Elastomeric composition comprising epdm and epr

Abstract

In some embodiments, this disclosure provides compositions comprising 5 phr–30 phr of a PEDM terpolymer having 1–10 wt% diene, 13–40 wt% ethylene, and 15–85 wt% propylene, based on the weight of the PEDM terpolymer. The compositions further comprise 70 phr–95 phr of a terpolymer having an ethylene content, C3–C4, and C4 content different from the first polymer. 12 Ethylene-based copolymers of α-olefins and, unnecessarily, one or more dienes.

Description

[0001] This invention patent application is a divisional application of the invention patent application with application number 201880034708.5, application date February 6, 2018, and invention title "Elastomer Composition Containing EPDM and EPR".

[0002] Priority Statement

[0003] This application claims priority and benefit to U.S. Patent Application Serial No. 62 / 485,649, filed April 14, 2017, the entire contents of which are incorporated herein by reference. Technical Field

[0004] This disclosure relates to polymer compositions comprising propylene-α-olefin-diene terpolymers, such as propylene-ethylene-diene (PEDM) terpolymers, and transmission belts and other articles comprising such terpolymers. Background Technology

[0005] Power transmission belts include V-belts, flat belts, toothed or synchronous belts, and multi-ribbed belts. Belt construction typically includes an elastomer belt body, a tension cable or other fabric tension member embedded in or spirally wound around the belt body, and other fabric reinforcements typically embedded in or covering one or more of the belt surface.

[0006] The elastomer tape may include one or more vulcanized rubber compositions, or elastomer compositions, such as thermoplastic elastomer compositions. The elastomer compositions used include ethylene-propylene-(optional diene) polymers, referred to as EP(D)M polymers or EP(D)M rubbers. EP(D)M polymer-based elastomer compositions require a suitable combination of processability and physical properties in both vulcanized and unvulcanized states to meet manufacturing and end-use application requirements.

[0007] Two noteworthy properties currently lacking in vulcanized EP(D)M compositions for drive belt applications are the balance between tack and green strength. Tack is the maximum force required to separate two identical composition samples (e.g., rubber specimens), while green strength is the tensile modulus measured at 25% or higher of the elongation of the composition sample (e.g., rubber specimen).

[0008] From a manufacturing perspective, for uncured EP(D)M compositions, the uncured elastomer sheets from the calender rolls should have sufficient tack to allow individual sheets to be joined to form sheets several times wider than the calendered sheets. The uncured elastomer should also have sufficient raw rubber strength to be rolled onto the core without sagging. EP(D)M polymers do not have sufficient tack and raw rubber strength for use (and for manufacturing) drive belts.

[0009] Tackiness and raw rubber strength are influenced by polymer crystallinity. Lower crystallinity results in higher tackiness. For example, the tackiness of an EP(D)M composition can be altered by reducing the ethylene content of the EP(D)M polymer, thereby reducing crystallinity. However, lower crystallinity reduces raw rubber strength. Furthermore, lower crystallinity is detrimental to properties such as abrasion resistance, which is also an important performance characteristic of drive belts. In practice, designing a single polymer (or polymer composition) with these distinct polymer characteristics to meet the requirements for tackiness and raw rubber strength is a synthetic challenge.

[0010] Hydrocarbon tackifiers have been used as additives in EP(D)M compositions to enhance tack. However, unhydrogenated tackifiers, when co-vulcanized with EP(D)M, do not exhibit long-term heat resistance due to their unsaturation. Hydrogenated tackifiers show better thermal stability; however, they are more expensive. Furthermore, tackifying resins, when introduced as additives rather than replacing EP(D)M polymer components, directionally increase the cost of EP(D)M formulations.

[0011] Some potentially relevant background references include: WIPO Publications WO 2016 / 053541, WO 2016 / 053542, WO 2016 / 114914; U.S. Patents 5,654,370; 5,571,868; 7,199,189; 7,390,866; 7,605,217; 7,867,433; 7,928,165; 8,013,093; 8,765,832 and 8,841,383; U.S. Patent Publication 2013 / 050488; and JR Beatty, Rubber Chem. & Tech., 42,1041 (1969) and GR Hamed, Rubber Chem. & Tech., 54,578 (1981).

[0012] Polymers and polymer compositions still need to have sufficient tack and raw rubber strength for use in drive belts. Summary of the Invention Invention Overview

[0014] Embodiments of this disclosure include compositions comprising, in minor amounts (e.g., 5 phr-30 phr of such a composition), a propylene-α-olefin-diene terpolymer, such as a first polymer of a propylene-ethylene-diene terpolymer (this terpolymer may be simply referred to herein as "PEDM," even if other α-olefins are considered as comonomers with propylene and diene in place of or to supplement ethylene, and similarly, other polyenes may be used in place of or to supplement diene, unless specifically indicated otherwise). The compositions of various embodiments also include, in major amounts (e.g., 70 phr-95 phr of the composition), a second polymer of an ethylene-based copolymer, such as a copolymer of ethylene-α-olefin and non-essential diene (e.g., EP(D)M polymer, or ethylene-butene-non-essential-diene (EB(D)M polymer)). It has been found that the compositions of this disclosure provide improved tack and / or raw rubber strength. The improved tack and / or raw rubber strength make the compositions ideal for, for example, drive belts, and particularly provide improved performance and / or superior manufacturing methods for drive belts.

[0015] In some embodiments, this disclosure provides compositions comprising 5 phr-30 phr of a PEDM terpolymer having 1 wt%-10 wt% of a polyene (e.g., a diene, especially a non-conjugated diene), 13 wt%-40 wt% of an α-olefin (e.g., ethylene), and 15 wt%-85 wt% of propylene, based on the weight of the PEDM terpolymer. The composition further comprises 70 phr-95 phr of an ethylene-based copolymer, the ethylene-based copolymer comprising: an ethylene content different from the α-olefin content of the first polymer; C3-C 12 α-olefin; and optionally, one or more polyenes (preferably one or more dienes).

[0016] In other embodiments, this disclosure provides compositions comprising a first polymer of 5 phr-30 phr, the first polymer being formed by polymerizing propylene, ethylene, and diene in the presence of a bridged fluorenyl-cyclopentadienyl Group 4 catalyst activated by an activator. The catalyst is represented by the following formula (I):

[0017]

[0018] J is a divalent bridging group. M is a group 4 transition metal. Each X is independently a monovalent anionic ligand, or two Xs may bond together with M to form a metallocycle ring, or two Xs may bond to form a chelate ligand, diene ligand, or alkylidene ligand. Each R 1 R 2 R 3 R4 R 5 R 6 R 7 R 8 R 9 and R 10 Independently, it is hydrogen, C1-C 50 Substituted or unsubstituted alkyl group, provided that R 1 and R 2 R 3 and R 4 R 5 and R 6 R 6 and R 7 R 8 and R 9 and R 9 and R 10 Any one or more pairs in the pairing can be bonded together unnecessarily to form a saturated or partially saturated cyclic or fused cyclic structure. The activator is a noncoordinate anionic activator. The composition also contains an ethylene-based copolymer of 75 phr-95 phr.

