阅读说明：本技术 包含热塑性硫化橡胶组合物的管子 (Pipe comprising thermoplastic vulcanizate composition ) 是由 K·安娜塔纳雷纳耶尔 A·K·多法斯 A·J·迪亚斯 于 2020-03-23 设计创作，主要内容包括：在一个实施方案中,热塑性硫化橡胶(TPV)组合物包含橡胶、热塑性聚烯烃和多面体低聚硅倍半氧烷,其中：基于所述橡胶和所述热塑性聚烯烃的总重量,所述橡胶的浓度为10wt％至80wt％；基于所述橡胶和所述热塑性聚烯烃的总重量,所述热塑性聚烯烃的浓度为20wt％至90wt％；和基于所述TPV组合物的总重量,所述多面体低聚硅倍半氧烷的浓度为0.1wt％至20wt％。在另一个实施方案中,制备动态硫化热塑性硫化橡胶组合物的方法包括在剪切条件下熔体加工至少一种热塑性树脂、至少一种橡胶、至少一种固化剂和至少一种多面体低聚硅倍半氧烷；以及形成动态硫化热塑性硫化橡胶组合物。在另一个实施方案中,提供了管子。(In one embodiment, a thermoplastic vulcanizate (TPV) composition comprises a rubber, a thermoplastic polyolefin, and a polyhedral oligomeric silsesquioxane, wherein: the concentration of the rubber is from 10 wt% to 80 wt%, based on the total weight of the rubber and the thermoplastic polyolefin; the thermoplastic polyolefin is present in a concentration of 20 to 90 wt%, based on the total weight of the rubber and the thermoplastic polyolefin; and the concentration of the polyhedral oligomeric silsesquioxane is 0.1 wt% to 20 wt% based on the total weight of the TPV composition. In another embodiment, a method of making a dynamically vulcanized thermoplastic vulcanizate composition includes melt processing under shear conditions at least one thermoplastic resin, at least one rubber, at least one curative, and at least one polyhedral oligomeric silsesquioxane; and forming a dynamically vulcanized thermoplastic vulcanizate composition. In another embodiment, a tube is provided.)

1. A thermoplastic vulcanizate (TPV) composition comprising:

rubbers, thermoplastic polyolefins, and polyhedral oligomeric silsesquioxanes, wherein:

the concentration of the rubber is from 10 wt% to 80 wt%, based on the total weight of the rubber and the thermoplastic polyolefin;

the thermoplastic polyolefin is present in a concentration of 20 to 90 wt%, based on the total weight of the rubber and the thermoplastic polyolefin; and

the polyhedral oligomeric silsesquioxane is present in a concentration of 0.1 wt% to 20 wt% based on the total weight of the TPV composition.

2. The TPV composition of claim 1 wherein the concentration of the rubber is 10 wt% to 30 wt%, based on the total weight of the rubber and the thermoplastic polyolefin, and the concentration of the thermoplastic polyolefin is 25 wt% to 75 wt%, based on the total weight of the rubber and the thermoplastic polyolefin.

3. The TPV composition of claim 1 or 2in which the polyhedral oligomeric silsesquioxane has the general formula [ RSiO ™_1.5]_xWherein x is 4 to 15.

4. The TPV composition of any one of claims 1-3, wherein the polyhedral oligomeric silsesquioxane has the general formula [ RSiO ™ ]_1.5]_xWherein R represents an organic substituent selected from H, siloxy, cycloaliphatic, linear aliphatic or aromatic groups.

5. The TPV composition of claim 4, wherein the polyhedral oligomeric silsesquioxane has the general formula [ RSiO ™ ]_1.5]_xWherein R represents an organic substituent selected from cyclic aliphatic or linear aliphatic.

6. The TPV composition of claim 1 or 2in which the polyhedral oligomeric silsesquioxane is octamethyl POSS ([ (CH)₃SiO_1.5)₈])。

7. The TPV composition of claim 1 or 2in which the polyhedral oligomeric silsesquioxane is octaisobutyl POSS ([ ((CH)₃)₂CHCH₂SiO_1.5)₈])。

8. The TPV composition of any of claims 1-7 further comprising a plasticizer.

9. The TPV composition of claim 8 wherein the plasticizer is selected from the group consisting of mineral oil, paraffin oil, polyisobutylene, synthetic oil, triisononyl trimellitate, low molecular weight alkyl esters, and combinations thereof.

10. The TPV composition of any of claims 1-9 wherein the TPV composition further comprises at least one of a filler, a slip agent, or a nucleating agent.

11. The TPV composition of claim 10 wherein the filler comprises calcium carbonate, clay, silica, talc, titanium dioxide, carbon black, mica, wood flour, or combinations thereof.

12. The TPV composition of any of claims 1-11 further comprising a cure system.

13. The TPV composition of claim 12 wherein the cure system comprises a phenolic resin, a peroxide, a maleimide, a hexamethylenediamine urethane, a silicon-based curing agent, a silane-based curing agent, a metal oxide, a sulfur-based curing agent, or a combination thereof.

14. The TPV composition of claim 12 wherein the cure system comprises at least one of a hydrosilylation curing agent and a phenolic resin curing agent.

15. The TPV composition of any of claims 1-14 wherein the rubber is ethylene propylene rubber, nitrile rubber, butyl rubber, halogenated butyl rubber, or a combination thereof.

16. The TPV composition of any of claims 1-15 wherein the ethylene propylene rubber is an ethylene propylene diene monomer rubber.

17. The TPV composition of claim 16 wherein the ethylene propylene diene monomer rubber comprises a diene component comprising ethylidene norbornene, vinyl norbornene, or combinations thereof.

18. The TPV composition of claim 15 wherein the butyl rubber is selected from the group consisting of isobutylene-isoprene rubber (IIR), brominated isobutylene-isoprene rubber (BIIR), chlorinated isobutylene-isoprene rubber (CIIR), and isobutylene para-methylstyrene rubber (BIMSM).

19. The TPV composition of claim 15 or claim 18 wherein the butyl rubber is an isobutylene-p-methylstyrene rubber comprising from 0.5 wt% to 25 wt% of p-methylstyrene, based on the total weight of the rubber.

20. The TPV composition of claim 15 wherein the butyl rubber is an isobutylene-isoprene rubber comprising from 0.5 wt% to 30 wt% isoprene based on the total weight of the rubber.

21. The TPV composition of claim 15 wherein the butyl rubber is a brominated isobutylene-isoprene rubber, a chlorinated isobutylene-isoprene rubber, or a combination thereof, comprising a halogenated weight percent of from 0.3 wt% to 7 wt%, based on the total weight of the rubber.

22. The TPV composition of claim 15 wherein the rubber is a nitrile rubber comprising 1, 3-butadiene or isoprene and acrylonitrile.

23. The TPV composition of claim 15 wherein the nitrile rubber has an acrylonitrile derived content of 20 wt% to 50 wt% based on the total weight of the nitrile based rubber.

24. The TPV composition of any of claims 1-23 wherein the TPV composition has a CO at 60 ℃ of greater than 40 barrer measured according to ISO 2782-1₂And (3) permeability.

25. The TPV composition of any of claims 1-24 wherein the TPV composition has an abrasion loss of 120mg/1000 cycles or less measured according to ASTM D4060.

26. The TPV composition of any of claims 1-25 wherein the TPV composition has a tensile strength at yield of 9MPa or greater measured at 23 ℃ on compression molded plaques according to ISO 37.

27. The TPV composition of any of claims 1-26 wherein the TPV composition has a tensile strain at yield of 7% or more as measured to compression molded plaques according ISO 37 at 23 ℃.

28. The TPV composition of any of claims 1-27 wherein the TPV composition has a thermal conductivity of 0.25W/m-K or less measured according to ASTM C518-17.

29. The TPV composition of any of claims 1-28 wherein the thermoplastic polyolefin is one or more of polypropylene, polyethylene, polybutene-1 or combinations thereof.

30. The TPV composition of any one of claims 1-29 having a hardness of 70 shore a to 60 shore D, wherein the shore a and shore D hardnesses are measured according to ASTM D2240 using a Zwick automatic durometer.

31. A process for preparing a dynamically vulcanized thermoplastic vulcanizate composition comprising:

melt processing under shear conditions at least one thermoplastic resin, at least one rubber, at least one curing agent, and at least one polyhedral oligomeric silsesquioxane; and

forming a dynamically vulcanized thermoplastic vulcanizate composition.

32. A tube, comprising:

an outer sheath comprising the TPV composition of any one of claims 1-30.

33. The tubing of claim 32 wherein the outer jacket has a thickness of 2mm to 30 mm.

34. The tube of claim 32 or 33, further comprising:

an inner shell; and

at least one reinforcement layer disposed at least partially around the inner shell.

35. A tube, comprising:

an intermediate sheath comprising the TPV composition of any of claims 1-30.

36. The pipe of claim 35 wherein the intermediate sheath has a thickness of 1mm to 10 mm.

37. The tube of claim 35 or 36, further comprising:

an inner shell;

at least one reinforcement layer disposed at least partially around the inner shell; and

an outer protective sheath disposed at least partially around the at least one reinforcing layer.

38. A tube, comprising:

a thermal insulation layer comprising the TPV composition of any of claims 1-30.

39. The pipe of claim 38 wherein the thermal insulation layer has a thickness of 2mm to 30 mm.

40. The pipe of claim 39 wherein the thermal insulation layer is applied as a layer wrapped in one or more layers of tape.

41. The tube of any one of claims 38-40, further comprising:

an inner shell;

at least one reinforcement layer disposed at least partially around the inner shell; and

an outer protective sheath disposed at least partially around the at least one reinforcing layer.

42. The tubing of any one of claims 32-41, wherein the tubing is flexible.

43. The tube of any one of claims 32-41, wherein the tube is rigid.

44. The pipe of any one of claims 32 to 43, wherein the pipe is for offshore or onshore applications.

Technical Field

Embodiments of the present disclosure generally relate to thermoplastic vulcanizate (TPV) compositions comprising polyhedral oligomeric silsesquioxanes, and more particularly, to the use of TPV compositions having polyhedral oligomeric silsesquioxanes in layers of pipes.

Background

Pipes (e.g., coiled tubing) are used to transport hydrocarbons and other fluids. The flexible pipe structure comprises layers made of, for example, polymer layers, metal layers and composite material layers. Flexible tubing typically includes an inner pressure sheath that contacts the fluid being transported in the flexible tubing, an outer sheath comprising a polymer composition, and an annular region between the inner and outer sheaths. The annular region includes an armor layer (or reinforcement layer) that provides support for the inner pressure jacket and an intermediate jacket having a polymer layer(s) supported by a reinforcing structure.

When a fluid (e.g., hydrocarbon) flows through the flexible pipe, a gas (e.g., CO)₂、H₂S, methane, and water vapor) may diffuse through the inner pressure jacket and into the annular region of the flexible tubing between the inner pressure jacket and the outer jacket. In the annular region, the gases accumulate and, upon contact with water and/or moisture, create acidic conditions that lead to corrosion of the armor, which is typically metallic. This corrosion contributes to the destruction and disassembly of the coiled tubing and involves costly downtime for fluid delivery and replacement of the coiled tubing. Furthermore, when the internal pressure exceeds the pressure outside the pipe, excessive accumulation of gas and condensate in the annular space may lead to rupture of the outer sheath. This risk is particularly high closer to the surface when the hydrostatic pressure is lower.

To reduce (or eliminate) deflectionCorrosion of metallic elements in the tubular, the polymer composition in the intermediate and/or outer sheath of the annular region should be permeable to acid gases, e.g. CO₂And H₂And S. Furthermore, because the polymer composition is exposed to gases and external marine conditions, the polymer composition should exhibit various properties, such as good resistance to physical and chemical degradation, hydrolysis resistance, good wear resistance, good crack propagation strength, and good fatigue strength.

Accordingly, there is a need for a high permeability polymeric composition, and its use in the intermediate and/or outer jacket of an annular region of a flexible pipe, having a balanced combination of mechanical and physical properties that can reduce (or eliminate) the accumulation of acid gases in the annular region of the flexible pipe.

