阅读说明：本技术 用于改进刚性-韧性平衡的硅酮增强的乙烯/α-烯烃互聚物 (Silicone reinforced ethylene/alpha-olefin interpolymers for improved stiffness-toughness balance ) 是由 吴高翔 J·C·芒罗 于 2019-08-27 设计创作，主要内容包括：一种组合物,其包括以下：A)乙烯/α-烯烃互聚物,其具有0.854到0.890g/cc的密度和0.2到30g/10min的熔融指数(I2)；B)硅酮油,其具有在25℃下≤5000cSt的粘度；和其中组分B的存在量为以组分A和B的总重量的重量计1.0wt％到5.0wt％。(A composition comprising the following: A) an ethylene/α -olefin interpolymer having a density from 0.854 to 0.890g/cc and a melt index (I2) from 0.2 to 30g/10 min; B) a silicone oil having a viscosity of less than or equal to 5000cSt at 25 ℃; and wherein component B is present in an amount of 1.0 wt% to 5.0 wt% based on the weight of the combined weights of components a and B.)

1. A composition, comprising:

A) an ethylene/α -olefin interpolymer having a density from 0.854 to 0.890g/cc and a melt index (I2) from 0.2 to 30g/10 min;

B) a silicone oil having a viscosity of less than or equal to 5000cSt at 25 ℃; and

wherein component B is present in an amount of 1.0 wt% to 5.0 wt% based on the weight of the combined weights of components A and B.

2. The composition of any of the preceding claims wherein the ethylene/a-olefin interpolymer of component a has a density from 0.860 to 0.880 g/cc.

3. The composition of any of the preceding claims, wherein the ethylene/a-olefin interpolymer of component a has a melt index (I2) from 0.5 to 10g/10 min.

4. The composition of any of the preceding claims, further comprising a propylene-based polymer.

5. The composition of claim 4, wherein the propylene-based polymer has a Melt Flow Rate (MFR) of from 1 to 120g/10 min.

6. The composition of claim 4 or 5, wherein the propylene-based polymer has a density from 0.890g/cc to 0.910 g/cc.

7. The composition of any of the preceding claims, wherein the composition does not include a peroxide curative.

8. The composition of any one of the preceding claims, wherein the composition further comprises talc.

9. The composition of any of the preceding claims, wherein the composition does not comprise a hydrocarbon oil.

10. The composition of any of the preceding claims, wherein the composition has a flexural modulus (1% secant) of 100 to 250 kpsi.

11. The composition of any one of the preceding claims, wherein the composition has a ph of 40 to 55kJ/m at 10 ℃²Izod Strength (Izod Strength).

12. The composition of any one of the preceding claims, wherein the composition has 30 to 50kJ/m at 0 ℃²The Izod strength of (2).

13. The composition of any one of the preceding claims, wherein the composition has 8.0 to 20kJ/m at-20 ℃²The Izod strength of (2).

14. The composition of any one of the preceding claims, wherein the composition has a ph at-10 ℃ of 15 to 25kJ/m²The Izod strength of (2).

15. An article comprising at least one component formed from the composition of any of the preceding claims.

Background

Ethylene/alpha-olefin elastomers have been used for decades as impact modifiers for polypropylene, particularly for talc filled polypropylene compositions commonly referred to as TPO compositions. TPO compositions are ubiquitous in the automotive industry, where they are used to make interior and exterior automotive parts, such as bumpers, inner door panels, air bag covers, and many other components. There is a need for elastomeric compositions to further improve the low temperature impact properties and melt flow of TPO compositions. Currently, lower density and higher melt index elastomers have been developed for this purpose; however, such elastomers typically reduce the rigidity of the TPO and are difficult to maintain in a free-flowing pellet form due to increased viscosity and tendency to plug or agglomerate during transport or storage, especially at elevated temperatures. Significant reduction in processing costs of the TPO compound due to the ethylene/alpha-olefin elastomer in the form of free-flowing pellets; there is a need for novel TPO compositions containing relatively low density and relatively low melt index elastomers with improved low temperature impact properties (toughness) and melt flow. Elastomeric resins and formulations are described in the following references: U.S. patent nos. 4535113, 5078085, 5585420, 5639810, 5902854, 5925703, 6417271, 6136937, 9023935, 9714337; and U.S. publication nos. 2007/0244234, 2008/0093768, 2010/676422. Other references include U.S. patent nos. 6080489, 6569931, and 9243140.

Heretofore, in TPO applications, silicone-based materials, particularly ultra high molecular weight Polydimethylsiloxane (PDMS) masterbatches, have been used to improve scratch resistance of TPO compositions. However, such formulations incorporating PDMS/silicone do not improve other physical properties of the TPO composition, such as stiffness-toughness balance and melt flow. As discussed, there is a need for TPO compositions having an improved balance of low temperature impact properties (toughness), melt flow and rigidity. This need has been met by the following invention.

Disclosure of Invention

A composition, comprising:

A) an ethylene/α -olefin interpolymer having a density from 0.854 to 0.890g/cc and a melt index (I2) from 0.2 to 30g/10 min;

B) a silicone oil having a viscosity of less than or equal to 5000cSt at 25 ℃; and

wherein component B is present in an amount of 1.0 wt% to 5.0 wt% based on the weight of the combined weights of components A and B.

Detailed Description

As described herein, the compositions have been found to provide excellent low temperature impact (toughness), excellent stiffness (flexural modulus), and improved melt flow (melt flow rate) in TPO applications. Such compositions have excellent stiffness and low temperature toughness, while at the same time significantly increasing the melt flow rate to maintain good processability.

As discussed above, there is provided a composition comprising:

A) an ethylene/α -olefin interpolymer having from 0.854 to 0.890g/cc, or from 0.855g/cc to 0.885g/cc, or from 0.860g/cc to 0.880g/cc, or from 0.865g/cc to 0.875g/cc (1g/cc ═ 1 g/cm-³) And a melt index (I2) of 0.2 to 30g/10min, or 0.3 to 20g/10min, or 0.4 to 10g/10min, or 0.5 to 5.0g/10min, or 0.5 to 2.0g/10 min;

B) a silicone oil having a viscosity of less than or equal to 5000cSt, or less than or equal to 4000cSt, or less than or equal to 3000cSt, or less than or equal to 2000cSt, or less than or equal to 1000cSt, or less than or equal to 500cSt at 25 ℃; and

wherein component B is present in an amount of 1.0 wt% to 5.0 wt%, or 1.0 wt% to 4.5 wt%, or 1.0 wt% to 4.0 wt%, or 1.0 wt% to 3.5 wt%, or 1.0 wt% to 3.0 wt%, based on the weight of the total of components A and B.

