content of at least 20 mol%, at least 25 mol%, at least 30 mol%, at least 35 mol%, at least 40 mol%, at least 45 mol%, at least 50 mol%, at least 55 mol%, at least 60 mol%, at least 65 mol%, at least 70 mol%, or at least 80 mol% relative to the total amount of monomer unit content within the copolymer-according to some embodiments, the copolymer has a comonomer unit content of less than 90 mol%, less than 80 mol%, less than 70 mol%, less than 65 mol%, less than 60 mol%, less than 55 mol%, less than 50 mol%, less than 45 mol%, less than 40 mol%, less than 35 mol%, less than 30 mol%, less than 25 mol%, or less than 20 mol%, less than 90 mol%, combinations of the above referenced ranges are possible (e.g., at least 40 mol% and less than 60 mol%), other ranges are also possible.

Degree of unsaturation

The copolymer may comprise polymeric chains. In some cases, at least 70% of these chains can each have terminal unsaturation, i.e., carbon-carbon double bonds in the terminal monomer units of the copolymer. For the avoidance of doubt, it is to be understood that the term "terminal unsaturation" means that at least one of the carbons of the carbon-carbon double bond is derived from a terminal monomeric unit. According to some embodiments, more than 50%, more than 55%, more than 60%, more than 65%, more than 70%, more than 75%, more than 80%, more than 85%, more than 90%, more than 95%, or more than 97% of the copolymer molecules each have terminal unsaturation. The percentage of polymeric chains exhibiting terminal unsaturation may be determined, for example, by FTIR spectroscopy, titration, or¹³C NMR measurement. See, for example, U.S. patent No. 5,128,056.

Terminal group

In some embodiments, at least some of the copolymers may be at one end with ethylene monomer or C₃-C₁₀α -termination of olefin monomers the unsaturation may be derived from ethylene monomers or from C₃-C₁₀α -olefin monomer if the terminal unsaturation is derived from an ethylene monomerIt may be a vinyl group or a disubstituted isomer of a vinyl group. If the terminal unsaturation is derived from C, as shown below₃-C₁₀α -an olefinic monomer, it can then be a terminal vinylidene group or a trisubstituted isomer of a terminal vinylidene group in some embodiments, more than 50%, more than 55%, more than 60%, more than 65%, more than 70%, more than 75%, more than 80%, more than 85%, more than 90%, or more than 95% of the terminal unsaturation is derived from C₃-C₁₀α -an olefin monomer, the terminal unsaturation having one or more of the following structural formulae (A) - (C):

for each of formulas (A) - (C), R represents C₁-C₈Alkyl (e.g. methyl (if C)₃-C₁₀α where the olefin is propylene), ethyl (if C₃-C₁₀α -the olefin is 1-butene), etc.), andindicating the bond to the remainder of the copolymer. In some embodiments, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, or greater than 95% of the unsaturated bonds are located at positions derived from C₃-C₁₀α -the terminal vinylidene groups of the olefin monomer are represented by the formulae (A) to (C).

As used herein, the term "terminal vinylidene" refers to a structure represented by formula (a). As used herein, the term "trisubstituted isomer of a terminal vinylidene group" refers to a structure represented by formula (B) and/or (C).

The terminal vinylidene group represented by the formula (A), the trisubstituted isomers of the terminal vinylidene groups represented by the formulae (B) and (C), and other types of terminal unsaturated bonds may be bonded through¹H-NMR. From the integrated intensity of each signal, the amount of each unsaturated bond can be determined, for example, as discussed in U.S. patent publication No. 2016/0257862. For the avoidance of doubt, the skilled person will understand that in formulae (B) and (C)Each of the first carbon atoms to the right is from the penultimate monomeric unit.

Copolymerization of olefins

In accordance with one or more embodiments, various methods for synthesizing the copolymers described herein are provided. One method is to make ethylene and C in the presence of a single-site coordination polymerization catalyst₃-C₁₀α -olefin polymerization to produce a polymer comprising ethylene derived units and C₃-C₁₀α -copolymers of olefin derived units.

According to one or more embodiments, the coordination polymerization catalyst may comprise a coordination metallocene. Metallocenes comprise a cyclopentadienyl anion ("Cp") bound to a metal center. The coordination metallocene may comprise zirconium. For example, the coordination metallocene may comprise Cp₂ZrCl₂. The coordination polymerization catalyst may additionally comprise a cocatalyst. The cocatalyst may comprise, for example, methylaluminoxane.

The copolymer may be produced in a reactor. Parameters that can be controlled during the process include pressure and temperature. The reaction may be operated continuously, semi-continuously or batchwise. Ethylene can be fed to the reactor by means of a metered ethylene gas feed. Extra C of the copolymer₃-C₁₀α -the olefin component (e.g., propylene) can be delivered by separate metered feeds the catalyst and cocatalyst can be delivered to the reactor in solution according to various embodiments, the weight percent of catalyst or cocatalyst in solution can be less than 20 wt.%, less than 15 wt.%, less than 10 wt.%, less than 8 wt.%, less than 6 wt.%, less than 5 wt.%, less than 4 wt.%, less than 3 wt.%, less than 2 wt.%, or less than 1 wt.%.

In some embodiments, the microstructure is obtained by uniformly spatially distributing the composition within the reactor. Methods to ensure homogeneity of the composition include, but are not limited to, stirring, feed location of the monomers, solvent and catalyst components, and methods of introduction. In some cases, additional factors that may affect compositional uniformity include ensuring operation at an optimal temperature and pressure space that provides a single fluid phase for the reactor based on reactor composition, and likely ensures reactor temperature and pressure conditions above the overall vapor-liquid phase behavior envelope of the feed composition. It is also contemplated that, at least in some instances, premixing of two or more of the feed components can be important, and that the premixing time and mixing intensity of the feed components is important to control uniformity within the reactor. Another subtle but important feature of certain embodiments is to ensure that there are no pockets of vapor within the reactor that would create a compositional gradient at the vapor-liquid interface or within the liquid. It is believed that lower temperatures are important to control the reactivity ratio in a way that results in a microstructure that is better than the statistical microstructure and tends to alternate microstructures. In various embodiments, some or all of the above may be important for controlling the microstructure within the polymer chains and additionally the comonomer composition variation from chain to chain.

Low metal and/or fluorine content

Copolymers with low metal content are desirable for many applications due to the deleterious effects of metals in various environments. For example, metal or ash can adversely affect aftertreatment devices employed in various types of engines. It is also desirable to ensure that the copolymer has a low fluorine content, since fluorine is ecologically undesirable in many environments.

As described herein, there are several ways to achieve low metal content in the copolymer. The present invention incorporates methods of purifying and removing impurities known to those skilled in the art. For example, in Giuseppe Forte and Sara Ronca, "" synthesis of disentangled ultra high molecular weight polyethylene: effect of Reaction Medium on Material Properties (Synthesis of discrete ultra-High Molecular Weight Polyethylene: infection of Reaction Medium Properties), "International Journal of Polymer science (2017, volume ID 3174419, page 8, 2017.doi:10.1155/2017/7431419 discloses a method for purifying polyvinyl compounds. The method for purifying the copolymer comprises reacting acidified methanol(CH₃OH/HCl) to a solution of the polymer/catalyst mixture in Dichloromethane (DCM). This results in precipitation of the "purified" polymer, while catalyst and other by-products remain in solution. The copolymer can then be filtered and rinsed off with additional methanol and dried under vacuum at 40 ℃.

According to one or more embodiments, the copolymer can be purified by passing the polymer/catalyst mixture through an adsorption column to achieve low metal content. The adsorption column contains an adsorbent, preferably activated alumina.

In a more preferred embodiment, the copolymer can be purified by stripping the polymer composition with a temperature controlled oil bath using toluene and a rotary evaporator to achieve low metal content.

In an alternative embodiment, the copolymer does not require a purification step. In this example, the copolymers of the present invention are preferably copolymerized using catalysts having a catalyst productivity of 200-1500kg of copolymer per gram of single-site catalyst, or 350-1500kg of copolymer per gram of single-site catalyst, or 500-1200kg of copolymer per gram of single-site catalyst, or 500-800 kg of copolymer per gram of single-site catalyst. Suitable single-site catalyst systems having these productivities may be selected from those known in the art. The catalyst may be selected for the production of copolymers having Mn in the range of 700-1400g/mol, or 550-650 g/mol. Selection of a suitable single-site catalyst can eliminate the need for a washing step to achieve low metal content of the copolymer.

Catalyst productivity, expressed as kg of polymer produced per gram of catalyst, can be improved by an effective catalyst system. The present invention incorporates the use of catalyst systems known to those skilled in the art that are capable of achieving high catalyst productivity. For example, U.S. patent No. 9,441,063 relates to a catalyst composition containing an activator-support and a half-metallocene titanium phosphonimide complex or a half-metallocene titanium imidoimidazolidine capable of producing polyolefins with high catalyst productivity at least up to 202kg polymer/g catalyst (551 kg polymer/g catalyst/hour with a residence time of 22 minutes, see example 5 and table 1, columns 47 and 48). Further, U.S. patent No. 8,614,277 relates to a process for preparing isotactic polypropylene and ethylene-propylene copolymers. U.S. Pat. No. 8,614,277 provides a catalyst system suitable for preparing copolymers at catalyst productivity levels greater than 200kg polymer/g catalyst. Wherein the catalyst provided is a metallocene comprising zirconium as its central atom. (see examples in tables 1a-1 c).

The copolymer can comprise a metal or ash content of 25ppmw or less, based on the total weight of the copolymer. Preferably, the metal or ash content of the copolymer is 10ppmw or less, or more preferably 5ppmw or less, or even more preferably 1ppmw or less, based on the total weight of the copolymer. Typically, the metal or ash content of the copolymer is derived from the single-site catalyst and optionally one or more co-catalysts employed in the copolymerization reactor.

These single-site catalysts may include metallocene catalysts. Zr and Ti metals are typically derived from such metallocene catalysts. Various cocatalysts may be employed in combination with the single-site catalyst. Such promoters may include boron and aluminum metals, as well as ecologically undesirable fluorine atoms or compounds. Thus, the metal or ash content of the copolymers of the present invention is such that it includes Zr. Total metal or ash of Ti, Al and/or B. Various suitable catalyst systems are described elsewhere herein.

The fluorine content of the copolymer may be less than 10ppmw, or less than 8ppmw, or less than 5ppmw, based on the total weight of the copolymer. Typically, the fluorine will come from a co-catalyst system based on boron compounds such as perfluoroarylboranes.

Copolymer functionalization

In accordance with one or more embodiments, the copolymers described herein can be functionalized by various mechanisms to produce dispersants useful for lubricating oils or dispersants useful for fuels (also referred to as fuel detergents). Dispersants are typically polymeric materials having a lipophilic component to provide oil solubility and a polar component to provide dispersibility. Dispersants used in lubricating oils are typically hydrocarbon polymers modified to contain nitrogen and ester based groups. In some cases, the dispersant can include a hydrocarbon polymer, such as a copolymer described herein. Dispersants may be used to maintain in suspension in oil any insolubles formed by oxidation and the like during use, which may prevent sludge flocculation and settling. The amount of dispersant employed can be determined and controlled by, for example, the effectiveness of a particular material to perform its dispersant function. Thus, in some cases, the dispersant may be formed by the reaction of a copolymer having end groups as discussed herein with a suitable functional moiety.

In accordance with one or more embodiments, the dispersants disclosed herein may reduce the total amount of dispersant required in a lubricating oil formulation necessary to meet certain industry standard performance criteria. In accordance with one or more embodiments, disclosed herein is a lubricating oil comprising a dispersant. Lubricating oils comprising the dispersants disclosed herein may exhibit improved cold weather performance, for example, as evidenced by meeting criteria associated with MRV testing. Methods of making and using the copolymers, dispersants, and lubricating oils are also generally described.

According to one or more embodiments, ethylene-C₃-C₁₀α -olefin copolymers may be used as the hydrocarbon tail or backbone of dispersants incorporated in lubricating oils that show good low temperature performance, as evidenced, for example, by the MRV test for engine oil lubricants.

In some embodiments, ethylene-C, as measured by GPC, can be used to prepare dispersants₃-C₁₀α -copolymer has a number average molecular weight of less than 5000, less than 3500, or less than 2500, an ethylene unit content of less than 80 mol%, less than 70 mol%, or 30-60 mol%, 70 mol% or more, 85 mol% or more, or 95 mol% or more of the copolymer having a carbon-carbon double bond in the terminal monomer unit, at least 70 mol%, at least 80 mol%, or at least 90 mol% of the terminal monomer unit having a carbon-carbon double bondThe terminal monomer units have a terminal unsaturation selected from the group consisting of a terminal vinylidene group, one or more trisubstituted isomers of a terminal vinylidene group, and any combination thereof; such as by¹³C NMR spectral determination of the average ethylene continuous chain Length n_c2Less than 2.6, less than 2.5, or less than 2.4; and a crossover temperature of less than-20 deg.C, less than-30 deg.C, or less than-40 deg.C. In various embodiments, some copolymers can have one, two, three, four, or more of any of the above recitations. In some further embodiments, the above copolymers are used to prepare a dispersant by one of the following chemical mechanisms: for example, a succinimide-succinimide process, a koch process, a mannich process, a hydroformylation-reduction-amination process or a halogenation-amination process.

Dispersants as described herein, such as hydrocarbyl amines, amides, carboxylic acids and functionalized diols, imidazolines, succinimides, succinamides, triazines, succinate esters/acids or ester/amides, mannich products, alkyl sulfonic acids, esters, hydrocarbyl hydroxybenzoates, betaines, and quaternary ammonium salts, and the like, can be prepared by, for example, functionalizing the above-described copolymers by various well-known chemical mechanisms to introduce one or more functional moieties into the copolymer via the double bonds in the terminal monomer units (see, e.g., the discussion of formulas (a) - (C) above). Thus, the copolymers described herein can be used to produce suitable dispersants by functionalizing carbon-carbon double bonds in the terminal monomer units of the copolymer to form functionalized copolymer molecules, where more than 70%, more than 75%, more than 80%, more than 85%, more than 90%, or more than 95% are derived from functionalizing the double bonds in the terminal monomer units shown in formulas (a), (B), and/or (C). For example, the functionalized moiety can be produced by any chemical derivatization of an atom or chemical moiety of the copolymers discussed herein, e.g., a carbon-carbon bond group (e.g., alkenyl, alkynyl), a carbon-nitrogen bond group, a carbon-oxygen bond group, a carbon-sulfur bond group, etc. Examples of chemical derivatization include, for example, imidization, succinimide formation (succinimide method), koch reaction (koch method), mannich reaction (mannich method), hydroformylation-reduction-amination method, or halogenation-amination method, for example, as described below. Methods for functionalizing copolymers are taught, for example, in U.S. patent No. 5,936,041.

Succinimide functionalization refers to a process wherein the copolymers described herein are converted to hydrocarbyl succinic acids or anhydrides, i.e., a copolymer backbone substituted with one or more succinic acid or anhydride groups, which is subsequently reacted with a polyamine to form a hydrocarbyl succinimide. Hydrocarbyl succinic acids or anhydrides may be prepared by derivatizing the double bond in the terminal monomer unit with an unsaturated organic acid reagent via thermal ene reaction and/or halo-condensation. See, for example, U.S. patent No. 7,897,696. In the hydrocarbyl succinic acid or anhydride, the ratio of succinic acid moieties to copolymer backbone is from 0.8:1 to 2:1, preferably from 1:1 to 1.6:1, more preferably from 1.2:1 to 1.5: 1.

The unsaturated organic acidic reagent of the disclosed process refers to an unsaturated substituted or unsubstituted carboxylic acid reagent, such as maleic or fumaric reactants of the general formula:

wherein X and X 'are the same or different, provided that at least one of X and X' is a group capable of reacting to esterify an alcohol, form an amide or amine salt with ammonia or an amine, form a metal salt with a reactive metal or substantially react with a metal compound, or otherwise function as an acylating agent. Typically, X and/or X' are-OH, -O-hydrocarbyl, -NH₂And X' together may be-O-to form an anhydride. In some cases, X and X' allow both carboxyl functions to enter the acylation reaction.