[0019] In particular, this application relates to the following aspects:

[0020] Item 1. Composition, comprising:

[0021] A propylene-α-olefin-diene (PEDM) terpolymer comprising 5-30 parts by weight per 100 parts by weight of rubber (phr), comprising 1-10 wt% diene, 13-40 wt% α-olefin and 15-85 wt% propylene, wherein the wt% is based on the weight of the PEDM terpolymer; and

[0022] 70-95 phr ethylene-based copolymers comprising ethylene, one or more C3-C 12 α-olefins and one or more dienes, not necessarily; wherein the amount of ethylene content (in wt%, based on the total weight of the ethylene-based copolymer) of the ethylene-based copolymer is different from the amount of α-olefin content (in wt%, based on the total weight of the PEDM ter copolymer).

[0023] 2. The composition of claim 1, wherein the PEDM is formed as follows: propylene, one or more α-olefins and one or more dienes are polymerized in the presence of a bridged fluorenyl-cyclopentadienyl Group 4 catalyst that has been activated by an activator.

[0024] The catalyst is represented by the following formula (I):

[0025]

[0026] Where J is a binary bridge basis;

[0027] M is a group 4 transition metal;

[0028] Each X is independently a monovalent anionic ligand, or two Xs are joined together to form a metal cyclic ring with M, or two Xs are joined to form a chelate ligand, diene ligand, or alkylidene ligand.

[0029] Each R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 Independently, it is hydrogen, C1-C 50 Substituted or unsubstituted alkyl group, provided that R 1 and R 2 R 3 and R 4 R 5 and R 6 R 6 and R 7 R 8 and R 9 and R 9 and R 10 In pairing, any one or more pairs can be bonded together unnecessarily to form saturated or partially saturated cyclic or fused cyclic structures; and

[0030] The activator is a noncoordinate anionic activator.

[0031] Item 3. The composition of Item 2, wherein the bridged fluorenyl-cyclopentadienyl Group 4 catalyst is dimethyl-1,1'-bis(4-triethylsilylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butyl-fluoren-9-yl)hafnium.

[0032] Item 4. The composition of Item 2 or 3, wherein the activator is N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate.

[0033] Item 5. A composition of any of the preceding items, wherein the PEDM terpolymer has an H content of less than 1 J / g. f .

[0034] Item 6. The composition of any of the preceding items, wherein the PEDM terpolymer has a crystallinity of 0.1% to 5% as determined by differential scanning calorimetry.

[0035] Item 7. A composition of any one of items 1-5, wherein the PEDM terpolymer has a random stereopropylene sequence.

[0036] Item 8. A composition of any of the preceding items, wherein the PEDM terpolymer has an α-olefin of ethylene and an ethylene content of 30 wt% to 40 wt%.

[0037] Item 9. A composition of any of the preceding items, wherein the diene of the PEDM terpolymer is one or more of the following substances: 5-ethide-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 1,4-hexadiene, alkyl dicyclopentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-heptadiene, 2-methyl-1,5-hexadiene, cyclooctadiene, 1,4-octadiene, 1,7-octadiene, 5-n-propylidene-2-norbornene, 5-(2-methyl-2-butenyl)-2-norbornene, and norbornene.

[0038] Item 10. The composition according to Item 9, wherein the diene of the PEDM terpolymer is 5-ethylidene-2-norbornene.

[0039] Item 11. A composition of any of the preceding items, wherein the PEDM terpolymer has a diene content of 2 wt% to 4 wt%.

[0040] Item 12. A composition of any of the preceding items, wherein the ethylene-based copolymer comprises 40-95 wt% ethylene, 0-10 wt% one or more dienes and C3-C4. 12 α-olefin, the wt% being based on the total weight of the ethylene-based copolymer.

[0041] Item 13. The composition of any of the preceding items, wherein the C3-C of the ethylene-based copolymer is... 12 The α-olefin is propylene or 1-butene.

[0042] Item 14. The composition of any of the preceding items, wherein the C3-C of the ethylene-based copolymer is... 12 The α-olefin is propylene.

[0043] Item 15. An elastomer composition that is at least partially crosslinked, wherein the elastomer is a reaction product of the following substances:

[0044] The composition according to any one of items 1-14;

[0045] One or more vulcanization activators; and

[0046] One or more vulcanizing agents.

[0047] The composition of item 16.15 further comprises one or more additives containing at least one of carbon black and / or processing oil.

[0048] Item 17. The composition of Item 16, wherein the composition comprises an alkane processing oil of 1 phr to 150 phr, the alkane processing oil having a viscosity of 80 to 600 CSt at 40°C.

[0049] The composition of item 18, 16, or 17 further comprises a mineral filler.

[0050] Item 19. A composition of any one of items 15-18, wherein the composition has a viscosity of about 4,000 Pa or greater and a raw rubber strength 25% modulus of about 1.7 MPa or greater.

[0051] Item 20. A composition of any one of items 15-19, wherein the composition has a tensile strength at break of 21.4 MPa or greater.

[0052] Item 21. A composition of any one of items 15-20, wherein the composition has a viscosity of at least about 3.4 kPa.

[0053] The composition of item 22 of item 21, wherein the composition has a viscosity of at least about 5.5 kPa.

[0054] Item 23. Transmission belt, including:

[0055] The composition according to any one of items 1-22.

[0056] The transmission belt of item 24.23 further comprises at least one of filler, plasticizer or stabilizer. Brief description of the attached diagram

[0057] Figure 1 This is a perspective view of a segment of a transmission belt according to some embodiments of this disclosure.

[0058] Figure 2 This is a perspective view of a segment of a drive belt according to another embodiment of this disclosure.

[0059] Figure 3 This is a perspective view of a segment of a transmission belt according to yet another embodiment of this disclosure.

[0060] Figure 4 It is a graph showing the curing state of PEDM with respect to the ethylene content according to various embodiments of this disclosure.

[0061] Figure 5 It is a graph showing the curing rate versus ethylene content of PEDM according to various embodiments of this disclosure.

[0062] Figure 6 It is a graph showing the tensile strength at break versus the ethylene content of PEDM according to various embodiments of this disclosure.

[0063] Figure 7 It is a graph showing the elongation at break (%) versus ethylene content in PEDM according to various embodiments of this disclosure.