The compositions of the present invention may comprise a combination of two or more embodiments described herein. Component a may comprise a combination of two or more embodiments described herein. Component B may comprise a combination of two or more embodiments described herein.

In one embodiment or combination of embodiments described herein, the silicone oil has a viscosity of ≥ 20cSt, or ≥ 30cSt, or ≥ 40cSt, or ≥ 50cSt, or ≥ 60cSt, or ≥ 70cSt, or ≥ 80cSt, or ≥ 90cSt, or ≥ 100cSt and ≤ 5000cSt, or ≤ 4500cSt, or ≤ 4000cSt, or ≤ 3500cSt, or ≤ 3000cSt, or ≤ 2500cSt, or ≤ 2000cSt at 25 ℃.

In one embodiment or combination of embodiments described herein, the silicone oil has a viscosity of 50 to 5000cSt at 25 ℃, 60 to 4000cSt at 25 ℃, or 70 to 3000cSt at 25 ℃, or 80 to 2000cSt at 25 ℃, or 90 to 1000cSt at 25 ℃, or 100 to 500cSt at 25 ℃.

In one embodiment or combination of embodiments described herein, the weight ratio of component a to component B is from 19 to 99, or from 24 to 76, or from 27 to 62, or from 32 to 49.

In one or a combination of embodiments described herein, the ethylene/a-olefin interpolymer of component a is in the form of pellets.

In one embodiment or combination of embodiments described herein, the ethylene/a-olefin interpolymer of component a is an ethylene/a-olefin copolymer. In another embodiment, the alpha-olefin is a C3 to C20 alpha-olefin, and further is a C3 to C10 alpha-olefin.

In one embodiment or combination of embodiments described herein, the ethylene/a-olefin interpolymer of component a is an ethylene/a-olefin/diene interpolymer, and further EPDM, and the diene is further ENB.

In one embodiment or combination of embodiments described herein, the ethylene/a-olefin interpolymer of component a is an ethylene/a-olefin/diene interpolymer, and further EPDM, and the diene is further ENB. In one embodiment or combination of embodiments described herein, the ethylene/α -olefin/diene interpolymer has a "peak area% (21.3 to 22.0 ppm)" of 3.0% or more, or 4.0% or more, or 5.0% or more, or 6.0% or more, or 7.0% or more, or 8.0% or more, or 9.0% or more, or 10% or more, or 11% or more, or 12% or more, or 13% or more, or 14% or more, or 15% or more, or 16% or more, or 17% or more, or 18% or more, or 19% or more, or 20% as determined by 13C NMR (propylene stereoisomeric tagging) as described herein. In one embodiment or combination of embodiments described herein, the ethylene/α -olefin/diene interpolymer has a "peak area% (21.3 to 22.0 ppm)" of ≦ 40%, or ≦ 35%, or ≦ 30%, as determined by 13C NMR as described herein.

In one embodiment or combination of embodiments described herein, component A has a density of 0.890 or less, or 0.888 or less, or 0.886 or less, or 0.884 or less, or 0.882 or less, or 0.880 or less, or 0.878 or less, or 0.876 or less, or 0.874g/cc or less. In one embodiment or combination of embodiments described herein, the at least one ethylene/α -olefin interpolymer of component A has ≧ 0.854gOr not less than 0.862, or not less than 0.864g/cc, or not less than 0.866, or not less than 0.868g/cc (1cc 1 cm)³) The density of (c).

In one embodiment or combination of embodiments described herein, the ethylene/a-olefin interpolymer of component a has from 0.854 to 0.900g/cc, or from 0.862g/cc to 0.890g/cc, or from 0.865g/cc to 0.885g/cc, or from 0.865g/cc to 0.875g/cc (1g/cc ═ 1 g/cm:)³) The density of (c).

In one embodiment or combination of embodiments described herein, the ethylene/α -olefin interpolymer of component a has a melt index (I2) from 0.2 to 30g/10min, or from 0.3 to 20g/10min, or from 0.4 to 10g/10min, or from 0.5 to 2.0g/10 min.

In one embodiment or combination of embodiments described herein, component A has a number average molecular weight (Mn (conv)) of 10,000 or more, or 20,000 or more, or 30,000 or more, or 40,000 or more, or 45,000g/mol or more. In one embodiment or combination of embodiments described herein, the at least one ethylene/α -olefin interpolymer of component A has a number average molecular weight (Mn) of 150,000 or less, or 120,000 or less, or 100,000 or less, or 90,000 or less, or 80,000g/mol or less.

In one embodiment or combination of embodiments described herein, component A has a weight average molecular weight (Mw (conv)) of 80,000 or more, or 85,000 or more, or 90,000 or more, or 95,000 or more, or 100,000 or more g/mol. In one embodiment or combination of embodiments described herein, the at least one ethylene/α -olefin interpolymer of component A has a number average molecular weight (Mw) of 300,000 or less, or 250,000 or less, or 200,000 or less, or 150,000g/mol or less.

In one embodiment or combination of embodiments described herein, component A has a molecular weight distribution (Mw (conv)/Mn (conv)) of 1.2 or more, or 1.5 or more, or 1.8 or more, or 2.0 or more, or 2.2 or more, or 2.5 or more. In one embodiment or combination of embodiments described herein, component A has a molecular weight distribution (Mw (conv)/Mn (conv)) of 3.5 or less, or 3.2 or less, 3.0 or less, or 2.8 or less.

In one embodiment or combination of embodiments described herein, component A has a tan delta (0.1rad/sec, 190 ℃) value of 30 or less, or 25 or less, or 20 or less, or 15 or less, or 12 or less and >0, or 1.0 or more, or 3.0 or more, or 5.0 or more, or 8.0 or more.