Maleic anhydride is a suitable unsaturated acidic reactant. Other suitable unsaturated acidic reactants include electron deficient olefins such as monophenyl maleic anhydride; monomethyl maleic anhydride, dimethyl maleic anhydride, N-phenyl maleimide and other substituted maleimides; an isomaleimide; fumaric acid, maleic acid and fumaric acid alkylhydrogen esters, fumaric acid and maleic acid dialkyl esters, fumaric acid and maleic acid; and maleic nitrile and fumaric nitrile.

The% activity of hydrocarbyl succinic anhydride can be determined using chromatographic techniques. This method is described in U.S. patent No. 5,334,321, columns 5 and 6.

The conversion of hydrocarbyl succinic acids or anhydrides to succinimides is well known in the art and can be accomplished by the reaction of a polyamine with a hydrocarbyl succinic acid or anhydride, where the polyamine has at least one basic nitrogen in the compound, as described in U.S. Pat. No. 3,215,707 and U.S. Pat. No. 4,234,435. Suitable polyamines may have at least three nitrogen atoms and about 4 to 20 carbon atoms. One or more oxygen atoms may also be present in the polyamine.

One particularly suitable group of polyamines for use in the present disclosure are polyalkylene polyamines, including alkylene diamines. Such polyalkylene polyamines may contain from about 2 to about 12 carbon atoms and from about 2 to about 24 carbon atoms. Preferably, the alkylene groups of such polyalkylene polyamines may contain from about 2 to about 6 carbon atoms, more preferably from about 2 to about 4 carbon atoms.

Particularly suitable polyalkylene polyamines are those having the formula: h₂N-(R₁NH)_a-H, wherein R₁Is a straight or branched chain alkylene group having from about 2 to about 6 carbon atoms, preferably from about 2 to about 4 carbon atoms, and most preferably about 2 carbon atoms, i.e., ethylene (-CH)₂CH₂-) according to the formula (I); and a is an integer of 1 to about 10, preferably 1 to about 4, and more preferably about 3.

Examples of suitable polyalkylene polyamines include, but are not limited to, ethylene diamine, propylene diamine, isopropylene diamine, butylene diamine, pentylene diamine, hexylene diamine, diethylene triamine, dipropylene triamine, dimethylaminopropylamine, diisopropylene triamine, dibutylene triamine, di-sec-butylene triamine, triethylene tetramine, tripropylene tetramine, triisobutyl tetramine, tetraethylene pentamine, pentaethylene hexamine, dimethylaminopropylamine, and mixtures thereof.

Particularly suitable polyalkylene polyamines are ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

Many polyamines suitable for use in the present disclosure are commercially available, and other polyamines can be prepared by methods well known in the art. For example, methods for preparing amines and reactions thereof are described in Sidgewick [ "organic Chemistry of Nitrogen (Nitrogen)", "Clarendon Press, Oxford (Oxford), 1966; noller, "Chemistry of Organic Compounds", sanddu (Saunders), Philadelphia (Philadelphia), 2 nd edition, 1957; and Kirk-Othmer, "Encyclopedia of Chemical Technology", 2 nd edition, especially volume 2, pages 99-116.

The reaction of the polyamine and hydrocarbyl succinic acid or anhydride yields a mono-, bis-, trisuccinimide, or other succinimide, depending on the charge ratio of the polyamine and succinic acid or anhydride. In some embodiments, the ratio between the hydrocarbyl succinic acid/anhydride and the polyamine is 1:1 to 3.2:1, or 2.5:1 to 3:1, or 2.9:1 to 3:1, or 1.6:1 to 2.5:1, or 1.6:1 to 2:1, or 1.6:1 to 1.8:1, 1.3:1 to 1.6:1, 1.4:1 to 1.6:1, or 1; 1 to 1.3:1, or 1.2:1 to 1.3: 1.

In some embodiments, the derivatized copolymer is prepared by a process comprising: (1) reacting ethylene-C as described herein₃-C₁₀α -olefin copolymer is coupled with an unsaturated mono-or dicarboxylic acid or anhydride to form a mono-or dicarboxylic acid or anhydride substituted copolymer, (2) reacting the mono-or dicarboxylic acid or anhydride substituted copolymer with a primary amine containing compound, and (3) optionally post-treating the reaction product of step (2).

The koch reaction is an organic reaction for synthesizing a tertiary carboxylic acid from an alcohol or an olefin. The reaction is a strong acid catalyzed carbonylation using carbon monoxide and typically occurs at high pressures in the range of 50 to 5,000kPa, typically requiring temperatures several hundred degrees above room temperature. Usually, strong mineral acids such as sulfuric acid, HF or BF are used for the reaction₃The process is carried out. Koch reactions are known in the art and comprise contacting a copolymer composition having at least one carbon-carbon double bond (e.g., in the terminal group) with an acid catalyst and carbon monoxide in the presence of water or an alcohol. The catalyst may be a classical bronsted catalystAcid or LouisLewis acid catalysts. The Koch reaction is conducted in a manner and under conditions sufficient to form a carbenium ion at the site of the carbon-carbon double bond. The carbenium ion reacts with carbon monoxide to form an acyl cation which in turn reacts with at least one nucleophilic trapping agent selected from the group consisting of water or at least one hydroxyl group or one thiol group containing compound. The copolymer reacts to form an acyl cation, which forms a functional group, such as a carbonyl functional group.

Koch functionalization refers to a process whereby a copolymer functionalized with at least one carboxylic acid, carboxylate ester, or thioester functional group is produced. The functionalized copolymer is functionalized via a koch reaction at the point of olefin unsaturation to form a carboxylic acid, carboxylic ester, or thioester. Methods for Koch Functionalization of Polymers are known in the art, as described, for example, in U.S. Pat. No. 5,629,434 entitled "Functionalization of Polymers Based on Koch chemistry and Derivatives Thereof" (functional characterization of Polymers Based on Koch chemistry and Derivatives Thereof "), which is incorporated herein by reference in its entirety and for all purposes.

In some embodiments, the derivatized copolymer is prepared by a process comprising: (1) reacting ethylene-C as described herein under Koch reaction conditions₃-C₁₀α -reacting the olefin copolymer with CO, and (2) coupling the reaction product of step (1) with an amine compound.

Mannich reactions are organic reactions involving the aminoalkylation of a carbon atom in the molecule adjacent to a carbonyl function or a carbon atom that is part of an activated phenyl group (e.g., a hydroxyaromatic compound). It is commonly used to prepare alkylphenol derived dispersants (also known as mannich dispersants). In some embodiments of the invention, the copolymers described herein react with phenol via electrophilic addition via a carbon-carbon double bond in the terminal monomer unit, and the resulting alkylphenol, i.e., the copolymer-substituted phenol, is then reacted with formaldehyde and an amine via a mannich reaction to provide the 2-aminomethyl-4-alkylphenol. Methods for mannich functionalization of polymer backbones are known in the art as described, for example, in U.S. patent nos. 2,098,869 and 5,608,029, both of which are incorporated herein by reference in their entirety and for all purposes.

In some embodiments, the derivatized copolymer is prepared by a process comprising: reacting an alkylphenol, an aldehyde, and an amine compound, wherein the alkylphenol is composed of a substituted or unsubstituted hydroxyaromatic compound described herein and ethylene-C₃-C₁₀α -olefin copolymer.

The hydroformylation-reduction-amination reaction involves reacting an aldehyde or ketone with an amino compound under condensation conditions sufficient to produce an imine intermediate, which is subsequently reacted under hydrogenation conditions sufficient to produce an amine dispersant. In some embodiments of the invention, copolymers having a carbon-carbon double bond in a terminal monomer unit as described herein are converted to an aldehyde or ketone by hydroformylation of this double bond. The resulting aldehyde or ketone can be reacted with an amine under reductive amination conditions to provide a dispersant. Methods of hydroformylation and reductive amination reactions are known in the art, as described, for example, in U.S. patent application publication 20140087985, which is incorporated herein by reference in its entirety and for all purposes.

In some embodiments, the derivatized copolymer is prepared by a process comprising: (1) reacting the above-described ethylene-C₃-C₁₀α -hydroformylation of olefin copolymers to form copolymers having terminal aldehyde moieties, and (2) reaction of the copolymers prepared in step (1) with an amine compound under reducing conditions.

The halogenation-amination reaction involves first halogenating the double bond in the terminal monomer units of the copolymer, and then reacting the halogen-substituted copolymer with an amine to provide the amine dispersant. See, for example, U.S. Pat. No. 5,225,092.

In some embodiments, the derivatized copolymer is prepared by a process comprising: (1) reacting ethylene-C as described herein₃-C₁₀α -olefin copolymer with a halogenating agent for forming a halogen-containing copolymer, and (2) coupling the halogen-containing copolymer of step (1) with an amine compound.

The amines or amino compounds which can be used in the Koch reaction, Mannich reaction, hydroformylation-reduction-amination reaction and halogenation-amination reaction can be the abovementioned ammonia, alkyl monoamines, dialkyl monoamines or polyamines. Unless otherwise specified, the amino group in the amine compound can be a primary amine, a secondary amine, a tertiary amine, or any mixture thereof. These amines may be hydrocarbyl amines, or may be hydrocarbyl amines including other groups such as one or more of hydroxyl, alkoxy, amide, nitrile, imidazoline, and the like.

By primary amine-containing compound is meant a compound as described above that contains at least one primary amine group, i.e., -NH₂An amine or amino compound of (a).

It is to be understood that other dispersants can be prepared from terminally unsaturated polymers by known chemical reactions at the double bonds in the terminal monomer units of the copolymer. Thus, in various embodiments, the present invention also includes such methods and dispersants prepared therefrom.

As a non-limiting example, a dispersant may be formed by reacting a copolymer as discussed herein with a suitable functional group (e.g., via a double bond at a terminal monomer unit) to produce a compound such as:

in these structures, R¹May be a hydrocarbon group derived from a copolymer; r²Can be divalent C₁-C₆An alkylene group; r³Can be divalent C₁-C₆An alkylene group; r⁴And R⁵Each of which independently may be H, C₁-C₆Alkyl, aryl, heteroaryl, and heteroaryl,Or with said R⁴And R⁵The attached N together form a5 or 6 membered ring optionally fused to an aromatic or non-aromatic ring; r⁶Can be H or C₁-C₆Alkyl, or-CH₂-(NH-R²)_n-NR⁴R⁵(ii) a Y may be a covalent bond or C (O); and n can be 0, 1,2, 3,4, 5,6, 7, or 8. These compounds are formed by functionalization reactions such as those described above, e.g., functionalization using succinimide, kochA reaction, a reductive amination reaction, a halogen-amination reaction or a mannich reaction.

With reference to formula (I) above, the functionalized copolymer can be a mono-succinimide, i.e., NR⁴R⁵Together are NH₂Or bis-succinimides, i.e. NR⁴R⁵Together are:

wherein R is¹Is a hydrocarbon group derived from a copolymer as described above.

Referring to formula (III), the functionalized copolymer may have one of the following structures:

post-treatment

The functionalized copolymer may also be post-treated by conventional methods by reaction with any of a variety of reagents known in the art. Among these are boron compounds, urea, thiourea, dimercaptothiadiazoles, carbon disulfide, aldehydes, ketones, carboxylic acids, anhydrides, nitriles, epoxides, cyclic carbonates and phosphorus compounds. See U.S. patent No. 5,241,003.

The boron compound used as the post-treatment agent may be selected from boron oxides, boron halides, boric acids, and boric acid esters in an amount to provide about 0.1 atomic proportion of boron per mole of nitrogen composition to about 20 atomic proportions of boron per atomic proportion of nitrogen used. The borated derivative copolymer may contain from about 0.05 to 2.0 wt%, such as from 0.05 to 0.7 wt%, of boron, based on the total weight of the borated nitrogen-containing dispersant compound.

The carboxylic acids used as post-treatment agents may be saturated or unsaturated mono-, di-or poly-carboxylic acids. Examples of carboxylic acids include, but are not limited to, maleic acid, fumaric acid, succinic acid, naphthalene dicarboxylic acids (e.g., 1, 8-naphthalene dicarboxylic acid).

The anhydride used as post-treatment agent may be selected from monounsaturated anhydrides (e.g. maleic anhydride), alkyl or alkylene substituted cyclic anhydrides (e.g. succinic anhydride or glutamic anhydride), aromatic carboxylic anhydrides (including naphthalic anhydrides, such as 1, 8-naphthalic anhydride).

Lubricating oil

In accordance with one or more embodiments, the dispersants described herein comprising functionalized copolymers can be incorporated into a large amount of base oil to produce a lubricating oil configured to pass MRV testing. The lubricating oil may further contain a viscosity index improver. It may additionally contain a pour point depressant. Suitable dispersants may have a TBN of from about 10 to about 65 on an oil-free basis, corresponding to from about 5 to about 30TBN if measured on a dispersant sample containing about 50% diluent oil.

According to some embodiments, the lubricating oil comprises a weight percentage of dispersant. In one or more embodiments, the dispersant comprises from about 0.1 wt% to about 15 wt%, or from about 0.1 wt% to about 10 wt%, or from about 3 wt% to about 10 wt%, or from about 1 wt% to about 6 wt%, or from about 7 wt% to about 12 wt%, based on the total final weight of the lubricating oil composition. In some embodiments, the lubricating oil composition utilizes a mixed dispersant system. A single type of dispersant or a mixture of two or more types of dispersants in any desired ratio may be used.

In some other embodiments, the lubricating oil composition is prepared from a lubricating additive package comprising 30 to 80 wt.% of a dispersant as described above.

According to some embodiments, the lubricating oil comprises a weight percentage of a viscosity index improver. In accordance with one or more embodiments, the viscosity index improver comprises less than 1 to 20 wt.%, 3 to 10 wt.%, or 5 to 9 wt.%, based on the total weight of the lubricating oil. Other values are also possible. Other potential components of the lubricating oil are described below.

Base oil

The base oil used in the lubricating oil compositions herein may be selected from any suitable base oil. Examples include Base oils in class I-V as specified in the American Petroleum Institute (API) guide for Base oil interchangeability (API) Base oil interchangeability Guidelines. The five base oils are as follows:

TABLE 4

I. And class II and III are mineral oil processing feedstocks. Group IV base oils contain true synthetic molecular species that are prepared by the polymerization of ethylenically unsaturated hydrocarbons. Many group V base oils are also true synthetic products and may include diesters, polyol esters, polyalkylene glycols, alkylated aromatics, polyphosphate esters, polyvinyl ethers and/or polyphenyl ethers, and the like, but may also be naturally occurring oils such as vegetable oils. It should be noted that although group III base oils are derived from mineral oils, the rigorous processing experienced by these fluids makes their physical properties very similar to some pure compositions, such as PAOs. Thus, in the industry, oils derived from group III base oils may be referred to as synthetic fluids.

The base oil used in the disclosed lubricating oil compositions can be a mineral oil, an animal oil, a vegetable oil, a synthetic oil, or mixtures thereof. Suitable oils may be derived from hydrocracking, hydrogenation, hydrofinishing, unrefined, refined and rerefined oils, and mixtures thereof.

Unrefined oils are those derived from a natural, mineral, or synthetic source with little or no additional purification treatment. Refined oils are similar to unrefined oils except that they have been treated in one or more purification steps, which may result in an improvement in one or more properties. Examples of suitable purification techniques are solvent extraction, secondary distillation, acid or base extraction, filtration, osmosis, and the like. Oils refined to edible quality may or may not be suitable. Edible oils may also be referred to as white oils. In some embodiments, the lubricating oil composition is free of edible oils or white oils.

Rerefined oils are also known as reclaimed or reprocessed oils. These oils are obtained similarly to refined oils, using the same or similar methods. Typically these oils are additionally processed by techniques directed to the removal of spent additives and oil breakdown products.

Mineral oil may include oil obtained by drilling or from plants and animals or any mixture thereof. For example, such oils may include, but are not limited to: castor oil, lard oil, olive oil, peanut oil, corn oil, soybean oil and linseed oil, as well as mineral lubricating oils, such as liquid petroleum oils and solvent-treated or acid-treated mineral lubricating oils of the paraffinic, naphthenic or mixed paraffinic-naphthenic types. Such oils may be partially or fully hydrogenated if desired. Oils derived from coal or shale may also be useful.