[0064] Figure 8 It is a graph showing the Tel-Tak peak force versus ethylene content in PEDM according to various embodiments of this disclosure.

[0065] Figure 9 This is a graph showing the 25% modulus of raw rubber strength versus ethylene content of PEDM according to various embodiments of this disclosure.

[0066] Figure 10A It is a graph showing the phase angle (tanδ) versus frequency of compositions containing PEDMA at 5 phr and 10 phr according to various embodiments of the present disclosure.

[0067] Figure 10B It is a graph showing the phase angle (tanδ) versus frequency of compositions containing PEDMB at 5 phr and 10 phr according to various embodiments of the present disclosure.

[0068] Figure 10C It is a graph showing the phase angle (tan δ) versus frequency of compositions containing PEDMC at 5 phr and 10 phr according to various embodiments of the present disclosure.

[0069] Figure 11A It is a graph showing the elastic modulus (G') of compositions containing PEDMA at 5 phr and 10 phr versus frequency according to various embodiments of the present disclosure.

[0070] Figure 11B It is a graph showing the elastic modulus (G') of compositions containing PEDMB at 5 phr and 10 phr versus frequency according to various embodiments of the present disclosure.

[0071] Figure 11C It is a graph showing the elastic modulus (G') of compositions containing PEDMC at 5 phr and 10 phr versus frequency according to various embodiments of the present disclosure.

[0072] Figure 12 It is a graph showing the Tel-Tak peak force versus ethylene content in PEDM according to various embodiments of this disclosure.

[0073] Figure 13 It is a graph showing the 100% modulus of raw rubber strength versus ethylene content of PEDM according to various embodiments of this disclosure.

[0074] Figure 14 It is a graph showing the rubber-to-rubber adhesion force versus temperature according to various embodiments of the present disclosure.

[0075] Figure 15 It is a diagram showing the modulus (MPa) of the compositions according to various embodiments of the present disclosure.

[0076] Figure 16 It is a diagram showing the fracture stress (MPa) of the composition according to various embodiments of the present disclosure.

[0077] Figure 17 It is a graph showing the elongation at break (%) of the compositions according to various embodiments of the present disclosure. Invention Details

[0078] Embodiments of this disclosure include compositions comprising a first polymer of a PEDM terpolymer in a minor amount (e.g., 5 phr-30 phr of the composition) and a second polymer of an ethylene-based copolymer in a major amount (e.g., 70 phr-95 phr of the composition). It has been found that the compositions of this disclosure provide improved tack and / or raw rubber strength for use in drive belts. These improved properties provide drive belts with improved performance for better application and improved manufacturing.

[0079] definition

[0080] As used herein, the term "polymer" is intended to include polymers having two or more monomers. The term "polymer" as used herein includes, but is not limited to, homopolymers, copolymers, terpolymers, and their alloys and blends. The term "polymer" as used herein also includes impact, block, graft, random, and alternating copolymers. The term "polymer" should also include all possible geometries unless otherwise specified. Such geometries can include isotactic, syndiotactic, and atactic (i.e., atactic) symmetrical configurations.

[0081] As used in this article, the term "blend" refers to a mixture of two or more polymers.

[0082] As used herein, the term "monomer" or "comonomer" can refer to the monomer used to form the polymer, i.e., the unreacted chemical compound in its pre-polymerization form, or it can refer to the monomer that has already been incorporated into the polymer (also referred to herein as "[monomer]-derived unit"). This article discusses various monomers, including propylene monomers, ethylene monomers, and diene monomers.

[0083] As used herein, the term "ethylene-based copolymer" includes copolymers of α-olefins and, not necessarily dienes, derived from ethylene and containing 3 or more carbon atoms, such as 3-12 carbon atoms, or, for example, 6-10 carbon atoms. In a preferred embodiment, the ethylene-based copolymer is an ethylene-propylene copolymer or an ethylene-propylene-diene polymer.

[0084] As used herein, “ethylene-propylene-diene polymer” (EP(D)M) is defined as a copolymer having an ethylene content (derived from ethylene monomers) and a propylene content (derived from propylene monomers), and optionally a diene content (derived from diene monomers, preferably non-conjugated diene monomers), wherein the ethylene content is 40 wt%–95 wt% (e.g., 41 wt%–95 wt%, e.g., 45 wt%–90 wt%, e.g., 50 wt%–80 wt%), the diene content is 0 wt%–15 wt%, and the remainder (i.e., the remaining wt% of the polymer) is primarily (e.g., allowing for minor impurities) or entirely propylene content, based on the weight of the polymer. EP(D)M can have a Mooney viscosity of 15–100 (ML, 1+4 @ 125°C) (measured according to ASTM D1646). The terms “EP(D)M” and “EPDM” are used interchangeably and have the same meaning unless the context otherwise specifies (e.g., when the polymer is referred to as explicitly containing diene monomers (one or more).

[0085] As used herein, the term "propylene-α-olefin-diene terpolymer" includes polymers derived from propylene, α-olefins (preferably ethylene), and diene monomers. As previously noted, propylene-α-olefin-diene terpolymers may be simply referred to as PEDM, even if other α-olefins are considered as comonomers replacing or supplementing ethylene in such terpolymers, and / or polyenes are considered as replacements or supplements for diene. Preferably, the PEDM terpolymer comprises a propylene content (derived from propylene monomers), an ethylene content (derived from ethylene monomers), and a diene content (derived from diene monomers). PEDM has an ethylene content of 8 wt% to 45 wt%, for example 12 wt% to 40 wt%, based on the weight of the polymer.

[0086] As used herein, “phr” refers to parts per 100 parts of rubber, where “rubber” is the total rubber content of the composition. In this document, both PEDM and ethylene-based copolymers (e.g., EP(D)M) are considered to contribute to the total rubber content, such that in a composition in which both are present, “total rubber” is the total weight of the PEDM and ethylene-based copolymer. Thus, for example, a composition having 30 parts by weight of PEDM and 70 parts by weight of the ethylene-based copolymer can be referred to as having 30 phr of PEDM and 70 phr of the ethylene-based copolymer. Other components added to the composition are calculated based on phr – that is, adding 50 phr of oil means, for example, that for every 100 g of total PEDM and ethylene-based copolymer, 50 g of oil is present in the composition. Unless otherwise specified, phr should be considered as a phr by weight.

[0087] As used in this article, "tensile strength" refers to the amount of stress required to cause a sample to break. It can be expressed in Pascals or pounds per square inch (PSI). ASTM D412-16 can be used to determine the tensile strength of polymers.