In one embodiment or combination of embodiments described herein, component A has a viscosity (V0.1 rad/sec, 190 ℃) of 1000 or more, 2000 or more, 4000 or more, 6000 or more, 8000 or more. In one embodiment or combination of embodiments described herein, component A has a viscosity (V0.1 rad/sec, 190 ℃) of 100,000 or 90,000 or 80,000 or 70,000 or 60,000 or 50,000 or 40,000 or 30,000 or 20,000 or 10,000.

In one embodiment or combination of embodiments described herein, component a has a viscosity ratio (V0.1 rad/sec, 190 ℃/V100 rad/sec, 190 ℃) of 1.0 to 30, or 2.0 to 20, or 3.0 to 15, or 4.0 to 10.

In one embodiment or combination of embodiments described herein, the composition comprises ≥ 10 wt.%, or ≥ 12 wt.%, or ≥ 14 wt.%, or ≥ 16 wt.%, or ≥ 18 wt.%, or ≥ 20 wt.% of the sum of component A and component B, by weight of the composition.

In one embodiment or combination of embodiments described herein, the composition includes 50 wt% or less, or 45 wt% or less, or 40 wt% or less, or 35 wt% or less, or 30 wt% or less, or 25 wt% or less of the sum of component A and component B, based on the weight of the composition.

In one embodiment or combination of embodiments described herein, the composition further comprises a propylene-based polymer.

In one embodiment or combination of embodiments described herein, the propylene-based polymer has a Melt Flow Rate (MFR) of 1.0 to 120g/10min, or 2.0 to 100g/10min, or 5.0 to 80g/10min, or 10 to 60g/10min, or 25 to 50g/10min, or 30 to 40g/10 min.

In one embodiment or combination of embodiments described herein, the propylene-based polymer has from 0.850 to 1.00g/cc, or from 0.860 to 0.980g/cc, or from 0.870 to 0.970g/cc, or from 0.880 to 0.960g/cc (1cc 1 cm)³) The density of (c).

In one embodiment or combination of embodiments described herein, the propylene-based polymer has a density of from 0.885 to 0.915g/cc, or from 0.890 to 0.910g/cc, or from 0.895 to 0.905 g/cc.

In one embodiment or combination of embodiments described herein, the propylene-based polymer has a MWD of 1.0 to 50, or 2.0 to 30, or 3.0 to 15, or 3.0 to 10, or 3.0 to 5.0.

In one embodiment or combination of embodiments described herein, the propylene-based polymer is a polypropylene homopolymer.

In one embodiment or combination of embodiments described herein, the propylene-based polymer is an impact co-polypropylene.

In one embodiment or combination of embodiments described herein, the propylene-based polymer is an impact co-polypropylene comprising from 5 to 20 wt%, or from 8 to 18 wt%, or from 10 to 15 wt%, based on the total weight of the propylene-based polymer, of a dispersed ethylene-propylene or propylene ethylene rubber phase, as determined by the xylene extraction process described below.

In one embodiment or combination of embodiments described herein, the propylene-based polymer is a propylene/a-olefin interpolymer, and further a propylene/a-olefin copolymer.

In one embodiment or combination of embodiments described herein, the propylene-based polymer is a propylene/ethylene interpolymer, and further a propylene/ethylene copolymer.

In one or a combination of embodiments described herein, the propylene-based polymer is present in an amount of 50 wt% or more, or 55 wt% or more, or 60 wt% or more, based on the weight of the composition.

In one or a combination of embodiments described herein, the propylene-based polymer is present in an amount of 90 wt% or less, or 85 wt% or less, or 70 wt% or less, based on the weight of the composition.

In one embodiment or combination of embodiments described herein, the composition comprises the sum of component A, component B, and propylene-based polymer at 70 wt% or more, or 75 wt% or more, or 80 wt% or more, or 85 wt% or more, based on the weight of the composition.

In one embodiment or combination of embodiments described herein, the composition comprises 98 wt% or less, or 95 wt% or less, or 90 wt% or less of the sum of component A, component B, and propylene-based polymer, based on the weight of the composition.

In one embodiment or combination of embodiments described herein, component a is present in an amount from 12 wt% to 50 wt%, or from 14 wt% to 40 wt%, or from 16 wt% to 30 wt%, or from 18 wt% to 25 wt%, by weight of the composition.

In one embodiment or combination of embodiments described herein, the weight ratio of propylene-based polymer to component a is from 1.0 to 5.0, or from 1.5 to 5.0, or from 2.0 to 5.0, or from 2.5 to 5.0.

In one embodiment or combination of embodiments described herein, the weight ratio of propylene-based polymer to component a is from 1.0 to 5.0, or from 1.2 to 4.5, or from 1.4 to 4.0, or from 1.6 to 3.5.

In one embodiment or combination of embodiments described herein, the composition further includes ≦ 0.100 wt% curing agent, or ≦ 0.050 wt%, or ≦ 0.020 wt%, or ≦ 0.010 wt%, or ≦ 0.005 wt% curing agent, based on the weight of the composition. In one embodiment or combination of embodiments described herein, the composition does not include a curing agent. Illustrative curing agents include sulfur-containing compounds such as elemental sulfur, 4' -dithiodimorpholine, bisthiocarboxamide disulfides and polysulfides, alkylphenol disulfides and 2-morpholino-dithiobenzothiazole; peroxides such as di-tert-butyl peroxide, tert-butylcumyl peroxide, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, di (tert-butylperoxyisopropyl) benzene, tert-butyl peroxybenzoate and 1, 1-di (tert-butylperoxy) -3,3, 5-trimethylcyclohexane; an azo compound; silanes, such as vinyltriethoxysilane or vinyltrimethoxysilane; dinitroso compounds, such as p-quinone-dioxime and p, p' -dibenzoyl quinone-dioxime; phenolic resins containing methylol or halomethyl functional groups.

In one embodiment or combination of embodiments described herein, the composition further includes ≦ 0.100 wt% peroxide curative, or ≦ 0.050 wt%, or ≦ 0.020 wt%, or ≦ 0.010 wt%, or ≦ 0.005 wt% based on the weight of the composition. In another embodiment, the composition does not include a peroxide curative.