Useful synthetic lubricating oils can include hydrocarbon oils such as polymerized, oligomerized, or interpolymerized olefins (e.g., polybutylenes, polypropylenes, propylene isobutylene copolymers); poly (1-hexene), poly (1-octene), trimers or oligomers of 1-decene, such as poly (1-decene), which are commonly referred to as alpha-olefins, and mixtures thereof; alkyl-benzenes (e.g., dodecylbenzene, tetradecylbenzene, dinonylbenzene, di- (2-ethylhexyl) -benzene); polyphenyls (e.g., biphenyls, terphenyls, alkylated polyphenyls); diphenylalkanes, alkylated diphenyl ethers and alkylated diphenyl sulfides and the derivatives, analogs and homologs thereof or mixtures thereof. Polyalphaolefins are typically hydrogenated materials.

Other synthetic lubricating oils include polyol esters, diesters, liquid esters of phosphorus-containing acids (e.g., tricresyl phosphate, trioctyl phosphate, and diethyl ester of decane phosphionic acid), or polymeric tetrahydrofurans. Synthetic oils may be produced by the Fischer-Tropsch reaction (Fischer-Tropsch reaction) and may typically be hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodiment, the oil may be prepared by a fischer-tropsch gas-liquid synthesis procedure, as well as other gas-liquid oils.

The bulk base oil included in the lubricating composition may be selected from group I, group II, group III, group IV, group V, and combinations of two or more of the foregoing, and wherein the bulk base oil is not a base oil resulting from providing an additive component or viscosity index improver in the composition. In another embodiment, the plurality of base oils included in the lubricating composition may be selected from group II, group III, group IV, group V, and combinations of two or more of the foregoing, and wherein the plurality of base oils is not a base oil resulting from providing an additive component or viscosity index improver in the composition.

The amount of oil of lubricating viscosity present may be the remainder amount from 100 wt% minus the sum of the amounts of performance additives including viscosity index improver(s) and/or pour point depressant(s) and/or other pre-treatment additives. For example, an oil of lubricating viscosity that may be present in the finished fluid may be "substantial," such as greater than about 50 wt.%, greater than about 60 wt.%, greater than about 70 wt.%, greater than about 80 wt.%, greater than about 85 wt.%, greater than about 90 wt.%, or greater than about 95 wt.%.

Viscosity index improver

The lubricating oil compositions herein may also optionally contain one or more viscosity index improvers. Suitable viscosity index improvers may include polyolefins (e.g., polyisobutylene), olefin copolymers (e.g., ethylene/propylene copolymers), hydrogenated styrene-isoprene polymers, styrene/maleate copolymers, hydrogenated styrene/butadiene copolymers, hydrogenated isoprene polymers, alpha-olefin maleic anhydride copolymers, polymethacrylates, polyacrylates, polyalkylstyrenes, hydrogenated alkenyl aryl conjugated diene copolymers, or mixtures thereof. Viscosity index improvers may include star polymers, and suitable examples are described in U.S. patent application publication No. 20120101017a 1.

The lubricating oil compositions herein may optionally contain one or more dispersant viscosity index improvers in addition to or in place of the viscosity index improvers. Suitable viscosity index improvers may include functionalized polyolefins, for example, ethylene-propylene copolymers that have been functionalized with the reaction product of an acylating agent (e.g., maleic anhydride) and an amine; with amine functionalized polymethacrylates, or esterified maleic anhydride-styrene copolymers reacted with amines.

The total amount of viscosity index improver and/or dispersant viscosity index improver can be from about 0.1 wt.% to about 20 wt.%, from about 0.1 wt.% to about 15 wt.%, from about 0.1 wt.% to about 12 wt.%, or from about 0.5 wt.% to about 10 wt.%, from about 3 wt.% to about 20 wt.%, from about 3 wt.% to about 15 wt.%, from about 5 wt.% to about 15 wt.%, or from about 5 wt.% to about 10 wt.% of the lubricating oil composition. In some embodiments, the viscosity index improver is a polyolefin or olefin copolymer having a number average molecular weight of 10,000-500,000, 50,000-200,000, or 50,000-150,000. In some embodiments, the viscosity index improver is a hydrogenated styrene/butadiene copolymer having a number average molecular weight of 40,000-500,000, 50,000-200,000, or 50,000-150,000. In some embodiments, the viscosity index improver is a polymethacrylate having a number average molecular weight of 10,000-500,000, 50,000-200,000, or 50,000-150,000.

Antioxidant agent

The lubricating oil compositions herein may also optionally contain one or more antioxidants. Antioxidant compounds are known and include, for example, phenolate, phenol sulfide, sulfurized olefin, thiophosphorylated terpene, sulfurized ester, aromatic amine, alkylated diphenylamine (e.g., nonyldiphenylamine, dinonyldiphenylamine, octyldiphenylamine, dioctyldiphenylamine), phenyl-alpha-naphthylamine, alkylated phenyl-alpha-naphthylamine, hindered non-aromatic amines, phenols, hindered phenols, oil-soluble molybdenum compounds, macromolecular antioxidants, or mixtures thereof. The antioxidant compounds may be used alone or in combination.

The hindered phenol antioxidant may contain a secondary butyl group and/or a tertiary butyl group as a sterically hindered group. The phenolic group may additionally be substituted with a hydrocarbyl group and/or a bridging group attached to a second aromatic group. Examples of suitable hindered phenol antioxidants include 2, 6-di-tert-butylphenol, 4-methyl-2, 6-di-tert-butylphenol, 4-ethyl-2, 6-di-tert-butylphenol, 4-propyl-2, 6-di-tert-butylphenol, or 4-butyl-2, 6-di-tert-butylphenol, or 4-dodecyl-2, 6-di-tert-butylphenol. In one embodiment, the hindered phenol antioxidant may be an ester and may include, for example, Irganox, which is commercially available from BASF^TML-135 is derived from the addition product of 2, 6-di-tert-butylphenol and an alkyl acrylate, wherein the alkyl group can contain from about 1 to about 18, or from about 2 to about 12, or from about 2 to about 8, or from about 2 to about 6, or about 4 carbon atoms. Another commercially available hindered phenol antioxidant can be an ester, and can include ETHANOX, available from the Jacobian Corporation (Albemarle Corporation)^TM4716。

Useful antioxidants may include diarylamines and high molecular weight phenols. In one embodiment, the lubricating oil composition may contain a mixture of diarylamines and high molecular weight phenols such that various antioxidants may be present in amounts sufficient to provide up to about 5 wt.%, based on the final weight of the lubricating oil composition. In one embodiment, the antioxidant can be a mixture of about 0.3 to about 1.5 wt.% diarylamine and about 0.4 to about 2.5 wt.% high molecular weight phenol, based on the final weight of the lubricating oil composition.

Examples of suitable olefins that may be sulfurized to form sulfurized olefins include propylene, butene, isobutylene, polyisobutylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof. In one embodiment, hexadecene, heptadecene, octadecene, nonadecene, eicosene, or mixtures thereof, as well as dimers, trimers, and tetramers thereof, are particularly useful olefins. Alternatively, the olefin may be a Diels-alder adduct of a diene (such as 1, 3-butadiene) and an unsaturated ester (such as butyl acrylate).

Another class of sulfurized olefins includes sulfurized fatty acids and esters thereof. The fatty acids are typically obtained from vegetable or animal oils and typically contain from about 4 to about 22 carbon atoms. Examples of suitable fatty acids and esters thereof include triglycerides, oleic acid, linoleic acid, palmitoleic acid, or mixtures thereof. Typically, the fatty acid is obtained from lard, pine oil, peanut oil, soybean oil, cottonseed oil, sunflower oil or mixtures thereof. The fatty acids and/or esters may be mixed with olefins, such as alpha-olefins.

The one or more antioxidants may be present in a range of from about 0 wt.% to about 20 wt.%, or from about 0.1 wt.% to about 10 wt.%, or from about 1 wt.% to about 5 wt.% of the lubricating oil composition.

Antiwear agent

The lubricating oil compositions herein may also optionally contain one or more antiwear agents. Examples of suitable anti-wear agents include, but are not limited to, metal thiophosphates; a metal dialkyl dithiophosphate; a phosphate ester or a salt thereof; one or more phosphate esters; a phosphite ester; phosphorus-containing carboxylic acid esters, ethers or amides; a sulfurized olefin; thiocarbamate-containing compounds including thiocarbamates, alkylene-coupled thiocarbamates, and bis (S-alkyldithiocarbamoyl) disulfides; and mixtures thereof. A suitable antiwear agent may be molybdenum dithiocarbamate. Phosphorus-containing anti-wear agents are more fully described in european patent 0612839. The metal in the dialkyldithiophosphates may be an alkali metal, an alkaline earth metal, aluminum, lead, tin, molybdenum, manganese, nickel, copper, titanium or zinc. A useful antiwear agent may be zinc dialkylthiophosphate.

Additional examples of suitable anti-wear agents include titanium compounds, tartrates, tartrimides, oil soluble amine salts of phosphorus compounds, sulfurized olefins, phosphites (such as dibutyl phosphite), phosphonates, thiocarbamate-containing compounds (such as thiocarbamates, thiocarbamate amides, thiocarbamate ethers, alkylene-coupled thiocarbamates, and bis (S-alkyldithiocarbamoyl) disulfides). The tartrate or tartrimide may contain alkyl ester groups, wherein the sum of the carbon atoms on the alkyl groups may be at least 8. In one embodiment, the anti-wear agent may include a citrate ester.

The antiwear agent may be present in a range including from about 0 wt.% to about 15 wt.%, or from about 0.01 wt.% to about 10 wt.%, or from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.% of the lubricating oil composition.

Boron-containing compounds

The lubricating oil compositions herein may optionally contain one or more boron-containing compounds.

Examples of boron-containing compounds include borate esters, borated fatty amines, borated epoxides, borated detergents, and borated dispersants, such as borated succinimide dispersants, as disclosed in U.S. patent No. 5,883,057.

The boron-containing compound, if present, may be used in an amount sufficient to provide up to about 8 wt.%, from about 0.01 wt.% to about 7 wt.%, from about 0.05 wt.% to about 5 wt.%, or from about 0.1 wt.% to about 3 wt.% of the lubricating oil composition.

Detergent composition

The lubricating oil composition may optionally additionally comprise one or more neutral, low-alkaline or high-alkaline detergents, and mixtures thereof. Suitable detergent bases include: phenates, sulphur-containing phenates, sulphonates, calixarenes (calixarates), salicylates (salixarates), salicylates, carboxylic acids, phosphoric acids, monothiophosphoric and/or dithiophosphoric acids, alkylphenols, sulphur-coupled alkylphenol compounds or methylene-bridged phenols. Suitable detergents and methods for their preparation are described in more detail in a number of patent publications, including U.S. Pat. No. 7,732,390 and the references cited therein. The detergent matrix may be salted with alkali or alkaline earth metals such as (but not limited to) the following: calcium, magnesium, potassium, sodium, lithium, barium or mixtures thereof. In some embodiments, the detergent is barium-free. Suitable detergents may include alkali or alkaline earth metal salts of petroleum sulfonic acid and long chain mono or dialkyl aryl sulfonic acids, where the aryl groups are benzyl, tolyl, and xylyl. Examples of suitable detergents include, but are not limited to: calcium phenate, sulfur-containing calcium phenate, calcium sulfonate, calixate, calcium salicylate, calcium carboxylate, calcium phosphate, calcium monothiophosphate and/or calcium dithiophosphate, calcium alkylphenol, sulfur-coupled alkylphenol calcium compounds, methylene-bridged calcium phenate, magnesium phenate, sulfur-containing magnesium phenate, magnesium sulfonate, calixate, magnesium salicylate, magnesium carboxylate, magnesium phosphate, magnesium monothiophosphate and/or magnesium dithiophosphate, magnesium alkylphenol, sulfur-coupled alkylphenol magnesium compounds, methylene-bridged magnesium phenate, sodium phenate, sulfur-containing sodium phenate, sodium sulfonate, sodium calixate, sodium salicylate, sodium carboxylate, sodium phosphate, sodium monothiophosphate and/or sodium dithiophosphate, sodium alkylphenol, sulfur-coupled alkylphenol sodium compounds, or methylene-bridged sodium phenate.

Overbased detergent additives are well known in the art and may be alkali metal or alkaline earth metal overbased detergent additives. Such detergent additives may be prepared by reacting a metal oxide or metal hydroxide with a substrate and carbon dioxide gas. The substrate is typically an acid, such as the following: such as an aliphatic substituted sulfonic acid, an aliphatic substituted carboxylic acid, or an aliphatic substituted phenol.

The term "overbased" refers to metal salts, such as those having sulfonic acids, carboxylic acids, and phenols, wherein the amount of metal present is in excess of stoichiometric. Such salts may have conversion levels in excess of 100% (i.e., they may contain more than 100% of the theoretical amount of metal required to convert the acid to its "normal", "neutral" salt). The expression "metal ratio" is commonly abbreviated MR and is used to denote the ratio of the total stoichiometric amount of metal in the overbased salt to the stoichiometric amount of metal in the neutral salt, according to known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is one, while in overbased salts, the MR is greater than one. They are commonly referred to as overbased, superbased or superbased salts and may be salts of organic sulfuric acids, carboxylic acids or phenols.

The overbased detergent of the lubricating oil composition may have a Total Base Number (TBN) of greater than about 200mg KOH/gram or greater, or as another example, about 250mg KOH/gram or greater, or about 350mg KOH/gram or greater, or about 375mg KOH/gram or greater, or about 400mg KOH/gram or greater.

Examples of suitable overbased detergents include, but are not limited to: overbased calcium phenates, overbased sulfur-containing calcium phenates, overbased calcium sulfonates, overbased calcium calixarates, overbased calcium salicylate, overbased calcium carboxylates, overbased calcium phosphates, overbased calcium monosulfuric and/or calcium dithiophosphates, overbased calcium alkylphenates, overbased sulfur-coupled calcium alkylphenates, overbased methylene-bridged calcium phenates, overbased magnesium phenates, overbased sulfur-containing magnesium phenates, overbased magnesium sulfonates, overbased magnesium calixarates, overbased magnesium salicylate, overbased magnesium salicylates, overbased magnesium carboxylates, overbased magnesium phosphates, overbased magnesium monosulfuric and/or magnesium dithiophosphates, overbased magnesium alkylphenates, overbased sulfur-coupled magnesium alkylphenates, or overbased methylene-bridged magnesium phenates.

The metal to substrate ratio of the overbased detergent may be 1.1:1, or 2:1, or 4:1, or 5:1, or 7:1, or 10: 1.

The TBN of the low alkaline/neutral detergent is at most 175mg KOH/g, or at most 150mg KOH/g. The low alkaline/neutral detergent may comprise a calcium-containing detergent. The low alkaline neutral calcium-containing detergent may be selected from the group consisting of calcium sulfonate detergents, calcium phenate detergents and calcium salicylate detergents. In some embodiments, the low alkaline/neutral detergent may be a calcium-containing detergent or a mixture of calcium-containing detergents. In some embodiments, the low alkaline/neutral detergent may be a calcium sulfonate detergent or a calcium phenate detergent.

The low-alkaline/neutral detergent may comprise at least 2.5 wt.% of the total detergent in the lubricating oil composition. In some embodiments, at least 4 wt.%, or at least 6 wt.%, or at least 8 wt.%, or at least 10 wt.%, or at least 12 wt.% or at least 20 wt.% of the total detergents in the lubricating oil composition are low-alkaline/neutral detergents that may optionally be low-alkaline/neutral calcium-containing detergents.

In certain embodiments, the one or more low-alkalinity/neutral detergents provide from about 50 to about 1000ppm by weight calcium to the lubricating oil composition, based on the total weight of the lubricating oil composition. In some embodiments, the one or more low-basic/neutral calcium-containing detergents provide from 75 to less than 800ppm, or from 100 to 600ppm, or from 125 to 500ppm by weight calcium to the lubricating oil composition, based on the total weight of the lubricating oil composition.