[0088] The “Mounney viscosity” used herein refers to the Mooney viscosity of a polymer or polymer composition. The polymer composition analyzed for Mooney viscosity determination should be substantially solvent-free. For example, the sample can be placed on a boiling steam stage in a hood to evaporate most of the solvent and unreacted monomers, and then dried overnight (12 hours, 90°C) in a vacuum oven according to laboratory analytical techniques prior to testing, or the test sample can be obtained from a de-volatile polymer (i.e., a polymer after de-volatile processing in industrial-scale methods). Unless otherwise stated, Mooney viscosity is measured using a Mooney viscometer according to ASTM D-1646, but with the following modifications / clarifications to the procedure. First, the sample polymer is pressed between two hot plates of a compression press prior to testing. The plate temperature is 125°C + / -10°C instead of the 50°C + / -5°C recommended in ASTM D-1646, as 50°C does not induce sufficient massing. Additionally, while ASTM D-1646 allows for some options for die protection, PET 36 microns should be used as die protection if any two options provide conflicting results. Furthermore, ASTM D-1646 does not specify the sample weight in paragraph 8; therefore, results may vary to some extent based on sample weight, so the Mooney viscosity determined using a sample weight of 21.5 + / - 2.7 g in the procedure of ASTM D-1646 paragraph 8 will be used as the standard. Finally, the remaining procedures given in D-1646 paragraph 8 prior to the test involve holding the sample in air at 23 + / - 3 °C for 30 min; the Mooney values ​​reported in this paper were determined after holding the sample in air at 24 + / - 3 °C for 30 min. The sample was placed on either side of the rotor according to the ASTM D-1646 test method; the torque required to rotate the viscometer rotor at 2 rpm was measured using a Mooney viscosity sensor. The results are reported in Mooney units (ML, 1+4 @ 125°C), where M is the Mooney viscosity value, L represents the large rotor (defined as ML in ASTM D1646-99), 1 is the preheating time (in minutes), 4 is the sample running time after motor start-up (in minutes), and 125°C is the test temperature. Therefore, a Mooney viscosity of 90 determined by the above method will be reported as 90 MU (ML, 1+4 @ 125°C). Alternatively, the Mooney viscosity may be reported as 90 MU; in this case, unless otherwise stated, this viscosity should be considered determined using the method just described. In some cases, a lower test temperature (e.g., 100°C) may be used, in which case the Mooney viscosity is reported as Mooney viscosity (ML, 1+4 @ 100°C), or @ T°C, where T is the test temperature.

[0089] The numerical ranges used in this document include the values ​​listed in the ranges. For example, the numerical range of "1 wt% - 10 wt%" includes 1 wt% and 10 wt% within the listed ranges.

[0090] Composition

[0091] The compositions of this disclosure comprise a minor amount (e.g., 5 phr-30 phr of the composition) of a first polymer of a random PEDM terpolymer and a major amount (e.g., 70 phr-95 phr of the composition) of a second polymer of a random ethylene-based copolymer. The compositions of this disclosure may contain the first polymer of the PEDM terpolymer in amounts of 1 phr-50 phr, such as 2 phr-40 phr, such as 3 phr-30 phr, such as 4 phr-20 phr, such as 5 phr-18 phr, such as 5 phr-30 phr, such as 5 phr-10 phr, based on the total amount of polymer content in the composition.

[0092] First polymer: PEDM terpolymer

[0093] The PEDM terpolymer disclosed herein has a polyene (preferably diene) content of 1-10 wt% and a C2 or C4-C content of 15-40 wt%. 12 The α-olefin (preferably ethylene) content and 15-85 wt% propylene content, said wt% being based on the weight of the PEDM terpolymer.

[0094] The PEDM terpolymer disclosed herein can have a heat of fusion of less than 1 J / g. f In at least one embodiment, the PEDM terpolymer is amorphous. Alternatively or additionally, the PEDM terpolymer may have a random stereopropylene sequence. In at least one embodiment, the PEDM terpolymer has a glass transition temperature (Tg) of -40°C to -2°C, for example -35°C to -30°C.

[0095] The PEDM terpolymer disclosed herein contains 8 wt% to 40 wt% C2 or C4-C 12The α-olefin comonomer (preferably ethylene) is based on the weight of the PEDM terpolymer. Other preferred ranges for the α-olefin (e.g., ethylene) content include 12 wt%-40 wt%, for example 25 wt%-40 wt%, for example 27 wt%-40 wt%, for example 30 wt%-40 wt%, for example 30 wt%-38 wt%, for example 30 wt%-34 wt%, for example 32 wt%-38 wt%, for example 34 wt%-38 wt%, for example approximately 35 wt%, based on the weight of the PEDM terpolymer. In other embodiments, the α-olefin (preferably ethylene) content may be in a lower range of 12-30 wt%, for example 13-25 wt% or even 13-20 wt%, based on the weight of the PEDM terpolymer.

[0096] As noted, the polyene is preferably (but not necessarily) a diene. Suitable dienes can be conjugated or non-conjugated. Preferably, the diene is non-conjugated. Dienes include 5-ethimide-2-norbornene (ENB); 1,4-hexadiene; 5-methylene-2-norbornene (MNB); 1,6-octadiene; 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene; 1,3-cyclopentadiene; 1,4-cyclohexadiene; vinylnorbornene (VNB); dicyclopentadiene (DCPD); and combinations thereof. Preferably, the diene is ENB or VNB.

[0097] Preferably, the PEDM terpolymer contains 0.2 wt% to 10 wt%, for example 0.5 wt% to 8 wt%, for example 0.8 wt% to 6 wt%, for example 1 wt% to 5 wt%, for example 2 wt% to 4 wt%, for example about 3 wt% of diene content, based on the weight of the terpolymer. Other preferred ranges may include 0.2 wt% to 5 wt%, for example 0.2 wt% to 4 wt%, for example 0.2 wt% to 3.5 wt%, for example 0.2 wt% to 3.0 wt%, for example 0.2 wt% to 2.5 wt%, based on the weight of the polymer. In at least one embodiment, the diene is 0.5 wt% to 10 wt%, for example 0.5 wt% to 4 wt%, for example 1 wt% to 3.5 wt%, for example 0.5 wt% to 3.0 wt%, for example about 3 wt% of 5-ethylidene-2-norbornene content, based on the weight of the polymer.

[0098] The PEDM terpolymers disclosed herein may have a weight-average molecular weight (Mw) of 5,000,000 or less, a number-average molecular weight (Mn) of 3,000,000 or less, and a z-average molecular weight (Mz) of 10,000,000 or less.