References cited in the information disclosure statement (37CFR 1.97(h)) include: U.S. patent nos. 4,402,346; U.S. patent nos. 6,716,919; U.S. patent nos. 8,256,469; U.S. patent publication numbers 2007/0119512; U.S. patent publication numbers 2012/0279575; U.S. patent publication numbers 2017/0254446; U.S. patent application publication numbers 2016/0076675; U.S. patent application publication numbers 2016/0186916; international application numbers WO 2011/120525; and Lefebvre, Xavier et al, "Development of reactive barrier polymers against interference for the oil and gas induction: from formation to qualification of the depth of differential multiprocessing model, "Oil & Gas Science and Technology-Revue d' IFP Energies novels 70.2 (2015): 291-303.

Disclosure of Invention

Summary of The Invention

In one embodiment, a thermoplastic vulcanizate (TPV) composition comprises a rubber, a thermoplastic polyolefin, and a polyhedral oligomeric silsesquioxane, wherein: the concentration of the rubber is from 10 wt% to 80 wt%, based on the total weight of the rubber and the thermoplastic polyolefin; the thermoplastic polyolefin is present in a concentration of 20 to 90 wt%, based on the total weight of the rubber and the thermoplastic polyolefin; and the concentration of the polyhedral oligomeric silsesquioxane is 0.1 wt% to 20 wt% based on the total weight of the TPV composition.

In another embodiment, a method of making a dynamically vulcanized thermoplastic vulcanizate composition includes melt processing under shear conditions at least one thermoplastic resin, at least one rubber, at least one curative, and at least one polyhedral oligomeric silsesquioxane; and forming a dynamically vulcanized thermoplastic vulcanizate composition.

In another embodiment, the pipe comprises an outer jacket comprising any of the TPV compositions described herein.

In another embodiment, the pipe comprises an intermediate sheath comprising any of the TPV compositions described herein.

In another embodiment, the pipe comprises a thermal insulation layer comprising any of the TPV compositions described herein.

In another embodiment, the flexible pipe comprises an abrasion resistant layer comprising any of the TPV compositions described herein.

Other and further embodiments are described below.

Drawings

So that the manner in which the above recited features of the present disclosure can be understood in detail, a more particular description of the disclosure, briefly summarized above, may be had by reference to embodiments, some of which are illustrated in the appended drawings. It is to be noted, however, that the appended drawings illustrate only exemplary embodiments and are therefore not to be considered limiting of its scope, for the disclosure may admit to other equally effective embodiments.

The figures illustrate a side view of a flexible pipe according to some embodiments.

Detailed Description

Embodiments of the present disclosure relate to TPV compositions comprising one or more polyhedral oligomeric silsesquioxanes, and the use of the composition(s) in a layer of flexible or rigid pipe (e.g., an outer jacket and/or an intermediate jacket). The inventors have surprisingly found that such compositions achieve higher gas and in particular CO relative to conventional polymers₂Permeability while maintaining tensile properties. Is contained inMetallic components and materials within the flexible pipe are better protected from acid gas corrosion because the TPV compositions described herein advantageously provide better gas permeability because gas diffuses faster through the layers of the flexible pipe.

For purposes of this disclosure, the terms "conduit," "tube," "hose," and "pipe" may be used interchangeably.

For purposes of this disclosure, the terms "shell", "jacket" and "layer" may be used interchangeably.

For purposes of this disclosure, the terms "armor", "armor element", and "reinforcement layer" may be used interchangeably.

For purposes of this disclosure, and unless otherwise specified, "composition" includes a component of the composition and/or a reaction product of two or more components of the composition.

Article of manufacture

Certain embodiments of the TPV compositions of the present invention are used to form layers made by extrusion and/or coextrusion, blow molding, injection molding, thermoforming, elastic welding (elasto-welding), compression molding and 3D printing, pultrusion, and other manufacturing techniques. The layers may be coextruded as separate layers or extruded as tapes and wound onto a tube (e.g., flexible pipe), such as an abrasion resistant layer or an insulating layer (e.g., a thermal insulating layer). The layer may be part of a flexible structure for transporting hydrocarbons extracted from offshore deposits and/or may transport water, heating fluids and/or chemicals injected into the formation in order to increase the production of hydrocarbons. In some embodiments, a TPV composition configured for use as at least a portion of a catheter can have a thickness of 2 millimeters (mm) to 30mm, encompassing any values and subgroups therebetween.

The figure schematically illustrates a side view of a flexible pipe 100 according to some embodiments. The flexible pipe comprises, from the inside outwards, an internal pressure sheath 5, a first armour layer 4, an intermediate sheath 3, a second armour layer 2 and an outer sheath 1. The inner pressure jacket 5 is in contact with oil and/or gas. The first armor layer 4 provides strength to the pipe and may be made of, for example, one or more layers of metal and/or a reinforcing polymer (e.g., carbon nanotube reinforced polyvinylidene fluoride (PVDF)). The intermediate sheath 3 provides thermal insulation and/or wear resistance. The intermediate sheath may be extruded as a single layer or as a tape and then wound onto the flexible pipe. The second armour layer 2 provides strength and pressure resistance to the pipe and may be made of, for example, one or more metal layers. The outer sheath 1 protects the tube structure and has wear and fatigue resistance. The outer sheath 1 and/or the intermediate sheath 3 are made of a material comprising one or more TPV compositions as described below.

Conventional materials for the outer sheath 1 include High Density Polyethylene (HDPE), polyamide-11 (PA11) and polyamide-12 (PA 12). The polymeric materials currently used for the outer jacket have a very low permeability to acid gases, further exacerbating corrosion. Conventional materials also exhibit poor low temperature performance, poor crack propagation strength, limited fatigue strength, and other negative characteristics. These drawbacks necessitate the compounding of such materials with plasticizers, such as N-butylbenzenesulfonamide (BBSA), which can migrate over time, causing embrittlement of the outer jacket layer.

Conventional materials for the intermediate sheath 3 include a single extruded or spiral wound layer of extruded tape of composite foam (syntactic foam) consisting of a polypropylene or polyurethane matrix with embedded non-polymeric (e.g. glass) (hollow) microspheres, HDPE and PVDF. The main drawback of such composite PP foam tapes is that they involve two manufacturing steps: producing an insulating tape and winding said tape onto a tubular body. Another disadvantage of such extruded tapes includes corrosion of the steel or metal wires forming the inner layer due to condensation of water vapor migrating from said layer through the insulating tape. Another disadvantage of the known insulation techniques is that in case of damage to the outer sheath, the annulus of the flexible pipe may be flooded, which increases the risk of corrosion of the metal armor wires. In addition, such foamed polymer insulation layers are easily crushed under internal and external pressure to press the tape layers, thereby reducing the thickness and thermal insulation properties thereof. It would therefore be of great interest to provide extrudable, dense thermal insulation layers with high permeability and acceptable insulation properties.

It has been surprisingly found that certain types of TPVs provide alternative and more robust materials for the outer and/or intermediate sheaths used for fluid containment. As described below, and in accordance with some embodiments, TPV compositions that may be used as an outer and/or intermediate sheath in a flexible pipe include a fully or partially crosslinked and/or cured rubber phase, a thermoplastic phase, a polyhedral oligomeric silsesquioxane, a filler, a plasticizer (e.g., an oil), and a curing agent. The cured rubber phase comprises one or more of ethylene-propylene rubber, nitrile rubber, butyl rubber, halogenated butyl rubber, or combinations thereof, and the thermoplastic phase (e.g., thermoplastic polyolefin) comprises one or more of a propylene-based polymer, an ethylene-based polymer, a butene-1-based polymer, or combinations thereof.

Certain embodiments of the present disclosure include flexible pipes/catheters that include a polymer layer jacket positioned as an inner layer, an intermediate layer (which may include a TPV composition), and/or an outer layer (which may include a TPV composition): 1) unbonded or bonded flexible pipes, tubes and hoses similar to those described in American Petroleum Institute (API) specification 17J and API specification 17K, 2) thermoplastic hoses similar to those described in API 17E, and 3) thermoplastic composite pipes similar to those described in norwegian classification societies (Det Norske Veritas, DNV) RP-F119. In other embodiments, the thermoplastic vulcanizate compositions of the present invention are used in composite tapes (e.g., carbon fibers, carbon nanotubes, or glass fibers embedded in a thermoplastic matrix) for thermoplastic composite tubes having structures similar to those described in DNV-RP-F119.

In some embodiments, the flexible pipe is a flexible underwater pipe.

In some embodiments, the flexible pipe comprises an outer sheath comprising a TPV composition extruded onto an outer armor layer or insulation layer of an unbonded flexible pipe. In some embodiments, the TPV composition is extruded as an outer jacket layer having a thickness of about 2mm to about 30 mm.

In some embodiments, the TPV composition is a thermal insulation layer. TPV compositions can have highly advantageous properties such as low thermal conductivity, high gas permeability, and stable thermal conductivity over time. The insulating layer may have a thickness of about 2mm to about 30 mm. In some embodiments, the TPV composition is applied as a wrapped insulation layer, such as a layer wrapped in one or more tapes. The tape may be extruded at any thickness, but in order to obtain a uniform surface, the tape advantageously has a thickness of at most about 10mm, for example about 0.1 to about 5 mm.

In some embodiments, the TPV composition may be an intermediate jacket between armor layers of a flexible pipe, whereby the TPV-based layer may act as a wear layer to protect the armor layers from wear damage. In some embodiments, the flexible tube comprises an intermediate sheath having a thickness of 1mm to 10 mm.

In some embodiments, the flexible tube comprises an inner pressure jacket; inner shells or carcasses (carcas); at least one armor layer (or reinforcement layer) disposed at least partially about the inner shell; and an outer jacket disposed at least partially around the at least one enhancement layer.

In some embodiments, the flexible pipe comprises a) an inner pressure jacket for confining fluid to be transported by the pipe, b) at least one armour layer (or reinforcement layer) arranged at least partially around the inner pressure jacket, c) at least one intermediate layer arranged at least partially around the at least one armour layer, d) at least one outer jacket arranged at least partially around the at least one intermediate layer and/or the at least one armour layer.

While the TPV composition will be described as being contained in the outer jacket of the flexible pipe, it should be understood that the TPV composition may alternatively or additionally be contained in other layers of the flexible pipe, such as in an intermediate jacket.

In some embodiments, the tube is rigid. In some embodiments, the rigid pipe structure comprises a metal-based layer, and at least one layer comprising any of the TPV compositions described herein. Rigid pipes can be used for wet insulation, for example.

While the present description is described in the context of a flexible pipe embodiment, it should be understood that the present description applies to umbilicals (umbilicals), thermoplastic composite pipes and thermoplastic hoses, flow lines, wet insulation pipes, and the like.

Formulation of TPV compositions

In some embodiments, a TPV composition can include an amount of rubber, such as an ethylene propylene terpolymer rubber (e.g., EPDM rubber), a nitrile rubber, a butyl rubber, or a combination thereof, i.e., about 80 wt.% or less of the rubber, about 50 wt.% or less of the rubber, such as about 40 wt.% or less of the rubber, such as about 30 wt.% or less, based on the total weight of the rubber and the thermoplastic polyolefin. In these or other embodiments, the amount of rubber in the TPV composition can be from about 10 wt% to about 80 wt%, such as from about 10 wt% to about 30 wt%, such as from about 12 wt% to about 25 wt%, such as from about 14 wt% to about 24 wt%, based on the total weight of the rubber and the thermoplastic polyolefin. The rubber may be in crosslinked or partially crosslinked form in the TPV composition.

In these and other embodiments, a TPV composition can include an amount of a thermoplastic phase (e.g., a thermoplastic polymer or a thermoplastic polyolefin), such as a propylene-based polymer, an ethylene-based polymer, a butene-1-based polymer, or a combination thereof, i.e., from about 20 wt% to about 90 wt% (e.g., from about 30 wt% to about 90 wt%, such as from about 50 wt% to about 90 wt%, such as from about 60 wt% to about 90 wt%), based on the total weight of the rubber and the thermoplastic polyolefin. In some embodiments, the concentration of thermoplastic polyolefin in the TPV composition is from about 20 wt% to about 80 wt%, such as from about 25 wt% to about 75 wt%, such as from about 27 wt% to about 70 wt%, such as from about 30 wt% to about 70 wt%, based on the total weight of the rubber and the thermoplastic polyolefin.