In some embodiments, the detergent is effective to reduce or prevent rust in the engine.

The detergent may be present from about 0 wt% to about 10 wt%, or from about 0.1 wt% to about 8 wt%, or from about 1 wt% to about 4 wt%, or greater than about 4 wt% to about 8 wt%.

Additional dispersant

Additional dispersants contained in the lubricant composition may include, but are not limited to, an oil soluble polymeric hydrocarbon backbone having functional groups capable of associating with the particles to be dispersed. Typically, the dispersant comprises an amine, alcohol, amide or ester polar moiety attached to the polymer backbone, typically via a bridging group. The dispersant may be selected from mannich dispersants as described in U.S. Pat. nos. 3,634,515, 3,697,574, and 3,736,357; ashless succinimide dispersants as described in U.S. Pat. nos. 4,234,435 and 4,636,322; amine dispersants as described in U.S. Pat. nos. 3,219,666, 3,565,804, and 5,633,326; koch dispersants as described in U.S. patent nos. 5,936,041, 5,643,859, and 5,627,259, and polyalkylene succinimide dispersants as described in U.S. patent No. 5,851,965; 5,853,434, respectively; and 5,792,729.

In various embodiments, the additional dispersant may be derived from Polyalphaolefin (PAO) succinic anhydride, olefin maleic anhydride copolymer. As an example, the additional dispersant may be described as poly-PIBSA. In another embodiment, the additional dispersant may be derived from an anhydride grafted with an ethylene-propylene copolymer. Another additional dispersant may be a high molecular weight ester or half ester amide.

Additional dispersants, if present, may be used in amounts sufficient to provide up to about 10 wt.%, based on the final weight of the lubricating oil composition. Other amounts of dispersants that may be used may be from about 0.1 wt% to about 10 wt%, or from about 3 wt% to about 8 wt%, or from about 1 wt% to about 6 wt%, based on the final weight of the lubricating oil composition.

Friction modifiers

The lubricating oil compositions herein may also optionally contain one or more friction modifiers. Suitable friction modifiers may include metal-containing and metal-free friction modifiers and may include, but are not limited to, imidazolines, amides, amines, succinimides, alkoxylated amines, alkoxylated ether amines, amine oxides, amidoamines, nitriles, betaines, quaternary amines, imines, amine salts, aminoguanidines, alkanolamides, phosphonates, metal-containing compounds, glycerol esters, sulfurized fatty compounds and olefins, sunflower oil, other naturally occurring vegetable or animal oils, dicarboxylic acid esters, esters or partial esters of polyols, and one or more aliphatic or aromatic carboxylic acids, and the like.

Suitable friction modifiers may contain hydrocarbyl groups selected from linear, branched or aromatic hydrocarbyl groups or mixtures thereof, and may be saturated or unsaturated. The hydrocarbyl group may be composed of carbon and hydrogen or heteroatoms such as sulfur or oxygen. The hydrocarbyl group may range from about 12 to about 25 carbon atoms. In some embodiments, the friction modifier may be a long chain fatty acid ester. In another embodiment, the long chain fatty acid ester may be a mono-or di-ester or a (tri) glyceride. The friction modifier may be a long chain fatty amide, a long chain fatty ester, a long chain fatty epoxide derivative, or a long chain imidazoline.

Other suitable friction modifiers may include organic, ashless (metal-free), nitrogen-free organic friction modifiers. Such friction modifiers may include esters formed by reacting carboxylic acids and anhydrides with alkanols, and typically include a polar terminal group (e.g., a carboxyl or hydroxyl group) covalently bonded to an oleophilic hydrocarbon chain. An example of an organic ashless, nitrogen-free friction modifier is generally known as Glycerol Monooleate (GMO), which may contain mono-, di-and tri-esters of oleic acid. Other suitable friction modifiers are described in U.S. patent No. 6,723,685, which is incorporated herein by reference in its entirety.

The amine-based friction modifier may include an amine or polyamine. Such compounds may have straight chain saturated or unsaturated hydrocarbon groups or mixtures thereof, and may contain from about 12 to about 25 carbon atoms. Additional examples of suitable friction modifiers include alkoxylated amines and alkoxylated ether amines. Such compounds may have linear saturated, unsaturated hydrocarbon groups or mixtures thereof. It may contain from about 12 to about 25 carbon atoms. Examples include ethoxylated amines and ethoxylated ether amines.

The amines and amides can be used as such or in the form of adducts or reaction products with boron compounds, such as boron oxides, boron halides, metaborates, boric acid or monoalkyl, dialkyl or trialkyl borates. Other suitable friction modifiers are described in U.S. Pat. No. 6,300,291, which is incorporated herein by reference in its entirety.

The friction modifier may optionally be present in a range of from about 0 wt% to about 10 wt%, or from about 0.01 wt% to about 8 wt%, or from about 0.1 wt% to about 4 wt%.

Component containing molybdenum

The lubricating oil compositions herein may also optionally contain one or more molybdenum-containing compounds. The oil soluble molybdenum compound may have the functional properties of an antiwear agent, an antioxidant, a friction modifier, or a mixture thereof. The oil soluble molybdenum compound may include molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, molybdenum dithiophosphinates, amine salts of molybdenum compounds, molybdenum xanthates, molybdenum thioxanthates, molybdenum sulfides, molybdenum carboxylates, molybdenum alkoxides, trinuclear organo-molybdenum compounds, and/or mixtures thereof. The molybdenum sulfide includes molybdenum disulfide. The molybdenum disulfide may be in the form of a stable dispersion. In one embodiment, the oil soluble molybdenum compound may be selected from the group consisting of molybdenum dithiocarbamates, molybdenum dialkyldithiophosphates, amine salts of molybdenum compounds, and mixtures thereof. In one embodiment, the oil soluble molybdenum compound may be a molybdenum dithiocarbamate.

Suitable examples of molybdenum compounds that may be used include the commercial materials sold under the following trademarks: molyvan 822 from van der bilt co., Ltd^TM、Molyvan^TMA、Molyvan 2000^TMAnd Molyvan 855^TMAnd Sakura-Lube available from Adeka Corporation^TMS-165, S-200, S-300, S-310G, S-525, S-600, S-700, and S-710, and mixtures thereof. Suitable molybdenum components are described in U.S. patent nos. 5,650,381; U.S. patent numbers RE37,363E 1; U.S. Pat. nos. RE 38,929E 1; and U.S. patent No. RE40,595E 1, which is incorporated herein by reference in its entirety.

Further, the molybdenum compound may be an acidic molybdenum compound. Including molybdic acid, ammonium molybdate, sodium molybdate, potassium molybdate and other alkali metal molybdates and other molybdenum salts, e.g., sodium hydrogen molybdate, MoOCl₄、MoO₂Br₂、Mo₂O₃Cl₆Molybdenum trioxide or similar acidic molybdenum compounds. Alternatively, the composition may provide molybdenum through a molybdenum/sulfur complex of a basic nitrogen compound, as described in, for example, U.S. patent nos. 4,263,152; 4,285,822; 4,283,295; 4,272,387, respectively; 4,265,773; 4,261,843; 4,259,195 and 4,259,194; and WO 94/06897, each of which is incorporated herein by reference in its entirety.

Another suitable class of organo-molybdenum compounds are trinuclear molybdenum compounds, such as Mo₃S_kL_nQ_zWherein S represents sulfur, L represents an independently selected ligand having an organic group in an amount sufficient to render the compound soluble or dispersible in oil, n is 1 to 4, k varies from 4 to 7, Q is selected from the group consisting of neutral electron donating compounds such as water, amines, alcohols, phosphines, and ethers, and z is in the range of 0 to 5 and includes non-stoichiometric values. In all organic groups of the ligands it is possibleIn total of at least 21 carbon atoms, such as at least 25, at least 30, or at least 35 carbon atoms. Other suitable molybdenum compounds are described in U.S. patent No. 6,723,685, which is incorporated herein by reference in its entirety.

The oil soluble molybdenum compound may be present in an amount sufficient to provide about 0.5ppm to about 2000ppm, about 1ppm to about 700ppm, about 1ppm to about 550ppm, about 5ppm to about 300ppm, or about 20ppm to about 250ppm molybdenum.

Transition metal-containing compound

In another embodiment, the oil soluble compound may be a transition metal containing compound or metalloid. Transition metals may include, but are not limited to: titanium, vanadium, copper, zinc, zirconium, molybdenum, tantalum, tungsten, and the like. Suitable metalloids include, but are not limited to: boron, silicon, antimony, tellurium, and the like.

In one embodiment, the oil-soluble transition metal-containing compound may be used as an antiwear agent, a friction modifier, an antioxidant, a deposit control additive, or one more of these functions. In one embodiment, the oil-soluble transition metal-containing compound can be an oil-soluble titanium compound, such as titanium (IV) alkoxide. Titanium-containing compounds that can be used in the disclosed technology or can be used to prepare the oil-soluble materials of the disclosed technology are various ti (IV) compounds, such as titanium (IV) oxide; titanium (IV) sulfide; titanium (IV) nitrate; titanium (IV) alkoxides, such as titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, titanium 2-ethylhexanoate; and other titanium compounds or complexes, including but not limited to titanium phenoxide; titanium carboxylates, such as titanium 2-ethyl-1-3-adipate or citrate or oleate; and (triethanolaminoate) titanium (IV) isopropoxide. Other forms of titanium contemplated within the disclosed technology include titanium phosphates, such as titanium dithiophosphates (e.g., titanium dialkyl dithiophosphates), and titanium sulfonates (e.g., titanium alkyl benzene sulfonates), or, generally, reaction products of titanium compounds reacted with various acidic materials to form salts (e.g., oil soluble salts). The titanium compounds can thus be derived in particular from organic acids, alcohols and diols. The Ti compound may also be present in a dimeric or oligomeric form, containing a Ti-O-Ti structure. Such titanium materials are commercially available or can be readily prepared by appropriate synthetic techniques that will be apparent to those skilled in the art. It is present in solid or liquid form at room temperature, depending on the specific compound. It may also be provided in the form of a solution in a suitable inert solvent.

In one embodiment, titanium may be supplied as a Ti modified dispersant, such as a succinimide dispersant. Such materials can be prepared by forming a titanium mixed anhydride between a titanium alkoxide and a hydrocarbyl-substituted succinic anhydride (e.g., an alkenyl- (or alkyl) succinic anhydride). The resulting titanate-succinate intermediate may be used as is, or may be reacted with any of a variety of materials, such as (a) polyamine succinimide/amide dispersants with free, condensable-NH functionality; (b) components of polyamine succinimide/amide dispersants, i.e., alkenyl- (or alkyl-) succinic anhydrides and polyamines, (c) hydroxyl-containing polyester dispersants prepared by the reaction of substituted succinic anhydrides with polyols, aminoalcohols, polyamines or mixtures thereof. Alternatively, the titanate-succinate intermediate may be reacted with other reagents such as alcohols, aminoalcohols, ether alcohols, polyether alcohols or polyols or fatty acids and the product thereof used directly to impart Ti to the lubricant, or additionally, reacted with succinic acid dispersants as described herein. As an example, 1 part (by mole) tetraisopropyl titanate may be reacted with about 2 parts (by mole) polyisobutylene-substituted succinic anhydride at 140 ℃ for 5 to 6 hours to provide a titanium modified dispersant or intermediate. The resulting material (30g) was additionally reacted with a succinimide dispersant derived from polyisobutylene-substituted succinic anhydride and a polyethylene polyamine mixture (127 g + diluent oil) at 150 ℃ for 1.5 hours to produce a titanium modified succinimide dispersant.

Another titanium-containing compound may be titanium alkoxides and C₆To C₂₅A reaction product of a carboxylic acid. The reaction product may be represented by the formula:

wherein m + n is 4; n is in the range of 1 to 3; r₄Is an alkyl moiety having in the range of 1-8 carbon atoms; r₁Selected from hydrocarbyl groups containing about 6 to 25 carbon atoms; r₂And R₃The same or different and selected from hydrocarbyl groups containing from about 1 to 6 carbon atoms; or by the formula:

wherein x is in the range of 0 to 3; r₁Selected from hydrocarbyl groups containing about 6 to 25 carbon atoms. R₂And R₃The same or different and selected from hydrocarbyl groups containing from about 1 to 6 carbon atoms; and/or R₄Is selected from H or C₆To C₂₅A carboxylic acid moiety. Suitable carboxylic acids may include, but are not limited to, caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, erucic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, phenylacetic acid, benzoic acid, neodecanoic acid, and the like.

In an embodiment, the oil soluble titanium compound may be present in the lubricating oil composition in an amount to provide from 0 to 3000ppm by weight titanium, or from 25 to about 1500ppm by weight titanium, or from about 35ppm to 500ppm by weight titanium, or from about 50ppm to about 300ppm by weight.

Other optional additives

Other additives may be selected to perform one or more functions required of the lubricating fluid. In addition, one or more of the noted additives can be multifunctional and provide functions in addition to or different from those specified herein.

Lubricating oil compositions according to the present disclosure may optionally comprise other performance additives. Other performance additives may be additives other than the specified additives of the present disclosure and/or may include one or more of the following: metal deactivators, viscosity index improvers, detergents, ashless TBN accelerators, friction modifiers, antiwear agents, corrosion inhibitors, rust inhibitors, dispersants, dispersant viscosity index improvers, extreme pressure agents, antioxidants, foam inhibitors, demulsifiers, emulsifiers, pour point depressants, seal swelling agents, and mixtures thereof. Typically, fully formulated lubricating oils will contain one or more of these performance additives.

Suitable metal deactivators may include benzotriazole derivatives (typically tolyltriazole), dimercaptothiadiazole derivatives, 1,2, 4-triazole, benzimidazole, 2-alkyldithiobenzimidazole or 2-alkyldithiobenzothiazole; foam inhibitors including copolymers of ethyl acrylate and 2-ethylhexyl acrylate and optionally vinyl acetate; demulsifiers including trialkyl phosphates, polyethylene glycols, polyethylene oxides, polypropylene oxides, and (ethylene oxide-propylene oxide) polymers; pour point depressants including esters of maleic anhydride-styrene, polymethacrylates, polyacrylates or polyacrylamides.

Suitable foam inhibitors include silicon based compounds such as silicones.

Suitable pour point depressants may include polymethyl methacrylate or mixtures thereof. The pour point depressant may be present in an amount sufficient to provide from about 0 wt.% to about 1 wt.%, from about 0.01 wt.% to about 0.5 wt.%, or from about 0.02 wt.% to about 0.04 wt.%, based on the final weight of the lubricating oil composition.

Suitable rust inhibitors may be a single compound or a mixture of compounds having the property of inhibiting corrosion of ferrous metal surfaces. Non-limiting examples of rust inhibitors useful herein include: oil-soluble high molecular weight organic acids such as 2-ethylhexanoic acid, lauric acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, behenic acid and cerotic acid, and oil-soluble polycarboxylic acids including dimer acids and trimer acids such as those produced from tall oil fatty acids, oleic acid and linoleic acid. Other suitable corrosion inhibitors include long chain alpha, omega-dicarboxylic acids having a molecular weight in the range of about 600 to about 3000, and alkenyl succinic acids in which the alkenyl group contains about 10 or more carbon atoms, such as tetrapropenyl succinic acid, tetradecenyl succinic acid, and hexadecenyl succinic acid. Another useful type of acidic corrosion inhibitor is a half ester of an alkenyl succinic acid having from about 8 to about 24 carbon atoms in the alkenyl group with an alcohol, such as polyethylene glycol. The corresponding half amides of such alkenyl succinic acids are also useful. Useful rust inhibitors are high molecular weight organic acids. In some embodiments, the engine oil is free of rust inhibitors.

The rust inhibitor, if present, can be used in an amount sufficient to provide about 0 wt.% to about 5 wt.%, about 0.01 wt.% to about 3 wt.%, about 0.1 wt.% to about 2 wt.%, based on the final weight of the lubricating oil composition.

In general, as one example, a suitable lubricant composition may include additive components in the ranges set forth in table 5 below.

