Ethylene / alpha-olefin interpolymer compositions with improved long-term heat aging performance

Abstract

To provide EPDM rubbers that provide formulations with improved continuous upper temperature resistance with maintained mechanical properties, low temperature flexibility, and elastic recovery.SOLUTION: A first composition comprises a first ethylene / α-olefin / diene interpolymer and a second ethylene / α-olefin interpolymer, wherein: the first composition comprises from 0.1 to 1.0 wt% diene, based on the weight of the first composition; and the first composition comprises from 40 to 70 wt% ethylene, based on the weight of the first composition.SELECTED DRAWING: None

Description

[Background technology]

[0001] Ethylene propylene ethylidene nobornene (EPDM) rubber is primarily used under the hood Dominant hydrocarbon elastomers used in the manufacture of crosslinked hoses for use in automobiles EPDM rubber is well known for its ease of processing, weather stability, and water resistance. However, conventional automotive hoses made therefrom have not been relied upon for long-term heat aging performance. However, there are limits.

[0002] EPDM based compounds are described in the following references: US2012 / 0116021, US201 5 / 0274867, US6566446, US6686419, US8299189, US9234093, US9422383, US9580587, EP0758346( A1), EP101175(B1), EP1433812(A1), EP1676879 (A2), EP2049590(A1), CA1334694C, WO2007 / 136 494, WO2011 / 041230, International Application P filed on December 26, 2016 CT / CN16 / 112090, DPSinha et al. dant Use Better Hose, Belt Compounds” Rubb er News (June, 2001), K. Dominic et al. f Automotive Wire and Cable and Recent A dvances” ACS Rubber Division Spring Techn ical Meeting, 1998, Paper No. 32, John Dick "Rubber Technology: Compounding and Tes ting for Performance”Chapter 6 “Elastomer "Selection" (2009, Hanser), Anthony G.Ferra dino,Rubber Chemistry and Technology,Vol. .76, pp704 (2003), P. Arjunan et al. ion of CR / EPM Blends for Power Transmiss ion Belt Application” Rubber World (Februa ry, 1997), Z. Tao et al. "Heat Resistant Elastomers s” Rubber Chemistry and Technology(2005,V 78, pp489), R. Ohm et al. “Optimizing the Heat Res istance of EPDM and NBR” ACS Rubber Divis ion Fall technical meeting,2000,Paper No. It is listed at .99.

[0003] Continuously improved high temperature resistance while maintaining mechanical properties, low temperature flexibility, and elastic recovery There is a need for EPDM rubber that provides an improved formulation. This need is addressed by the following inventions: is fulfilled by. Summary of the Invention

[0004] A first ethylene / α-olefin / diene interpolymer and a second ethylene / A first composition comprising an α-olefin polymer, The first composition contains 0.1 to 1.0 weight percent of a diene, based on the weight of the first composition. Including, The first composition comprises 40 to 70% by weight of ethylene based on the weight of the first composition. Includes. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] As discussed above, the first ethylene / α-olefin / diene interpolymer and a second ethylene / α-olefin interpolymer. R, The first composition comprises, based on the weight of the first composition, 0.1 to 1.0 weight percent of a diene; or 0.2 to 1.0 wt. % of a diene, or 0.3 to 1.0 wt. % of a diene, The first composition contains 40 to 70% by weight of ethylene based on the weight of the first composition. nothing.

[0006] These first compositions are readily crosslinkable (e.g., using sulfur and peroxide curing). to form formulations that can be crosslinked and have excellent retention of mechanical properties after heat aging Additional improvements include excellent low temperature flexibility and elasticity, high Unmet needs for automotive hose applications include low green strength and low iridescence. Meet the need.

[0007] The first composition may include a combination of two or more embodiments described herein. The ethylene / α-olefin / diene interpolymer may comprise two or more of the ethylene / α-olefin / diene interpolymers described herein. The second ethylene / α-olefin interpolymer may comprise a combination of the following embodiments: may include a combination of two or more embodiments described herein.

[0008] In one embodiment or combination of embodiments described herein, the first interpoly the first interpolymer and the second interpolymer are 95% by weight or more of the total weight of the first composition, or It constitutes 98% by weight or more, or 99% by weight or more.

[0009] In one embodiment, the first ethylene / α-olefin / diene interpolymer is Based on the weight of the ethylene / α-olefin / diene interpolymer, 250,0 Mw of 0.00 to 500,000 g / mol, and diene content of 0.01 to 0.80 wt.% has.

[0010] In one embodiment or combination of embodiments described herein, the first ethylene / α The ethylene / α-olefin / diene interpolymer is a first ethylene / α-olefin / diene interpolymer. 0.20 to 0.80 weight percent, or 0.25 to 0.7 weight percent, based on the weight of the terpolymer. 5% by weight, or 0.30 to 0.70% by weight, or 0.35 to 0.65% by weight, or It has a diene content of 0.40 to 0.60% by weight.

[0011] In one embodiment or combination of embodiments described herein, the first ethylene / α The ethylene / α-olefin / diene interpolymer is a first ethylene / α-olefin / diene interpolymer. 55 to 80 weight percent, or 60 to 75 weight percent, based on the weight of the terpolymer; It has a C2 (polymerized ethylene) content of 65-70% by weight.

[0012] In one embodiment or combination of embodiments described herein, the first ethylene / α - the olefin / diene interpolymer is from 250,000 to 400,000 g / mol; or 270,000 to 380,000 g / mol, or 300,000 to 360,00 0 g / mol or weight average molecular weight (Mw) between 320,000 and 340,000 g / mol has.

[0013] In one embodiment or combination of embodiments described herein, the first ethylene / α - the olefin / diene interpolymer is from 150,000 to 200,000 g / mol; or 155,000 to 190,000 g / mol, or 160,000 to 180,00 0 g / mol or 160,000-170,000 g / mol number average molecular weight (Mn) Yes.

[0014] In one embodiment or combination of embodiments described herein, the first ethylene / α - the olefin / diene interpolymer is from 500,000 to 700,000 g / mol; or 550,000 to 680,000 g / mol, or 580,000 to 660,00 0 g / mol, or a z-average molecular weight (Mz) between 600,000 and 640,000 g / mol Yes.

[0015] In one embodiment or combination of embodiments described herein, the first ethylene / α -Olefin / diene interpolymers are 1.70-2.40, or 1.80-2. 30, or 1.90-2.20, or 2.00-2.10 molecular weight distribution (Mw / Mn ).

[0016] In one embodiment or combination of embodiments described herein, the first ethylene / α the olefin / diene interpolymer is from 80 to 100, or from 82 to 98 g / mol; or 84 to 96 g / mol, or 86 to 94 g / mol Mooney viscosity (ML1+4, 1 25°C). Mooney viscosity is measured without oil or fillers unless otherwise stated. The viscosity of the interpolymer of 1.

[0017] In one embodiment or combination of embodiments described herein, the first ethylene / α -Olefin / diene interpolymers: 250,000 Pa·s~650,000 Pa·s a·s, or 300,000Pa·s to 600,000Pa·s, or 350,00 0 Pa·s to 550,000 Pa·s, or 400,000 Pa·s to 500,000 It has a melt viscosity V0.1 in Pa·s (0.1 rad / s, 190°C).

[0018] In one embodiment or combination of embodiments described herein, the first ethylene / α -Olefin / diene interpolymers: 8,000 Pa·s to 15,000 Pa·s , or 9,000 Pa·s to 14,000 Pa·s, or 10,000 Pa·s to 1 Melt viscosity V of 3,000 Pa·s or 11,000 Pa·s to 12,000 Pa·s 100 (100 rad / sec, 190°C).

[0019] In one embodiment or combination of embodiments described herein, the first ethylene / α -Olefin / diene interpolymer is 35-45, or 36-42, or 37 It has a rheological ratio (RR or V0.1 / V100) of ~40.

[0020] In one embodiment or combination of embodiments described herein, the first ethylene / α The olefin / diene interpolymer is an EPDM.