In one embodiment or combination of embodiments described herein, the composition further includes ≥ 0.1 wt.%, or ≥ 0.2 wt.%, or ≥ 0.5 wt.%, or ≥ 1.0 wt.%, or ≥ 2.0 wt.%, or ≥ 3.0 wt.%, or ≥ 4.0 wt.%, or ≥ 5.0 wt.%, or ≥ 0.6 wt.%, or ≥ 7.0 wt.%, or ≥ 8.0 wt.%, or ≥ 9.0 wt.%, or ≥ 10 wt.% inorganic filler (e.g. talc), based on the weight of the composition. In one embodiment or combination of embodiments described herein, the composition further includes ≦ 40 wt% inorganic filler (e.g., talc), or ≦ 35 wt%, or ≦ 30 wt%, or ≦ 25 wt%, or ≦ 20 wt% inorganic filler, based on the weight of the composition.

In one embodiment or combination of embodiments described herein, the composition comprises from 5 wt% to 30 wt% or from 10 wt% to 25 wt% of a filler, such as talc, by weight of the composition. Other fillers include the following: calcium carbonate, clay, carbon black, silica, titanium dioxide, diatomaceous earth.

In one embodiment or combination of embodiments described herein, the weight ratio of filler to component a is from 0.80 to 1.20, or from 0.85 to 1.15, or from 0.90 to 1.10, or from 0.95 to 105. In another embodiment, the filler is selected from talc, calcium carbonate, clay, carbon black, silica, titanium dioxide, or diatomaceous earth, and is further selected from talc, calcium carbonate, carbon black, silica, or titanium dioxide, and is further selected from talc, carbon black, or silica. In one embodiment, the filler is talc.

In one embodiment or combination of embodiments described herein, the composition comprises carbon black. In another embodiment, the carbon black is present in an amount of 5.0 wt% to 50 wt%, based on the weight of the composition.

In one embodiment or combination of embodiments described herein, the composition has a flexural modulus (1% secant) of 100 to 250kpsi, or 120 to 250kpsi, or 140 to 250kpsi, or 160 to 250kpsi, or 180 to 250 kpsi.

In one embodiment or combination of embodiments described herein, the composition has a pH of 40 to 60kJ/m at 10 ℃²Or 40 to 55kJ/m²Izod Strength (Izod Strength).

In one embodiment or combination of embodiments described herein, the composition has a pH of 30 to 50kJ/m at 0 ℃²The Izod strength of (2).

In one embodiment or combination of embodiments described herein, the composition has a pH of 15 to 25kJ/m at-10 ℃²The Izod strength of (2).

In one embodiment or combination of embodiments described herein, the composition has 8.0 to 20kJ/m at-20 ℃²The Izod strength of (2).

In one embodiment or combination of embodiments described herein, the composition has a Melt Flow Rate (MFR) of 10 to 20g/10min or 12 to 18g/10 min.

In one embodiment or combination of embodiments described herein, the composition further comprises ≥ 0.1 wt.%, or ≥ 0.2 wt.%, or ≥ 0.5 wt.% by weight of the composition, of one or more antioxidants. In one embodiment or combination of embodiments described herein, the composition further comprises 2.0 wt.% or less, or 1.5 wt.% or less, or 1.0 wt.% or less of one or more antioxidants, based on the weight of the composition.

In one embodiment or combination of embodiments described herein, the composition includes ≦ 1.00 wt%, or ≦ 0.50 wt%, or ≦ 0.10 wt%, or ≦ 0.05 wt% hydrocarbon oil. In another embodiment, the composition does not include a hydrocarbon oil.

In one embodiment or combination of embodiments described herein, the composition includes ≦ 1.00 wt% styrene-based polymer (including a majority amount of polymerized styrene, based on the weight of the polymer), or ≦ 0.50 wt%, or ≦ 0.10 wt%, or ≦ 0.05 wt%. In another embodiment, the composition does not include a styrene-based polymer. In one embodiment or combination of embodiments described herein, the composition includes ≦ 1.00 wt% styrene block copolymer rubber, or ≦ 0.50 wt%, or ≦ 0.10 wt%, or ≦ 0.05 wt%. In another embodiment, the composition does not include a styrenic block copolymer rubber. In one embodiment or combination of embodiments described herein, the composition includes ≦ 1.00 wt% styrene-butadiene rubber, or ≦ 0.50 wt%, or ≦ 0.10 wt%, or ≦ 0.05 wt%. In another embodiment, the composition does not include styrene-butadiene rubber.

In one embodiment or combination of embodiments described herein, the composition includes 1.00 wt.% or less, or 0.50 wt.% or less, or 0.10 wt.% or less, or 0.05 wt.% or less polybutadiene. In another embodiment, the composition does not include polybutadiene.

In one embodiment or combination of embodiments described herein, the composition includes ≦ 1.00 wt% polyisoprene, or ≦ 0.50 wt%, or ≦ 0.10 wt%, or ≦ 0.05 wt%. In another embodiment, the composition does not include polyisoprene.

In one embodiment or combination of embodiments described herein, the composition includes ≦ 1.00 wt% or ≦ 0.50 wt% or ≦ 0.10 wt% or ≦ 0.05 wt% polymer including fluoro group. In another embodiment, the composition does not include a polymer comprising a fluoro group.

In one embodiment or combination of embodiments described herein, the composition includes ≦ 1.00 wt%, or ≦ 0.50 wt%, or ≦ 0.10 wt%, or ≦ 0.05 wt% perfluoroalkyl compound (compound including at least one perfluoroalkyl group). In another embodiment, the composition does not include a perfluoroalkyl compound.

Also provided is an article comprising at least one component formed from the composition of one or a combination of the embodiments described herein.

In one or a combination of embodiments described herein, the article is selected from the group consisting of: injection molded parts, foams, automotive parts, building and construction materials, and shoe components. In one or a combination of embodiments described herein, the article is selected from the group consisting of: bumper panels, door facings, instrument panels, airbag covers, and fenders. The articles of the present invention may comprise a combination of two or more of the embodiments described herein.