[0099] Molecular weights (number-average molecular weight (Mn), weight-average molecular weight (Mw), and z-average molecular weight (Mz)) were determined using a Polymer Laboratories Model 220 high-temperature gel permeation chromatography-size exclusion chromatography (GPC-SEC) system equipped with online differential refractive index (DRI), light scattering (LS), and viscometer (VIS) detectors. Separation was performed using three Polymer Laboratories PLgel 10 m Mixed-B columns at a flow rate of 0.54 ml / min and a nominal injection volume of 300 μL. The detectors and columns were housed in an oven maintained at 135°C. The feed stream from the SEC column was directed into a miniDAWN (Wyatt Technology, Inc.) optical flow chamber and then into the DRI detector. The viscometer was located within the SEC oven, downstream of the DRI detector. A detailed description of these detectors and their calibration has been provided, for example, by T. Sun, P. Brant, RR Chance, and W.W. Graessley in Macromolecules, Vol. 34, No. 19, pp. 6812-6820 (2001).

[0100] The solvent used for SEC experiments was prepared by dissolving 6 g of butylated hydroxytoluene (BHT) as an antioxidant in 4 L of Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.7 μm glass pre-filter, followed by a 0.1 μm Teflon filter. The TCB was then degassed using an in-line degasser before entering the SEC. A polymer solution was prepared by placing the dried polymer in a glass container, adding the desired amount of the aforementioned BHT-stabilized TCB, and then heating the mixture at 160 °C for approximately 2 hours with continuous stirring. All quantities were measured by gravimetric analysis. The TCB density used for polymer concentration, expressed in mass / volume units, was 1.463 g / ml at 22 °C and 1.324 g / ml at 135 °C. Injection concentrations were 1.0–2.0 mg / ml, with lower concentrations used for higher molecular weight samples. The DRI detector and syringe were purged before testing each sample. The flow rate in the device was then increased to 0.5 ml / min, and DRI stabilization was allowed for 8–9 hours before injecting the first sample. The concentration (c) at each point in the chromatogram was calculated by subtracting the baseline DRI signal (I) from the following equation. DRI )calculate:

[0101]

[0102] Where K DRIThe constant (dn / dc) is determined by correcting the DRI using a series of monodisperse polystyrene standard samples with molecular weights of 600-10M. It represents the refractive index increment of the system. At 145°C and λ=690 nm, the refractive index n of TCB is 1.500. For the purposes of this invention and the appended claims, (dn / dc) = 0.1048 for ethylene-propylene copolymers, and (dn / dc) = 0.01048-0.0016ENB for EPDM containing ENB as a diene, where ENB is the ENB content in the ethylene-propylene-diene terpolymer (wt%). When other non-conjugated polyenes are used instead of ENB (or other non-conjugated polyenes besides ENB), ENB is taken as the weight percentage of the total non-conjugated polyenes. The value (dn / dc) for other polymers and copolymers (including PEDM terpolymers) is 0.1. The units for the parameters used throughout this SEC method description satisfy: concentration in g / cm³. 3 Molecular weight is expressed in g / mol, and intrinsic viscosity is expressed in dL / g.

[0103] The light scattering (LS) detector is a high-temperature miniDAWN (Wyatt Technology, Inc.). The main components are an optical flow channel, a 30 mW, 690 nm laser diode light source, and a 45-degree-of-freedom laser diode. o 90 o and 135 o An array of three photodiodes was placed at the collection angle. The molecular weight M at each point in the chromatogram was determined by analyzing the LS output value using a Zimm model of static light scattering (MB Huglin, Light Scattering from Polymer Solutions, Academic Press, 1971).

[0104]

[0105] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at scattering angle θ, c is the polymer concentration determined from DRI analysis, A2 is the second virial coefficient (for the purposes of this invention, A2 = 0.0015 for ethylene homopolymers and A2 = 0.0015-0.00001 EE for ethylene-propylene copolymers, where EE is the ethylene content (weight percentage) in the ethylene-propylene copolymer). P(θ) is the shape factor of the monodisperse random coil, and Ko is the optical constant of the system.

[0106]

[0107] Where N Adn / dc is Avogadro's constant, and (dn / dc) is the refractive index increment of the system. At 145℃ and λ=690 nm, the refractive index of TCB is n=1.500.

[0108] The PEDM terpolymer of this disclosure may have a Mw of 5,000 g / mol to 5,000,000 g / mol, for example 10,000 g / mol to 1,000,000 g / mol, for example 20,000 g / mol to 500,000 g / mol, for example 50,000 g / mol to 400,000 g / mol. The PEDM terpolymer may also have a Mn of 2,500 g / mol to 2,500,000 g / mol, for example 5,000 g / mol to 500,000 g / mol, for example 10,000 g / mol to 250,000 g / mol, for example 25,000 g / mol to 200,000 g / mol. The PEDM terpolymer can have an Mz of 10,000 g / mol to 7,000,000 g / mol, for example 50,000 g / mol to 1,000,000 g / mol, for example 80,000 g / mol to 700,000 g / mol, for example 100,000 g / mol to 500,000 g / mol. For the purposes of this application, in cases where DRI and LS measurements conflict, LS measurements should be used for Mw and Mz, while DRI measurements should be used for Mn.

[0109] The molecular weight distribution index (MWD = (Mw / Mn)) of the PEDM terpolymer disclosed herein can be 1.5-40. For example, the PEDM terpolymer can have an MWD of 1.5-40, such as 1.8-20, such as 2.0-10, such as 2.0-5, such as 3-4.5. In one or more embodiments, the MWD of the PEDM terpolymer is 1.8-5, such as 1.8-3. Furthermore, although the MWD (polydispersity) is taken as Mw / Mn, in cases where DRI and LS measurements contradict each other, the MWD should be determined as Mw (measured by LS) / Mn (measured by DRI), or Mw... LS / Mn DRI .

[0110] The PEDM terpolymer disclosed herein can have a content of 0.85 g / cm³. 3 -0.92 g / cm 3 , or 0.87 g / cm 3 -0.90 g / cm 3 , or 0.88 g / cm 3 -0.89 g / cm3 The density is measured at room temperature according to the ASTM D-1505 test method.

[0111] The PEDM terpolymer of this disclosure may have a melt flow rate (MFR, 2.16 kg weight, 230 °C) equal to or greater than 0.2 g / 10 min as measured according to ASTM D-1238. In at least one aspect, the MFR (2.16 kg, 230 °C) is 0.5 g / 10 min to 200 g / 10 min, for example 1 g / 10 min to 100 g / 10 min, for example 2 g / 10 min to 30 g / 10 min, for example 5 g / 10 min to 30 g / 10 min, for example 10 g / 10 min to 30 g / 10 min, for example 10 g / 10 min to 25 g / 10 min. In at least one aspect, the MFR (2.16 kg, 230 °C) is approximately 7.5 g / 10 min.