In some embodiments, a TPV composition may comprise polyhedral oligomeric silsesquioxane material(s) in an amount of about 0.1 wt% or more, such as from about 0.1 wt% to about 20 wt%, such as from about 1 wt% to about 15 wt%, such as from about 2 wt% to about 10 wt%, based on the total weight of the TPV composition.

In some embodiments, when the thermoplastic phase can comprise a blend of a propylene-based polymer and an ethylene-based polymer, the thermoplastic phase can comprise from about 51 wt% to about 100 wt% of the propylene-based polymer (e.g., from about 65 wt% to about 99.5 wt%, such as from about 85 wt% to about 99 wt%, such as from about 95 wt% to about 98 wt%), based on the total weight of the thermoplastic phase, with the remainder of the thermoplastic phase comprising the ethylene-based polymer. For example, in some embodiments, the thermoplastic phase can include about 0 wt% to about 49 wt% of the ethylene-based polymer (e.g., about 1 wt% to about 15 wt%, such as about 2 wt% to about 5 wt%), based on the total weight of the thermoplastic phase.

In some embodiments, fillers (e.g., calcium carbonate, clay, silica, talc, titanium dioxide, carbon black, nucleating agents, mica, wood flour, and the like, and blends thereof, as well as inorganic and organic nanofillers) may be present in the TPV composition in an amount of from about 0.1 wt% to about 10 wt% (e.g., from about 1 wt% to about 7 wt%, such as from about 2 wt% to about 5 wt%), based on the total weight of the TPV composition. The amount of filler that may be used may depend, at least in part, on the type of filler and the amount of extender oil used.

In some embodiments, oil (e.g., extender oil) may be present in the TPV composition in an amount of from about 10 wt% to about 40 wt% (e.g., from about 12 wt% to about 35 wt%, such as from about 14 wt% to about 32 wt%), based on the weight of the total TPV composition. The amount of oil added may depend on the desired properties, and its upper limit may depend on the compatibility of the particular oil and blend ingredients; and this limit can be exceeded when excessive bleeding of oil occurs. The amount of oil may depend at least in part on the type of rubber. High viscosity rubbers have higher oil build up. When low molecular weight ester plasticizers are employed, the ester plasticizers are generally used in amounts of about 40 wt% or less, for example about 35 wt% or less, based on the total TPV composition.

In some embodiments, the TPV composition includes a curing agent. The amount and type of curing agent that can be used in the TPV compositions described herein is discussed below.

In some embodiments, and when used, a TPV composition can include a processing additive (e.g., a polymer processing additive) in an amount of from about 0.1 wt% to about 20 wt%, based on the total weight of the TPV composition.

In some embodiments, the TPV compositions can optionally include reinforcing and non-reinforcing fillers, colorants, antioxidants, nucleating agents, stabilizers, rubber processing oils, lubricants, antiblocking agents, antistatic agents, waxes, blowing agents, pigments, flame retardants, antistatic agents, slip masterbatches, silicone-based slip agents (e.g., Dow Corning available from the Dow Chemical Company^TMHMB-0221 masterbatch), uv inhibitors, antioxidants, and other processing aids known in the art of rubber and TPV compounding. These additives may be used in the TPV composition in amounts up to about 20 wt%, based on the total weight of the TPV composition.

Polyhedral oligomeric silsesquioxanes

TPV compositions include polyhedral oligomeric silsesquioxane (POSS) compounds. POSS compounds are monodisperse nanostructured chemicals. POSS compounds have a hybrid (e.g., organic-inorganic) composition in which the internal backbone is composed primarily of inorganic silicon-oxygen bonds. The exterior of the nanostructure includes reactive and/or non-reactive organic functional groups (R), which ensure compatibility and tailorability of the nanostructure with organic polymers. POSS compounds can have low density, can exhibit excellent flame retardancy, and can have diameters in the range of, for example, about 0.5nm to about 50 nm.

In some embodiments, the POSS compounds have specific organic groups selected to ensure compatibility with other materials of the TPV compositions.

POSS compounds are compounds represented by the formula

[RSiO_1.5]_x

Wherein x is an integer representing the molar degree of polymerization (e.g., from about 2 to about 36, such as from about 4 to about 24, such as from about 4 to about 15, such as from about 6 to about 12), and each occurrence of R represents a substituent (e.g., each occurrence of R is independently selected from H, siloxy, hydrocarbyl, cyclic or linear, saturated or unsaturated, aliphatic or aromatic groups, which may additionally include reactive functional groups such as alcohols, thiols, esters, amines, amides, aldehydes, ketones, olefins, ethers, thioethers, epoxy, carbamates, carbonates, anhydrides, carboxylic acids, acid halides, amines, nitriles, imines, isocyanates, nitro, aromatic hydrocarbons, or halides). The hydrocarbyl group may be an alkyl group (e.g., C1 to C10), an alkenyl group (e.g., C2 to C10), an alkynyl group (e.g., C2 to C10), an aryl group (e.g., phenyl and benzyl), or a heteroaryl group.

In some embodiments, each RSiO_1.5The R groups of the groups may be the same group (known as a homoleptic system) or different groups (known as heteroleptic systems).

In some embodiments, POSS compounds may also have a functionalized heteroleptic type represented by the formula:

[(RSiO_1.5)_n(RXSiO_1.0)_m]

wherein m and n are integers and m + n ≦ about 36 indicating a molar degree of polymerization, and each instance of R is as defined above, and X includes, but is not limited to, OH, Cl, Br, I, alkoxy (OR), acetate (OOCR), peroxy (OOR), amine (NR)₂) And isocyanate (NCO).

In some embodiments, POSS molecular silicas are of different sizes, with functionalities compatible with the composition of the TPV. Exemplary polyhedral oligomeric silsesquioxanes include: [ (RSiO)_1.5)₆]、[(RSiO_1.5)₈]、[(RSiO_1.5)₁₀]And [ (RSiO)_1.5)₁₂]Wherein each R group is the same or different.

Other exemplary polyhedral oligomeric silsesquioxanes include: octamethyl POSS ([ (CH)₃SiO_1.5)₈]) (MS 0830), octaisobutyl POSS ([ ((CH)₃)₂CHCH₂SiO_1.5)₈]) (MS 0825) and Octavinyl POSS ([ (CH)₂CHSiO_1.5)_n]) They are all available from Hybrid plastics inc (Hattiesburg, MS, u.s.).

In some embodiments, the polyhedral oligomeric silsesquioxane is blended (e.g., by mechanical means) into the TPV composition. In some embodiments, the polyhedral oligomeric silsesquioxane is present in a thermoplastic phase, a rubber phase, or a combination thereof.

Rubber phase

Rubbers useful in forming the rubber phase include those polymers that can be cured or crosslinked by phenolic resins or hydrosilylation curing agents (e.g., silane-containing curing agents), peroxides with coagents, moisture curing via silane grafting or azides. Reference to a rubber may include mixtures of more than one rubber. Non-limiting examples of rubbers include olefin elastomer terpolymers, nitrile rubbers, butyl rubbers such as isobutylene-isoprene rubber (IIR), brominated isobutylene-isoprene rubber (BIIR), and isobutylene paramethylstyrene rubber (BIMSM), and mixtures thereof. In some embodiments, the olefin elastomer terpolymer includes an ethylene-based elastomer, such as an ethylene-propylene-non-conjugated diene rubber.

1. Ethylene-propylene rubber

The term ethylene-propylene rubber refers to a rubbery terpolymer (e.g., an ethylene-propylene-diene terpolymer or an EPDM terpolymer) polymerized from ethylene, at least one other alpha-olefin monomer, and at least one diene monomer. The alpha-olefin monomer may include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, or combinations thereof. In one embodiment, the alpha-olefin comprises propylene, 1-hexene, 1-octene, or combinations thereof. The diene monomer may include 5-ethylidene-2-norbornene (ENB); 5-vinyl-2-norbornene (VNB); divinylbenzene; 1, 4-hexadiene; 5-methylene-2-norbornene; 1, 6-octadiene; 5-methyl-1, 4-hexadiene; 3, 7-dimethyl-1, 6-octadiene; 1, 3-cyclopentadiene; 1, 4-cyclohexadiene; dicyclopentadiene or a combination thereof. Where multiple alpha-olefin monomers or diene monomers are used, the polymers prepared from ethylene, alpha-olefin monomers, and diene monomers may be referred to as terpolymers or even tetrapolymers.

In some embodiments, where the diene monomer comprises 5-ethylidene-2-norbornene (ENB) or 5-vinyl-2-norbornene (VNB), the ethylene-propylene rubber may comprise at least about 1 wt% of the diene monomer (e.g., at least about 3 wt%, such as at least about 4 wt%, such as at least about 5 wt%, such as at least about 10 wt%), based on the total weight of the ethylene-propylene rubber. In other embodiments, when the diene comprises ENB or VNB, the ethylene-propylene rubber may comprise from about 1 wt% to about 15 wt% diene monomer (e.g., from about 3 wt% to about 15 wt%, such as from about 5 wt% to about 12 wt%, such as from about 7 wt% to about 11 wt%), based on the total weight of the ethylene-propylene rubber.

In some embodiments, the ethylene-propylene rubber comprises one or more of the following:

1) an ethylene-derived content of from about 10 wt% to about 99.9 wt%, such as from about 10 wt% to about 90 wt%, such as from about 12 wt% to about 90 wt%, such as from about 15 wt% to about 90 wt%, such as from about 20 wt% to about 80 wt%, such as from about 40 wt% to about 70 wt%, such as from about 45 wt% to about 65 wt%, based on the total weight of the ethylene-propylene rubber. In some embodiments, the ethylene-derived content is from about 40 wt% to about 85 wt%, for example from about 40 wt% to about 85 wt%, based on the total weight of the ethylene-propylene rubber.

2) From about 0.1 to about 15 wt.%, such as from about 0.1 wt.% to about 5 wt.%, such as from about 0.2 wt.% to about 10 wt.%, such as from about 2 wt.% to about 8 wt.%, or from about 4 wt.% to about 12 wt.%, such as from about 4 wt.% to about 9 wt.%) based on the total weight of the ethylene-propylene rubber. In some embodiments, the diene-derived content is from about 3 wt% to about 15 wt%, based on the total weight of the ethylene-propylene rubber.

3) The remainder of the ethylene-propylene rubber includes an alpha-olefin derived content (e.g., C)₂-C₄₀E.g. C₃-C₂₀E.g. C₃-C₁₀Olefins, such as propylene).

4) A weight average molecular weight (Mw) of about 100,000g/mol or more (e.g., about 200,000g/mol or more, such as about 400,000g/mol or more, such as about 600,000g/mol or more). In these or other embodiments, the Mw is about 1,200,000g/mol or less (e.g., about 1,000,000g/mol or less, such as about 900,000g/mol or less, such as about 800,000g/mol or less). In these or other embodiments, the Mw can be from about 400,000g/mol to about 3,000,000g/mol (e.g., from about 400,000g/mol to about 2,000,000, such as from about 500,000g/mol to about 1,500,000g/mol, such as from about 600,000g/mol to about 1,200,000g/mol, such as from about 600,000g/mol to about 1,000,000 g/mol).

5) A number average molecular weight (Mn) of about 20,000g/mol or more (e.g., about 60,000g/mol or more, such as about 100,000g/mol or more, such as about 150,000g/mol or more). In these or other embodiments, the Mn is less than about 500,000g/mol (e.g., about 400,000g/mol or less, such as about 300,000g/mol or less, such as about 250,000g/mol or less).

6) A Z average molecular weight (Mz) of from about 10,000g/mol to about 7,000,000g/mol (e.g., from about 50,000g/mol to about 3,000,000g/mol, such as from about 70,000g/mol to about 2,000,000g/mol, such as from about 75,000g/mol to about 1,500,000g/mol, such as from about 80,000g/mol to about 700,000g/mol, such as from about 100,000g/mol to about 500,000 g/mol).