[0021] In one embodiment or combination of embodiments described herein, the second ethylene / α -Olefin interpolymer is an ethylene / α-olefin / diene interpolymer and also EPDM.

[0022] In one embodiment or combination of embodiments described herein, the first ethylene / α -olefin / diene interpolymer and a second ethylene / α-olefin interpolymer The polymers are each independently EPDM.

[0023] In one embodiment or combination of embodiments described herein, the second ethylene / α -olefin interpolymers are ethylene / α-olefin copolymers, as well as ethylene ethylene / propylene copolymer; or ethylene / α-olefin / diene interpolymer and EPDM.

[0024] In one embodiment or combination of embodiments described herein, the first composition comprises 1. A Mw of 150,000 to 400,000 g / mol, based on the weight of the composition; and In a further embodiment, the first composition has a diene content of 0.01 to 0.50 wt.%. 95% by weight or more, or 98% by weight or more, or The polymer comprises at least 99 weight percent of the first interpolymer and the second interpolymer combined.

[0025] In one embodiment or combination of embodiments described herein, the first composition comprises 0.10 to 0.80% by weight, or 0.15 to 0.75% by weight, based on the weight of the composition. %, or 0.20 to 0.70% by weight, or 0.25 to 0.65% by weight of diene In a further embodiment, the first composition has an amount, based on the weight of the first composition, of: 95% by weight or more, or 98% by weight or more, or 99% by weight or more of a first interpolymer The total of the first interpolymer and the second interpolymer.

[0026] In one embodiment or combination of embodiments described herein, the first composition comprises 40 to 65% by weight, or 40 to 62% by weight, or 40 In a further embodiment, the first set has a C2 (polymerized ethylene) content of about 60% by weight. The composition may be 95% by weight or more, or 98% by weight or more, based on the weight of the first composition, comprises 99% by weight or more of the total of the first interpolymer and the second interpolymer. .

[0027] In one embodiment or combination of embodiments described herein, the first composition comprises 40 to 70% by weight, or 42 to 62% by weight, or 45 to 65% by weight, based on the weight of the composition of In a further embodiment, the first set has a C2 (polymerized ethylene) content of about 65% by weight. The composition may be 95% by weight or more, or 98% by weight or more, based on the weight of the first composition, comprises 99% by weight or more of the total of the first interpolymer and the second interpolymer. .

[0028] In one embodiment or combination of embodiments described herein, the first composition comprises: 60,000-320,000 g / mol, or 180,000-300,000 g / mol or 200,000 to 280,000 g / mol, or 220,000 to 260, In a further embodiment, the first composition has a weight average molecular weight (Mw) of 10,000 g / mol. 95% by weight or more, or 98% by weight or more, or The polymer comprises at least 99 weight percent of the first interpolymer and the second interpolymer combined.

[0029] In one embodiment or combination of embodiments described herein, the first composition comprises 8 4,000 to 120,000 g / mol, or 86,000 to 100,000 g / mol, or 88,000-98,000 g / mol, or 90,000-96,000 g / mol In a further embodiment, the first composition has a number average molecular weight (Mn) of 95% or more by weight, or 98% or more by weight, or 99% or more by weight, based on the weight of the composition The total of the first interpolymer and the second interpolymer is

[0030] In one embodiment or combination of embodiments described herein, the first composition comprises 4 40,000-660,000 g / mol, or 460,000-640,000 g / mol or 480,000 to 620,000 g / mol, or 500,000 to 600, In a further embodiment, the first composition has a z-average molecular weight (Mz) of 10,000 g / mol. is 95% by weight or more, or 98% by weight or more, or 9 The polymer comprises greater than or equal to 9 weight percent of the first interpolymer and the second interpolymer combined.

[0031] In one embodiment or combination of embodiments described herein, the first composition comprises 2 .10~3.20, or 2.20~3.00, or 2.30~2.90, or 2. In a further embodiment, the first group has a molecular weight distribution (Mw / Mn) of 40 to 2.80. The composition may be 95% by weight or more, or 98% by weight or more, based on the weight of the first composition, comprises 99% by weight or more of the total of the first interpolymer and the second interpolymer. .

[0032] In one embodiment or combination of embodiments described herein, the first composition comprises 7 0-90, or 72-90, or 74-88, or 76-88 g / mol, or 7 Mooney viscosity (ML1+4, 125°C) of 8 to 88 g / mol or 80 to 86 g / mol The Mooney viscosity is measured for the first composition without oil or fillers, unless otherwise specified. In a further embodiment, the first composition has a viscosity of about 1000 mg / kg based on the weight of the first composition. 95% by weight or more, or 98% by weight or more, or 99% by weight or more of the first interpo The total of the first interpolymer and the second interpolymer is included.

[0033] In one embodiment or combination of embodiments described herein, the first composition comprises: ,500Pa·s~7,500Pa·s, or 2,000Pa·s~6,000Pa·s s, or 2,500 Pa·s to 6,500 Pa·s, or 3,000 Pa·s to 6, It has a melt viscosity V100 (100 rad / s, 190°C) of 1,000 Pa·s. In some embodiments, the first composition comprises 95% or more by weight, based on the weight of the first composition. or 98% or more, or 99% or more by weight of the first interpolymer and the second interpolymer; Includes the sum of terpolymers.

[0034] In one embodiment or combination of embodiments described herein, the first composition comprises 8 Rheology ratio (RR or V0.1) from 0 to 46, or 10 to 44, or 12 to 42 / V100). In a further embodiment, the first composition has a weight percent of the first composition. Based on the above, 95% by weight or more, or 98% by weight or more, or 99% by weight or more of the first ingredient Includes the sum of the terpolymer and the second interpolymer.

[0035] In one embodiment or combination of embodiments described herein, the first composition comprises 0. Tan Delta (190°C) of .8 to 4.0, or 1.0 to 3.8, or 1.2 to 3.6 In a further embodiment, the first composition has 9 to 100% by weight of the first composition. 5% by weight or more, or 98% by weight or more, or 99% by weight or more of the first interpolymer and the second interpolymer.

[0036] In one embodiment or combination of embodiments described herein, the first composition comprises - It has a Tm of 15°C to 55°C, or -18°C to 52°C, or -20°C to 50°C. In yet another embodiment, the first composition comprises 95% by weight or more, based on the weight of the first composition. or 98% or more, or 99% or more by weight of the first interpolymer and the second interpolymer Includes the sum of interpolymers.

[0037] In one embodiment or combination of embodiments described herein, the first composition comprises: The Tm is between 6°C and 54°C, between 18°C ​​and 52°C, or between 20°C and 50°C. In an embodiment, the first composition comprises 95% or more by weight, based on the weight of the first composition; At least 98% by weight, or at least 99% by weight, of the first interpolymer and the second interpolymer. - Includes the total of polymers.

[0038] In one embodiment or combination of embodiments described herein, the first composition comprises - 45℃~-65℃, or -50℃~-60℃, or -52℃~-58℃, or -5 In a further embodiment, the first composition has a Tg of 4° C. to −56° C. Based on the weight of the product, 95% by weight or more, or 98% by weight or more, or 99% by weight or more of the The total of the first interpolymer and the second interpolymer.

[0039] In one embodiment or combination of embodiments described herein, the first composition comprises: 5% or less, or 12% or less, or 10% or less, or 8% or less, or 5% or less In a further embodiment, the first composition has a crystallinity of 0.1 to 0.5%, based on the weight of the first composition. In the present invention, 95% by weight or more, 98% by weight or more, or 99% by weight or more of the first interlayer The total of the polymer and the second interpolymer.

[0040] In one embodiment or combination of embodiments described herein, the first composition comprises 0. having a percent crystallinity of .5% to 15%, or 0.5% to 12%, or 0.5% to 10% In a further embodiment, the first composition comprises 95% by weight of the first composition. % or more, or 98% or more, or 99% or more by weight of a first interpolymer, and The second interpolymer is included in the total.