Additive and application

The composition may include one or more additives such as fillers, antioxidants, flame retardants, blowing agents, colorants or pigments, and thermoplastic polymers and other additives. Other additives include, but are not limited to, fillers, flame retardants, colorants or pigments, thermoplastic polymers, and combinations thereof. Such additives may be employed in the desired amounts to achieve their desired effects. Suitable fillers include, but are not limited to, clay, talc, or carbon black. In one embodiment or combination of embodiments described herein, the composition further comprises at least one antioxidant. Illustrative antioxidants include, but are not limited to, peroxy and alkoxy radical scavengers (amines and hindered phenols), hydroperoxide decomposers, and synergists.

In one embodiment or combination of embodiments described herein, the composition further comprises a thermoplastic polymer. Illustrative polymers include, but are not limited to, propylene-based polymers, ethylene-based polymers, and olefin multi-block interpolymers. Suitable ethylene-based polymers include, but are not limited to, High Density Polyethylene (HDPE), Linear Low Density Polyethylene (LLDPE), Very Low Density Polyethylene (VLDPE), Ultra Low Density Polyethylene (ULDPE), homogeneously branched linear ethylene polymers, and homogeneously branched substantially linear ethylene polymers, which are homogeneously branched long chain branched ethylene polymers.

The compositions of the present invention may be used to prepare a variety of articles or component parts or portions thereof. The compositions of the present invention can be converted into the final article by any of a number of conventional methods and equipment. Illustrative methods include, but are not limited to, injection molding, extrusion, calendering, compression molding, and other typical thermoset material forming methods. Articles include, but are not limited to, sheets, foams, molded articles, and extruded parts. Other articles include automotive parts, bumpers, fascia, door trim, airbag covers, fenders, tailgate and liftgates, computer parts, building materials, and footwear components. A skilled artisan can easily add this list. The composition is particularly suitable for injection-molded parts of automobiles.

Definition of

Unless stated to the contrary, implied from the context, or customary in the art, all parts and percentages are by weight and all test methods are current as of the filing date of this disclosure. As used herein, the term "composition" and similar terms mean a mixture or blend of two or more materials that make up the composition as well as reaction products and decomposition products formed from the materials of the composition.

The transitional words (or terms) "comprising", "including", "having" and their derivatives are not intended to exclude the presence of any other component, step or procedure, whether or not specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term "comprising" may include any other additive, adjuvant or compound (whether polymeric or of another type) unless stated to the contrary. In contrast, the term "consisting essentially of … …" excludes from any subsequently listed range any other components, steps or procedures other than those not important to operation. The term "consisting of … …" excludes any component, step, or procedure not specifically recited or recited.

As used herein, the term "polymer" refers to a polymeric compound prepared by polymerizing monomers of the same or different type. The generic term polymer thus embraces the term homopolymer (employed to refer to polymers prepared from only one type of monomer, with the understanding that trace amounts of impurities can be incorporated into the polymer structure) and the term interpolymer as defined below. Trace amounts of impurities (e.g., catalyst residues) can be incorporated into and/or within the polymer.

As used herein, the term "interpolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. The generic term interpolymer thus encompasses both copolymers (used to refer to polymers prepared from two different types of monomers) and polymers prepared from more than two different types of monomers (e.g., terpolymers (three different monomer types) and tetrapolymers (four different monomer types)).

As used herein, "ethylene/a-olefin interpolymer" and similar terms refer to a polymer that comprises, in polymerized form, ethylene and a-olefin. In one embodiment, the "ethylene/a-olefin interpolymer" comprises a majority weight percent of ethylene (based on the weight of the interpolymer).

As used herein, "ethylene/a-olefin/diene interpolymer" and similar terms refer to a polymer (e.g., a non-conjugated diene) that comprises, in polymerized form, ethylene, an a-olefin, and a diene. In one embodiment, the "ethylene/a-olefin/diene interpolymer" comprises a majority weight percent of ethylene (based on the weight of the interpolymer).

As used herein, the term "ethylene/a-olefin copolymer" and similar terms refer to a copolymer that includes, in polymerized form, 50 wt% or the majority of ethylene (based on the weight of the copolymer) and a-olefin as the only monomer types.

As used herein, the term "ethylene-based polymer" and similar terms refer to a polymer that includes, in polymerized form, 50 wt% or a majority weight percent of ethylene monomer (based on the weight of the polymer), and optionally may include one or more comonomers.

As used herein, the term "propylene-based polymer" and similar terms refer to a polymer that includes, in polymerized form, a majority weight percent of propylene monomer (based on the weight of the polymer), and optionally may include one or more comonomers.

As used herein, the term "propylene/α -olefin interpolymer" and similar terms refer to a polymer that comprises, in polymerized form, a majority weight percent of propylene monomer (based on the weight of the polymer) and an α -olefin.

As used herein, the term "propylene/α -olefin copolymer" and similar terms refer to a copolymer that includes, in polymerized form, a majority of propylene monomer (based on the weight of the copolymer) and an α -olefin as the only monomer type.

As used herein, the term "propylene/ethylene interpolymer" and similar terms refer to a polymer that comprises, in polymerized form, a majority weight percent of propylene monomer (based on the weight of the polymer) and ethylene.

As used herein, the term "propylene/ethylene copolymer" and similar terms refer to a copolymer that includes, in polymerized form, a majority of propylene (based on the weight of the copolymer) and ethylene as the only monomer types.

As is known in the art, a "hydrocarbon" contains only carbon and hydrogen atoms.

Embodiments of the invention include, but are not limited to, the following:

1. a composition, comprising:

A) an ethylene/α -olefin interpolymer having a density from 0.854 to 0.890g/cc and a melt index (I2) from 0.2 to 30g/10 min;

B) a silicone oil having a viscosity of less than or equal to 5000cSt at 25 ℃; and

wherein component B is present in an amount of 1.0 wt% to 5.0 wt% based on the weight of the combined weights of components A and B.

2. The composition of example 1, wherein the ethylene/a-olefin interpolymer of component a is in the form of pellets.

3. The composition of embodiment 1 or embodiment 2 wherein the ethylene/a-olefin interpolymer of component a is an ethylene/a-olefin copolymer.

4. The composition of embodiment 3 wherein the alpha-olefin is a C3-C20 alpha-olefin.

5. The composition of embodiment 1 or embodiment 2 wherein the ethylene/a-olefin interpolymer of component a is an ethylene/a-olefin/diene interpolymer.