7) A polydispersity index (Mw/Mn; PDI).

8) A dry Mooney viscosity (ML) according to ASTM D-1646 of about 10MU to about 500MU or about 50MU to about 450MU₍₁₊₄₎At 125 ℃ C. In these or other embodiments, the mooney viscosity is 250MU or more, for example 350MU or more.

9) Glass transition temperature (T) determined by Differential Scanning Calorimetry (DSC) according to ASTM E1356_g) About-20 c or less (e.g., about-30 c or less, such as about-50 c or less). In some embodiments, T_gFrom about-20 ℃ to about-60 ℃.

Ethylene-propylene rubbers may be manufactured or synthesized by using various techniques. For example, these terpolymers can be synthesized by employing solution, slurry or gas phase polymerization techniques, or combinations thereof, employing various catalyst systems including Ziegler-Natta systems, including vanadium catalysts, and in various phases such as solution, slurry or gas phase. Exemplary catalysts include single site catalysts, including constrained geometry catalysts involving group IV-VI metallocenes. In some embodiments, EPDM can be prepared via conventional ziegler-natta catalysts using slurry processes, particularly those that include vanadium compounds (as disclosed in U.S. patent No. 5,783,645), as well as metallocene catalysts (which are also disclosed in U.S. patent No. 5,756,416). Other catalyst systems, such as Brookhart catalyst systems, may also be employed. Optionally, such EPDM can be prepared in a solution process using the catalyst system described above.

Some elastomeric terpolymers are available under the trade name Vistalon^TM(ExxonMobilChemical Co.；Houston，Tex.)、Keltan^TM(Arlanxeo Performance Elastomers；Orange，TX.)、Nordel^TMIP(Dow)、NORDEL MG^TM(Dow)、Royalene^TM(Lion Elastomers), KEP (Kumho Polychem) and Suprene^TM(SKGlobalchemical) is commercially available. Specific examples include Vistalon3666, Vistalon9600, Keltan 9950C, Keltan 8550C, KEP 8512, KEP 9590, Keltan 5469Q, Keltan 4969Q, Keltan 5469C and Keltan4869C, Royalene 694, Royalene 677, Suprene 512F, Nordel 6555, Nordel 4571XFM, Royalene 515.

In some embodiments, the ethylene propylene rubber may be obtained in an oil extended form, containing from about 50phr to about 200phr of process oil, for example from about 75phr to about 120phr of process oil, based on 100phr of elastomer.

2. Nitrile rubber

Suitable nitrile rubbers include rubber polymers of 1, 3-butadiene or isoprene and acrylonitrile. Exemplary nitrile rubbers include polymers of 1, 3-butadiene and about 20-50 wt% acrylonitrile.

In some embodiments, the nitrile rubber includes one or more of the following features:

1) about 20 wt.% or more (e.g., about 20 wt.% to about 50 wt.%, 25 wt.% to about 45 wt.%, such as 30 wt.% to about 40 wt.%, such as about 35 wt.% to about 40 wt.%) of acrylonitrile-derived content, based on the total weight of the nitrile rubber.

2) When the nitrile rubber is a copolymer of isoprene and acrylonitrile, about 10 wt% to about 99.9 wt% (e.g., about 10 wt% to about 90 wt%, e.g., 12 wt% to about 90 wt%, e.g., about 15 wt% to about 90 wt%, e.g., about 20 wt% to about 80 wt%, e.g., about 40 wt% to about 70 wt%, e.g., about 50 wt% to about 70 wt%, e.g., about 55 wt% to about 65 wt%, e.g., about 60 wt% to about 65 wt%) of the isoprene-derived content based on the total weight of the ethylene-propylene rubber. In some embodiments, the ethylene-derived content is from about 40 wt% to about 85 wt%, for example from about 40 wt% to about 85 wt%, based on the total weight of the composition.

3) When the nitrile rubber is a copolymer of 1, 3-butadiene and acrylonitrile, about 10 wt.% to about 99.9 wt.% (e.g., about 10 wt.% to about 90 wt.%, e.g., 12 wt.% to about 90 wt.%, e.g., about 15 wt.% to about 90 wt.%, e.g., about 20 wt.% to about 80 wt.%, e.g., about 40 wt.% to about 70 wt.%, e.g., about 50 wt.% to about 70 wt.%, e.g., about 55 wt.% to about 65 wt.%, e.g., about 60 wt.% to about 65 wt.%) of the 1, 3-butadiene-derived content is based on the total weight of the ethylene-propylene rubber. In some embodiments, the ethylene-derived content is from about 40 wt% to about 85 wt%, for example from about 40 wt% to about 85 wt%, based on the total weight of the composition.

4) A weight average molecular weight (Mw) of about 100,000g/mol or more (e.g., about 200,000g/mol or more, such as about 400,000g/mol or more, such as about 600,000g/mol or more). In these or other embodiments, the Mw is about 1,200,000g/mol or less (e.g., about 1,000,000g/mol or less, such as about 900,000g/mol or less, such as about 800,000g/mol or less). In these or other embodiments, the Mw can be from about 500,000g/mol to about 3,000,000g/mol (e.g., from about 500,000g/mol to about 2,000,000, such as from about 500,000g/mol to about 1,500,000g/mol, such as from about 600,000g/mol to about 1,200,000g/mol, such as from about 600,000g/mol to about 1,000,000 g/mol).

Nitrile Rubber is available from many commercial sources disclosed in Rubber World Blue Book.

Functionalized nitrile rubbers having one or more graft-forming functional groups may be used to prepare the block copolymers of the present disclosure. The above-mentioned "graft-forming functional groups" are different from and complementary to the olefinic and cyano groups normally present in nitrile rubbers. Carboxyl-modified nitrile rubbers having carboxyl groups and amine-modified nitrile rubbers having amino groups may also be used in the TPV compositions described herein.

3. Butyl rubber

In some embodiments, the butyl rubber comprises copolymers and terpolymers of isobutylene and at least one other comonomer. Useful comonomers include isoprene, divinyl aromatic monomers, alkyl-substituted vinyl aromatic monomers, and mixtures thereof. Exemplary divinylaromatic monomers include vinyl styrene. Exemplary alkyl-substituted vinyl aromatic monomers include alpha-methylstyrene and para-methylstyrene. These copolymers and terpolymers may also be halogenated butyl rubbers (also referred to as halobutyl rubbers), for example in the case of chlorinated butyl rubbers and brominated butyl rubbers. In some embodiments, these halogenated polymers may be derived from monomers such as para-bromomethylstyrene.

In some embodiments, butyl rubber includes copolymers of isobutylene and isoprene, and copolymers of isobutylene and para-methylstyrene, terpolymers of isobutylene, isoprene and vinyl styrene, branched butyl rubber, and brominated copolymers of isobutylene and para-methylstyrene (resulting in copolymers having para-bromomethylstyrene based monomer units). These copolymers and terpolymers may be halogenated. Exemplary butyl rubbers include isobutylene-isoprene rubber (IIR), brominated isobutylene-isoprene rubber (BIIR), chlorinated isobutylene-isoprene rubber (CIIR), and isobutylene p-methylstyrene rubber (BIMSM).

In some embodiments, the butyl rubber includes one or more of the following features:

1) when the butyl rubber comprises isobutylene-isoprene rubber, the rubber may comprise from about 0.5 wt% to about 30 wt% (e.g., from about 0.8 wt% to about 5 wt%) of isoprene, with the remainder being isobutylene, based on the total weight of the rubber.

2) When the butyl rubber comprises isobutylene-para-methylstyrene rubber, the rubber may comprise from about 0.5 wt.% to about 25 wt.% (e.g., from about 2 wt.% to about 20 wt.%) para-methylstyrene, based on the total weight of the rubber, with the remainder being isobutylene.

3) When isobutylene-paramethylstyrene rubbers are halogenated, for example, with bromine and/or chlorine, these halogenated rubbers may have a percent halogenation of from about 0 wt.% to about 10 wt.% (e.g., from about 0.3 wt.% to about 7 wt.%), with the remainder being isobutylene, based on the total weight of the rubber.

4) When isobutylene-isoprene rubber is halogenated, for example with bromine and/or chlorine, these halogenated rubbers may have a percent halogenation of from about 0 wt% to about 10 wt% (e.g., from about 0.3 wt% to about 7 wt%), based on the total weight of the rubber, with the remainder being isobutylene.

5) When the butyl rubber comprises isobutylene-isoprene-divinylbenzene, the rubber may comprise from about 95 wt% to about 99 wt% (e.g., from about 96 wt% to about 98.5 wt%) isobutylene, based on the total weight of the rubber, and from about 0.5 wt% to about 5 wt% (e.g., from about 0.8 wt% to about 2.5 wt%) isoprene, based on the total weight of the rubber, with the remainder being divinylbenzene.

6) When the butyl rubber comprises halogenated butyl rubber, the butyl rubber may comprise about 0.1 wt% to about 10 wt% halogen (e.g., about 0.3 wt% to about 7 wt%, such as about 0.5 wt% to about 3 wt%), based on the total weight of the rubber.

7) A glass transition temperature (Tg) of about-55 deg.C or less (e.g., about-58 deg.C or less, such as about-60 deg.C or less, such as about-63 deg.C or less).

8) A weight average molecular weight (Mw) of about 100,000g/mol or more (e.g., about 200,000g/mol or more, such as about 400,000g/mol or more, such as about 600,000g/mol or more). In these or other embodiments, the Mw is about 1,200,000g/mol or less (e.g., about 1,000,000g/mol or less, such as about 900,000g/mol or less, such as about 800,000g/mol or less). In these or other embodiments, the Mw can be from about 500,000g/mol to about 3,000,000g/mol (e.g., from about 500,000g/mol to about 2,000,000, such as from about 500,000g/mol to about 1,500,000g/mol, such as from about 600,000g/mol to about 1,200,000g/mol, such as from about 600,000g/mol to about 1,000,000 g/mol).

Butyl Rubber is available from many commercial sources disclosed in Rubber World Blue Book. For example, halogenated and non-halogenated copolymers of isobutylene and isoprene are available under the trade name Exxon Butyl^TM(ExxonMobil Chemical Co.) commercially available, halogenated and unhalogenated copolymers of isobutylene and para-methylstyrene are available under the trade name EXXPRO^TM(ExxonMobil chemical Co.) A STAR-BRANCHED BUTYL rubber is commercially available under the trade name STAR BRANCHED BUTYL^TM(ExxonMobil Chemical Co.) commercially available, and a copolymer containing p-bromomethylstyrene-based monomer units is commercially available under the trade designation EXXPRO 3745(ExxonMobil Chemical Co.). Halogenated and non-halogenated terpolymers of isobutylene, isoprene and divinyl styrene may be sold under the trade name Polysar Butyl^TM(Lanxess; Germany) are commercially available.

In some embodiments, the rubber (e.g., ethylene-propylene rubber, nitrile rubber, or butyl rubber) may be highly cured. In some embodiments, the rubber is advantageously partially or fully (fully) cured. The degree of cure can be measured as follows: the amount of rubber extractable from the TPV composition was determined by using cyclohexane or boiling xylene as the extractant. Such a method is disclosed in U.S. Pat. No. 4,311,628, which is incorporated herein by reference for purposes of U.S. patent practice. In some embodiments, the rubber has a degree of cure in which no more than about 5.9 wt.%, such as no more than about 5 wt.%, such as no more than about 4 wt.%, such as no more than about 3 wt.% is extractable by cyclohexane at 23 ℃, as described in U.S. patent No. 5,100,947 and 5,157,081, which are incorporated herein by reference for purposes of U.S. patent practice. In these or other embodiments, the rubber is cured to an extent wherein greater than about 94 wt.%, such as greater than about 95 wt.%, such as greater than about 96 wt.%, such as greater than about 97 wt.% of the rubber is insoluble in 23 ℃ cyclohexane. Alternatively, in some embodiments, the rubber has a degree of cure such that the crosslink density is at least 4 x 10^-5Mole/ml rubber, e.g. at least 7X 10^-5Mole/ml rubber, e.g. at least 10X 10^-5Mol/ml rubber. See also Ellul et al, "Cross proteins and phase morphologies in dynamic vacutained TPEs", Rubber Chemistry and Technology, Vol.68, pp.573-584 (1995).