[0041] In one embodiment or combination of embodiments described herein, the diene of the first composition the diene content of the first ethylene / α-olefin / diene interpolymer; The ratio to is 0.80 to 2.20, or 0.90 to 2.10, or 1.00 to 2. 00, or 1.10 to 1.90, or 1.20 to 1.80. In the first composition, the first composition comprises 95% or more by weight, or 98% or more by weight, based on the weight of the first composition. % or more, or 99% or more by weight of the first interpolymer and the second interpolymer Includes the total of

[0042] In one embodiment or combination of embodiments described herein, the C2 of the first composition A first ethylene / α-olefin / diene interpolymer having a (polymerized ethylene) content of The ratio of C2 (polymerized ethylene) content to C2 content is 0.50 to 1.10, or 0.55 to 1. In a further embodiment, the first composition is 95% or more, or 98% or more, or 99% or more by weight based on the weight of the composition. % or more of the total of the first interpolymer and the second interpolymer.

[0043] In one embodiment or combination of embodiments described herein, the first composition comprises The first ethylene / α-olefin / diene interpolymer having a knee viscosity (ML1+4, 125°C) - The ratio to the polymer's Mooney viscosity (ML1+4, 125°C) is 0.75 to 1.05 , or 0.80 to 1.00, or 0.85 to 0.95. The Mooney viscosity is, in particular, Unless otherwise specified, the viscosity is that of the first composition without oil or fillers. , unless otherwise specified, is the viscosity of the first interpolymer without oil or filler. In a further embodiment, the first composition comprises 95% by weight, based on the weight of the first composition. or more, or 98% by weight or more, or 99% by weight or more of the first interpolymer and the second interpolymer. The total of the interpolymers of 2 is included.

[0044] In one embodiment or combination of embodiments described herein, the Mw of the first composition to the Mw of the first ethylene / α-olefin / diene interpolymer is 0 .60~0.90, or 0.65~0.85, or 0.70~0.80. In one embodiment, the first composition comprises, based on the weight of the first composition, 95% by weight or more or 98% by weight or more, or 99% by weight or more of the first interpolymer and the second interpolymer. Includes the sum of terpolymers.

[0045] In one embodiment or combination of embodiments described herein, the Mn of the first composition to the Mn of the first ethylene / α-olefin / diene interpolymer is 0 .45 to 0.75, or 0.50 to 0.70, or 0.55 to 0.65. In one embodiment, the first composition comprises, based on the weight of the first composition, 95% by weight or more or 98% by weight or more, or 99% by weight or more of the first interpolymer and the second interpolymer. Includes the sum of terpolymers.

[0046] In one embodiment or combination of embodiments described herein, the Mz of the first composition to the Mz of the first ethylene / α-olefin / diene interpolymer is 0 .82 to 0.96, or 0.84 to 0.97, or 0.86 to 0.96. In one embodiment, the first composition comprises, based on the weight of the first composition, 95% by weight or more or 98% by weight or more, or 99% by weight or more of the first interpolymer and the second interpolymer. Includes the sum of terpolymers.

[0047] In one embodiment or combination of embodiments described herein, the MW of the first composition The ratio of D to the MWD of the first ethylene / α-olefin / diene interpolymer is , 1.15 to 1.45, or 1.20 to 1.40, or 1.25 to 1.35. In a further embodiment, the first composition comprises 95% or more by weight, based on the weight of the first composition. or 98% by weight or more, or 99% by weight or more of the first interpolymer and the second interpolymer. The total includes interpolymers of

[0048] In one embodiment or combination of embodiments described herein, the V0 of the first composition 0.1 (0.1 rad / sec, 190° C.) of the first ethylene / α-olefin / diene The ratio of V0.1 (0.1 rad / sec, 190°C) of the terpolymer is 0.05 to 0.55, or 0.10 to 0.50, or 0.15 to 0.45. In one embodiment, the first composition comprises 95% or more by weight, based on the weight of the first composition. 8% by weight or more, or 99% by weight or more of the first interpolymer and the second interpolymer Includes total of Rimer.

[0049] In one embodiment or combination of embodiments described herein, the first composition comprises 3 0 to 40 weight percent of a first ethylene / α-olefin / diene interpolymer, and In a further embodiment, the first composition further comprises EPDM, based on the weight of the first composition. Based on the above, 95% by weight or more, 98% by weight or more, or 99% by weight or more of the first intermetallic compound is The total of the first interpolymer and the second interpolymer.

[0050] In one embodiment or combination of embodiments described herein, the first composition comprises 6 0 to 70 wt. % of a second ethylene / α-olefin interpolymer, and further In a further embodiment, the first composition comprises, based on the weight of the first composition, 95% by weight or more, or 98% by weight or more, or 99% by weight or more of a first interpolymer The total of the first interpolymer and the second interpolymer.

[0051] In one embodiment or combination of embodiments described herein, the first composition comprises 0. .890 or less, or 0.880 or less, or 0.875 or less, or 0.870 or less, or has a density of 0.865 or less, or 0.860 or less g / cc. In this embodiment, the first composition comprises 95% or more by weight, based on the weight of the first composition, % or more, or 99% or more, by weight, of the first interpolymer and the second interpolymer. Includes the sum of the

[0052] In one embodiment or combination of embodiments described herein, the first composition comprises: 5.0% or more as determined by 3C NMR (propylene stereoregularity marker) , 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 Peak area percentage (21.3-22.0 ppm) of 14% or more or 15% or more In a further embodiment, the first composition comprises 95% by weight of the first composition. % or more, or 98% or more, or 99% or more by weight of a first interpolymer, and The second interpolymer is included in the total.

[0053] In one embodiment or combination of embodiments described herein, the first composition comprises: 40% or less as determined by 3C NMR (propylene stereoregularity marker); or 35% or less, or 30% or less "Peak area% (21.3-22.0 ppm)" In a further embodiment, the first composition has 9 to 100% by weight of the first composition. 5% by weight or more, or 98% by weight or more, or 99% by weight or more of the first interpolymer and the second interpolymer.

[0054] Also provided are compositions comprising the first composition and additives of any one or more of the embodiments described herein. Compositions including the above-mentioned are also provided.

[0055] In one embodiment or combination of embodiments described herein, the additive is MgO, ZnO, or a combination thereof and further MgO or ZnO and further MgO. In further embodiments or combinations of embodiments described herein, the addition of the first composition The weight ratio of the additive is 2.0 to 8.0, or 3.0 to 7.0, or 4.0 to 6.0. It is.

[0056] In one embodiment or combination of embodiments described herein, the first composition is a composition comprising 26% to 42% by weight, or 28% to 40% by weight, based on the weight of the composition, is present in an amount of 30% to 38% by weight, or 32% to 36% by weight.

[0057] In one embodiment or combination of embodiments described herein, MgO is present in the composition. 4.0% to 10% by weight, or 5.0% to 9.0% by weight, is present in an amount of 6.0% to 8.0% by weight.

[0058] In one embodiment or combination of embodiments described herein, the additive is MgO. and the weight ratio of the first composition to MgO is 2.0 to 8.0, or 3.0 to 7.0, or It is 4.0 to 6.0.

[0059] In one embodiment or combination of embodiments described herein, the composition further comprises a curing agent. In addition, the curing agent is a peroxide.

[0060] In one embodiment or combination of embodiments described herein, a curing agent (e.g., oxide) is present in an amount of 2.0% by weight to 3.0% by weight, or 2.2% by weight, based on the weight of the composition. % to 2.8% by weight, or 2.4% to 2.6% by weight.

[0061] In one embodiment or combination of embodiments described herein, the Mg to hardener The weight ratio is 2.2 to 3.2, or 2.4 to 3.0, or 2.6 to 2.8.

[0062] In one embodiment or combination of embodiments described herein, the composition further comprises a filler. Additionally, the filler is carbon black.