6. The composition of any of the preceding embodiments, wherein the ethylene/a-olefin interpolymer of component a has a density from 0.860 to 0.880 g/cc.

7. The composition of any of the preceding embodiments, wherein the ethylene/a-olefin interpolymer of component a has a melt index (I2) from 0.5 to 10g/10 min.

8. The composition of any of the preceding embodiments, wherein the composition comprises ≧ 90 wt% component A, based on the total weight of components A and B.

9. The composition of any of the preceding embodiments, wherein the composition comprises ≧ 10 wt% of the sum of component A and component B, based on the total weight of the components.

10. The composition of any one of the preceding embodiments, further comprising a propylene-based polymer.

11. The composition of embodiment 10 wherein the propylene-based polymer has a Melt Flow Rate (MFR) of from 1 to 120g/10 min.

12. The composition of embodiment item 10 or embodiment item 11, wherein the propylene-based polymer has a density from 0.890g/cc to 0.910 g/cc.

13. The composition of any one of embodiments items 10 through 12, wherein the propylene-based polymer has a MWD of from 2.0 to 30.

14. The composition of any of embodiments 10-13, wherein the propylene-based polymer is a polypropylene homopolymer or an impact co-polypropylene

15. The composition of any of embodiments 10-14, wherein the propylene-based polymer is present in an amount ≧ 50 wt% based on the weight of the composition.

16. The composition of any one of embodiments 10-15, wherein the composition comprises ≧ 70 wt% of the sum of component A, component B, and propylene-based polymer, based on the weight of the composition.

17. The composition of any of embodiments 10-16 wherein the weight ratio of the propylene-based polymer to component a is from 1.0 to 5.0.

18. The composition of any of the preceding embodiments, wherein the composition does not comprise a peroxide curative.

19. The composition of any one of the preceding embodiments, wherein the composition further comprises talc.

20. The composition of embodiment 19, wherein the talc is present in an amount of 5.0 to 35 wt% based on the weight of the composition.

21. The composition of any of the preceding embodiments, wherein the composition does not comprise a hydrocarbon oil.

22. The composition of any one of the preceding embodiments, wherein the composition has a flexural modulus (1% secant) of 100 to 250 kpsi.

23. The composition of any one of the preceding embodiments, wherein the composition has a pH of 40 to 55kJ/m at 10 ℃²The Izod strength of (2).

24. The composition of any one of the preceding embodiments, wherein the composition has a pH of 30 to 50kJ/m at 0 ℃²The Izod strength of (2).

25. The composition of any one of the preceding embodiments, wherein the composition has 8.0 to 20kJ/m at-20 ℃²The Izod strength of (2).

26. The composition of any one of the preceding embodiments, wherein the composition has a pH of 15 to 25kJ/m at-10 ℃²The Izod strength of (2).

27. The composition of any of the preceding embodiments, wherein the composition has a Melt Flow Rate (MFR) of 10 to 20g/10 min.

28. An article comprising at least one component formed from the composition of any of the preceding embodiments.

Test method

Density of

Polymer density was measured according to ASTM D-792.

Melt index

The melt index (I2) of the ethylene-based polymer was measured according to ASTM D-1238, condition 190 ℃/2.16 kg. The melt index (I5) of the ethylene-based polymer was measured according to ASTM D-1238, condition 190 ℃/5.0 kg. The melt index (I10) of the ethylene-based polymer was measured according to ASTM D-1238, condition 190 ℃/10.0 kg. The high load melt index (I21) of the ethylene-based polymer was measured according to ASTM D-1238, condition 190 ℃/21.0 kg. For propylene-based polymers, Melt Flow Rate (MFR) is measured according to ASTM D-1238, condition 230 ℃/2.16 kg.

Xylene extraction

The current process was established according to the ASTM xylene extraction method with minor modifications. Specifically, 4. + -. 0.3g of polymer are weighed (the weight of M is recorded)To 0.0001g) and added to a reflux flask with 200ml of suppressed ortho-xylene solvent. The solvent was heated to boiling and reflux at the setting was started. Reflux was maintained for 30 minutes and then air cooled to room temperature. Thereafter, the flask was placed in a water bath at 25 ℃ for 45 minutes, and then 100ml of the filtered solution was measured with a graduated cylinder. 100ml of the filtrate was then transferred to an aluminum pan. Aluminum dish (M)₁) The weight of (c) needs to be carefully measured to the nearest 0.0001g after the pan is heated at 150 ℃ for a minimum of 2 hours to remove moisture and cooled to room temperature in a desiccator. To evaporate the solvent in the aluminum pan, the pan was gently heated on a hot plate. After complete evaporation of the solvent, the pan was then placed in a 100 ± 5 ℃ vacuum oven for approximately 2 hours. Subsequently, the dish was cooled to room temperature in a desiccator, after which the aluminum dish was weighed again to allow M₂To the nearest 0.0001 g. The weight fraction of the extract material was then calculated using the following formula: f 2 × (M)₂-M₁)/M。

Differential Scanning Calorimetry (DSC)

Differential Scanning Calorimetry (DSC) was used to measure the crystallinity of ethylene (PE) based samples and propylene (PP) based samples. Approximately "5 to 8 mg" of the film sample was weighed and placed in a DSC pan. The lid was crimped to the pan to ensure a closed atmosphere. The sample pan was placed in a DSC unit and then heated at a rate of approximately 10 ℃/min to a temperature of 180 ℃ for PE (230 ℃ for PP). The sample was held at this temperature for three minutes. The sample was then cooled at a rate of 10 ℃/min to-60 ℃ for PE (-40 ℃ for PP) and held isothermal at that temperature for three minutes. The sample was then heated at a rate of 10 ℃/min until completely melted (second heating). By using the heat of fusion (H) determined from the second heating curve_f) The percent crystallinity is calculated by dividing by the theoretical heat of fusion 292J/g for PE (165J/g for PP) and multiplying this number by 100 (e.g.,% crystallinity ═ H_f/292J/g) × 100 (for PE)).

Unless otherwise stated, the melting point(s) (T) of each polymer_m) Determined by the second heating curve, and the crystallization temperature (T)_c) Determined from the first cooling curve.