[0112] The PEDM terpolymers of this disclosure can have Mooney viscosity (ML, 1+4 @ 125°C) of less than 100, for example less than 75, for example less than 60, for example less than 30, for example less than 20, for example less than 15, for example about 14 MU. For example, in PEDM according to some embodiments, the Mooney viscosity can be in the range of 5, 10 or 12 MU to 20, 25 or 30 MU.

[0113] The PEDM terpolymers of this disclosure preferably have a random stereopolypropylene sequence. Alternatively, they are preferably amorphous, meaning they will show no melting peak when subjected to differential scanning calorimetry (DSC) testing. Alternatively, the PEDM according to some embodiments may show minute melting peaks, such that they can be observed to have Hf < 1 J / g according to the DSC method described herein. Furthermore, when the PEDM shows any melting peak, such peak may be a single peak, or the PEDM may show secondary melting peaks adjacent to the main peak. For the purposes of this document, these secondary melting peaks are collectively considered as a single melting point, wherein the highest of these peaks (relative to the baseline described herein) is considered the melting point of the PEDM terpolymer.

[0114] According to yet another embodiment, the crystallinity of the PEDM terpolymer can be expressed as a percentage of crystallinity (i.e., % crystallinity), determined according to the DSC procedure described herein. Although the PEDM according to some embodiments is amorphous (and can therefore be said to have 0% crystallinity), if the PEDM according to various other embodiments shows any crystallinity, it preferably has 0.1%-5%, more preferably 0.1%-3% % crystallinity. (Crystalllinity is determined by dividing (i) the measured heat of fusion by (ii) the heat of fusion of 100% crystalline polyethylene, which has a value of 293 J / g (B. Wunderlich, Thermal Analysis, Academic Press, 1990, pp. 417-431)).

[0115] The DSC procedure for determining the melting point (Tm) and / or heat of fusion (Hf) (or without it) of PEDM terpolymers comprises the following: The polymer is pressed in a hot press at a temperature of 200°C–230°C, and the resulting polymer sheet is suspended in air under ambient conditions (20–23.5°C) to cool. 6–10 mg of the polymer sheet is removed using a die. This 6–10 mg sample is annealed at room temperature (22°C) for 80–100 hours. At the end of this stage, the sample is placed in a DSC (Perkin Elmer PyrisOne Thermal Analysis System) and cooled to -30°C to -50°C at a rate of approximately 10°C / min and held at -50°C for 10 minutes. The sample is then heated at 10°C / min to reach a final temperature of 200°C. The sample is held at 200°C for 5 minutes. A second cooling-heating cycle is then performed using the same conditions as described above. The events from the two cycles, namely the “first melt” and the “second melt,” are recorded separately. The exothermic reaction is recorded as the area beneath the sample's melting peak, which typically exists between 0°C and 200°C. It is measured in Joules and is the Ht of the polymer. f The melting point temperature and Hf mentioned in this article refer to the first melting.

[0116] Furthermore, as mentioned above, when a sample shows no melting peak, as in the case of amorphous polymers, it can be said to have no Hf. However, for example, even some amorphous or near-amorphous PEDM samples may show minute melting peaks, such that Hf on the first melt can be observed to be < 1 J / g. Therefore, for the purposes of this application, when PEDM has Hf < 1 J / g, or when it shows no discernible melting peak, PEDM can be considered amorphous, both of which are observations taken from the first melt in the aforementioned DSC procedure.

[0117] Some embodiments of the PEDM terpolymer may have a glass transition temperature (Tg) of -45°C to -2°C, for example -40°C to -25°C, -40°C to -20°C, -35°C to -25°C, -40°C to -15°C, or -35°C to -15°C; or -20°C to -2°C, for example -15°C to -2°C, for example -10°C to -2°C, for example -5°C to -2°C.

[0118] Catalyst system:

[0119] The PEDM terpolymers disclosed herein can be synthesized using a catalyst system comprising at least one catalyst and at least one activator.

[0120] Catalysts: The PEDM terpolymers of this disclosure can be synthesized using any suitable metallocene catalyst system, but preferably the catalyst system results in the PEDM terpolymer having a randomized polypropylene sequence and / or little or no crystallinity. Suitable metallocene catalyst systems include bridged fluorenyl-cyclopentadienyl Group 4 catalysts (and / or Cp-fluorenyl variants), mono-Cp amino (amido) Group 4 catalysts (and / or mono-Cp amino variants), biphenylphenol (BPP) transition metal catalysts, pyridylamino transition metal catalysts, and / or pyridyldiamino transition metal catalysts.

[0121] Particularly preferred metallocene catalysts according to some embodiments include fluorenyl-cyclopentadienyl Group 4 catalysts represented by the following formula (I):

[0122]

[0123] Wherein: J is a divalent bridging base (preferably containing C, Si, or both);

[0124] M is a group 4 transition metal (in some embodiments, Hf is preferred);

[0125] Each X is independently a monovalent anionic ligand, or two Xs may bond together with M to form a metallocycle ring, or two Xs may bond to form a chelate ligand, diene ligand, or alkylidene ligand; and

[0126] Each R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 and R 10 Independently, it is hydrogen, C1-C50 Substituted or unsubstituted alkyl groups (preferably unsubstituted C1-C) 10 Alkyl group, more preferably C1-C5 alkyl group, under the condition that R 1 and R 2 R 3 and R 4 R 5 and R 6 R 6 and R 7 R 8 and R 9 and R 9 and R 10 Any one or more pairs in a pair may be bonded together unnecessarily to form a saturated or partially saturated cyclic or fused cyclic structure. The activated and unactivated (precursor) forms of the compounds represented by the following formula (I) are covered by the following formula (I).

[0127] In at least one embodiment, J is a bridging group containing carbon and / or silicon atoms, such as a dialkylsilyl group; preferably J is selected from -CH2-, -CH2CH2-, -C(CH3)2-, -SiMe2-, -SiEt2-, -SiPh2-, -Si(Me)(C6H5)-, -C(Ph)2-, -C( p -(Et)3SiPh)2-, -C(Si(Et)3)2-, (CH2)3Si=, (CH2)4Si= and (CH2)5Si=, where Me is methyl, Et is ethyl, Ph is phenyl, and further wherein each (CH2) x Si indicates a cyclic methylene silyl structural moiety having x carbon and silicon atoms in the cyclic group, for example, where x is 4 in this compound and J is cyclotetramethylene methylene silyl.