[0063] In one embodiment or combination of embodiments described herein, the filler is 20% to 36% by weight, or 22% to 34% by weight, based on the weight of the composition; Or it is present in an amount of 24% to 32% by weight.

[0064] In one embodiment or combination of embodiments described herein, the loading of the first composition The weight ratio of the agent to the agent is 0.6 to 1.8, or 0.8 to 1.6, or 1.0 to 1.4. be.

[0065] In one embodiment or combination of embodiments described herein, the composition comprises 5.0M Pa or more, or 5.5MPa or more, or 6.0MPa or more, or 6.5MPa or more , or has an average tensile stress at break of 7.0 MPa or more, or 7.5 MPa or more.

[0066] In one embodiment or combination of embodiments described herein, the composition comprises 300% or more than 320%, or more than 340%, or more than 360%, or more than 380% or has an elongation at break of 400% or more.

[0067] In one embodiment or combination of embodiments described herein, the composition is After 1008 hours (6 weeks) in air, the tensile strength is at least 50% or at least 55% of the original or retains 60% or more and 35% or more, or 40% or more of its original elongation at break; or Retain 45% or more.

[0068] In one embodiment or combination of embodiments described herein, the composition is After 1008 hours (6 weeks) in air, it retains 50% to 65% of its original tensile strength. Retains 35% to 50% of elongation at break.

[0069] Also, a crosslinking composition comprising the first composition of any one or more of the embodiments described herein. will also be provided.

[0070] Also provided is a crosslinked composition comprising the composition of any one or more of the embodiments described herein. will be done.

[0071] The composition may include a combination of two or more embodiments as described herein. .

[0072] Also included herein is at least one composition formed from the composition of any one or more of the embodiments described herein. Also provided is an article including at least one component.

[0073] In one embodiment or combination of embodiments described herein, the article comprises: : Injection molded parts, foams, automotive parts (i.e. hoses and belts, tires), construction and construction materials, building and construction materials, and shoe components. In one embodiment or combination of embodiments described herein, the article comprises: The adhesive is selected from the group consisting of a rubber band, a belt, and a gasket.

[0074] An article may comprise a combination of two or more embodiments described herein.

[0075] The present invention also provides a method for preparing a composition according to one or more of the embodiments described herein. In one embodiment, the process comprises the steps of: Below: Polymerization of ethylene, alpha-olefins (α-olefins), and dienes In a further embodiment, the ethylene, the α-olefin, and the diene are The polymerisation is carried out in two reactors in a continuous solution polymerisation process.

[0076] Some embodiments are listed below. a) As discussed above, a first ethylene / α-olefin / diene interpolymer and a second ethylene / α-olefin interpolymer, The first composition contains 0.1 to 1.0 weight percent of a diene, based on the weight of the first composition. Including, The first composition comprises 40 to 70% by weight of ethylene based on the weight of the first composition. Includes. b) the first ethylene / α-olefin / diene interpolymer is a first ethylene 250,000 to 500,000 based on the weight of the α-olefin / diene interpolymer ,000 g / mol, and a diene content of 0.01 to 0.80 wt.%. A first composition according to item a). c) the first ethylene / α-olefin / diene interpolymer is EPDM; A first composition according to any one of a) or b) above. d) a first ethylene / α-olefin / diene interpolymer and a second ethylene / α-olefin / diene interpolymer; Each of the olefin / α-olefin interpolymers is independently EPDM. ) The first composition described in any one of the above. e) the first composition has a molecular weight of 150,000 to 400,000 based on the weight of the first composition; 00g / mol, and a diene content of 0.01 to 0.50 wt.%. ) to d). f) the first composition comprises 0.10 to 0.80% by weight, based on the weight of the first composition; or 0.15 to 0.75% by weight, or 0.20 to 0.70% by weight, or 0.25 to The first composition according to any one of a) to e) above, having a diene content of 0.65% by weight. composition g) the first composition comprises 40 to 70% by weight, or 4 The above having a C2 (polymerized ethylene) content of 2 to 62% by weight, or 45 to 65% by weight. The first composition according to any one of a) to f). h) the first composition has a viscosity of 2.10 to 3.20, or 2.20 to 3.00, or 2. The above has a molecular weight distribution (Mw / Mn) of 30 to 2.90, or 2.40 to 2.80. The first composition according to any one of a) to g). i) the first composition has a molecular weight of 72 to 90, or 74 to 88, or 76 to 86 g / mol; or a Mooney viscosity (ML1+4, 1) of 78 to 88 g / mol, or 80 to 86 g / mol 25°C). j) the first composition has a percent crystallinity of 15% or less, or 10% or less, or 5% or less; The first composition according to any one of a) to i) above, k) the Mooney viscosity (ML1+4, 125°C) of the first composition, -Mooney Viscosity (ML1+4, 125°C) of Olefin / Diene Interpolymers The ratio is 0.75 to 1.05, or 0.80 to 1.00, or 0.85 to 0.95. The first composition according to any one of a) to j) above. l) the first interpolymer and the second interpolymer comprise a total weight of the first composition; The above a) to k) constitute 95% by weight or more, 98% by weight or more, or 99% by weight or more of the amount of the ) The first composition described in any one of the above. m) The first composition is determined by 13C NMR (propylene stereoregularity marker). If specified, it must be 5.0 or higher, or 6.0 or higher, or 7.0 or higher, or 8.0 or higher; or 9.0 or higher, or 10 or higher, or 11 or higher, or 12 or higher, or 13 or higher or 14 or more, or 15 or more "Peak area% (21.3-22.0 ppm)" The first composition described in any one of a) to l) above. n) A composition comprising the first composition according to any one of a) to m) above and an additive. . o) The composition according to n) above, wherein the additive is ZnO, MgO, or even MgO. p) the first composition is 26% by weight to 42% by weight, or 8% to 40% by weight, or 30% to 38% by weight, or 32% to 36% by weight The composition according to n) or o) above, wherein the composition is present in an amount of q) the weight ratio of the first composition to the additive (e.g., MgO) is 2.0 to 8.0; or 3.0 to 7.0, or 4.0 to 6.0, any one of the above a) to p). The composition described. r) The composition has a tensile strength of 50% of its original after 1008 hours (6 weeks) in air at 150°C. Retains 0% or more, or 55% or more, or 60% or more, and 35% or more of the original elongation at break or retain 40% or more, or 45% or more, as described in any one of a) to q) above. The composition described above. s) The composition has a tensile strength of 50% of its original after 1008 hours (6 weeks) in air at 150°C. 0% to 65% of the original elongation at break and 35% to 50% of the original elongation at break, The composition according to any one of the preceding claims. t) the composition comprises a majority amount of polymerized propylene, based on the weight of the polymer; .50% by weight or less, or 0.10% by weight or less, or 0.05% by weight or less, or 0. 10.01% by weight or less of a propylene-based polymer, Composition. In a further embodiment, the composition does not include a propylene-based polymer. u) A crosslinked composition comprising the composition according to any one of a) to t) above. v) at least one composition formed from any one of a) to u) above; An article that contains components.

[0077] Ethylene / α-Olefin / Diene Interpolymer The first composition comprises a first ethylene / α-olefin / diene interpolymer. In a preferred embodiment, the second ethylene / α-olefin interpolymer is independently and is an ethylene / α-olefin / diene interpolymer.

[0078] Each ethylene / α-olefin / diene interpolymer may independently be, in polymerized form, Includes ethylene, α-olefins, and dienes. α-olefins are aliphatic or In one embodiment, the α-olefin is any of the C 3 ~ C 20 Aliphatic compounds, preferably C 3 ~C 16 Aliphatic compounds, and more preferably C 3 ~C 10 It is an aliphatic compound. 3 ~C 10 Aliphatic α-olefins are Preferably, the olefin is selected from the group consisting of 1-butene, 1-hexene, and 1-octene. Preferably, it is propylene.