Despite the fact that the rubber may be partially or fully cured, the compositions of the present disclosure may be processed and reprocessed by conventional plastic processing techniques such as extrusion, injection molding, blow molding, and compression molding. The rubber within these thermoplastic elastomers may be in the form of finely divided and well dispersed particles of vulcanized or cured rubber within a continuous thermoplastic phase or matrix. In some embodiments, a co-continuous morphology or phase inversion may be achieved. In those embodiments in which the cured rubber is in the form of finely divided and well-dispersed particles within the thermoplastic medium, the rubber particles can have an average diameter of about 50 μm or less (e.g., about 30 μm or less, such as about 10 μm or less, such as about 5 μm or less, such as about 1 μm or less). In some embodiments, at least about 50% of the particles, such as about 60% of the particles, such as about 75% of the particles, have an average diameter of about 5 μm or less, such as about 2 μm or less, such as about 1 μm or less.

Thermoplastic phase

In some embodiments, the thermoplastic phase of the TPV composition useful for the outer jacket of a flexible pipe includes a polymer that can flow above its melting temperature. In some embodiments, the major component of the thermoplastic phase comprises at least one thermoplastic polyolefin, such as polypropylene (e.g., a homopolymer, a random copolymer, or an impact copolymer, or a combination thereof), an ethylene-based polymer (e.g., polyethylene), a butylene-based polymer (e.g., polybutylene), or a combination thereof. In some embodiments, the thermoplastic phase may also include as a minor component at least one thermoplastic polyolefin, such as an ethylene-based polymer (e.g., polyethylene), a propylene-based polymer (e.g., polypropylene), or a butene-based polymer (e.g., polybutene or polybutene-1).

1. Propylene-based polymers

Propylene-based polymers include those solids, i.e., plastic resins typically having a high molecular weight comprising predominantly units derived from the polymerization of propylene. In some embodiments, at least 75%, in other embodiments, at least 90%, in other embodiments, at least 95%, and in other embodiments, at least 97% of the propylene-based polymer units are derived from the polymerization of propylene. In particular embodiments, these polymers include homopolymers of propylene. The homopolymer polypropylene may comprise linear chains and/or chains with long chain branching.

In some embodiments, the propylene-based polymer may also include units derived from the polymerization of ethylene and/or alpha-olefins such as 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof. Specifically included are propylene with ethylene or higher alpha-olefins (as described above) or with C₁₀-C₂₀Reactor, impact and random copolymers of olefins.

In some embodiments, the propylene-based polymer includes one or more of the following features:

1) the propylene-based polymer may include a semi-crystalline polymer. In some embodiments, these polymers may be characterized by a crystallinity of at least about 25 wt% or greater (e.g., about 55 wt% or greater, such as about 65 wt% or greater, such as about 70 wt% or greater). The crystallinity can be determined as follows: the heat of fusion (Hf) of the sample was divided by the heat of fusion of the 100% crystalline polymer, which is considered to be 209 joules/gram for polypropylene.

2) About 52.3J/g or more (e.g., about 100J/g or more, such as about 125J/g or more, such as about 140J/g or more) Hf.

3) The weight average molecular weight (Mw) is from about 50,000g/mol to about 2,000,000g/mol (e.g., from about 100,000g/mol to about 1,000,000g/mol, such as from about 100,000g/mol to about 600,000g/mol or from about 400,000g/mol to about 800,000g/mol) as determined by GPC with polystyrene standards.

4) The number average molecular weight (Mn) is from about 25,000g/mol to about 1,000,000g/mol (e.g., from about 50,000g/mol to about 300,000g/mol) as determined by GPC with polystyrene standards.

5) G 'of 1 or less (e.g., 0.9 or less, 0.8 or less, e.g., 0.6 or less, e.g., 0.5 or less)'_vis。

6) A Melt Flow Rate (MFR) (ASTM D1238, 2.16kg weight @230 ℃) of about 0.1g/10min or more (e.g., about 0.2g/10min or more, e.g., about 0.2g/10min or more). Alternatively, the MFR is from about 0.1g/10min to about 50g/10min, such as from about 0.5g/10min to about 5g/10min, such as from about 0.5g/10min to about 3g/10 min.

7) The melting temperature (Tm) is from about 110 ℃ to about 170 ℃ (e.g., from about 140 ℃ to about 168 ℃, e.g., from about 160 ℃ to about 165 ℃).

8) A glass transition temperature (Tg) of from about-50 deg.C to about 10 deg.C (e.g., from about-30 deg.C to about 5 deg.C, such as from about-20 deg.C to about 2 deg.C).

9) A crystallization temperature (Tc) of about 75 ℃ or more (e.g., about 95 ℃ or more, such as about 100 ℃ or more, such as about 105 ℃ or more (e.g., about 105 ℃ to about 130 ℃)).

In some embodiments, the propylene-based polymer comprises a homopolymer of high crystallinity isotactic or syndiotactic polypropylene. Such polypropylene may have a density of about 0.89 to about 0.91g/mL, with the largely isotactic polypropylene having a density of about 0.90 to about 0.91 g/mL. In addition, high and ultra-high molecular weight polypropylenes with fractional melt flow rates can be employed. In some embodiments, the polypropylene resin can exhibit an MFR (ASTM D-1238; 2.16kg @230 ℃) of about 10dg/min or less (e.g., about 1.0dg/min or less, such as about 0.5dg/min or less).

In some embodiments, the polypropylene comprises a homopolymer, random copolymer, or impact copolymer polypropylene, or a combination thereof. In some embodiments, the polypropylene is a High Melt Strength (HMS) Long Chain Branched (LCB) homopolymer polypropylene.

Propylene-based polymers may be synthesized by using suitable polymerization techniques known in the art, for example, conventional ziegler-natta type polymerizations, and catalysis employing single-site organometallic catalysts, including metallocene catalysts.

Examples of polypropylenes that can be used in the TPV compositions described herein include ExxonMobil^TMPP5341 (available from ExxonMobil); achieve^TMPolypropylene resins with broad molecular weight distribution as described in PP6282NE1 (available from ExxonMobil) and/or US 9,453,093 and US 9,464,178; and other polypropylene resins described in US20180016414 and US 20180051160; waymax MFX6 (available from Japan Polypropylene core.); borealis Daploy^TMWB140 (available from Borealis AG) and Braskem Ampleo 1025MA and Braskem Ampleo1020GA (available from Braskem Ampleo) and other suitable polypropylenes.

In one or more embodiments, the thermoplastic component is or includes isotactic polypropylene. In some embodiments, the thermoplastic component contains one or more crystalline propylene homopolymers or propylene copolymers having a melting temperature of about 110 ℃ to about 170 ℃ or higher as measured by DSC. Example copolymers of propylene include, but are not limited to, terpolymers of propylene, impact copolymers of propylene, atactic polypropylene and mixtures thereof. Example comonomers have about 2 carbon atoms or about 4 to about 12 carbon atoms. In some embodiments, the comonomer is ethylene.

The term "random polypropylene" as used herein broadly means a single phase copolymer of propylene having up to about 9 wt%, for example from about 2 wt% to about 8 wt%, of an alpha-olefin comonomer. Example alpha-olefins have about 2 carbon atoms or from about 4 to about 12 carbon atoms. In some embodiments, the alpha-olefin comonomer is ethylene.

In one or more embodiments, the thermoplastic resin component may be or include a "propylene-based copolymer. "propylene-based copolymer" includes at least two different types of monomer units, one of which is propylene. Suitable monomer units include, but are not limited to, ethylene and C₄To C₂₀Such as 1-butene, 4-methyl-1-pentene, 1-hexene or 1-octene and 1-decene, or mixtures thereof. In some embodiments, ethylene is copolymerized with propylene such that the propylene-based copolymer includes propylene-derived units (units derived from propylene monomers on the polymer chain) and ethylene-derived units (units derived from ethylene monomers on the polymer chain).

2. Ethylene-based polymers

Ethylene-based polymers include those solids, typically high molecular weight plastic resins, that include primarily units derived from the polymerization of ethylene. In some embodiments, at least 90%, in other embodiments, at least 95%, and in other embodiments, at least 99% of the units of the ethylene-based polymer are derived from ethylene polymerization. In particular embodiments, these polymers include homopolymers of ethylene.

In some embodiments, the ethylene-based polymer may also include units derived from the polymerization of alpha-olefin comonomers such as propylene, 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, and mixtures thereof.

In some embodiments, the ethylene-based polymer includes one or more of the following features:

1) a Melt Index (MI) (ASTM D-1238, 2.16kg @190 ℃ C.) of from about 0.1dg/min to about 1,000dg/min (e.g., from about 1.0dg/min to about 200dg/min, such as from about 7.0dg/min to about 20.0 dg/min).

2) A melt temperature (Tm) of from about 140 ℃ to about 90 ℃ (e.g., from about 135 ℃ to about 125 ℃, e.g., from about 130 ℃ to about 120 ℃).

The ethylene-based polymer may be prepared by usingSuitable polymerization techniques known in the art, for example, conventional Ziegler-Natta type polymerizations, and catalytic syntheses employing single-site organometallic catalysts, including metallocene catalysts. Some ethylene-based polymers are commercially available. The vinyl copolymer may be sold under the trade name ExxonMobil^TMPolyethylene (available from ExxonMobilofHouston, TX) is commercially available and includes metallocene-produced linear low density polyethylene, including exceeded^TM、Enable^TMAnd Exceed^TMXP. Examples of vinyl thermoplastic polymers that may be used in certain embodiments of the TPV compositions of the invention described herein include ExxonMobil HD7800P, ExxonMobil HD6706.17, ExxonMobil HD7960.13, ExxonMobil HD9830, ExxonMobil AD60-007, Exced XP8318ML, excepted^TMXP 6056ML、Exceed 1018HA、Enable^TM2010 series, Enable^TM2305 series and ExxonMobil^TMLLDPE LL (e.g., 1001, 1002YB, 3003 series), all available from ExxonMobil of Houston, TX. Additional examples of ethylene-based thermoplastic polymers that may be used in certain embodiments of the TPV compositions of the invention described herein include Innate^TMST50 and Dowlex^TMAvailable from The Dow Chemical Company of Midland, MI.

In some embodiments, the ethylene-based polymer comprises low density polyethylene, linear low density polyethylene, or high density polyethylene. In some embodiments, the ethylene-based polymer may be a High Melt Strength (HMS) Long Chain Branched (LCB) homopolymer polyethylene.

3. Butene-1-based polymers

Butene-1 based polymers include those solid, usually high molecular weight, isotactic butene-1 resins comprising predominantly units derived from the polymerization of butene-1.

In some embodiments, the butene-1 based polymer comprises an isotactic poly (butene-1) homopolymer. In some embodiments, the butene-1 based polymer may further comprise units derived from the polymerization of alpha-olefin comonomers such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-hexene, and mixtures of two or more thereof.

In some embodiments, the butene-1 based polymer includes one or more of the following features:

1) at least 90 wt% or more of the units of the butene-1 based polymer are derived from the polymerization of butene-1 (e.g., about 95 wt% or more, such as about 98 wt% or more, such as about 99 wt% or more). In some embodiments, these polymers include homopolymers of butene-1.

2) The Melt Index (MI) (ASTM D1238, 2.16kg @190 ℃) is from about 0.1dg/min to 800dg/min (e.g., from about 0.3dg/min to about 200dg/min, such as from about 0.3dg/min to about 4.0 dg/min). In these or other embodiments, the MI is about 500dg/min or less (e.g., about 100dg/min or less, such as about 10dg/min or less, such as about 5dg/min or less).

3) The melting temperature (Tm) is from about 130 ℃ to about 110 ℃ (e.g., from about 125 ℃ to about 115 ℃, e.g., from about 125 ℃ to about 120 ℃).