TABLE 5

The above percentages for each component represent the weight percent of each component, based on the weight of the total final lubricating oil composition. The remainder of the lubricating oil composition is comprised of one or more base oils.

The additives used to formulate the compositions described herein can be blended into the base oil individually or in various sub-combinations. However, it may be suitable to blend all of the components simultaneously using an additive concentrate (i.e., additive plus diluent, such as a hydrocarbon solvent).

Fully formulated lubricants typically contain an additive package, referred to herein as a dispersant/inhibitor package or DI package, which will supply the features required in the formulation. Suitable DI packages are described, for example, in U.S. patent nos. 5,204,012 and 6,034,040. The types of additives included in the additive package may be dispersants, seal swell agents, antioxidants, foam inhibitors, lubricants, rust inhibitors, corrosion inhibitors, demulsifiers, viscosity index improvers, and the like. Some of these components are well known to those skilled in the art and are typically used in conventional amounts with the additives and compositions described herein.

In all embodiments described herein, the lubricant or additive composition may additionally comprise one or more of the following: detergents, dispersants, friction modifiers, antioxidants, rust inhibitors, viscosity index improvers, emulsifiers, demulsifiers, corrosion inhibitors, antiwear agents, metal dihydrocarbyl dithiophosphates, ash free amine phosphates, antifoamants, and pour point depressants, and any combination thereof.

Fuel composition

In accordance with one or more embodiments, the functionalized copolymers described herein can be introduced as functionalized dispersants (also known as fuel detergents) with other additives in gasoline, biodiesel, or diesel to produce fuel compositions or fuel additive compositions. According to one or more embodiments, the fuel composition comprises less than 0.5%, or less than 0.1% of a fuel additive composition comprising a functionalized dispersant. Other values are also possible. Embodiments of the fuel composition or fuel additive composition may contain more than 500 parts per million (ppm), or less than 300ppm, or less than 100ppm, or less than 50ppm, or less than 10ppm of the functionalized fuel dispersant. Examples of other additives that may be used include, but are not limited to, corrosion or rust inhibitors, antistatic dispersants, dehazers, demulsifiers, anti-icing agents, biocides, defoamers, drag reducers, friction modifiers, anti-active matter recession additives, phenolic antioxidants, cold flow improvers, combustion improvers, metal deactivators, friction modifiers, conductivity improvers, and pour point depressants. See, for example, U.S. patent No. 5,405,417.

In selecting a functionalized fuel dispersant, it is important to ensure that the selected dispersant is soluble or stably dispersible in the additive package and the finished fuel composition, is compatible with the other components of the composition, and does not significantly interfere with the performance characteristics of the composition, such as rust prevention, corrosion inhibition, improved lubricity, and improved lead compatibility, which (where appropriate) is required or desired throughout the finished fuel composition.

For convenience, the functionalized fuel dispersant may be provided in concentrate form for dilution. Such concentrates form part of the present disclosure and typically comprise from about 99 to about 1 weight percent of the additive and from about 1 to about 99 weight percent of a solvent or diluent for the additive which may be miscible and/or capable of being dissolved in the gasoline or diesel fuel in which the concentrate may be used. The solvent or diluent may be gasoline, diesel oil, mineral oil (paraffinic or naphthenic), aromatic oil, synthetic oil, or derivatives thereof. In general, the functionalized fuel dispersant additive may be employed in small amounts sufficient to improve the performance characteristics and properties of the base fluid.

It is to be understood that the individual components used may be individually blended into the base fluid, or may be blended therein in various sub-combinations, if desired. In general, the particular order of such blending steps may not be critical. Further, such components may be blended as separate solutions in the diluent. However, according to various embodiments, the additive components may be blended in the form of a concentrate, as this simplifies the blending operation, reduces the possibility of blending errors, and takes advantage of the compatibility and solubility characteristics provided by the overall concentrate.

In a further embodiment, the present disclosure is directed to a method for lubricating an engine by lubricating the engine with the lubricant composition of any of the preceding embodiments.

In a further embodiment, the present invention relates to the use of a lubricating composition according to any one of the preceding embodiments to lubricate an engine.

The following definitions of terms are provided to clarify the meaning of certain terms as used herein. Additional disclosure of various embodiments of the invention are provided below.

The terms "oil composition", "lubricating oil", "lubricant composition", "lubricating composition", "fully formulated lubricant composition", "lubricant", "crankcase oil", "crankcase lubricant", "engine oil", "engine lubricant", "motor oil" and "motor lubricant" are to be considered as synonymous terms which are completely interchangeable, all referring to a finished lubricating product comprising a major amount of base oil and a minor amount of additive composition.

As used herein, the terms "additive package", "additive concentrate", "additive composition", "engine oil additive package", "engine oil additive concentrate", "crankcase additive package", "crankcase additive concentrate", "motor oil additive package", "motor oil concentrate" are considered to be synonymous terms that are fully interchangeable, all referring to the portion of a lubricating oil composition that does not include a substantial base oil stock mixture. The additive package may or may not include a viscosity index improver or pour point depressant.

The term "overbased" relates to metal salts, for example of sulphonic acids, carboxylic acids, salicylic acid and/or phenols, in which the amount of metal present is in excess of the stoichiometric amount. Such salts may have conversion levels in excess of 100% (i.e., they may contain more than 100% of the theoretical amount of metal required to convert the acid to its "normal", "neutral" salt). The expression "metal ratio" is commonly abbreviated MR and is used to denote the ratio of the total stoichiometric amount of metal in the overbased salt to the stoichiometric amount of metal in the neutral salt, according to known chemical reactivity and stoichiometry. In normal or neutral salts, the metal ratio is one, while in overbased salts, the MR is greater than one. They are commonly referred to as overbased, superbased or superbased salts and may be salts of organic sulfuric acids, carboxylic acids, salicylic acids and/or phenols.

As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl group" is used in its ordinary sense, as is well known to those skilled in the art. Specifically, it refers to a group having a carbon atom directly attached to the rest of the molecule and having predominantly hydrocarbon character. Examples of hydrocarbyl groups include:

(a) hydrocarbon substituents, that is, aliphatic substituents (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic substituents substituted with aromatic, aliphatic, and alicyclic groups, as well as cyclic substituents wherein the ring is completed by another portion of the molecule (e.g., two substituents together form an alicyclic moiety);

(b) substituted hydrocarbon substituents, that is, substituents containing non-hydrocarbon groups that do not alter the predominantly hydrocarbon substituent in the context of this disclosure (e.g., halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, amino, alkylamino, and sulfoxy); and

(c) hetero-substituents, i.e., substituents, while having a predominantly hydrocarbon character in the context of this disclosure, contain atoms other than carbon in a ring or chain otherwise composed of carbon atoms. Heteroatoms can include sulfur, oxygen, and nitrogen, and encompass substituents as pyridyl, furyl, thienyl, and imidazolyl. In general, no more than two, e.g., no more than one, non-hydrocarbon substituent will be present for every ten carbon atoms in the hydrocarbyl group; typically, no non-hydrocarbon substituents will be present in the hydrocarbyl group.

The term "weight percent" as used herein means the percentage of the stated component by weight of the entire composition, unless explicitly stated otherwise.

The terms "soluble", "oil-soluble" or "dispersible" as used herein may but do not necessarily indicate that the compound or additive is soluble, miscible or capable of being suspended in all proportions in the oil. However, the foregoing terms do mean that they are, for example, soluble, suspendable, soluble or stably dispersible in oil to an extent sufficient to exert their intended effects in the environment in which the oil is employed. Furthermore, the additional incorporation of other additives may also permit the incorporation of higher levels of particular additives, if desired.

The term "TBN" as used herein is used to denote the total base number in mg KOH/g as measured by the method of ASTM D2896.

The term "alkyl" as used herein refers to a straight, branched, cyclic, and/or substituted saturated chain moiety of from about 1 to about 100 carbon atoms.

The term "alkenyl" as used herein refers to a straight, branched, cyclic, and/or substituted unsaturated chain moiety of about 3 to about 10 carbon atoms.

The term "aryl" as used herein refers to monocyclic and polycyclic aromatic compounds, which may include alkyl, alkenyl, alkaryl, amino, hydroxyl, alkoxy, halogen substituents, and/or heteroatoms, including, but not limited to, nitrogen, oxygen, and sulfur.

The lubricants, combinations of components, or individual components of the present description may be suitable for use in various types of internal combustion engines. Suitable engine types may include, but are not limited to, heavy duty diesel engines, passenger cars, light duty diesel engines, medium speed diesel engines, or marine engines. The internal combustion engine may be a diesel fuel engine, a gasoline fuel engine, a natural gas fuel engine, a biofuel engine, a hybrid diesel/biofuel engine, a hybrid gasoline/biofuel engine, an ethanol fuel engine, a hybrid gasoline/ethanol fuel engine, a Compressed Natural Gas (CNG) fuel engine, or a mixture thereof. The diesel engine may be a compression ignition engine. The gasoline engine may be a spark ignition engine. Internal combustion engines may also be used in combination with electric or battery power. An engine so configured is commonly referred to as a hybrid engine. The internal combustion engine may be a 2-stroke, 4-stroke or rotary engine. Suitable internal combustion engines include marine diesel engines (e.g., inland marine), aviation piston engines, low-load diesel engines, and motorcycle, automobile, locomotive, and truck engines. A particularly preferred type of engine in which the lubricant composition of the present invention may be used is a Heavy Duty Diesel (HDD) engine.

HDD engines are generally known to produce soot levels in the range of about 2% to about 3% in lubricants. In addition, soot levels can reach levels of up to about 8% in older models of HDD engines. In addition, Gasoline Direct Injection (GDi) engines also have soot in their lubricating fluids. The test of the GDi engine running 312 hours using the ford chain wear test produced a soot level of 2.387% in the lubricant. Soot levels in direct fuel injected gasoline engines may range from about 1.5% to about 3%, depending on the manufacturer and operating conditions. For comparison, a non-direct injection gasoline engine was also tested to determine the amount of soot generated in the lubricant. The results of this test show only about 1.152% soot in the lubricant.

The synergistic dispersants of the present invention are preferred for use in these types of engines based on the higher levels of soot produced by HDD and GDi engines. For use in HDD engines and direct fuel injection gasoline engines, soot present in the oil may range from about 0.05% to about 8%, depending on the age of the engine, the manufacturer, and operating conditions. In some embodiments, the soot level in the lubricating composition is greater than about 1.5%, or preferably the soot level is from about 1.5% to about 8%, and most preferably the soot level in the lubricating liquid is from about 2% to about 3%.

Internal combustion engines may contain components of one or more of aluminum alloys, lead, tin, copper, cast iron, magnesium, ceramics, stainless steel, composites, and/or mixtures thereof. The component may be coated, for example, with a diamond-like carbon coating, a lubricious coating, a phosphorous-containing coating, a molybdenum-containing coating, a graphite coating, a nanoparticle-containing coating, and/or mixtures thereof. The aluminum alloy may include aluminum silicate, aluminum oxide, or other ceramic materials. In one embodiment, the aluminum alloy is an aluminum silicate surface. As used herein, the term "aluminum alloy" is intended to be synonymous with "aluminum composite" and describes a component or surface that includes aluminum and another component that intermix or react at a microscopic or near-microscopic level, regardless of their specific structure. This would include any conventional alloy having a metal other than aluminum and a composite or alloy-like structure having non-metallic elements or compounds (e.g., having a ceramic-like material).

The lubricating oil composition for an internal combustion engine may be suitable for use in any engine lubricant, regardless of the sulfur, phosphorus, or sulfated ash (ASTM D-874) content. The sulfur content of the engine oil lubricant may be about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less, or about 0.3 wt% or less, or about 0.2 wt% or less. In one embodiment, the sulfur content may range from about 0.001 wt% to about 0.5 wt%, or from about 0.01 wt% to about 0.3 wt%. The phosphorus content can be about 0.2 wt% or less, or about 0.1 wt% or less, or about 0.085 wt% or less, or about 0.08 wt% or less, or even about 0.06 wt% or less, about 0.055 wt% or less, or about 0.05 wt% or less. In one embodiment, the phosphorus content can be about 50ppm to about 1000ppm, or about 325ppm to about 850 ppm. The total sulfated ash content may be about 2 wt% or less, or about 1.5 wt% or less, or about 1.1 wt% or less, or about 1 wt% or less, or about 0.8 wt% or less, or about 0.5 wt% or less. In one embodiment, the sulfated ash content may be from about 0.05 wt% to about 0.9 wt%, or from about 0.1 wt% or from about 0.2 wt% to about 0.45 wt%. In another embodiment, the sulfur content may be about 0.4 wt% or less, the phosphorus content may be about 0.08 wt% or less, and the sulfated ash is about 1 wt% or less. In yet another embodiment, the sulfur content can be about 0.3 wt% or less, the phosphorus content can be about 0.05 wt% or less, and the sulfated ash can be about 0.8 wt% or less.

In one embodiment, the lubricating oil composition is an engine oil, wherein the lubricating oil composition may have (i) a sulfur content of about 0.5 wt.% or less, (ii) a phosphorus content of about 0.1 wt.% or less, and (iii) a sulfated ash content of about 1.5 wt.% or less.

In one embodiment, the lubricating oil composition is suitable for use in a 2-stroke or 4-stroke marine diesel internal combustion engine. In one embodiment, the marine diesel internal combustion engine is a 2-stroke engine. In some embodiments, the lubricating oil composition is not suitable for use in a 2-stroke or 4-stroke marine diesel internal combustion engine for one or more reasons including, but not limited to, high sulfur content of the fuel used to power the marine engine and high TBN required for a suitable marine engine oil (e.g., greater than about 40TBN in a suitable marine engine oil).

In some embodiments, the lubricating oil composition is suitable for use in engines powered by low sulfur fuels, such as fuels containing from about 1 to about 5% sulfur. Highway vehicle fuels contain about 15ppm sulfur (or about 0.0015% sulfur).

Low speed diesel is typically referred to as a marine engine, medium speed diesel is typically referred to as a locomotive, and high speed diesel is typically referred to as highway vehicles. Lubricating oil compositions may be suitable for only one or all of these types.

Additionally, the lubricants of the present description may be adapted to meet one or more industry specification requirements, such as ILSAC GF-3, GF-4, GF-5, GF-6, CK-4, FA-4, CJ-4, CI-4Plus, CI-4, ACEA A1/B1, A2/B2, A3/B3, A3/B4, A5/B5, C1, C2, C3, C4, C5, E4/E6/E7/E9, Euro 5/6, JASO DL-1, low SAPS, medium SAPS, or original equipment manufacturer specifications, such as Dexos^TM1、Dexos^TM2. MB approval 229.51/229.31, VW 502.00, 503.00/503.01, 504.00, 505.00, 506.00/506.01, 507.00, 508.00, 509.00, BMW Longlife-04, Porsche C30, PeugeotCars B712290, B712296, B712297, B712300, B712302, B712312, B712007, B712008, Ford WSS-M2C153-H, WSS-M2C930-A, WSS-M2C945-A, WSS-M2C913A, WSS-M2C913-B, WSS-M2C913-C, GM 6094-M, Chrysler MS-6395, or any past or future PCMO or HDD specifications not mentioned herein. In some embodiments, the amount of phosphorus in the finished fluid is 1000ppm or less, or 900ppm or less, or 800ppm or less for Passenger Car Motor Oil (PCMO) applications.

Other hardware may not be suitable for use with the disclosed lubricant. "functional fluid" is a term that encompasses various fluids, including but not limited to tractor hydraulic fluid; the power transmission fluid comprises automatic transmission fluid, stepless transmission fluid and manual transmission fluid; hydraulic fluid, including tractor hydraulic fluid; some gear oil; a power steering fluid; fluids for wind turbines, compressors; some industrial fluids; and a fluid associated with a driveline component. It should be noted that within each of these fluids, such as within automatic transmission fluids, there are a variety of different types of fluids, as the various transmissions have different designs resulting in the need for fluids having significantly different functional characteristics. This is in contrast to the term "lubricating fluid" which is not used to generate or transmit power.