[0079] Suitable examples of dienes include C 4 -C 40 Exemplary non-conjugated dienes include The dienes include linear acyclic dienes such as 1,4-hexadiene and 1,5-heptadiene. 5-Methyl-1,4-hexadiene, 2-Methyl-1,5-hexadiene, 6-Methyl 1,5-heptadiene, 7-methyl-1,6-octadiene, 3,7-dimethyl-1 ,6-Octadiene, 3,7-Dimethyl-1,7-Octadiene, 5,7-Dimethyl-1 ,7-octadiene, 1,9-decadiene, and mixed isomers of dihydromyrcene. Branched chain acyclic dienes; 1,4-cyclohexadiene, 1,5-cyclooctadiene, and Monocyclic alicyclic dienes such as 1,5-cyclododecadiene; tetrahydroindene, methyl Polycyclic alicyclic fused and bridged ring dienes such as 5-methylene-2- Norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-vinyl- 2-Norbornene, 5-Propenyl-2-Norbornene, 5-Isopropylidene-2-Norbornene Norbornene, 5-(4-cyclopentenyl)-2-norbornene, and 5-cyclohexene Alkenyl, alkylidene, cycloalkenyl, and cycloalkylene such as cyclohexyl-2-norbornene. and cycloalkylidenenorbornene. In one embodiment, the diene is ENB, diphenylene. Cyclopentadiene, 1,4-hexadiene, 7-methyl-1,6-octadiene In an embodiment, the diene is ENB.

[0080] In one embodiment or combination of embodiments described herein, each ethylene / α-olefin Olefin / diene interpolymer is an ethylene / α-olefin / diene terpolymer In a further embodiment, the interpolymer is ethylene / propylene. In a further embodiment, the terpolymer is an ethylene / diene terpolymer (EPDM). The ene is 5-ethylidene-2-norbornene (ENB).

[0081] In one embodiment or combination of embodiments described herein, the diene is 5-vinyl 1,5-Hexadiene (HD), Dicyclopentadiene (Dc) (DCPD), or 5-ethylidene-2-norbornene (ENB).

[0082] The ethylene / α-olefin / non-conjugated diene interpolymers are the two The EPDM terpolymer may comprise any combination of one or more of the embodiments described herein. The embodiments may include a combination of two or more of the above-mentioned embodiments.

[0083] In one embodiment or combination of embodiments described herein, the first ethylene / α -olefin / diene interpolymer and a second ethylene / α-olefin / diene interpolymer The total weight of the interpolymer is 95% by weight or more, based on the weight of the first composition; and is 96% by weight or more, or 97% by weight or more, or 98% by weight or more, or 99% by weight or more Above.

[0084] In one embodiment, the first composition has a CdS ratio of 0.890 or less, or 0.880 or less, or 0.875 or less, or 0.870 or less, or 0.865 or less, or 0.860g / In one embodiment, the first composition has a density of 0.850 g / cc or greater. or has a density of 0.855 g / cc or greater (1 cc = 1 cm3). In one embodiment, the first composition is 20 / 80 to 40 / 60, or 25 / 75 to 40 / 60, or 30 / 70 to 40 / 60 of the first interpolymer. The weight ratio of the polymer to the

[0085] The first composition may comprise a combination of two or more embodiments described herein.

[0086] Additives and Applications The composition may contain, among other things, oils, crosslinking (or vulcanizing) agents, fillers, antioxidants, flame retardants, foaming agents, The composition may include one or more additives such as adhesives, colorants or pigments, and thermoplastic polymers.

[0087] In one embodiment, the oil is selected from the group consisting of non-aromatic oils, paraffinic oils, naphthenic oils, and combinations thereof. Suitable oils include SUNPAR 2280, PARA 2280, and combinations thereof. Includes LUX 6001, HYDROBRITE 550, and CALSOL 5550. The oil may include, but is not limited to, two or more embodiments as described herein. The present invention may include a combination of the above aspects.

[0088] Exemplary crosslinking / vulcanizing agents include, among others, elemental sulfur, 4,4'-dithiodimorpholine , thiuram di- and polysulfides, alkylphenol disulfides, and 2-molybdenum disulfides. Sulfur-containing compounds such as fluorodithiobenzothiazole; di-tert-butyl peroxide; Tert-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di-(te rt-butylperoxy)hexane, di-(tert-butyl-peroxyisopropyl)be benzene, tert-butyl peroxybenzoate, and 1,1-di-(tert-butyl Peroxides such as peroxy)-3,3,5-trimethylcyclohexane; azo compounds; biphenyls Silanes such as vinyltri-ethoxysilane or vinyltri-methoxysilane; p-quinones -dioxime and dinitroso compounds such as p,p'-dibenzoylquinone-dioxime Phenol-formaldehyde containing hydroxymethyl or halomethyl functional groups hydroresins; and other types of radical generators (e.g., NO-breaking types and C- C-break type) and the like. The suitability of any of these crosslinking / vulcanizing agents is well known to those skilled in the compounding art. In one embodiment, the crosslinking / vulcanizing agent comprises a sulfur-containing compound.

[0089] Additional additives include fillers, flame retardants, colorants or pigments, thermoplastic polymers, and Such additives include, but are not limited to, those combinations. The fillers may be used in any desired amount to achieve the desired effect. These include, but are not limited to, earth, talc, or carbon black.

[0090] In one embodiment or combination of embodiments described herein, the composition of the invention comprises: Further included is at least one antioxidant. Exemplary antioxidants include peroxy and alkoxy. Hoxy radical traps (amines and hindered phenols), hydroperoxides These include, but are not limited to, decontaminants, decontaminants, and synergists.

[0091] In one embodiment or combination of embodiments described herein, the composition of the invention comprises: Exemplary polymers include propylene-based polymers, ethylene-based polymers, and the like. 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), a homogeneously branched linear ethylene polymer, and Homogeneously branched substantially linear ethylene polymers (i.e., homogeneously branched long chain branched Polymers that are ethylene polymers.

[0092] The compositions of the present invention can be used to prepare a variety of articles, or components or parts thereof. The compositions of the present invention can be used in any of a number of conventional methods and devices. It can then be converted into a finished product by one of several processes. Exemplary processes include extrusion, calendering, These include, but are not limited to, machining, compression molding, and other typical thermoset forming processes. Articles include, but are not limited to, sheets, foams, molded articles, and extruded parts. Additional articles include, but are not limited to, automotive parts, weather stripping, belts, hoses, construction Building profiles, wire and cable jacketing, flooring, gaskets, tires and tire construction These include components, computer parts, building materials, and footwear components. This list can be easily expanded without undue experimentation. The compositions of the present invention are particularly suitable for use as hoses for automotive cooling hoses. For example, the compositions of the present invention may comprise: Can be used for engine cooling hoses.

[0093] definition Unless stated to the contrary, implicit from the context, or in the art, Unless otherwise customary, all parts and percentages are by weight and all test methods are as specified in this document. The disclosure is current as of the filing date.

[0094] As used herein, the term "composition" and similar terms refer to a composition that includes Mixtures or blends of two or more materials, including, but not limited to, reaction products formed from the materials of the composition. This refers to products and decomposition products.

[0095] "Comprising," "Including," "Having" The transitional phrases "compounds" and their derivatives are not intended to be limiting unless the same is specifically disclosed. It is not intended to exclude the presence of any additional components, steps, or procedures. For the avoidance of doubt, the assertion made through the use of the word "including" All compositions are either polymeric or not unless stated to the contrary. Regardless, any additional additives, adjuvants, or compounds may be included. In general, the term "consisting essentially of" means anything except anything that is not essential to operability. " " excludes from the scope of the ensuing recitation any other component, step, or procedure. The term "comprising" does not include any component, step, or method not specifically defined or listed. Exclude a step or procedure.