4) The density, as determined according to ASTM D792, is from about 0.897g/mL to about 0.920g/mL, such as from about 0.910g/mL to about 0.920 g/mL. In these or other embodiments, the density is about 0.910g/mL or more, such as 0.915g/mL or more, such as about 0.917g/mL or more.

Butene-1 based polymers may be synthesized by using suitable polymerization techniques known in the art, for example, conventional Ziegler-Natta type polymerizations, and catalysis employing single site organometallic catalysts, including metallocene catalysts. Some butene-1 based polymers are commercially available. For example, some isotactic poly (1-butene) are commercially available under the tradenames Polybutene Resins or PB (Basell).

Other ingredients

In some embodiments, a TPV composition useful for the outer jacket of a flexible pipe may include a polymer processing additive. The processing additive may be a polymer resin having a very high melt flow index. These polymer resins include linear and branched polymers having a melt flow rate of about 500dg/min or more, such as about 750dg/min or more, such as about 1000dg/min or more, such as about 1200dg/min or more, such as about 1500dg/min or more. Mixtures of various branched or various linear polymer processing additives, as well as mixtures of both linear and branched polymer processing additives, may be employed. Unless otherwise indicated, reference to polymer processing additives may include linear and branched additives. The linear polymer processing additive comprises a polypropylene homopolymer and the branched polymer processing additive comprises a diene-modified polypropylene polymer. TPV compositions including similar processing additives are disclosed in U.S. patent No.6, 451,915, which is incorporated herein by reference for purposes of U.S. patent practice.

Fillers and extenders that can be used include conventional inorganic materials such as calcium carbonate, clay, silica, talc, titanium dioxide, carbon black, nucleating agents, mica, wood flour, and the like, and blends thereof, as well as inorganic and organic nanoscale fillers.

Nucleating agent

The term "nucleating agent" refers to any additive that creates nucleation sites for the growth of thermoplastic crystals from a molten state into a solid, cooled structure. In other words, the nucleating agent provides sites for the growth of thermoplastic crystals when the thermoplastic is cooled from its molten state.

The nucleating agent provides a plurality of nucleation sites for the thermoplastic component to crystallize upon cooling. Surprisingly, such multiple nucleation sites promote uniform crystallization within the thermoplastic vulcanizate composition, thereby allowing the composition to crystallize throughout the cross-section in a shorter time and at higher temperatures. Such multiple nucleation sites generate a greater number of smaller crystals within the thermoplastic vulcanizate composition, which requires less cooling time.

This uniform cooling profile enables the formation of extruded articles of the TPV compositions of the invention having a thickness greater than 2mm, for example greater than 5mm, greater than 10mm, or even greater than 15 mm. Extruded articles of the TPV compositions of the invention can have a thickness greater than 20mm and still exhibit effective cooling (e.g., from cross machine direction) at the extrusion temperatureThe outer surface of the cross-section cools to the inner surface of the cross-section) without sacrificing mechanical strength. Such extrusion temperatures are equal to or above the melting point of the thermoplastic component. Exemplary nucleating agents include, but are not limited to, dibenzylidene sorbitol-based compounds, sodium benzoate, sodium phosphate salts, and lithium phosphate salts. For example, the nucleating agent may include sodium 2, 2' -methylene-bis- (2, 6-di-t-butylphenyl) phosphate, which may be sold under the trade name Hyperform^TMFrom Milliken&Company of Spartanburg, SC is commercially available. Another specific nucleating agent is norbornane (bicyclo (2.2.1) heptane carboxylate, which is commercially available from Ciba Specialty Chemicals of Basel, Switzerland.

Processing oil/plasticizer

In some embodiments, the TPV composition may include a plasticizer such as an oil, for example, a mineral oil, a synthetic oil, or a combination thereof. These oils may also be referred to as plasticizers or extenders. Mineral oils may include aromatic oils, naphthenic oils, paraffinic and isoparaffinic oils, synthetic oils, and combinations thereof. In some embodiments, the mineral oil may be treated or untreated. Useful mineral oils may be sold under the trade name SUNPAR^TM(Sun Chemicals). Other oils may be under the trade name PARALUX^TM(Chevron) and PARAMOUNT^TM(Chevron). Other oils that may be used include hydrocarbon oils and plasticizers, such as synthetic plasticizers. Many additive oils are derived from petroleum fractions and have specific ASTM designations depending on whether they fall into the paraffinic, naphthenic or aromatic hydrocarbon oil categories. Other types of additive oils include alpha olefinic synthetic oils, such as liquid polybutenes and polyisobutylenes. Additive oils other than petroleum-based oils may also be used, such as oils derived from coal tar and pine tar, as well as synthetic oils such as polyolefin materials. Other plasticizers include triisononyl trimellitate (TINTM). In addition, vegetable or animal oils may also be used as plasticizers and/or processing aids in the TPV compositions.

Examples of oils include base stocks. According to the American Petroleum Institute (API) classification, base stocks are divided into five groups based on their saturates content, sulfur level, and viscosity index (table 1). Lubricating oil (lube) base stocks are typically produced on a large scale from non-renewable petroleum sources. Both group I, II and group III basestocks are derived from crude oils by large scale processing (e.g., solvent extraction, solvent or catalytic dewaxing, and hydroisomerization, hydrocracking and isodewaxing, and hydrofinishing). See "New lube Plants Using State-of-the-art hydroDewarming Technology" in Oil & Gas Journal on 1/9/1997; krishna et al, "Next Generation isocyanate and Hydrofining Technology for Production of High Quality Base Oils", 2002NPRA Lubricants and wax Meeting, 11 months, 14-15 days 2002; gedeon and Yenni, "Use of" Clean "Paraffin Processing Oils to Improve TPE Properties", supplied by TPES 2000Philadelphia, Pa, on9 months 27-28 days 1999.

Group III base stocks may also be produced from synthetic hydrocarbon liquids obtained from natural gas, coal, or other fossil resources, and group IV base stocks are Polyalphaolefins (PAOs) and are produced by oligomerization of alpha olefins, such as 1-decene. Group V binders include all binders not belonging to groups I-IV, such as cycloalkanes, polyalkylene glycols (PAG) and esters.

In some embodiments, the synthetic oil includes oligomers and polymers of butenes including isobutylene, 1-butene, 2-butene, butadiene, and mixtures thereof. In some embodiments, these oligomers may exhibit a number average molecular weight (Mn) of from about 300g/mol to about 9,000g/mol, and in other embodiments, from about 700g/mol to about 1,300 g/mol. In some embodiments, these oligomers comprise isobutylene-based monomeric units. Exemplary synthetic oils include polyisobutylene, poly (isobutylene-co-butylene), and mixtures thereof. In some embodiments, the synthetic oil may include a poly linear alpha olefin, a poly branched alpha olefin, a hydrogenated poly alpha olefin, and mixtures thereof.

In some embodiments, the synthetic oil comprises a synthetic polymer or copolymer having a viscosity of about 20cP or greater, such as about 100cP or greater, for example about 190cP or greater, wherein the viscosity is measured by a Brookfield viscometer according to ASTM D-4402 at 38 ℃. In these or other embodiments, the viscosity of these oils may be about 4,000cP or less, for example about 1,000cP or less.

Useful synthetic oils may be sold under the trade name Polybutene^TM(Soltex; Houston, Tex.) and Indopol^TM(Ineos) is commercially available. The white synthetic oil may be sold under the trade name SPECTRASYN^TM(ExxonMobil) (formerly SHF fluid (Mobil)), Elevast^TM(ExxonMobil) and white oils produced by gas-liquid technology, e.g. Risella^TMX415/420/430(Shell) or Primol^TM(ExxonMobil) series white oils, e.g. Primol^TM352、Primol^TM382、Primol^TM542 or Marcol^TM82、Marcol^TM52、Drakeol^TM(Pentaro) series white oils, e.g. Drakeol^TM34 or a combination thereof. Oils as described in U.S. Pat. No. 5,936,028 can also be employed.

In some embodiments, the addition of certain low to medium molecular weight (<10,000g/mol) organic esters and alkyl ether esters to the TPV compositions of the invention significantly reduces the Tg of the polyolefin and rubber components and the overall composition. The addition of certain low to medium molecular weight (<10,000g/mol) organic esters and alkyl ether esters improves low temperature properties, particularly flexibility and strength. It was surprisingly observed that such formulations have enhanced permeability and abrasion resistance. These effects are believed to be achieved by partitioning the ester into the polyolefin and rubber components of the composition. Particularly suitable esters include monomeric and oligomeric aliphatic esters having low molecular weights (e.g., average molecular weights in the range of about 2000 or less, such as about 600 or less). In certain aspects, the ester is selected to be compatible or miscible with both the polyolefin and rubber components of the composition, e.g., the ester is mixed with the other components to form a single phase. Esters found suitable include monomeric alkyl monoesters, monomeric alkyl diesters, oligomeric alkyl monoesters, oligomeric alkyl diesters, monomeric alkyl ether monoesters, monomeric alkyl ether diesters, oligomeric alkyl ether monoesters, oligomeric alkyl ether diesters, and mixtures thereof. The effect of polymeric aliphatic and aromatic esters was found to be significantly less effective, while phosphate esters were largely ineffective.

Examples of esters that have been found to be suitable for use in the TPV compositions of the invention include diisooctyl dodecanedioate, dioctyl sebacate, butoxyethyl oleate, n-butyl tallate (n-butyl tallate), isooctyl oleate, isooctyl tallate, dialkyl azelate, diethylhexyl sebacate, alkyl ether diesters of glutaric acid, oligomers thereof, and mixtures thereof. Other analogs contemplated for use in the TPV compositions of the invention include alkyl ether mono-and di-adipates, mono-and di-alkyl adipates, glutarates, sebacates, azelates, ester derivatives of castor oil or tall oil, and oligomeric mono-and diesters or mono-and dialkyl ether esters derived therefrom. Isooctyl resinate and n-butyl resinate are useful. These esters may be used alone in the composition or as a mixture of different esters, or they may be used in combination with conventional hydrocarbon oil diluents or processing oils (e.g., paraffin oils). In certain embodiments, the amount of ester plasticizer in the TPV composition ranges from about 0.1 wt% to about 40 wt%, based on the total weight of the TPV composition. In certain embodiments, the ester plasticizer is isooctyl resinate. Such esters are useful as Plasthall^TMCommercially available from Hallstar of Chicago, IL. In certain embodiments, the ester plasticizer is n-butyl resinate.

Preparation of TPV compositions

In some embodiments, the rubber is cured or crosslinked by dynamic vulcanization. The term dynamic vulcanization refers to a process for the vulcanization or curing of rubber contained in a blend with a thermoplastic resin wherein the rubber is crosslinked or vulcanized under high shear conditions at a temperature above the melting point of the thermoplastic polyolefin. The rubber may be cured by the use of various curing agents. Exemplary curing agents include phenolic resin curing systems, peroxide curing systems, and silicon-containing curing systems, such as hydrosilylation and silane graft/moisture cure. The dynamic vulcanization may occur in the presence of the polyolefin, or the polyolefin may be added after the dynamic vulcanization (e.g., post-addition), or both (e.g., some polyolefin may be added before the dynamic vulcanization and some polyolefin may be added after the dynamic vulcanization).

In some embodiments, the rubber may be simultaneously crosslinked and dispersed as fine particles within the thermoplastic matrix, although other morphologies may also be present. Dynamic vulcanization may be accomplished by mixing the thermoplastic elastomer components at elevated temperatures in conventional mixing equipment such as roll mills, stabilizers, banbury mixers, brabender mixers, continuous mixers, mixing extruders, and the like. Methods for preparing TPV compositions are described in U.S. Pat. nos. 4,311,628, 4,594,390, 6,503,984 and 6,656,693, although methods employing low shear rates may also be used. A multi-step process may also be employed whereby ingredients, such as additional thermoplastic resins, may be added after dynamic vulcanization is achieved, as disclosed in International application No. PCT/US 04/30517.

In some embodiments, a method for preparing a dynamically vulcanized thermoplastic vulcanizate includes melt processing at least one thermoplastic resin, at least one rubber, at least one curing agent, and at least one polyhedral oligomeric silsesquioxane under shear conditions. In some embodiments, melt processing may be conducted under high shear conditions. The shear conditions are similar to those present when producing TPV compositions using common melt processing equipment such as brabender or banbury mixers (laboratory scale instruments) and commercial twin screw extruders.