Gel permeation chromatography

The chromatographic system consisted of Polymer Laboratories model PL-210 or Polymer Laboratories model PL-220. The column and the conveyor belt chamber were operated at 140 ℃. The columns were three Polymer Laboratories10 micron Mixed B columns. The solvent used was 1,2,4 trichlorobenzene. The samples were prepared at a concentration of "50 ml solvent with 0.1 g polymer". The solvent used to prepare the samples contained "200 ppm of Butylated Hydroxytoluene (BHT)". The samples were prepared by gentle stirring at 160 ℃ for two hours. The injection volume was 100 microliters and the flow rate was 1.0 milliliters/minute.

Calibration of GPC column sets was performed with 21 "narrow molecular weight distribution polystyrene standards" having molecular weights in the range of 580 to 8,400,000 grams/mole, arranged as six "cocktail" mixtures, and differing by at least ten times between individual molecular weights. Standards were purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standard was prepared with "50 ml of solvent containing 0.025 g" for molecular weights equal to or greater than 1,000kg/mol, and with "50 ml of solvent containing 0.05 g" for molecular weights less than 1,000 kg/mol. The polystyrene standards were dissolved at 80 ℃ for 30 minutes with gentle stirring. The narrow standards mixtures were run first, and the order of decreasing "highest molecular weight" components was followed to minimize degradation. The polystyrene standard peak molecular weight was converted to polyethylene molecular weight using the following equation: m polyethylene ═ A × (M polystyrene)^BWhere M is molecular weight, A has a value of 0.431 and B is equal to 1.0 (as described in Williams and Ward, journal of Polymer science: Polymer Kunststoff (J.Polym.Sc., Polym.Let.), 6,621 (1968)). Polyethylene equivalent molecular weight calculations were performed using Viscotek TriSEC software version 3.0.

Dynamic Mechanical Spectroscopy (DMS)

Small angle oscillatory shear (melt DMS) was performed using a TA Instruments ARES equipped with a "25 mm parallel plate" under a nitrogen purge. The time between sample loading and the start of the test was set to five minutes for all samples. The experiment was carried out at 190 ℃ with a frequency range of 0.1 to 100 rad/s. The strain amplitude was adjusted from 1% to 3% based on the reaction of the sample. The stress was analyzed in terms of amplitude and phase, from which the storage modulus (G'), loss modulus (G "), dynamic viscosity η ·, and tan δ were calculated. The samples used for dynamic mechanical spectroscopy were "25 mm diameter x 3.3mm thick" compression molded discs formed at 180 ℃ and 10MPa molding pressure for five minutes and then quenched for two minutes between cold pressed plaques (15-20 ℃). The rheology ratio of 0.1rad/sec viscosity to 100rad/sec viscosity (V0.1/V100 at 190 ℃; also referred to as "RR") was recorded.

Mooney (Mooney) viscosity

The mooney viscosity (ML1+4 at 125 ℃) of an interpolymer (e.g., an ethylene/α -olefin/diene interpolymer or polymer blend) was measured according to ASTM 1646-04 using a large rotor, at one minute preheat time and four minutes rotor run time. The apparatus is an Alpha Technologies Mooney viscometer 2000.

The Mooney viscosity (ML1+4, at 100 ℃) of the compositions (formulations) was measured according to ASTM 1646-04 using a large rotor at one minute warm-up time and four minutes rotor operating time. The apparatus is an Alpha Technologies Mooney viscometer 2000.

13C NMR method for EPDM compositional analysis and stereo-isomerism (% mm)

Samples were prepared by "adding" approximately "2.6 g" of a "50/50 tetrachloroethane-d 2/o-dichlorobenzene mixture" to "0.2 g sample" in a 10mm NMR tube, said mixture being "0.025M" in chromium acetyl acetonate (relaxant). The sample was dissolved and homogenized by heating the tube and its contents to 150 ℃. Data were collected using a Bruker 400MHz spectrometer equipped with a Bruker Dual DUL high temperature cryoprobe. Data were acquired using "160 scans per data file", a six second pulse repetition delay, and a sample temperature of 120 ℃. The acquisition was performed using a spectral width of 25,000Hz and a file size of 32K data points. NMR spectroscopic analysis of each composition of the examples was performed using the following analytical methods. The quantitative amount of monomer present in the EPDM can also be calculated using the following equations (1 to 9). The ethylene mole number was calculated to normalize the spectral range of 55.0 to 5.0ppm to 1000 integral units. The contribution at the normalized integrated area accounts for only 7 of the ENB carbons. 111 and 147ppm ENB diene peaks were excluded from the calculation due to concerns that double bonds may react at high temperatures.

Equation 1

Equation 2 moles of ENB CH3(13.6-14.7 ppm);

equation 3 moles of propylene CH3(19.5-22.0 ppm):

equation 4

Equation 5

Equation 6

Equation 7

Equation 8

Equation 9

Propylene stereoisomerism,% area mm, 13C NMR

The degree of stereoisomerism,% mm, was quantified using 13C NMR spectroscopic analysis of EPDM samples. NMR was performed as described above in "50/50 mixture of tetrachloroethane-d 2/o-dichlorobenzene". The NMR spectroscopic analysis of the EPDM of the present invention (see above) showed a significance of 3.5% of the total integrated area typically greater than 19.5ppm to 22.0ppm,% peak area from 21.3ppm to 22.0ppm rmmr, mmmr, mmmm. The peak reactions in this region are generally associated with differences in propylene stereoisomerism (% mm) that have been incorporated into EPDM. Similar analysis can be performed on another type of ethylene/α -olefin/diene interpolymer. The spectroscopic data refer to the EEE backbone (three or more repeat units of polymerized ethylene) at 30 ppm. Thus, "peak area% (21.3ppm to 22.0 ppm)" { [ (area of 21.3ppm to 22.0 ppm)/(total integrated area of 19.5ppm to 22.0ppm) ] × 100 }.

Experiment of

Material

The materials used in this study are shown in table 1 below and the structures shown. Note that the viscosity of PMX-200 was measured at 25 ℃ and UCON was measured at 40 ℃^TMOSP-460 andviscosity of 6001R.

Table 1: polymers and additives

MI is at 2.16kg, 190 ℃ and MFR is at 2.16kg, 230 ℃. Random distribution of octenes (α -olefins).

Trademark and registered trademark symbols are not performed below.