[0128] In at least one implementation, R 6 and R 9 Each is a C1-C4 alkyl group, preferably a C4 alkyl group such as tert-butyl; R 1 -R 4 R 5 R 7 R 8 and R 10 Each is independently methyl, ethyl, or H (preferably, each is H); J is selected from any of the above groups (preferably J is ( p -(Et)3SiPh)2C); M is Hf; each X is independently a C1-C3 alkyl or halide (preferably each X is methyl).

[0129] A particularly preferred fluorenyl-cyclopentadienyl Group 4 catalyst according to some embodiments is dimethyl-1,1'-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tert-butyl-fluoren-9-yl)hafnium.

[0130] Activator: The terms "co-catalyst" and "activator" are used interchangeably herein and include any compound that can activate any of the aforementioned catalyst compounds (including either or both of the first and second metallocene catalyst compounds) by converting a neutral catalyst compound ("unactivated") into a catalytically active catalyst compound cation ("activated"). Suitable activators are described in paragraphs

[0110] -

[0115] of WIPO Publication WO 2016 / 114914 A1, the contents of which are incorporated herein by reference; and / or in paragraphs

[0110] -

[0133] of U.S. Patent Publication 2015 / 0025209, the contents of which are incorporated herein by reference.

[0131] In some embodiments of this disclosure, particularly useful activators include noncoordinate anionic (NCA) activators, such as those in paragraph

[0124] of U.S. Patent Publication No. 2015 / 0025209, and also those in columns 7 and 20-21 of U.S. Patent No. 8,658,556, the description of which is incorporated herein by reference. Specific examples of suitable NCA activators include: N,N-dimethylphenylammonium tetra(pentafluorophenyl)boronate, N,N-dimethylphenylammonium tetra(perfluoronaphthyl)boronate, N,N-dimethylphenylammonium tetra(perfluorobiphenyl)boronate, and triphenylcarbon tetra(perfluoronaphthyl)boronate. Tetra(perfluoronaphthyl)boronic acid bis(C4-C) 20 Alkyl)methylammonium, tetra(pentafluorophenyl)boronic acid Me3NH + Me3NH tetra(heptafluoro-2-naphthyl)boronic acid + And tetra(pentafluorophenyl)borate bis(hydrogenated tallow alkyl)methylammonium. A particularly preferred NCA activator is tetra(pentafluorophenyl)borate N,N-dimethylphenylammonium.

[0132] The catalyst disclosed herein can be activated online in a catalyst feed line or polymerization reactor. Furthermore, the molar ratio of activator to catalyst is 0.1:1 to 1000:1, for example 0.5:1 to 100:1, for example 2:1 to 50:1. A preferred molar ratio is 1:1.

[0133] In some embodiments, an activator (one or more) is contacted with a catalyst compound to form a catalyst system comprising an activated catalyst and activator and / or other charge-balanced structural portions, and then the catalyst system is contacted with one or more monomers to form a PEDM terpolymer. In other embodiments, the activator may be co-fed with one or more monomers into a reactor having a catalyst. Preferably, the catalyst is contacted with the activator and then fed into the polymerization zone of the reactor.

[0134] Second polymer

[0135] The compositions disclosed herein comprise a second polymer different from the PEDM terpolymer described above. The second polymer is preferably an ethylene-based copolymer. In at least one embodiment, the composition comprises a blend of a PEDM terpolymer and one or more ethylene-based copolymers (one or more).

[0136] The compositions of this disclosure may contain one or more second polymers (ethylene-based copolymers) in amounts of about 50 phr to about 99 phr, such as about 60 phr to about 99 phr, such as about 70 phr to about 98 phr, such as about 70 phr to about 95 phr, such as about 75 phr to about 95 phr, such as about 85 phr to about 95 phr, wherein 100 parts of the rubber base are taken as the total weight of the first polymer (e.g., PEDM) and the second polymer (e.g., ethylene-based copolymer) in the composition.

[0137] The ethylene-based copolymers of this disclosure contain an ethylene content different from that of the first polymer. In at least one embodiment, the ethylene-based copolymer has an ethylene content of at least 40 wt%, preferably at least 50, 55, 60, 65, 70, or 75 wt%, and in various embodiments, at most 99 wt%, such as at most 95, 90, 85, 80, 75, or 70 wt% (again based on the weight of the ethylene-based copolymer). The ethylene-based copolymers of this disclosure further contain C3-C 12 The content of α-olefins and, optionally, the content of polyenes (preferably dienes) containing one or more polyenes (preferably one or more dienes). C3-C 12α-olefins include propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and their branched isomers. Propylene is particularly preferred according to some embodiments (e.g., such that the ethylene-based copolymer can be an EP(D)M copolymer), while butene (1-butene) is preferred in other embodiments (e.g., such that the ethylene-based copolymer can be an EB(D)M copolymer).

[0138] Regarding the polyenes, any suitable polyenes in PEDM are suitable for inclusion in ethylene-based copolymers, with VNB or ENB being preferred, especially ENB. According to other embodiments, suitable polyenes may include conjugated dienes. Conjugated dienes include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-di(C1-C5 alkyl)-1,3-butadiene, such as 2,3-dimethyl-1,3-butadiene, 2,3-diethyl-1,3-butadiene, 2-methyl-3-ethyl-1,3-butadiene, or 2-methyl-3-isopropyl-1,3-butadiene, aryl-1,3-butadiene, 1,3-pentadiene, or 2,4-hexadiene. Dienes also include vinyl aromatic compounds: styrene, o-, m-, or p-methylstyrene, commercial mixtures of "vinyltoluene", p-(tert-butyl)styrene, methoxystyrene, chlorostyrene, vinyltrimethylbenzene, or vinylnaphthalene. The ethylene-based copolymers of various embodiments preferably have a polyene content of 0-20 wt%, for example 0-15 wt%, preferably 1-10 wt%, 2-9 wt%, or 3-7 wt%, and any of the lower to upper limits of the above are also considered in various embodiments.

[0139] Additionally, in some embodiments, the ethylene-based copolymers of this disclosure may have an isotactic polypropylene content.

[0140] According to some embodiments, the ethylene-based copolymers exhibit higher crystallinity than PEDM; for example, it can have Hf > 1 J / g. According to other embodiments, the crystallinity of the ethylene-based copolymers of this disclosure can be expressed as a percentage of crystallinity (i.e., % crystallinity), determined according to the DSC procedure described herein. The ethylene-based copolymers can have a % crystallinity of 5%-80%, for example 10%-60%, for example 20%-40%. (Crystalllinity is determined by dividing the measured heat of fusion by the heat of fusion of 100% crystalline polyethylene, which has a value of 293 J / g (B. Wunderlich, Thermal Analysis, Academic Press, 1990, pp. 417-431)).