The term "shear" is added to mean that the polyhedral oligomeric silsesquioxane is incorporated into the TPV composition by mixing and intensive mixing at high shear temperatures.

One skilled in the art will be readily able to determine an adequate or effective amount of the sulfiding agent to be used without undue calculation or experimentation.

As noted above, the TPV compositions are dynamically vulcanized by various methods, including the use of a cure system, wherein the cure system includes a curative, such as a phenolic resin curative, a peroxide curative, a maleimide curative, a hexamethylenediamine urethane curative, a silicon-based curative (including a hydrosilylation curative, a silane-based curative, such as a silane-grafted and then moisture-cured), a metal oxide-based curative (such as ZnO for butyl rubber), a sulfur-based curative, or combinations thereof.

Useful phenolic curing systems are disclosed in U.S. Pat. Nos. 2,972,600, 3,287,440, 5,952,425, and 6,437,030.

In some embodiments, the phenolic resin curing agent comprises a resole resin (resole resin) that can be prepared by condensation of an alkyl substituted phenol or unsubstituted phenol with an aldehyde, such as formaldehyde, in an alkaline medium or by condensation of a difunctional phenolic diol. The alkyl substituent of the alkyl-substituted phenol may have from about 1 to about 10 carbon atoms, such as a dimethylol phenol or a phenolic resin, which is substituted in the para position with an alkyl group having from about 1 to about 10 carbon atoms. In some embodiments, a blend of octylphenol-formaldehyde resin and nonylphenol-formaldehyde resin is employed. The blend comprises from about 25 wt% to about 40 wt% octylphenol-formaldehyde and from about 75 wt% to about 60 wt% nonylphenol-formaldehyde, for example from about 30 wt% to about 35 wt% octylphenol-formaldehyde and from about 70 wt% to about 65 wt% nonylphenol-formaldehyde. In some embodiments, the blend comprises about 33 wt% octylphenol-formaldehyde and about 67 wt% nonylphenol-formaldehyde resin, wherein each of the octylphenol-formaldehyde and nonylphenol-formaldehyde comprises methylol groups. This blend can be dissolved in paraffin oil at approximately 30% solids without phase separation.

Useful phenolic resins are available under the trade name SP-1044, SP-1045(Schenectady International; Schenectady, N.Y.), which may be referred to as alkylphenol-formaldehyde resins.

Examples of phenolic resin curing agents include those defined according to the following general formula:

wherein Q is selected from-CH₂-、-CH₂-O-CH₂-a divalent group of (a); m is 0 or a positive integer from 1 to 20, and R' is an organic group. In some embodiments, Q is a divalent group-CH₂-O-CH₂-, m is 0 or a positive integer from 1 to 10, R' is a radical having less than 20An organic group of carbon atoms. In other embodiments, m is 0 or a positive integer from 1 to 10, and R' is an organic group having from 4 to 12 carbon atoms.

In some embodiments, the phenolic resin is used in combination with a halogen source (e.g., stannous chloride) and a metal oxide or reducing compound (e.g., zinc oxide).

In some embodiments, the phenolic resin may be used in an amount of about 2 to about 6 parts by weight, such as about 3 to about 5 parts by weight, such as about 4 to about 5 parts by weight, per 100 parts by weight of rubber. The complementary amount of stannous chloride may comprise from about 0.5 parts by weight to about 2.0 parts by weight, such as from about 1.0 parts by weight to about 1.5 parts by weight, such as from about 1.2 parts by weight to about 1.3 parts by weight, based on 100 parts by weight of rubber. In combination therewith, about 0.1 to about 6.0 parts by weight, such as about 1.0 to about 5.0 parts by weight, such as about 2.0 to about 4.0 parts by weight of zinc oxide can be used. In some embodiments, the olefin rubber used with the phenolic curative includes diene units derived from 5-ethylidene-2-norbornene.

In some embodiments, useful peroxide curatives include organic peroxides. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, α -bis (t-butylperoxy) diisopropylbenzene, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane (DBPH), 1-di (t-butylperoxy) -3,3, 5-trimethylcyclohexane, n-butyl-4, 4-bis (t-butylperoxy) valerate, benzoyl peroxide, lauroyl peroxide, dilauroyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, and mixtures thereof. In addition, diaryl peroxides, ketone peroxides, peroxydicarbonates, peroxyesters, dialkyl peroxides, hydroperoxides, peroxyketals, and mixtures thereof may be used. Useful peroxides and methods of their use in the dynamic vulcanization of TPV compositions are disclosed in U.S. patent No. 5,656,693.

In some embodiments, a peroxide curative is employed with the coagent. Examples of coagents include triallylcyanurate, triallylisocyanurate, triallylphosphate, sulfur, N-phenyl bismaleimide, zinc diacrylate, zinc dimethacrylate, divinylbenzene, 1, 2-polybutadiene, trimethylolpropane trimethacrylate, butanediol diacrylate, trifunctional acrylic esters, dipentaerythritol pentaacrylate, multifunctional acrylates, delayed cyclohexane dimethanol diacrylate, multifunctional methacrylates, metal salts of acrylic and methacrylic acids, and oximes such as quinone dioxime. To maximize the efficiency of peroxide/coagent crosslinking, mixing and dynamic vulcanization can be performed in a nitrogen atmosphere.

In some embodiments, the silicon-containing cure system may include a silicon hydride compound having at least two Si — H groups. The silicon hydride compounds useful in the practice of the present disclosure include methylhydrogenpolysiloxanes, methylhydrodimethylsiloxane copolymers, alkylmethyl-co-methylhydrogenpolysiloxanes, bis (dimethylsilyl) alkanes, bis (dimethylsilyl) benzenes, and mixtures thereof.

Catalysts useful for hydrosilylation include group VIII transition metals. These metals include palladium, rhodium and platinum, and complexes of these metals. Useful silicon-containing curing agents and curing systems are disclosed in U.S. Pat. No. 5,936,028, U.S. Pat. No. 4,803,244, U.S. Pat. No. 5,672,660, and U.S. Pat. No. 7,951,871.

In some embodiments, the silane-containing compound may be used in an amount of about 0.5 to about 5.0 parts by weight (e.g., about 1.0 to about 4.0 parts by weight, such as about 2.0 to about 3.0 parts by weight) per 100 parts by weight of rubber. The amount of catalyst make-up may include from about 0.5 parts metal to about 20.0 parts metal per million parts by weight of rubber (e.g., from about 1.0 part metal to about 5.0 parts metal, such as from about 1.0 part metal to about 2.0 parts metal). In some embodiments, the olefin rubber used with the hydrosilylation curing agent includes diene units derived from 5-vinyl-2-norbornene.

For example, the phenolic resin may be used in an amount of about 2 parts by weight to about 10 parts by weight (e.g., about 3.5 parts by weight to about 7.5 parts by weight, such as about 5 parts by weight to about 6 parts by weight) based on 100 parts by weight of the rubber. In some embodiments, the phenolic resin may be used in combination with stannous chloride and optionally zinc oxide. Stannous chloride may be used in amounts of about 0.2 to about 10 parts by weight (e.g., about 0.3 to about 5 parts by weight, such as about 0.5 to about 3 parts by weight) based on 100 parts by weight of the rubber. The zinc oxide can be used in an amount of about 0.25 parts by weight to about 5 parts by weight (e.g., about 0.5 parts by weight to about 3 parts by weight, such as about 1 part by weight to about 2 parts by weight) based on 100 parts by weight of the rubber.

Alternatively, in some embodiments, the peroxide may be present in an amount of about 1X 10 parts by weight based on 100 parts by weight of the rubber^-5Molar to about 1X 10^-1Mols, e.g. about 1X 10^-4Molar to about 9X 10^-2Mols, e.g. about 1X 10^-2Molar to about 4X 10^-2Molar amounts are used. The amount may also be expressed as weight per 100 parts by weight of rubber. However, such amount may vary depending on the curing agent used. For example, where 4, 4-bis (t-butylperoxy) diisopropylbenzene is used, the amount used may comprise from about 0.5 parts by weight to about 12 parts by weight, such as from about 1 part by weight to about 6 parts by weight, based on 100 parts by weight of rubber. One skilled in the art will be readily able to determine an adequate or effective amount of coagent that can be used with the peroxide without undue calculation or experimentation. In some embodiments, the amount of coagent employed is similar in moles to the moles of curative employed. The amount of the auxiliary may also be expressed as weight per 100 parts by weight of the rubber. For example, where a triallylcyanurate coagent is used, the amount used may include from about 0.25phr to about 20phr, such as from about 0.5phr to about 10phr, based on 100 parts by weight of rubber.

Slip agent

In certain embodiments, the TPV compositions of the present invention may optionally contain a slip agent in addition to the rubber, thermoplastic resin, processing oil and filler when the crosslinked rubber is cured with a phenolic or peroxide-based curing system. Slip agents may be defined as a class of fillers or additives intended to reduce the coefficient of friction of a TPV composition while also improving abrasion resistance. Examples of slip agents include silicone-based additives (e.g., polysiloxanes), ultra-high molecular weight polyethylene, blends of silicone-based additives (e.g., polysiloxanes) and ultra-high molecular weight polyethylene, molybdenum disulfide, halogenated and non-halogenated compounds based on aliphatic fatty chains, fluorinated polymers, perfluorinated polymers, graphite, and combinations thereof. Slip agents are selected having a molecular weight suitable for use in oil, paste or powder form.

Slip agents useful in TPV compositions include, but are not limited to, fluorinated or perfluorinated polymers, such as Kynar^TM(available from Arkema of King of Prussia, Pa.), Dynamar^TM(available from 3M of Saint Paul, MN), molybdenum disulfide or a compound based on aliphatic fatty chains, whether halogenated or not, or polysiloxanes. In some embodiments, the slip agent may be migrating or non-migrating.

In some embodiments, the polysiloxane comprises a migrating siloxane polymer that is liquid under standard pressure and temperature conditions. Suitable polysiloxanes are high molecular weight, substantially linear Polydimethylsiloxanes (PDMS). In addition, the polysiloxane can have a viscosity at room temperature of about 100 to about 100,000cSt, for example about 1,000 to about 10,000cSt or about 5,000cSt to about 10,000 cSt.

In certain embodiments, the polysiloxane further comprises R groups, which are selected based on the desired curing mechanism of the composition comprising the first polysiloxane. Typically, the curing mechanism is by condensation curing or addition curing, but generally via an addition curing process. For condensation reactions, two or more R groups per molecule should be hydroxyl or hydrolyzable groups, such as alkoxy groups containing up to about 3 carbon atoms. For addition reactions, and in some embodiments, two or more R groups per molecule can be unsaturated organic groups, typically alkenyl or alkynyl groups, for example up to about 8 carbon atoms. One suitable commercially available material that can be used as the first polysiloxane is XIAMETER^TMPMX-200 Silicone fluid (available from Dow Corning of Midland, MI). At a certain pointIn some embodiments, the TPV compositions described herein contain from about 0.2 wt% to about 20 wt%, such as from about 0.5 wt% to about 15 wt% or from about 0.5 wt% to about 10 wt% polysiloxane.

In certain embodiments, the polysiloxane, e.g., polyorganosiloxane, comprises a non-migrating polysiloxane bonded to the thermoplastic material. The polysiloxane is reactively dispersed in the thermoplastic material, which may be any homopolymer or copolymer of ethylene and/or an alpha-olefin such as propylene, 1-butene, 1-hexene, 1-octene, 2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene and mixtures thereof. In one embodiment, the thermoplastic material is a polypropylene homopolymer. Suitable methods for reactively bonding polysiloxanes to organic thermoplastic polymers such as polyolefins are disclosed in international patent publication nos. WO2015/132190 and WO2015/150218, the entire contents of which are incorporated herein by reference for U.S. patent practice.