With regard to tractor hydraulic fluids, for example, these fluids are common products for all lubricant applications in tractors except for lubricating the engine. These lubrication applications may include lubrication of the gearbox, power take-off and one or more clutches, rear axles, reduction gears, wet brakes, and hydraulic accessories.

When the functional fluid is an automatic transmission fluid, the automatic transmission fluid must have sufficient friction for the clutch plates to transmit power. However, the coefficient of friction of the fluid has a tendency to decrease due to the temperature effects caused by the fluid heating up during operation. It is important that the tractor hydraulic fluid or automatic transmission fluid maintain its high coefficient of friction at high temperatures, otherwise the brake system or automatic transmission may fail. This is not a function of the engine oil.

Tractor fluids, and for example Super Tractor Universal Oil (STUO) or Universal Tractor Transmission Oil (UTTO), can combine engine oil performance with transmission, differential, final drive planetary gears, wet brakes, and hydraulic performance. While many of the additives used to formulate a UTTO or STUO fluid are functionally similar, they can have deleterious effects if not properly incorporated. For example, some anti-wear and extreme pressure additives used in engine oils can be extremely corrosive to copper components in hydraulic pumps. Detergents and dispersants used for gasoline or diesel engine performance can be detrimental to wet brake performance. Friction modifiers specifically designed to eliminate wet brake noise may lack the thermal stability necessary for engine oil performance. Each of these fluids, whether functional, tractor, or lubricating, is designed to meet specific and stringent manufacturer requirements.

The engine oils as discussed herein may be formulated by adding one or more additives (as described in detail below) to an appropriate base oil formulation. The additives may be combined with the base oil in the form of an additive package (or concentrate) or, alternatively, may be combined with the base oil alone (or as a mixture of the two). Fully formulated engine oils may exhibit improved performance characteristics based on the additives added and their respective proportions.

The details and advantages of the disclosure may be realized and obtained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that the description herein is only exemplary and explanatory and is not restrictive of the disclosure, as claimed.

All patents and publications cited herein are fully incorporated by reference in their entirety.

The following examples are illustrative of the methods and compositions of the present disclosure and are not limiting. Other suitable modifications and adaptations of the various conditions and parameters normally encountered in the art and apparent to those skilled in the art are within the spirit and scope of the present disclosure.

Examples of the invention

An Anton-Paar model MCR302 rheometer was used to simultaneously measure the viscous and elastic properties of the oil as it cooled at approximately 1 deg.c/minute. All measurements were performed using parallel plate geometry. To eliminate moisture condensation on the sample and plate, the system was mounted in a thermal control enclosure with a nitrogen purge. The rheometer was operated in an oscillatory mode with an angular frequency of 2 rad/sec and an angular displacement of 1 mrad. All data were collected in the linear viscoelastic region.

Example 1

The 300mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst and cocatalyst. The reaction is continuously operated; catalyst (0.127 wt% Cp)₂ZrCl₂Toluene solution of (c), cocatalyst (5.0 wt% MMAO in toluene), solvent (toluene), and olefin monomer. The reactor was operated at 70psig full liquid and stirred with a four-bladed inclined turbine wheel operating at 220 rpm. Immediately prior to introduction into the reactor, the catalyst and cocatalyst solutions were mixed at feed rates of 0.90 and 0.90 g/min, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and cocatalyst solutions at feed rates of 2.71, 15.22 and 11.71 g/min, respectively. The reactor temperature was maintained at 65 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 2.78 g/min.

By passing¹The copolymer composition was determined by H-NMR to be 49 mol% ethylene. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 1159g/mol and 3.73, respectively. By passing¹The molecular weight of the copolymer, measured by H-NMR, is 1038g/mol and is determined by¹The olefin distribution of the copolymer as measured by H-NMR was 96.5% me-vinylidene, 1.6% β -vinylidene, 1.3% disubstituted and 0.6% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 1.68. The crossover temperature as measured by oscillatory rheometry is below the instrument limit of about-73.5 ℃.

Example 2

A300 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and for propylene, toluene, catalyst and co-promoterHigh pressure metering pumps for the individual feeds of catalyst. The reaction is continuously operated; catalyst (0.127 wt% Cp)₂ZrCl₂Toluene solution of (c), cocatalyst (5.0 wt% MMAO in toluene), solvent (toluene), and olefin monomer. The reactor was operated at 70psig full liquid and stirred with a four-bladed inclined turbine wheel operating at 220 rpm. Immediately prior to introduction into the reactor, the catalyst and cocatalyst solutions were mixed at feed rates of 0.87 and 0.87 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and cocatalyst solutions at feed rates of 2.78, 15.51 and 10.65 g/min, respectively. The reactor temperature was maintained at 68 ℃ as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 3.22 g/min.

By passing¹The copolymer composition was determined by H-NMR to be 46 mol% ethylene. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 1466g/mol and 2.22, respectively. By passing¹The molecular weight of the copolymer, measured by H-NMR, is 780g/mol and¹the olefin distribution of the copolymer as measured by H-NMR was 96.0% me-vinylidene, 1.8% β -vinylidene, 1.3% disubstituted and 0.9% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 1.54. The crossover temperature as measured by oscillatory rheometry is below the instrument limit of about-77.6 ℃.

Example 3

The 300mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst and cocatalyst. The reaction is continuously operated; catalyst (0.077 wt% Cp)₂ZrCl₂Toluene solution of (c), cocatalyst (1.248 wt% MMAO in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 763psig and stirred with a four-bladed inclined turbine wheel operating at 900 rpm. Immediately prior to introduction into the reactor, the catalyst and cocatalyst solutions were mixed at feed rates of 1.02 and 0.82 g/min, respectively. Ethylene, propyleneAnd toluene were also mixed together and fed into the reactor separately from the catalyst and cocatalyst solutions at feed rates of 2.23, 3.30 and 9.31 grams/minute, respectively. The reactor temperature was maintained at 76 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 3.57 g/min.

By passing¹The copolymer composition was determined by H-NMR to be 65 mol% ethylene. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 2085g/mol and 3.42, respectively. By passing¹The copolymer has a molecular weight of 1645g/mol, determined by H-NMR and¹the olefin distribution of the copolymer as measured by H-NMR was 95.1% me-vinylidene, 1.8% β -vinylidene, 1.3% disubstituted and 1.8% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 2.60. The crossover temperature as measured by oscillatory rheometry was-24.5 ℃.

Example 4

The 300mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst and cocatalyst. The reaction is continuously operated; continuous feed catalyst (0.075 wt% Cp)₂ZrCl₂Toluene solution of (c), cocatalyst (1.0 wt% MMAO in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 708psig and stirred with a four-bladed inclined turbine impeller operated at 1000 rpm. Immediately prior to introduction into the reactor, the catalyst and cocatalyst solutions were mixed at feed rates of 0.89 and 0.91 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and cocatalyst solutions at feed rates of 2.23, 3.59 and 9.36 g/min, respectively. The reactor temperature was maintained at 75 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 3.47 g/min.

By passing¹The copolymer composition was determined by H-NMR to be 65 mol% ethylene. The relative number average molecular weights and PDI of the copolymers measured by GPC were 2326g/mol and 3.35. By passing¹The molecular weight of the copolymer, measured by H-NMR, was 1824g/mol and¹the olefin distribution of the copolymer as measured by H-NMR was 95.6% me-vinylidene, 1.7% β -vinylidene, 1.1% disubstituted and 1.6% vinyl/allyl¹³The average ethylene continuous chain link length measured by C-NMR was 2.52. The crossover temperature as measured by oscillatory rheometry was-27.0 ℃.

Example 5

The 300mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst and cocatalyst. The reaction is continuously operated; catalyst (0.150 wt% Cp)₂ZrCl₂Toluene solution of (c), cocatalyst (2.0 wt% MMAO in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 715psig and stirred with a four-bladed inclined turbine impeller operated at 1000 rpm. Immediately prior to introduction into the reactor, the catalyst and cocatalyst solutions were mixed at feed rates of 1.28 and 1.26 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and cocatalyst solutions at feed rates of 2.23, 2.60 and 9.38 grams/minute, respectively. The reactor temperature was maintained at 75 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 3.4 g/min.

By passing¹The copolymer composition was determined by H-NMR to be 64 mol% ethylene. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 1241g/mol and 3.00, respectively. By passing¹The molecular weight of the copolymer, measured by H-NMR, is 1114g/mol and is determined by¹The olefin distribution of the copolymer as measured by H-NMR was 95.5% me-vinylidene, 1.9% β -vinylidene, 1.3% disubstituted and 1.4% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 2.39. The crossover temperature as measured by oscillatory rheometry was-35.8 ℃.

Example 6

300mL Parr reactorEquipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas and a high pressure metering pump for separate feeds of propylene, toluene, catalyst and cocatalyst. The reaction is continuously operated; catalyst (0.167 wt% Cp)₂ZrCl₂Toluene solution of (c), cocatalyst (2.222 wt% MMAO in toluene), solvent (toluene), and olefin monomer. The reactor was operated at 696psig full liquid and stirred with a four-bladed inclined turbine wheel operating at 1000 rpm. Immediately prior to introduction into the reactor, the catalyst and cocatalyst solutions were mixed at feed rates of 0.66 and 0.65 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and cocatalyst solutions at feed rates of 3.09, 8.11 and 3.10 g/min, respectively. The reactor temperature was maintained at 80 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 6.63 g/min.

By passing¹The copolymer composition was determined by H-NMR to be 58 mol% ethylene. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 3202g/mol and 2.03, respectively. By passing¹The molecular weight of the copolymer, measured by H-NMR, is 1310g/mol and is determined by¹The olefin distribution of the copolymer as measured by H-NMR was 95.7% me-vinylidene, 1.5% β -vinylidene, 1.6% disubstituted and 1.2% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 2.02. The crossover temperature as measured by oscillatory rheometry was-72.7 ℃.

Example 7

The 300mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst and cocatalyst. The reaction is continuously operated; continuous feed catalyst (0.165 wt% Cp)₂ZrCl₂Toluene solution of (c), cocatalyst (2.2 wt% MMAO in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 703psig and stirred with a four-bladed inclined turbine impeller operated at 1000rpm. Immediately prior to introduction into the reactor, the catalyst and cocatalyst solutions were mixed at feed rates of 1.21 and 1.20 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and cocatalyst solutions at feed rates of 2.23, 2.51 and 8.50 g/min, respectively. The reactor temperature was maintained at 75 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 3.48 g/min.

By passing¹The copolymer composition was determined by H-NMR to be 68 mol% ethylene. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 2838g/mol and 1.87, respectively. By passing¹The molecular weight of the copolymer, measured by H-NMR, was 1203g/mol and¹the olefin distribution of the copolymer as measured by H-NMR was 94.6% me-vinylidene, 2.1% β -vinylidene, 1.3% disubstituted and 2.0% vinyl/allyl¹³The average ethylene continuous chain link length measured by C-NMR was 2.72. The crossover temperature as measured by oscillatory rheometry was-13.7 ℃.

Example 8

The 300mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst and cocatalyst. The reaction is continuously operated; catalyst (0.182 wt% Cp)₂ZrCl₂Toluene solution of (c), cocatalyst (2.42 wt% MMAO in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 704psig and stirred with a four-bladed inclined turbine impeller operated at 1000 rpm. Immediately prior to introduction into the reactor, the catalyst and cocatalyst solutions were mixed at feed rates of 1.15 and 1.14 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and cocatalyst solutions at feed rates of 2.20, 2.40 and 7.97 g/min, respectively. The reactor temperature was maintained at 75 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 3.53 g/min.

By passing¹The copolymer composition was determined by H-NMR to be 67 mol% ethylene. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 2269g/mol and 2.17, respectively. By passing¹The molecular weight of the copolymer, measured by H-NMR, was 1167g/mol and¹the olefin distribution of the copolymer as measured by H-NMR was 94.6% me-vinylidene, 2.2% β -vinylidene, 1.3% disubstituted and 1.9% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 2.65. The crossover temperature as measured by oscillatory rheometry was-18.5 ℃.

Example 9

The 300mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst and cocatalyst. The reaction is continuously operated; catalyst (0.167 wt% Cp)₂ZrCl₂Toluene solution of (c), cocatalyst (2.222 wt% MMAO in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 701psig and stirred with a four-bladed inclined turbine wheel operating at 1000 rpm. Immediately prior to introduction into the reactor, the catalyst and cocatalyst solutions were mixed at feed rates of 0.78 and 0.89 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst and cocatalyst solutions at feed rates of 3.34, 7.77 and 3.20 grams/minute, respectively. The reactor temperature was maintained at 89 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 7.98 g/min.

By passing¹The copolymer composition was 56 mol% ethylene as determined by H-NMR. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 3173g/mol and 2.02, respectively. By passing¹The molecular weight of the copolymer, measured by H-NMR, is 1281g/mol and is determined by¹The olefin distribution of the copolymer as measured by H-NMR was 94.9% me-vinylidene, 2.0% β -vinylidene, 1.8% disubstituted and 1.3% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 2.05. By oscillatory rheological measurementsThe measured crossover temperature was below-37 ℃.

Example 10

The 100mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst, cocatalyst, and scavenger. The reaction is continuously operated; continuous feed catalyst (0.011 wt% Cp)₂ZrMe₂Toluene solution of (c), cocatalyst (0.023 wt% FAB in toluene), scavenger (0.0080 wt% TEAL in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 1520psig and stirred with a four-bladed inclined turbine wheel operating at 1041 rpm. Immediately prior to introduction into the reactor, the catalyst, cocatalyst and scavenger solutions were mixed at feed rates of 0.31, 0.32 and 0.52 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, cocatalyst and scavenger solutions at feed rates of 0.60, 2.98 and 6.31 g/min, respectively. The reactor temperature was maintained at 134 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 0.96 g/min.

By passing¹The copolymer composition was determined by H-NMR to be 55 mol% ethylene. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 2883g/mol and 2.05, respectively. By passing¹The molecular weight of the copolymer, measured by H-NMR, was 1411g/mol and¹the olefin distribution of the copolymer as measured by H-NMR was 76.6% me-vinylidene, 14.1% β -vinylidene, 7.2% disubstituted and 2.1% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 2.60. The crossover temperature as measured by oscillatory rheometry was-22.4 ℃.

Example 11

The 100mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst, cocatalyst, and scavenger. The reaction is continuously operated; continuous feedCatalyst (0.141 wt% Cp)₂ZrMe₂Toluene solution of (c), cocatalyst (0.144 wt% FAB in toluene), scavenger (0.032 wt% TEAL in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 1553psig and stirred with a four-bladed inclined turbine impeller operated at 1000 rpm. Immediately prior to introduction into the reactor, the catalyst, cocatalyst and scavenger solutions were mixed at feed rates of 0.22, 0.49 and 0.25 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, cocatalyst and scavenger solutions at feed rates of 1.75, 2.55 and 7.04 grams/minute, respectively. The reactor temperature was maintained at 120 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 2.53 g/min.

By passing¹The copolymer composition was determined by H-NMR to be 62 mol% ethylene. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 2318g/mol and 1.98, respectively. By passing¹The molecular weight of the copolymer, measured by H-NMR, was 1199g/mol and¹the olefin distribution of the copolymer as measured by H-NMR was 75.6% me-vinylidene, 16.8% β -vinylidene, 6.3% disubstituted and 1.4% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 2.22. The crossover temperature as measured by oscillatory rheometry is below-37 ℃.

Example 12

The 100mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst, cocatalyst, and scavenger. The reaction is continuously operated; catalyst (0.04 wt% Cp)₂ZrMe₂Toluene solution of (c), cocatalyst (0.083 wt% FAB in toluene), scavenger (0.005 wt% TEAL in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 1533psig and stirred with a four-bladed inclined turbine impeller operated at 1000 rpm. Immediately prior to introduction into the reactor, the catalyst, cocatalyst and scavenger solutions were at 0.32, 0.34 andmixed at a feed rate of 0.33 g/min. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, cocatalyst and scavenger solutions at feed rates of 1.60, 3.05 and 3.68 grams/minute, respectively. The reactor temperature was maintained at 98 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 3.69 g/min.