[0096] As used herein, the term "polymer" refers to polymers of the same or different types. It refers to a polymeric compound prepared by polymerizing monomers of the type: The general term polymer is homopolymer (a polymer structure in which trace amounts of impurities are not incorporated) To refer to a polymer prepared from only one monomer type, with the understanding that the monomers may be mixed together. and interpolymers, as that term is defined herein below. Trace amounts of impurities such as catalyst residues are removed from and / or into the polymer. It can be incorporated.

[0097] As used herein, the term "interpolymer" refers to a polymer that is It refers to a polymer prepared by polymerization of different types of monomers. The generic term for polymers is copolymers (polymers prepared from two different types of monomers). (used to refer to polymers), and those prepared from three or more different types of monomers Polymers that can be synthesized (e.g., terpolymers (three different monomer types) and tetrapolymers) It contains four different monomer types.

[0098] As used herein, the term "ethylene-based polymer" and similar terms refer to , in polymerized form, at 50% by weight or at most 50% by weight (based on the weight of the polymer) "ethylene" refers to a polymer that contains ethylene monomer and may optionally contain one or more comonomers.

[0099] As used herein, "ethylene / α-olefin / diene interpolymer" refers to a " refers to a polymer that, in polymerized form, contains ethylene, an α-olefin, and a diene. In one embodiment, the "ethylene / α-olefin / diene interpolymer" refers to It contains a majority weight percent ethylene (based on the weight of the interpolymer).

[0100] As used herein, "ethylene / α-olefin interpolymer" and The same term refers to a polymeric mixture of ethylene and an α-olefin, and optionally another comonomer. In a preferred embodiment, the term "ethylene / α-olefin interpolymer" refers to a polymer that includes an ethylene / α-olefin interpolymer. The "polymer" is an ethylene / α-olefin / diene interpolymer.

[0101] As used herein, "ethylene / α-olefin copolymers" and similar The term refers to copolymers that, in polymerized form, contain 50% or a majority by weight of ethylene, based on the weight of the copolymer. and an α-olefin as the only monomer type.

[0102] Test Method Gel Permeation Chromatography The chromatography system was Polymer Laboratories Mo del PL-210 or Polymer Laboratories Model The column and carousel compartments were operated at 140 °C. The columns were three Polymer Laboratories, 10 micron Mix The column was ed-B. The solvent was 1,2,4 trichlorobenzene. To prepare the samples, a concentration of 0.1 g polymer per ml solvent was prepared. The solvent used contained 200 ppm of butylated hydroxytoluene (BHT). The samples were prepared by stirring lightly at 160°C for 2 h. The injection volume was 100 The volume was microliters and the flow rate was 1.0 milliliters / minute.

[0103] The calibration of the GPC column set was performed using 6 MW NMR spectra with at least one order of magnitude separation between individual molecular weights. The 580-8,400,000 g / mol range was placed in a "cocktail" mixture of The study was carried out using 21 "narrow molecular weight distribution polystyrene standards" with molecular weights of 100 to 1500 mm. was purchased from Polymer Laboratories (Shropshire, UK). Polystyrene standards with molecular weights of 1,000 kg / mol or more are classified as "50 mm" or "100 mm". 0.025 grams per liter of solvent, if the molecular weight is less than 1,000 kg / mol The polystyrene standards were prepared at 0.05 grams in 50 milliliters of solvent. The solution was dissolved at 80°C for 30 minutes with gentle stirring. The standards mixtures were run in order of decreasing "highest molecular weight" component first. Polystyrene standards The product peak molecular weight was converted to polyethylene molecular weight using the following formula: M polyethylene = A×(Mpolystyrene)B, where M is the molecular weight and A has a value of 0.431; B is equal to 1.0 (Williams and Ward, J. Polym. Sc. , Polym. Lett., 6, 621 (1968). Len equivalent molecular weight calculations were performed using Viscotek TriSEC software version 3.0 This was done using

[0104] 13C NMR Method for EPDM Composition Analysis The sample was placed in a 10 mm NMR tube as a 0.2 g sample, and then diluted with chromium acetylacetonate. Approximately 2.6 g of tetrachloroethane-d The mixture was prepared by adding a 50 / 50 mixture of chloroform and o-dichlorobenzene. The sample was dissolved and homogenized by heating the vessel and its contents to 150°C. The Bruker 4 is equipped with a Bruker Dual DUL high temperature CryoProbe. The data was collected using a 100 MHz spectrometer. The acquisition was performed using a pulse repetition delay of 6 seconds at a sample temperature of 120 °C. A spectral width of 25,000Hz and a file size of 32K data points were used. The NMR spectrum analysis of each composition in the examples was carried out using the following analytical method: did.

[0105] Dynamic mechanical spectroscopy (DMS) Small angle oscillatory shear (molten DMS) was performed in a T with a "25 mm parallel plate" under nitrogen purge. The test was carried out using ARES Instruments. The time at which the sample was heated was set to 5 min for all samples. The experiments were performed at frequencies ranging from 0.1 to 100 rad / s. The strain amplitude was calculated based on the response of the sample from 1 to 3%. The stress response was analyzed in terms of amplitude and phase, from which the storage modulus (G'), loss modulus (L) and elastic modulus (L) were calculated. The elastic modulus (G"), dynamic viscosity η*, and tan delta were calculated. The material is a compression molded disk with a diameter of 25 mm and a thickness of 3.3 mm, which is subjected to a temperature of 180°C and 10 MPa. The molded product was molded at a molding pressure of 1000 for 5 minutes, and then quenched between cooling platens (15 to 20°C) for 2 minutes. The rheology ratio (V0.1 / V100 at 190°C; also called "RR") was recorded. -shaped molecules (with no detectable long chain branching) typically have an RR of 8 or less.

[0106] Differential Scanning Calorimetry (DSC) Crystallization of ethylene-based (PE) samples (including EPDM) and propylene-based (PP) samples Differential scanning calorimetry (DSC) is used to measure the degree of oxidation. The mixture was compression molded into a film at 5000 psi for 2 minutes at ℃. The film sample was about 5-8 mg. Weigh out and place in the DSC dish. Crimp the lid onto the dish to ensure a closed atmosphere. Place the sample dish in the D The sample was placed in an SC cell and heated to 180°C for PE (180°C for PP) at a rate of about 10°C / min. The sample is heated to a temperature of 230°C. The sample is held at this temperature for 3 minutes. The sample is then heated to a temperature of 230°C. Cool to -90°C for PE (-90°C for PP) at a rate of °C / min and hold at that temperature for 3 minutes. The sample is then heated at a rate of 10°C / min until it is completely melted (step The percent crystallinity is calculated by multiplying the heat of fusion (Hf) determined from the second heat curve by the P Divide by the theoretical heat of fusion of 292 J / g for E (165 J / g for PP) and multiply this amount by 10 Calculate by multiplying by 0 (e.g., crystallinity % = (Hf / 292 J / g) x 1 00 (for PE). Unless otherwise stated, the melting point (Tm) of each polymer is determined from the second heat curve. and the crystallization temperature (Tc) is determined from the first cooling curve.

[0107] Mooney Viscosity Mooney viscosity (ML1+4 at 125°C) was measured according to ASTM 1646 for 1 minute. The measurements were taken at a preheat time and a rotor run time of 4 minutes. The equipment was Alpha Techno The viscosity of each compounded composition was measured using a Logies Mooney Viscometer 2000. The viscosity was measured using an uncured blanket so that the viscosity of the uncured composition could be examined. The samples were conditioned at room temperature for 24 hours before testing.

[0108] Coach Mooney The scorch properties of each composition were measured using Alpha Tec Measured using a hnologies Mooney Viscometer 2000 The Mooney viscometer was set at 125°C. The Mooney scorch value was calculated for a small rotor. It is reported as the time it takes for "x Mooney units" to rise above a minimum viscosity (e.g. (For example, t5 is a "5 Mooney unit" increase in viscosity). Total test time was 30 minutes, with preheat The time was 1 minute. The viscosity of the composition was measured at an uncured temperature so that the scorch characteristics could be examined. The viscosity was measured from a cured blanket and cured with a viscometer. Samples were conditioned at room temperature for 24 hours before testing. did.