A) Composition (absorption or mixing pill)

B) Representative procedures

For each composition (except the control polymer), the polymer pellets (about 10 pounds) were either imbibed with oil or melt-mixed with a twin-screw extruder as shown in table 2 below. The absorption process is carried out at room temperature and ambient pressure for 5 minutes to 72 hours. For the absorption process, the elastomer pellets are placed in a plastic bag with the oil and tumbled to ensure that the pellets are evenly coated with the oil.

Table 2: list of compositions and incorporation methods of EG8100 incorporating silicone oil.

Wt% based on the weight of silicone oil and EG 8100. N/A is not applicable.

C) Composition (TPO)

Representative procedures

Each composition (TPO) was compounded in a twin screw extruder, i.e., a Coperion ZSK-25mm twin screw extruder equipped with a water bath and strand cutter. The extruder arrangement and the temperature profile of the samples are shown in table 3. All components except talc were dry blended in plastic bags and then fed into the main feed throat via a loss-in-weight feeder. Talc was fed into the main feed port via a separate powder feeder.

TABLE 3 compounding conditions of TPO

ZSK-25

Region 1

Region 2

Region 3

Region 4

Region 5

Region 6

Region 7

Region 8

Extruding machine

Set point

130℃

180℃

200℃

200℃

200℃

200℃

200℃

200℃

300RPM

Table 4: composition (TPO formulation)

Wt% based on the weight of the TPO composition. N/A is not applicable.

D) Results

Injection molding

ASTM D638 type I tensile bars were injection molded by a Toyo injection molder. The forming conditions were optimized to ensure minimal defects in the formed parts via various control experiments. The key injection molding settings are listed in table 5.

Table 5: injection molding settings

Flexural modulus, 1% sec, kpsi

Flexural modulus was measured according to ASTM D790 using an injection molded type I tensile bar and INSTRON tester. A test speed of 0.05in/min was selected. Five test samples were measured and the average value reported.

Izod Strength, kJ/m²(-20 ℃ C., -10 ℃ C., -0 ℃ C. and 10 ℃ C.)

Notched IZOD testing was performed in accordance with ASTM D256. Samples were die cut from the injection molded stretch I-bars to final dimensions of "2.5 inches by 0.5 inches by 0.125 inches". The sample was notched using an automatic notch cutter at 0.1 inch along the length, center, thickness of the sample. The cut half angle was 22.5 deg., and the radius of curvature of the tip was 0.01 inch. Samples were conditioned at 23+/-2 ℃ and 50 +/-10% relative humidity for at least 40 hours. For samples tested at non-ambient temperatures, the samples were further conditioned for a minimum of one hour at the test temperature. Here, the test was performed at four temperatures (-20 ℃, -10 ℃,0 ℃ and 10 ℃), and each temperature was repeated five times to obtain an average value.

It should be noted that because of the inherent batch-to-batch variation in TPO performance testing, there is often variation in the same TPO formulation if it is tested at different times in different batches. Thus, TPOs made and tested from the same experimental batch were compared as shown below.

In table 6, the melt flow rate and stiffness characteristics of TPO compositions prepared from different types of oils are shown. It was observed that the inventive composition (inventive SC1) resulted in a much improved MFR compared to the comparative composition SCA. At the same time, the addition of silicone-based oil results in a decrease in the stiffness margin of the TPO composition. On the other hand, the use of oils based on polyethers (composition SCD) and on paraffins (composition SCC) gives a similar degree of improvement in melt flow, but both have a lower stiffness.

TABLE 6 melt flow and rigidity of TPO Compounds when incorporated with different oils

Wt% based on the weight of the TPO composition.

As shown in Table 7, TPO compositions (inventive SC2 and inventive SC3) having a silicone oil concentration of 0.5 wt% in the TPO composition also greatly improved low temperature impact properties compared to unmodified TPO (composition SCE); see especially the Izod strength at-10 ℃. Additionally, the rigidity of the TPO composition is not adversely affected by the incorporation of silicone oil. On the other hand, it was also observed that the stiffness and toughness of the TPO composition was not affected by the method used to incorporate the silicone oil. The "5 minute absorption (invention 2)" and "twin screw compounding (invention 3)" of the first composition comprising components a and B resulted in TPO compositions having similar stiffness and low temperature impact properties.

TABLE 7 flexural rigidity and impact strength of TPOs when 0.5 wt% silicone oil was incorporated in the TPO formulation via pellet absorption and twin screw extruder compounding.

Wt% based on the weight of the TPO composition.

Finally, in table 8, TPO compositions containing silicone oils of different viscosities and different concentrations are compared. It was found that 0.5 wt% silicone oil, in addition to the ultra high molecular weight PDMS modified TPO composition at 0.5 wt% PDMS, improved the low temperature toughness (especially at 0 ℃) and melt flow of the TPO composition to at least some extent. In contrast, the ultra-high molecular weight PDMS typically used to improve the scratch resistance of TPOs tends to reduce the low temperature toughness of the TPO composition (see composition SCF).

At a fixed viscosity (350cSt), silicone oils at concentrations ranging from 0.2 wt% to 1.0 wt% in the total TPO composition (1.0 wt% to 5.0 wt% based on the weight of silicone oil and elastomer; inventive SC2, inventive SC4, and inventive SC5) are observed to have improvements in low temperature toughness (especially at 0 ℃) or melt flow, or both, at least to some extent. These results show that compositions of the present invention within the proposed oil composition range provide an improved flow-stiffness-toughness balance for TPO compositions.

Because the base ethylene/α -olefin interpolymers in the inventive samples (inventive 1-7) are the same as in the control (control A), it is expected that the novel compositions will provide an advantage in pellet handling over compositions containing "lower density and higher melt index" ethylene/α -olefin interpolymers, since we can use the inventive compositions to obtain "good MFR TPO compositions with good low temperature impact properties" and avoid the sticky pellet situation that results from using lower density, higher melt index interpolymers to obtain the same "MFR compositions with good low temperature impact properties".

Table 8: flexural rigidity, melt flow, and impact strength of TPOs when silicone oil/ultra-high molecular weight PDMS of different concentrations and different viscosities were incorporated into the TPO formulations.

Wt% based on the weight of the TPO composition.