By passing¹The copolymer composition was measured by H-NMR to be 45 mol% ethylene. The relative number average molecular weight and PDI of the copolymer measured by GPC were 2628g/mol and 2.00, respectively. By passing¹The molecular weight of the copolymer, determined by H-NMR, was 1410g/mol and¹the olefin distribution of the copolymer as measured by H-NMR was 81.2% me-vinylidene, 13.0% β -vinylidene, 5.2% disubstituted and 0.6% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 1.62. The crossover temperature as measured by oscillatory rheometry is below-37 ℃.

Example 13

The 100mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst, cocatalyst, and scavenger. The reaction is continuously operated; catalyst (0.04 wt% Cp)₂ZrMe₂Toluene solution of (a), cocatalyst (0.082 wt% FAB in toluene), scavenger (0.01 wt% TEAL in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 1533psig and stirred with a four-bladed inclined turbine wheel operating at 1019 rpm. Immediately prior to introduction into the reactor, the catalyst, cocatalyst and scavenger solutions were mixed at feed rates of 0.52, 0.52 and 0.37 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, cocatalyst and scavenger solutions at feed rates of 1.78, 2.76 and 3.98 grams/minute, respectively. The reactor temperature was maintained at 119 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 3.5 g/min.

By passing¹The copolymer composition was 54 mol% ethylene as determined by H-NMR. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 1673g/mol and 1.97, respectively. By passing¹The copolymer has a molecular weight of 913g/mol, measured by H-NMR, and¹the olefin distribution of the copolymer as measured by H-NMR was 79.2% me-vinylidene, 14.7% β -vinylidene, 5.0% disubstituted and 1.1% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 1.99. The crossover temperature as measured by oscillatory rheometry is below-37 ℃.

Example 14

The 100mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst, cocatalyst, and scavenger. The reaction is continuously operated; catalyst feed continuously (0.093 wt% Cp)₂ZrMe₂Toluene solution of (c), cocatalyst (0.191 wt% FAB in toluene), scavenger (0.011 wt% TEAL in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 1462psig and stirred with a four-bladed inclined turbine wheel operating at 1000 rpm. Immediately prior to introduction into the reactor, the catalyst, cocatalyst and scavenger solutions were mixed at feed rates of 0.65, 0.68 and 0.63 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, cocatalyst and scavenger solutions at feed rates of 1.70, 2.20 and 6.85 grams/minute, respectively. The reactor temperature was maintained at 105 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 2.63 g/min.

By passing¹The copolymer composition was determined by H-NMR to be 67 mol% ethylene. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 3004g/mol and 2.04, respectively. By passing¹The molecular weight of the copolymer, measured by H-NMR, is 1504g/mol and¹the olefin distribution of the copolymer as measured by H-NMR was 83.0% me-vinylidene, 11.0% β -vinylidene, 5.0% disubstituted and 2.0% vinyl/allylAnd (4) a base. By passing¹³The average ethylene continuous chain length measured by C-NMR was 2.64. The crossover temperature as measured by oscillatory rheometry was-20.0 ℃.

Example 15

The 100mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and high pressure metering pumps for separate feeds of propylene, toluene, catalyst, cocatalyst, and scavenger. The reaction is continuously operated; continuous feed catalyst (0.008 wt% Cp)₂ZrMe₂Toluene solution of (c), cocatalyst (0.015 wt% FAB in toluene), scavenger (0.011 wt% TEAL in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 1549psig and stirred with a four-bladed inclined turbine wheel operating at 1008 rpm. Immediately prior to introduction into the reactor, the catalyst, cocatalyst and scavenger solutions were mixed at feed rates of 0.37, 0.40 and 0.27 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, cocatalyst and scavenger solutions at feed rates of 0.48, 3.0 and 6.98 grams/minute, respectively. The reactor temperature was maintained at 140 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 0.61 g/min.

By passing¹The copolymer composition was 57 mol% ethylene as determined by H-NMR. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 3000g/mol and 2.23, respectively. By passing¹The copolymer has a molecular weight of 1505g/mol, as measured by H-NMR, and¹the olefin distribution of the copolymer as measured by H-NMR was 76.6% me-vinylidene, 13.7% β -vinylidene, 7.6% disubstituted and 2.1% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 2.59. The crossover temperature measured by oscillatory rheometry was 0.7 ℃.

Example 16

A100 mL Parr reactor was equipped with a water jacket for temperature control, a nitrogen purge receiver for pressure control, a metered feed of ethylene gas, and for propylene, toluene, and,High pressure metering pumps for separate feeds of catalyst, cocatalyst and scavenger. The reaction is continuously operated; catalyst (0.015 wt% Cp)₂ZrMe₂Toluene solution of (c), cocatalyst (0.031 wt% FAB in toluene), scavenger (0.009 wt% TEAL in toluene), solvent (toluene), and olefin monomer. The reactor was operated flooded at 1539psig and stirred with a four-bladed inclined turbine impeller operated at 1001 rpm. Immediately prior to introduction into the reactor, the catalyst, cocatalyst and scavenger solutions were mixed at feed rates of 0.26, 0.26 and 0.46 grams/minute, respectively. Ethylene, propylene and toluene were also mixed together and fed to the reactor separately from the catalyst, cocatalyst and scavenger solutions at feed rates of 0.52, 3.04 and 6.62 grams/minute, respectively. The reactor temperature was maintained at 140 ℃, as measured by an 1/8 inch thermocouple in the reactor. The production rate of the copolymer was measured gravimetrically to be 0.64 g/min.

By passing¹The copolymer composition was 57 mol% ethylene as determined by H-NMR. The relative number average molecular weight and PDI of the copolymer as measured by GPC were 2331g/mol and 2.38, respectively. By passing¹The molecular weight of the copolymer, measured by H-NMR, was 1197g/mol and¹the olefin distribution of the copolymer as measured by H-NMR was 76.9% me-vinylidene, 14.4% β -vinylidene, 6.9% disubstituted and 1.8% vinyl/allyl¹³The average ethylene continuous chain length measured by C-NMR was 2.57. The crossover temperature as measured by oscillatory rheometry was-17.8 ℃.

The following table summarizes some of the above experiments.

TABLE 6

Functionalized examples of alpha-olefin copolymers

ASA example 1

An ethylene propylene copolymer (example 1)168.5g (0.16mol) and maleic anhydride 23.5g (0.24mol) were charged to a 350mL PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50 ℃ and purged with nitrogen for 15 minutes with stirring. The reactor temperature was raised to 235 ℃ and maintained at that temperature for 6 hours while stirring. The reaction mixture was then cooled to 90 ℃ and transferred to a 500mL round bottom flask. The reaction mixture was then heated and unreacted maleic anhydride was removed in vacuo. Analysis and analysis: acid value: 0.966 and 91.0% functionalized copolymer.

ASA example 2

An ethylene propylene copolymer (example 2)150g (0.19mol) and maleic anhydride 28.3g (0.29mol) were charged to a 350mL PARR pressure reactor equipped with a stirrer and thermocouple. The reaction mixture was heated to 50 ℃ and purged with nitrogen for 15 minutes with stirring. The reactor temperature was raised to 235 ℃ and maintained at that temperature for 6 hours while stirring. The reaction mixture was then cooled to 90 ℃ and transferred to a 500mL round bottom flask. The reaction mixture was then heated and unreacted maleic anhydride was removed in vacuo. Analysis and analysis: acid value: 1.24 and 91.6% functionalized copolymer.

ASA example 3

An ethylene propylene copolymer (example 3)822.5g (0.5mol) and maleic anhydride 73.55g (0.75mol) were charged to a 2L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50 ℃ and purged with nitrogen for 15 minutes with stirring. The reactor temperature was raised to 235 ℃ and maintained at that temperature for 6 hours while stirring. The reaction mixture was then cooled to 90 ℃ and transferred to a 2L round bottom flask. The reaction mixture was then heated and unreacted maleic anhydride removed in vacuo to give 827.5g of product. Analysis and analysis: acid value: 0.577 and 85.4% functionalized copolymer.

ASA example 4

An ethylene propylene copolymer (example 4)900g (0.49mol) and maleic anhydride 72.65g (0.74mol) were charged to a 2L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50 ℃ and purged with nitrogen for 15 minutes with stirring. The reactor temperature was raised to 235 ℃ and maintained at that temperature for 6 hours while stirring. The reaction mixture was then cooled to 90 ℃ and transferred to a 2L round bottom flask. The reaction mixture was then heated and unreacted maleic anhydride removed in vacuo to give 901.4g of product. Analysis and analysis: acid value: 0.571 and 84.8% functionalized copolymer.

ASA example 5

An ethylene propylene copolymer (example 5)781g (0.7mol) and maleic anhydride 103.1g (1.05mol) were charged to a 2L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50 ℃ and purged with nitrogen for 15 minutes with stirring. The reactor temperature was raised to 235 ℃ and maintained at that temperature for 6 hours while stirring. The reaction mixture was then cooled to 90 ℃ and transferred to a 1L round bottom flask. The reaction mixture was then heated and unreacted maleic anhydride removed in vacuo to give 846.5g of product. Analysis and analysis: acid value: 0.986 and 88.6% functionalized copolymer.

ASA example 6

An ethylene propylene copolymer (example 6)1000g (0.76mol) and maleic anhydride 112.3g (1.15mol) were charged to a 2L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50 ℃ and purged with nitrogen for 15 minutes with stirring. The reactor temperature was raised to 235 ℃ and maintained at that temperature for 6 hours while stirring. The reaction mixture was then cooled to 90 ℃ and transferred to a 2L round bottom flask. The reaction mixture was then heated and unreacted maleic anhydride removed in vacuo to give 1076.8g of product. Analysis and analysis: acid value: 0.76 and 78% functionalized copolymer.

ASA example 7

450g (0.374mol) of ethylene propylene copolymer (example 7), 450g (0.386mol) of ethylene propylene copolymer (example 8) and 111.79g (1.14mol) of maleic anhydride were charged to a 2L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50C and purged with nitrogen for 15 minutes with stirring. The reactor temperature was raised to 235 ℃ and maintained at that temperature for 6 hours while stirring. The reaction mixture was then cooled to 90 ℃ and transferred to a 2L round bottom flask. The reaction mixture was then heated and unreacted maleic anhydride removed in vacuo to give 960.2g of product. Analysis and analysis: acid value: 0.923 and 87.0% of functionalized copolymer.

ASA example 8

845.2g (0.66mol) of ethylene propylene copolymer (example 9) and 97.0g (0.99mol) of maleic anhydride were charged to a 2L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50 ℃ and purged with nitrogen for 15 minutes with stirring. The reactor temperature was raised to 235 ℃ and maintained at that temperature for 6 hours while stirring. The reaction mixture was then cooled to 90 ℃ and transferred to a 2L 3N-round bottom flask. The reaction mixture was then heated and unreacted maleic anhydride removed in vacuo to give 904.2g of product. Analysis and analysis: acid value: 0.858 and 82.2% functionalized copolymer.

ASA example 9

An ethylene propylene copolymer (example 10)150.0(0.11mol) and maleic anhydride 15.7g (0.159mol) were charged to a 350mL PARR pressure reactor equipped with a stirrer and thermocouple. The reaction mixture was heated to 50 ℃ and purged with nitrogen for 15 minutes with stirring. The reactor temperature was raised to 235 ℃ and maintained at that temperature for 6 hours while stirring. The reaction mixture was then cooled to 90 ℃ and transferred to a 500mL 3N-round bottom flask. The reaction mixture was then heated and unreacted maleic anhydride removed in vacuo to yield 155.3g of product. Analysis and analysis: acid value: 0.72 and 85.6% functionalized copolymer.

ASA example 10

An ethylene propylene copolymer (example 11)150.0g (0.125mol) and maleic anhydride 18.4g (0.19mol) were charged to a 350mL PARR pressure reactor equipped with a stirrer and thermocouple. The reaction mixture was heated to 50 ℃ and purged with nitrogen for 15 minutes with stirring. The reactor temperature was raised to 235 ℃ and maintained at that temperature for 6 hours while stirring. The reaction mixture was then cooled to 90 ℃ and transferred to a 500mL 3N-round bottom flask. The reaction mixture was then heated and unreacted maleic anhydride removed in vacuo to give 159.5g of product. Analysis and analysis: acid value: 0.78 and 81.3% functionalized copolymer

ASA example 11

An ethylene propylene copolymer (example 12)150.0g (0.11mol) and maleic anhydride 15.7g (0.160mol) were charged to a 350mL PARR pressure reactor equipped with a stirrer and thermocouple. The reaction mixture was heated to 50 ℃ and purged with nitrogen for 15 minutes with stirring. The reactor temperature was raised to 235 ℃ and maintained at that temperature for 6 hours while stirring. The reaction mixture was then cooled to 90 ℃ and transferred to a 500mL 3N-round bottom flask. The reaction mixture was then heated and unreacted maleic anhydride removed in vacuo to yield 155.6g of product. Analysis and analysis: acid value: 0.685 and 85.3% of functionalized copolymer.

ASA example 12

An ethylene propylene copolymer (example 13)1000g (1.1mol) and maleic anhydride 161.2(1.64mol) were charged to a 2L PARR pressure reactor equipped with a stirrer and a thermocouple. The reaction mixture was heated to 50 ℃ and purged with nitrogen for 15 minutes with stirring. The reactor temperature was raised to 235 ℃ and maintained at that temperature for 6 hours while stirring. The reaction mixture was then cooled to 90 ℃ and transferred to a 500mL 3N-round bottom flask. The reaction mixture was then heated and unreacted maleic anhydride removed in vacuo to give 1108.5g of product. Analysis and analysis: acid value: 1.057 and 83.8% functionalized copolymer succinimide examples

Dispersant example 1

EPSA (ASA example 1)62.3g (0.06mol) were charged to a 250mL three-necked flask equipped with an overhead stirrer, Dean-Stark trap and condenser. The EPSA was stirred and heated to 160 ℃ under nitrogen. Tetraethylenepentamine 6.3g (0.033mol) was added dropwise via an addition funnel. The reaction mixture was heated under vacuum with stirring for 3 hours. At this point 56.3g of process oil was added and the reaction product was filtered using a pressure filter to give 102g of succinimide product.

Dispersant example 2

EPSA (ASA example 2)64.4g (0.08mol) were charged to a 250mL three-necked flask equipped with an overhead stirrer, a dean-Stark trap and a condenser. The EPSA was stirred and heated to 160 ℃ under nitrogen. Tetraethylenepentamine 8.4g (0.044mol) was added dropwise via an addition funnel. The reaction mixture was heated under vacuum with stirring for 3 hours. At this point 60.5g of process oil was added and the reaction product was filtered using a pressure filter to give 110g of succinimide product.

Dispersant example 3

EPSA (ASA example 3)769.8g (0.44mol) were charged to a 2L resin kettle equipped with an overhead stirrer, a dean-Stark trap and a condenser. The EPSA was stirred and heated to 160 ℃ under nitrogen. 46.7g (0.247mol) of tetraethylenepentamine was added dropwise via addition funnel. The reaction mixture was heated under vacuum with stirring for 3 hours. At this point 584.1g of process oil was added and the reaction product was filtered using a pressure filter to give 1363g of succinimide product.

Dispersant example 4

EPSA (ASA example 5)770.8g (0.76mol) were charged to a 2L resin kettle equipped with an overhead stirrer, a dean-Stark trap and a condenser. The EPSA was stirred and heated to 160 ℃ under nitrogen. 79.8g (0.42mol) of tetraethylenepentamine was added dropwise via an addition funnel. The reaction mixture was heated under vacuum with stirring for 3 hours. At this point 660.9g of process oil was added and the reaction product was filtered using a pressure filter to give 1431.7g of the succinimide product.

Dispersant example 5

EPSA (ASA example 6)1032.8g (0.786mol) were charged to a 2L resin kettle equipped with an overhead stirrer, a dean-Stark trap and a condenser. The EPSA was stirred and heated to 160 ℃ under nitrogen. 82.5g (0.44mol) tetraethylenepentamine was added dropwise via addition funnel. The reaction mixture was heated under vacuum with stirring for 3 hours. At this point 645.8g of process oil was added and the reaction product was filtered using a pressure filter to give 1647.5g of the succinimide product.