[0109] MDR analysis The MDR cure characteristics of each formulation were determined using Alpha Te Measurements were performed using a MDR 2000 Rheometer. The DR test was carried out at 160°C for 30 minutes. The rheology of each compound was Measurements were taken from samples of the cured blanket that were subsequently cured during the MDR analysis. The mixture was adjusted to 0.05g at room temperature for 24 hours. Mooney Low, Mooney High, Tan Delta Low, Tan Delta Yes, the time it takes to reach a certain percentage of cure (e.g. t95 is the time it takes to reach 95% cure) Viscoelastic properties such as the time (in minutes) to reach a temperature of 100°C were measured during the cure cycle. .

[0110] FTIR Method for EPDM Composition Analysis Terpene containing ethylene, propylene, and 5-ethylidene-2-norbornene The ethylene content of the polymer was determined using ASTM D3900. ASTM D6047 for norbornene or dicyclopentadiene content was used and analyzed.

[0111] 13C NMR Method for EPDM Composition Analysis and Tacticity (%mm) Chromium acetylacetonate (relaxant) at 0.025M, tetrachloroethylene Approximately 2.6 g of a 50 / 50 mixture of tan-d2 and orthodichlorobenzene was added to a 10 mm The sample was prepared by adding 0.2 g of sample to an NMR tube. The contents were heated to 150° C. to dissolve and homogenize the sample. Bruker 400M with Bruker Dual DUL High Temperature CryoProbe The data was collected using a 30 Hz spectrometer. Data was split into 160 scans per data file. ", acquired using a pulse repetition delay of 6 seconds at a sample temperature of 120 °C. Acquisitions were performed over a 25 The experiment was carried out using a spectral width of 1,000 Hz and a file size of 32K data points. He carried out the

[0112] The NMR spectrum analysis of each composition in the examples was carried out using the following analytical methods. The amount of monomer present in EPDM can be calculated using the following formulas (1-9): By calculating the moles of ethylene, the spectrum of 55.0 to 5.0 ppm can be calculated. The contribution under the normalized integral area is ENB Only seven of the carbons are in the 111 and 112 positions due to concerns that the double bonds may react at high temperatures. and the ENB diene peak at 147 ppm are excluded from the calculation.

number

number

[0113] Propylene stereoregularity %mm area 13C NMR 13C NMR spectroscopy of EPDM samples was used to determine the stereoregularity level (%mm) The NMR was performed as described above using the “tetrachloroethane-d2 / orthodichlorobenzene” method. The NMR spectrum analysis of the EPDM of the present invention was carried out on a 50 / 50 mixture of benzene. (see above) is "Peak area % [rmr, mm mr, mmmm], typically with a total integral area of ​​19.5 ppm to 22.0 ppm. Peak responses in this region are typically seen in EPDM-incorporated This is related to the difference in propylene tacticity (%mm) that is being measured. This can also be done for ethylene / α-olefin / diene interpolymers of the same type. Spectral data shows that the EEE structure (three or more repeats of polymerized ethylene) at 30 ppm Units).

[0114] Dynamic mechanical spectroscopy (DMS) Small angle oscillatory shear (molten DMS) was performed in a T with a "25 mm parallel plate" under nitrogen purge. The test was carried out using ARES Instruments. The time at 0.1–100 rad / s was set to 5 min for all samples. The measurements were performed at 190 °C over a frequency range of 100 s. The strain amplitude was determined based on the response of the sample. The stress response was analyzed in terms of amplitude and phase, and the analysis revealed that the storage The elastic modulus (G'), loss modulus (G''), dynamic viscosity η*, and tan delta were calculated. The specimen for dynamic mechanical spectroscopy was a compression molded disk measuring 25 mm in diameter and 3.3 mm in thickness. It was formed at 180°C and 10 MPa molding pressure for 5 minutes, and then cooled on a cooling plate. The mixture was quenched at 15-20°C for 2 minutes. Rheo of Viscosity in Radians / Second (V0.1 / V100 at 190°C, also called "RR") The rheology ratio was recorded. Linear molecules (no detectable long chain branching) typically have a value below 8. The presence of oil in the polymer may reduce the observed RR. Therefore, the RR value of the polymer-containing oil (RROE_polymer) is used to calculate the polymer ( The following equation was used to estimate the RR of the RR polymers: RR Polymer = RROE_Polymer / (wt% oil*(-0.01988)+1.03 twenty one)

[0115] Compression set Compression set was measured at 23°C and 100°C according to ASTM D395. A disk with a diameter of 29 mm (±0.5 mm) and a thickness of 12.7 (±0.5 mm). was punched out from a compression molded plaque prepared as described in the compression molding section. (See Experimental Section.) Each button specimen was inspected for notches, uneven thickness and non-uniformity. The buttons selected from the samples were inspected and tested (without these defects). Compression set was performed on two specimens per test piece and the average result of the two specimens was reported. The button sample is placed in a compression device having two metal plates that can be pressed together; The button specimen was fixed in place at 75% of its original height. Place the device in the oven and heat it at the appropriate temperature for the specified time (23°C or 100°C for 22 In this test, the stress is released at the test temperature and the thickness of the sample is equilibrated at room temperature for 30 minutes. Compression set is a measure of the recovery of a sample after compression and is calculated using the formula: CS=(H 0 -H 2 ) / (H 0 -H 1 )(where H 0 is the original thickness of the sample, H 1 Use The thickness of the spacer bar, H 2 is the final thickness of the sample after the compression force is removed) Calculate.

[0116] Tensile stress-strain properties Tensile properties were determined using small dog-bone specimens having dimensions as specified in ASTM D-1708. The measurements were performed using test specimens that were die cut using a micro-tensile die with a die shape. Cut specimens were prepared from compression molded plaques as described in the compression molding section. The tensile properties (tensile strength and elongation) were measured according to ASTM D-4 INSTRON MODEL produced by INSTRU-MET according to method 12 Measured at room temperature in the 1122 machine direction.

[0117] experiment Representative Synthesis of the First Composition - Sequential Polymerization Polymerization reactions are carried out under steady-state conditions, i.e., constant reactant concentrations of solvent, monomer, and catalyst. Rapid and continuous dosing, as well as constant recovery of unreacted monomer, solvent, and polymer The reactor system was cooled and pressurized to prevent the formation of a vapor phase. Monomer: Ethylene (CAS 74-85-1), Propylene (CAS 115-07-1), 5-Ethyl Norbornene, ENB (CAS 16219-75-3).

[0118] The polymer composition is prepared by solution polymerization using a continuous stirred tank reactor followed by a loop reactor. The ethylene was produced using the ISOPAR E (available from ExxonMobil) process. ) into a mixture of solvents, propylene is introduced, and 5-ethylidene-2-norbornene ( ENB) were introduced to form the reactor feed streams, respectively. The catalyst was fed separately to each reactor. Cocatalyst 1 and cocatalyst 2 were used to activate the catalyst in situ. As a result, the outlet of each reactor was: It was a mixture of polymer, solvent, and reduced levels of initial monomer. The outlet of the polymer was fed directly to the second reactor (unless sampled). The molecular weight was determined by varying the temperature of each reactor, the monomer conversion, and / or the addition of chain terminators such as hydrogen. The temperature was controlled by adjusting the pressure.