In some embodiments, the polysiloxane may comprise predominantly D and/or T units and contain some alkenyl functionality, which facilitates reaction with the polymer matrix. There is a covalent bond between the polysiloxane and the polypropylene. In some embodiments, the reaction product of polysiloxane and polypropylene has a number average molecular weight of about 0.2kg/mol to about 100 kg/mol. The number average molecular weight of the reaction product of the polyorganosiloxane and the polymer matrix is at least 1.1 times, such as at least 1.3 times, the number average molecular weight of the base polyorganosiloxane. In some embodiments, the second polyorganosiloxane has a size loading of from about 20 wt% to about 50 wt%.

One example of a slip agent is HMB-0221. HMB-0221 is provided as a granulated concentrate containing the reaction product of an ultra-high molecular weight siloxane polymer reactively dispersed in a polypropylene homopolymer. HMB-0221 is commercially available from Dow Corning of Midland, Mich. In certain embodiments, the TPV compositions described herein contain from about 0.2 wt% to about 20 wt%, such as from about 0.2 wt% to about 15 wt% or from about 0.2 wt% to about 10 wt% of a non-migrating polysiloxane.

Properties of TPV compositions

In some embodiments, TPV compositions useful as polymeric outer jackets in flexible pipes include one or more of the following properties.

In some embodiments, the TPV composition exhibits carbon dioxide (CO) of about 30 barrer or greater, such as about 40 barrer or greater, such as about 50 barrer or greater₂) Permeability (at 60 ℃).

In some embodiments, the TPV composition exhibits an attrition loss of 120mg or less, such as about 90mg or less, such as about 70mg or less, after 1000 cycles.

In some embodiments, the TPV composition exhibits a tensile strength at yield of about 7MPa, such as about 8MPa, such as about 9MPa, for example about 10 MPa.

In some embodiments, the TPV composition exhibits a young's modulus of about 200MPa, such as about 250MPa, for example about 300 MPa.

In some embodiments, the TPV compositions exhibit a tensile strain at yield of about 7% or greater, such as about 9% or greater, such as about 11% or greater, such as about 13% or greater.

In some embodiments, a TPV composition exhibits a thermal conductivity of about 0.30W/m-K or less, such as about 0.25W/m-K or less, such as about 0.20W/m-K or less.

In some embodiments, the TPV compositions exhibit a coefficient of friction (static) of about 0.8 or less, such as about 0.7 or less, for example about 0.65 or less.

In some embodiments, the TPV compositions exhibit a coefficient of friction (dynamic) of about 0.8 or less, such as about 0.7 or less, for example about 0.65 or less.

Abrasion loss was measured according to ASTM D4060-14, where the method was performed on both sides of a 4 "round sample cut from a compression molded plaque. The wheel H-22 was used with a weight of 1kg and 1000 revolutions. The wheels were surface conditioned prior to testing each sample (or after each 1000 cycles).

Thermal conductivity was measured according to ASTM C518-17, where the method was performed on a TA FOX50-190 instrument. A compression molded plastic panel was die cut into 2 inch diameter disc samples. The samples were measured at 25 ℃. Each material was measured in duplicate.

Young's modulus, tensile strength at yield and tensile strain at yield were measured according to ISO 37. The samples were tested on compression molded plastic plates at 23 ℃ using a crosshead speed of 2 in/min.

In some embodiments, the TPV composition has a hardness of about 70 shore a to about 60 shore D, such as about 40 shore a to about 80 shore a, such as about 50 shore a to about 70 shore a, such as about 55 shore a to about 70 shore a. Shore A hardness was measured according to ASTM D2240 (15 second delay) using a Zwick automatic durometer. Shore D hardness was measured according to ASTM D2240 using a Zwick automatic durometer.

Measuring CO according to ISO 2782-1:2012(E)₂Gas permeability, where the thickness of each sample was measured at 5 points evenly distributed over the sample permeation area. The compression molded test specimens were bonded to the holder with a suitable adhesive that cured at the test temperature. The chamber was evacuated by pulling a vacuum on both sides of the film. With CO at 60 deg.C₂The gas exposes the high pressure side of the membrane to the test pressure. The test pressure and temperature were maintained during the test, and the temperature and pressure were recorded periodically. The sample was placed under pressure until steady state permeation was reached (3-5 times time lag (. tau.)).

Experiment of

Table 2 lists the ingredients and amounts (parts per 100 parts rubber, phr) used in each sample, and the results of the physical tests of the invention and comparative examples, CO, performed on each sample are provided in Table 2₂Permeability, wear loss, and other mechanical and physical properties. Those samples corresponding to the present disclosure are denoted by "ex." and those for comparison are denoted by the letter "C". Comparative example 1(C1), example 1(Ex1) and example 2(Ex2) were prepared to include 75phr of oil extended EPDM (Vistalon)^TM3666) The TPV composition of (1). Comparative example 2(C2), comparative example 3(C3), example 3(Ex3), example 4(Ex4), example 5(Ex5) and example 6(Ex6) are compositions comprising non-oil extended EPDM (Vistalon)^TM9600) The TPV composition of (1). All comparative samples and runs except C3, Ex5 and Ex6The samples of examples all contain a silicone slip agent (DOW-Corning)^TMHMB-0221 masterbatch). The examples and comparative examples were prepared as follows.

Sample preparation using a Brabender mixer

The preparation of the thermoplastic vulcanizates was carried out under nitrogen in a laboratory Brabender-Plasticorr (model EPL-V5502). The mixing bowl has a capacity of 85ml, wherein a cam-type rotor is used. The plastic is first added to a mixing bowl, which is heated to 180 ℃ at a rotor speed of 100 rpm. After the plastic has melted (2 minutes), the mixer is filled with rubber, inorganic additives and processing oil. After the molten polymer blend is homogenized (stable torque is obtained in 3-4 minutes), the curing agent is added to the mixture, which may result in an increase in motor torque.

Mixing was continued for an additional 4 minutes after which the molten TPV was removed from the mixer and pressed while hot into sheets between Teflon plates, which were cooled, cut and compression molded at about 400 ° F. Compression molding was performed using a Wabash press (model 12-1212-2TMB) with cavity sizes of 4.5 "by 0.06" in a 4-cavity Teflon coated mold. The material in the mold was initially preheated at about 400F (204.4 c) on a 4 "ram at a pressure of 2 tons for about 2-2.5 minutes, then the pressure was raised to 10 tons and heating continued for about 2-2.5 minutes. The mold platen was then cooled with water and the mold pressure released after cooling (140 ° F). Dog-bone type samples can be cut from the molded (aged 24 hours at room temperature) sheet for tensile testing (0.16 "width, 1.1" test length (excluding flaps at the ends)).

SnCl₂(MB) is an anhydrous stannous chloride polypropylene masterbatch. SnCl₂MB contains 45 wt% stannous chloride and 55 wt% polypropylene having an MFR (ASTM D1238, 230 ℃ C. and 2.16kg weight) of 0.8g/10 min.

Zinc oxide (ZnO) is Kadox 911.

Phenolic curing agents (phenolic resin in oil, 30 wt% phenolic resin and 70 wt% oil) are resole type resins available from Schenectady International.

The filler is Icep^TMK glueSoil (available from Burgess).

The elastomeric (rubber) terpolymer is EPDM (Vistalon 3666)^TMOr Vistalon9600^TM) And the molecular properties of each EPDM are as provided above. Polypropylene is under the trade name PP5341^TM(ExxonMobil) obtained from polypropylene.

The oils of samples C1, C2, Ex1 and Ex2 are under the tradename Paramount6001R^TMParaffin oil obtained from Chevron Phillips, whereas the oils of samples C3, Ex5 and Ex6 are available under the tradename Plasthall^TM100 (Hallstar).

Abrasion loss was measured according to ASTM D4060-14, where the method was performed on both sides of a 4 "round sample cut from a compression molded plaque. The wheel H-22 was used with a weight of 1kg and 1000 revolutions. The wheels were surface conditioned prior to testing each sample (or after each 1000 cycles).

Thermal conductivity was measured according to ASTM C518-17, where the method was performed on a TA FOX50-190 instrument. A compression molded plastic panel was die cut into 2 inch diameter disc samples. The samples were measured at 25 ℃. Each material was measured in duplicate.

Young's modulus, tensile strength at yield and tensile strain at yield were measured according to ISO 37. The samples were tested at 23 ℃ using a crosshead speed of 2 in/min.

Measuring CO according to ISO 2782-1:2012(E)₂Gas permeability, where the thickness of each sample was measured at 5 points evenly distributed over the sample permeation area. The compression molded test specimens were bonded to the holder with a suitable adhesive that cured at the test temperature. The chamber was evacuated by pulling a vacuum on both sides of the film. With CO at 60 deg.C₂The gas exposes the high pressure side of the membrane to the test pressure. The test pressure and temperature were maintained during the test, and the temperature and pressure were recorded periodically. The sample was placed under pressure until steady state permeation was reached (3-5 times time lag (. tau.)).

The static and dynamic coefficients of friction were measured on compression moulded plaques according to ISO 8295: 1995. The coefficient of friction against the glass slide was measured on an AFT170500D machine at a speed of 100mm/min and a residence time of 15 seconds.

POSS studied included octamethyl POSS [ (CH)₃SiO_1.5)₈]And octaisobutyl POSS [ ((CH)₃)₂CHCH₂SiO_1.5)₈](all available from Hybrid Plastics Inc.) and exhibit excellent compatibility with polyolefins while increasing the total free volume of the TPV matrix. The data in table 2 show that when the TPV composition comprises polyhedral oligomeric silsesquioxanes, the permeability is greatly enhanced at elevated temperatures without compromising mechanical properties. For example, oil-extended EPDM CO₂Permeability improvement of greater than about 15%, CO of non-oil extended EPDM₂The permeability increase is greater than about 30%. The tensile properties and thermal conductivity were consistent from sample to sample. In addition, the coefficient of friction is reduced by the inclusion of POSS in the TPV compositions.

Surprisingly, unlike other plasticizers that increase the free volume of a TPV composition and reduce the tensile properties of a TPV composition, it was unexpectedly observed that octamethyl POSS and octaisobutyl POSS contribute to increased permeability while maintaining the tensile properties of a TPV composition. Furthermore, the coefficient of friction is surprisingly reduced by the inclusion of POSS in the TPV composition, which allows for similar or improved overall abrasion resistance. Finally, it has been surprisingly found that POSS acts as a processing aid when used as part of a TPV composition, as typical inorganic nanofillers generally increase viscosity and reduce the extrudability of the material.

Thus, the TPV composition exhibits excellent gas permeability and has excellent mechanical properties. The data indicate that the TPV compositions disclosed herein are advantageously useful materials for layers in flexible pipe, such as the outer and intermediate jackets, particularly when enhanced permeability is desired.

All documents described herein, including any priority documents and/or test procedures, are incorporated by reference in their entirety for all jurisdictions in which the present invention is not inconsistent with this disclosure. In addition, all documents and references (including test procedures, publications, patents, journal articles, and the like) cited herein are incorporated by reference in their entirety, provided that the disclosure is not inconsistent with the description of this disclosure. It will be apparent from the foregoing summary and the specific embodiments that, while forms of embodiments have been illustrated and described, various modifications can be made without departing from the spirit and scope of the embodiments. Accordingly, it is not intended that the disclosure be limited thereby. Likewise, the term "comprising" is considered synonymous with the term "including". Likewise, whenever a composition, element, or group of elements precedes the transitional term "comprising," it is understood that it is also contemplated to have the transitional term "consisting essentially of," "consisting of," or "being" in front of the listed composition, element, or group of elements, and vice versa, for example, the term "comprising," "consisting essentially of," or "consisting of" also includes the product of a combination of elements listed after that term.

For the sake of brevity, only certain numerical ranges are explicitly disclosed herein. However, a certain lower limit may be combined with any other upper limit to define a range not explicitly recited, similarly, a certain lower limit may be combined with any other lower limit to define a range not explicitly recited, and similarly, a certain upper limit may also be combined with any upper limit to define a range not explicitly recited. In addition, each point or individual value between two endpoints is included in a range, even if not explicitly recited. Thus, each point or individual value can serve as a lower or upper limit on its own with other points or individual values or other lower or upper limits in combination to define a range not explicitly recited.