Dispersant example 6

EPSA (ASA example 7)872.1g (0.525mol) were charged to a 2L resin kettle equipped with an overhead stirrer, a dean-Stark trap and a condenser. The EPSA was stirred and heated to 160 ℃ under nitrogen. Tetraethylenepentamine 55.2g (0.29mol) was added dropwise via addition funnel. The reaction mixture was heated under vacuum with stirring for 3 hours. At this point 593.8g of process oil was added and the reaction product was filtered using a pressure filter to give 1394g of succinimide product.

Dispersant example 7

EPSA (ASA example 8)886.8g (0.80mol) was charged to a 2L resin kettle equipped with an overhead stirrer, a dean-Stark trap and a condenser. The EPSA was stirred and heated to 160 ℃ under nitrogen. 84g (0.44mol) of tetraethylenepentamine were added dropwise via an addition funnel. The reaction mixture was heated under vacuum with stirring for 3 hours. At this point 711.6g of process oil was added and the reaction product was filtered using a pressure filter to give 1572.2g of the succinimide product.

Dispersant example 8

EPSA (ASA example 9)120.0g (0.087mol) was charged to a 500mL 3-neck round bottom flask equipped with an overhead stirrer, a dean-Stark trap, and a condenser. The EPSA was stirred and heated to 160 ℃ under nitrogen. Tetraethylenepentamine 9.14g (0.048mol) was added dropwise via an addition funnel. The reaction mixture was heated under vacuum with stirring for 3 hours. At this point 93.3g of process oil was added and the reaction product was filtered using a pressure filter to give 196.9g of succinimide reaction product.

Dispersant example 9

EPSA (ASA example 10)120.0g (0.094mol) was charged to a 500mL 3-neck round-bottom flask equipped with an overhead stirrer, a dean-Stark trap, and a condenser. The EPSA was stirred and heated to 160 ℃ under nitrogen. Tetraethylenepentamine 9.87g (0.052mol) was added dropwise via addition funnel. The reaction mixture was heated under vacuum with stirring for 3 hours. At this point 83.3g of process oil was added and the reaction product was filtered using a pressure filter to give 191.5g of succinimide reaction product.

Dispersant example 10

EPSA (ASA example 11)120.0g (0.082mol) was charged to a 500mL 3-neck round-bottom flask equipped with an overhead stirrer, a dean-Stark trap, and a condenser. The EPSA was stirred and heated to 160 ℃ under nitrogen. Tetraethylenepentamine 8.64g (0.046mol) was added dropwise via an addition funnel. The reaction mixture was heated under vacuum with stirring for 3 hours. At this point 91.9g of process oil was added and the reaction product was filtered using a pressure filter to give 200.7g of succinimide reaction product.

Dispersant example 11

EPSA (ASA example 12)1000g (1.06mol) were charged to a 2L resin kettle equipped with an overhead stirrer, a dean-Stark trap and a condenser. The EPSA was stirred and heated to 160 ℃ under nitrogen. 111g (0.59mol) of polyvinylamine was added dropwise via an addition funnel. The reaction mixture was heated under vacuum with stirring for 3 hours. At this point 767.7g of process oil was added and the reaction product was filtered using a pressure filter to give 1544.4g of succinimide reaction product.

Dispersant example 12

EPSA (ASA example 1)70.1g (0.068mol) were charged to a 250mL round bottom 3-neck flask equipped with an overhead stirrer, a dean-Stark trap and a condenser. ASA was stirred and heated to 160 ℃ under nitrogen. Tetraethylenepentamine 8.48g (0.024mol) was added dropwise via addition funnel. The reaction mixture was heated under vacuum with stirring for 3 hours. At this point 19.3g Aromatic 150 was added and filtered in a pressure filter to give the succinimide product.

Dispersant example 13

An EP-copolymer substituted mannich product is prepared from an EP-copolymer substituted hydroxyphenol, an aldehyde, and dibutylamine under mannich reaction conditions similar to those used to prepare polyisobutylene-substituted mannich products. EP copolymer-substituted hydroxyphenols were prepared by alkylation with p-hydroxybenzenes of copolymer example 2.

Dispersant example 14

Under similar conditions as for the preparation of the other copolymers of the invention described above, an ethylene propylene copolymer having an ethylene unit content of 62% was prepared.

The above copolymer (100g, 0.11mol) and 250mL of heptane were charged to a 1L 3-necked round bottom flask equipped with an overhead stirrer and thermocouple. To the stirred solution was added 51.9g (0.212mol) of a hydrogen bromide acetic acid solution under nitrogen at room temperature over a period of 1 hour. The reaction mixture was heated at 45 ℃ for 2 hours. Add 200mL of water, stir and stand overnight. The aqueous layer was removed by water treatment, and 200mL of heptane was added to the organic layer. Washed with 24g of 25% w/w sodium carbonate solution. The aqueous layer was removed and the organic layer was filtered through sodium sulfate. The organic solvent was removed by concentration in vacuo to give 100g of the desired bromine-containing product.

75g (.073mol) of the above bromine-containing product and 35g xylene were charged to a 500mL 3-necked round bottom flask equipped with an overhead stirrer, condenser and thermocouple. Dimethylaminopropylamine (72.8g (0.7mol)) was added to the stirred solution via an addition funnel at room temperature under nitrogen. The reaction mixture was heated at 145 ℃ for 3 hours and then cooled to 60 ℃. To the reaction mixture was added 50mL of 47% sodium hydroxide solution and stirred for 2 hours. The resulting organic layer was separated and washed three times with water in a separatory funnel and dried over magnesium sulfate. Concentration in vacuo afforded 66.8g of the desired product (found 2.42 wt% N, calculated 2.68 wt%)

Formulation examples

In these examples, the dispersants of the present invention and comparative dispersants were blended into a finished oil of SAE 5W-30 quality. Including olefin copolymers commercially available from Afton Chemicals, Corp., Va., USA, of Virginia5751 as Viscosity Index Improver (VII). The base oils used in the examples were RHT120, commercially available from Safety Kleen Corp, Tex., USA, or a mixture of Phillips 66PP100N, 225N and Ultra-S-4, commercially available from ConocoPhillips (TX USA), Comphie oil, Tex. From the winning industry of Germany (Evonik Industries (Germany))1500 or5714 used as a pour point depressant at 0.2 wt%. The low temperature properties of these formulations were evaluated in a Mini Rotary Viscometer (MRV) test at-35 ℃ (ASTM D4684). The results are shown in the following table:

TABLE 7

MRV value equal to or less than 60,000cP passed the test. Above 60,000cP is a test failure.

Viscosity too large to measure, i.e. MRV value >60,000 cP.

As shown in the table above, dispersant examples 2,4, 7, and 9-11, prepared from copolymers having low crossover temperatures and low ethylene continuous link lengths, facilitated passing the MRV test.

Examples of Low Metal and/or fluorine content

A 300mL stirred autoclave was used to prepare a sample containing at least 1kg of ethylene-propylene copolymer. The number-average molecular weight of the copolymer was 2085g/mol, and the content of ethylene units was 65%. The reaction conditions for preparing the copolymer are shown in table 8 below.

TABLE 8

C2/C3Feed molar ratio	1.0
		Temperature (. degree.C.)	76
Pressure (psig)	750
		Al/Zr ratio	66
Stirring (rpm)	1000
		Zr concentration (mm/Kg)	0.161
Ethylene feed (slpm)	1.75
		Propylene feed (g/min)	3.30

"Slpm" is standard liters per minute at 25 ℃ and 101.325 kPa. The test was run for 50 minutes and the initial sample was discarded. The reaction is then operated continuously 6¹/₂Hours, and the reactor effluent was collected and sampled every 30 to 45 minutes. A total of ten samples were collected, washed with water and rotary evaporated as discussed below. Each sample was weighed and the polymer content determined.

TABLE 9

Polymer content and sample quality

Sample (I)	Polymer content (wt%)	Quality (g)
			Initial	4.6％
1	17.8％	553.5
			2	21.9％	511.7
3	23.2％	550.7
			4	23.8％	625.5
5	23.8％	708.2
			6	23.9％	771.2
7	23.9％	795.0
			8	24.4％	741.1
9	24.4％	790.6
			10	24.4％	796.9

Washing step

The polymer sample was washed in a 4 liter glass separation kettle equipped with an overhead stirrer and an electrical heating mantle. Toluene was used to strip the samples in a2 liter Buchi RR III rotary evaporator and the temperature was maintained using a temperature controlled oil bath.

One liter of distilled water was charged into the separation tank, and then samples 1 to 4 were charged into the tank. The kettle was heated to 50 ℃ and stirred for 25 minutes. After that, the stirring was stopped and the phases were separated, and a total of 1664 g of toluene-polymer phase was removed without breaking the aqueous layer.

After this step, a total of 1479 grams of polymer from samples 5-6 were charged to the kettle. The composition was again stirred at 50 ℃ for 25 minutes and then allowed to separate. An additional 1286 g of toluene layer was then decanted from the aqueous layer.

Next, samples 7-8 were processed as above and a total of 1341 grams was decanted from the aqueous layer.

Sample 9 was then charged to the kettle, stirred at 50 ℃ for 25 minutes, and allowed to separate overnight. The next morning 615 grams were removed from the aqueous layer and the last sample 10 was added. After the charge, the composition was stirred at 50 ℃ and the phases were separated, 746 g of toluene-polymer composition being decanted off. Then, an additional 214 grams of toluene were added to the kettle to dilute the polymer/toluene layer near the aqueous interface. 172 grams of toluene were then removed and a total of 1134 grams of the aqueous layer was drained from the kettle. The layer contained a visible amount of alumina as well as toluene.

The rotary evaporator was heated to 120 ℃ and 10mm Hg vacuum. The toluene-polymer solution recovered from the kettle was charged into a rotary evaporator in a semi-batch manner for nine hours while recovering toluene at the top of the column. The polymer remained in the rotary evaporator during operation and the vacuum was gradually increased to 24mm Hg as the polymer concentration increased in order to maintain the necessary boiling rate. After all charges were fed, the rotary evaporator temperature was raised to 140 ℃ and the vacuum increased to 29mm Hg. The rotary evaporator was maintained under these conditions for approximately 90 minutes.

Finally, the rotary evaporator was cooled and then drained, and a total of 1310 grams of polymer was recovered.

Figure 5 shows a plot of temperature and olefin flow rate into the reactor. This figure shows the unit operating steadily during the test. The perturbation in propylene flow rate was from a separate sample collection.

FIG. 6 shows the measured polymer molecular weight and ethylene incorporation for the first six samples. The first sample was discarded, but all remaining samples were used to prepare the composite sample.

While several embodiments of the invention have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and/or structures for performing the function and/or obtaining the results and/or one or more of the advantages described herein, and each of such variations and/or modifications is deemed to be within the scope of the present invention. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and/or configurations will depend upon the specific application or applications for which the teachings of the present invention is/are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, the invention may be practiced otherwise than as specifically described and claimed. The present invention is directed to each individual feature, system, article, material, kit, and/or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and/or methods, if such features, systems, articles, materials, kits, and/or methods are not mutually inconsistent, is included within the scope of the present invention.

All definitions, as defined and used herein, should be understood to control dictionary definitions, definitions in documents incorporated by reference, and/or ordinary meanings of the defined terms.

The indefinite articles "a" and "an" as used herein in the specification and the claims are to be understood as meaning "at least one" unless explicitly indicated to the contrary.

The phrase "and/or" as used herein in the specification and claims should be understood to mean "one or two" of the elements so combined, i.e., the elements present in some cases combined and in other cases separated. Multiple elements listed with "and/or" should be interpreted in the same manner, i.e., "one or more" of the elements so combined. In addition to the elements specifically identified by the "and/or" clause, other elements, whether related or unrelated to those elements specifically identified, may optionally be present. Thus, as a non-limiting example, when used in conjunction with open language such as "comprising," references to "a and/or B" may, in one embodiment, refer to a alone (optionally including elements other than B); in another embodiment, only B (optionally including elements other than a) is referred to; in yet another embodiment, reference is made to both a and B (optionally including other elements); and the like.

As used herein in the specification and claims, "or" should be understood to have the same meaning as "and/or" as defined above. For example, when separating items in a list, "or" and/or "should be interpreted as inclusive, i.e., including at least one of the plurality or list elements, but also including more than one of the plurality or list elements, and optionally additional unlisted items. Only terms explicitly indicated as opposite, such as "only one" or "exactly one", or "consisting of" when used in the claims, will be meant to encompass exactly one of the plurality or list of elements. In general, the term "or" as used herein should only be construed to indicate an exclusive alternative (i.e., "one or the other but not both") to the exclusive term, such as "either," one, "" only one, "or" exactly one. "consisting essentially of … …" when used in the claims shall have its ordinary meaning as used in the patent law field.

As used herein in the specification and claims, with reference to a list of one or more elements, the phrase "at least one" should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each element specifically listed within the list of elements, and not excluding any combinations of elements in the list of elements. This definition also allows that, in addition to the elements specifically identified within the list of elements referred to by the phrase "at least one," there may optionally be elements, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, "at least one of a and B" (or, equivalently, "at least one of a or B," or, equivalently "at least one of a and/or B") can refer, in one embodiment, to at least one, optionally including more than one, a, with no B present (and optionally including elements other than B); in another embodiment, refers to at least one, optionally including more than one, B, with no a present (and optionally including elements other than a); in yet another embodiment, to at least one, optionally including more than one, a, and at least one, optionally including more than one, B (and optionally including other elements); and the like.

When the word "about" is used herein to refer to an algebraic word, it should be understood that yet another embodiment of the present invention includes a number that is not modified by the presence of the word "about".

It should also be understood that, in any method claimed herein that includes more than one step or action, the order of the steps or actions of the method is not necessarily limited to the order in which the steps or actions of the method are recited, unless specifically indicated to the contrary.

In the claims, as well as in the specification above, all transitional phrases such as "comprising," including, "" carrying, "" having, "" containing, "" involving, "" holding, "" consisting of,. or the like are to be construed as open-ended, i.e., meaning including but not limited to. Only the transition phrases "consisting of" and "consisting essentially of … …" should be closed or semi-closed transition phrases, respectively, as set forth in the United States Patent Office Manual of Patent filing Procedure, revision 07.2015, section 2111.03.

Each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the disclosure being indicated by the following claims.

The applicant does not intend to dedicate any disclosed embodiments to the public, and to the extent any disclosed modifications or alterations may not literally fall within the scope of the claims, they are considered to be part hereof under the doctrine of equivalents.

It is to be understood that each component, compound, substituent or parameter disclosed herein is to be interpreted as disclosed for use alone or in combination with one or more of each other component, compound, substituent or parameter disclosed herein.

It is also to be understood that each amount/value or range of amounts/values for each component, compound, substituent or parameter disclosed herein is to be construed as also disclosed in combination with each amount/value or range of amounts/values disclosed for any other component, compound, substituent or parameter disclosed herein, and thus, for the purposes of this description, any combination of amounts/values or ranges of amounts/values for two or more components, compounds, substituents or parameters disclosed herein are also disclosed in combination with each other.

It will also be understood that each range disclosed herein is to be interpreted as disclosing each particular value with the same number of significant digits within the range disclosed. Thus, a range of 1-4 is to be interpreted as an explicit disclosure of the values 1, 2, 3 and 4.

It is also to be understood that each lower limit of each range disclosed herein is to be interpreted as disclosed in combination with each upper limit of each range and each specific value within each range for the same component, compound, substituent or parameter disclosed herein. Accordingly, the disclosure is to be construed as a disclosure of all ranges obtained by combining each lower limit of each range with each upper limit of each range or each specific value within each range, or by combining each upper limit of each range with each specific value within each range.

Furthermore, the particular amounts/values of a component, compound, substituent or parameter disclosed in the specification or examples are to be interpreted as disclosing the lower or upper limit of a range and, thus, may be combined with the lower or upper limit of any other range or with the particular amounts/values of the same component, compound, substituent or parameter disclosed elsewhere in this application to form a range for that component, compound, substituent or parameter.