[0119] After polymerization, a small amount of water is introduced into the reactor outlet stream as a catalyst deactivator, and the reactor outlet stream is concentrated to a solids content of 100%. The unreacted monomer was then introduced into a flash vessel where the monomer concentration had increased by at least 100%. - a portion of the ENB, ethylene, and propylene, and unused diluent The polymerization reactor was further described in detail below. See also U.S. Patent Nos. 5,977,251 and 6,545,088. The monomer feed rates and polymerization temperatures as well as other conditions are listed in Tables 1 and 2 below. The properties of the first composition are shown in Table 3. [Table 1] [Table 2]

[0120] As can be seen in Table 3, EPDM 01 and EPDM 02 are NORDEL 4 570 and NORDEL 4770. The EPDM composition also has a high specificity with respect to the %mm (meso diad) stereoregularity in the EPDM. In the case of association, it is indicated by a significant "NMR peak area % of 21.3 to 22.0 ppm". It also contains EPDM with an unexpectedly large amount of propylene stereoregularity, as shown in FIG. [Table 3]

[0121] Formulations (Inventive Compositions and Comparative Compositions) The raw materials and test formulations of the examples and comparative examples of the present invention are shown in Tables 4 and 5, respectively. are listed below. [Table 4] [Table 5]

[0122] Formulation and Mixing Each compound (composition) was mixed in an internal rubber mixer, i.e., in accordance with ASTM D 3182. The mixture was mixed in a Banbury Lab Mixer BR 1600 (batch mixer). The mixer was equipped with a pair of two-blade rotors. The batch weight was adjusted to 75 vol.% fill in the mixer bowl. The rotor speed was adjusted for the duration of the mix cycle (total mix time approximately 5 minutes). The rpm was kept constant at 50 rpm. A thermocouple was used to measure the melting temperature of the mixture. Using a simple "upside down" mixing procedure, (carbon black, CaCO 3 , MAGLITE D, VANOX CDPA, and VANOX MTI) were added first, followed by oil (SU NPAR 2280) into the mixing bowl and add the first component (EPDM or EPDM blend). The peroxide curing system ( VULCUP 40KE, SARET SR 517 HP) was then added to the mixture. Once the melt temperature reached 105°C, the final blend mixture was dropped into a tray. The mixture was then transferred to a reliable 6-inch two-roll mill. Mixing was performed on the two-roll mill at ambient conditions. The compound batch was rolled five times in a two-roll mill. Each compound sheet (uncured) had a thickness of approximately 0.09 inches. It had a thickness.

[0123] Compound properties (rheological and mechanical) Mooney Viscosity The Mooney viscosity of each compounded composition was determined so that the viscosity of the uncured composition could be determined. The measurements were made using samples taken from the uncured compound sheets. Mooney Viscosity (ML at 100°C) 1+4) according to ASTM 1646 with 1 minute preheat time and 4 minutes rotor operation The measurement was performed in hours. The equipment was an Alpha Technologies Mooney Vi The scometer is 2000.

[0124] MDR analysis The cure rate profile of each formulation (composition) at 180°C was measured according to ASTM D5289 According to Alpha Technology Moving Die Rheomet The MDR test was performed at 180°C for 30 minutes. Rheology or torque curves for each formulation were recorded as a function of time for 18 Curing as a function of time (at 180°C) measured from uncured sheet samples at a temperature of 0°C The profile was examined. The minimum S' torque (ML), the maximum S' torque (MH, or 100 % cure), and the time to reach a certain percentage of cure (e.g., t95 is the time to reach 95% cure). The viscoelastic properties, such as the time (in minutes) to reach a cured state, were measured during the cure cycle. See Table 6. [Table 6]

[0125] Compression Molded Plaque (6" x 6" x 0.077") The mechanical properties of each compound were measured from vulcanized sheets cured in a compression molder (tensile, and Shore A hardness). Samples from uncured compound sheets were cut into The slab weights were calculated based on the specific gravity of the compound. The mill direction was marked and the sample was labeled. Spray with Camie 999 Dry Silicone Spray from Campbell The mold (6 in. x 6 in. x 0.077 in.) was placed on the platen. The sample was carefully placed in a mold that was preheated to a temperature of 180°C. The platens were closed. To vulcanize the sample, the sample was vulcanized for 18 minutes using the plaque's "t95 data + 3 minutes". The material was placed under a minimum compressive pressure of 3.5 MPa (500 psi) at 0°C. At the end of the curing period, (t95 data + 3 minutes), the lower platen opened automatically. The sample in the mold was removed and The hardening was stopped by immediately placing the specimens in water (room temperature). Prior to this, the samples were conditioned in air at room temperature for at least 18 hours.

[0126] Physical properties of the vulcanizates (original and aged samples) After curing, the cured specimens / vulcanizates were conditioned at ambient conditions for at least 18 hours before testing. The properties are listed in Tables 4, 5A, 5B, and 5C below. Tensile stress-strain properties

[0127] The original tensile properties were measured using "dumbbell" specimens having dimensions as specified in ASTM D-412. Using a tensile die shaped as above, specimens were die cut from the cured plaque. Three die cut specimens were cut from one plaque.

[0128] For heat aging tensile property measurements, first, the test specimens were heated to 100°C in the same manner as described in ASTM D-412. The hardened plaque was then stretched using a "dumbbell" shaped pulling die having dimensions equal to: These test pieces were then die-cut from the mold. The heat-aged tensile properties were then measured for these heat-aged samples. The tensile properties (tensile strength and elongation) were measured using test specimens according to ASTM D-412 and was measured at room temperature according to ASTM D-573 method. Shore A hardness properties

[0129] Shore A hardness properties were measured using 100% JIS B 10111-1010, each having dimensions as set forth in ASTM D-412. Measurements were taken using three stacked die-cut specimens (dumbbells). Ikat specimens were cut from the compression molded plaques prepared as described above. Hardness properties were measured at room temperature according to ASTM D-2240 method. [Table 7]

[0130] The heat aging properties of the vulcanizates are shown in Table 8 below. As can be seen from the table, the compositions of the present invention It has good mechanical properties and exhibits excellent long-term heat aging properties compared to the comparative compositions. In addition, the samples of compositions 1 and 2 of the present invention were aged in air at 150° C. for 1008 hours. After that, the comparison shows an increase of 8 and 9 Shore A units, respectively, while the comparison shows an increase of 14 units. This indicates an increase in [Table 8]

Claims

1. A first composition comprising 30 to 40 weight percent of a first ethylene / α-olefin / diene interpolymer and 60 to 70 weight percent of a second ethylene / α-olefin interpolymer, the first composition comprises 0.1 to 1.0 wt. % of a diene, based on the weight of the first composition; the first composition comprises 45 to 65 weight percent ethylene, based on the weight of the first composition; the first ethylene / α-olefin / diene interpolymer has a weight average molecular weight (Mw) of 250,000 to 500,000 g / mole, and a diene content of 0.40 to 0.60 wt%, and a C2 (polymerized ethylene) content of 55 to 80 wt%, based on the weight of the first ethylene / α-olefin / diene interpolymer; the first composition having a weight average molecular weight (Mw) of 200,000 to 280,000 g / mol, a crystallinity of 0.5 to 12%, and １３ It has a "peak area % (21.3-22.0 ppm)" of 5.0% or more as determined by C NMR, and The first composition comprises a total of 95 weight percent or more of the first ethylene / α-olefin / diene interpolymer and the second ethylene / α-olefin interpolymer, based on the weight of the first composition, wherein the ratio of the C2 (polymerized ethylene) content of the first composition to the C2 (polymerized ethylene) content of the first ethylene / α-olefin / diene interpolymer is from 0.50 to 1.10, and the ratio of the Mooney viscosity (ML1+4, 125° C.) of the first composition to the Mooney viscosity (ML1+4, 125° C.) of the first ethylene / α-olefin / diene interpolymer is from 0.75 to 1.

05.

2. 2. The first composition of claim 1, wherein the first ethylene / α-olefin / diene interpolymer and the second ethylene / α-olefin interpolymer are each independently an EPDM.

3. 3. The first composition according to claim 1 or 2, wherein the first composition has a molecular weight distribution (Mw / Mn) of 2.10 to 3.

20.

4. The first composition of any one of claims 1 to 3, wherein the first interpolymer and the second interpolymer constitute 95 wt% or greater of the total weight of the first composition.

5. A crosslinked composition comprising the composition of any one of claims 1 to 4.

6. An article comprising at least one component formed from the composition of any one of claims 1 to 5.

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