[0141] Ethylene-based copolymers can be ethylene-propylene copolymers and, in particular, EP(D)M terpolymers (e.g., Vistalon). TM 706, Tafmer TM Or Versify TM ) or EB(D)M terpolymers. The ethylene-based copolymers of this disclosure may have a weight-average molecular weight (Mw) of 10,000 g / mol to 400,000 g / mol, for example, 100,000 g / mol to 200,000. They may also, or alternatively, have a melting point (DSC) of less than 110°C, for example, less than 100°C.

[0142] The compositions described herein may comprise a single ethylene-based copolymer or a mixture of several ethylene-based copolymers, wherein the ethylene-based copolymer may be used in combination with any type of synthetic elastomer other than ethylene-based copolymers, or even with polymers other than elastomers, such as thermoplastic polymers.

[0143] In at least one embodiment, the second polymer (an ethylene-based copolymer) is a polyethylene-polybutadiene block copolymer, wherein the polyethylene-polybutadiene block copolymer is a block copolymer having the general formula: PE—XL—fPB, wherein “PE” is a polyethylene block having a weight-average molecular weight of 1,000-150,000 g / mol, “fPB” is a functionalized polar polybutadiene block having a weight-average molecular weight of 500 g / mol-30,000 g / mol, and “XL” is a crosslinked structural portion covalently linking the PE and fPB blocks; and wherein the maximum energy loss (Tangentδ) of the immiscible polyolefin domain is a temperature within the range of -30°C to 10°C.

[0144] In at least one embodiment, the composition of this disclosure comprises 15 wt%-60 wt% of a styrene copolymer; 1 wt%-60 wt% of a polybutadiene polymer; 1 wt%-60 wt% of natural rubber or synthetic polyisoprene; 15 wt%-60 wt% of a functionalized styrene copolymer; 1 wt%-60 wt% of a functionalized polar polybutadiene polymer; or 1 wt%-60 wt% of natural rubber or functionalized synthetic polyisoprene.

[0145] Polymer blends

[0146] The compositions of this disclosure can be formed by combining a first polymer (PEDM) and a second polymer (an ethylene-based copolymer) using any suitable method known in the field of polymer processing. For example, the compositions can be prepared by blending the first and second polymers in solution and removing the blend overall. Such polymer compositions have predetermined amounts of the first and second polymers and can be prepared by the independent polymerization of the first and second elastomeric polymer components. Such separate polymerization can be carried out in a series or parallel polymerization reactor or in a single polymerization reactor having at least two different polymerization catalysts. A recovery procedure for such predetermined compositions is described in U.S. Patent No. 4,722,971, which is incorporated herein by reference. This disclosure includes conventional Ziegler-Natta catalyst systems; however, metallocene catalyst systems are also contemplated in this disclosure.

[0147] In at least one embodiment, the method for preparing a composition of a first polymer (PEDM) and a second polymer (ethylene-based copolymer) comprises contacting a first metallocene catalyst with ethylene, propylene, and diene in a first reactor to form the first polymer. The first polymer comprises 1 wt%-10 wt% diene content, for example 2 wt%-4 wt%, based on the total weight of the polymer; 8 wt%-45 wt% ethylene content, for example 12 wt%-40 wt% (e.g., 30-40 wt%, or 12-25 wt%), based on the total weight of the polymer; and 50 wt%-91 wt%, for example 55-85 wt% atactic propylene content. The method further comprises contacting a second metallocene catalyst with ethylene and propylene, and optionally diene, in a second reactor (or a first reactor) to form the second polymer, for example an EP copolymer or an EP(D)M terpolymer. The method may include transferring a first polymer to a second reactor or transferring a second polymer to a first reactor, and recovering from the second reactor or the first reactor a composition comprising 1 phr to 20 phr, for example, about 5 phr to 30 phr, for example, about 5 phr to about 15 phr of the first polymer and 70 phr to 99 phr of the second polymer. The recovered polymer composition may then be crosslinked, for example, as described in more detail below.

[0148] Alternatively, in at least one embodiment, the blend of the first polymer and the second polymer can be prepared by combining the first polymer from the first reactor and the second polymer from the second reactor and mixing them, for example, in a production extruder, such as an injection molding machine or an extruder on a continuous extrusion production line.

[0149] In at least one embodiment, the method of blending the polymer can be in a batch mixer, such as a Banbury mixer.TM Or Brabender TM The polymer melts are blended in a mixer. Blending can also include blending a first polymer and a second polymer melt in an extruder, such as a single-screw extruder or a twin-screw extruder. Extrusion techniques for polymer blends are well known in the art and are described in more detail, for example, PLASTICS EXTRUSION TECHNOLOGY ,F.Hensen,Ed. (Hanser,1988),pp.26-37,and POLYPROPYLENE HANDBOOK , EP Moore, Jr. Ed. (Hanser, 1996), pp. 304-348.

[0150] The first and second polymers can also be blended through a combination of methods, such as dry blending followed by melt blending in an extruder, or batch blending of some components followed by melt blending with other components in an extruder. Double cone mixers, belt mixers, or other suitable mixers can also be used, or in a Farrel continuous mixer (FCM). TM In the process, the first polymer and the second polymer are blended.

[0151] Composition

[0152] The compositions disclosed herein include and / or the reaction products of the first and second polymers described above (as polymer blends or other forms) (and are in any form: pellets, bundles, or other forms). The compositions disclosed herein may also include and / or be the reaction products of any one or more additives. Additives include curing agents, crosslinking agents, fillers, processing oils, plasticizers, compatibilizers, crosslinking agents, etc.

[0153] In embodiments in which a curing agent, such as a crosslinking agent or a vulcanizing agent, is present in the composition, the polymer of the composition may be present in a form that is at least partially crosslinked (i.e., at least a portion of the polymer chains are crosslinked to each other, for example, due to the typical curing process for EP(D)M rubber). Accordingly, specific embodiments provide at least partially crosslinked elastomer compositions obtained by mixing compositions comprising: (a) a first polymer (PEDM) and a second polymer (an ethylene-based copolymer) (which may be mixed according to any of the methods described above for polymer blends); (b) one or more vulcanization activators; (c) one or more vulcanizing agents; and / or (d) one or more additional additives.

[0154] Suitable vulcanization activators include zinc oxide, stearic acid, etc. These activators can be mixed in amounts of 0.1 phr to 20 phr. Different vulcanization activators can be present in different amounts. For example, when the vulcanization activator includes zinc oxide, zinc oxide can be present in amounts of 1 phr to 20 phr, such as 2.5 phr to 10 phr (e.g., about 5 phr), while stearic acid is preferably used in amounts of 0.1 phr to 5 phr, such as 0.1 phr to 2 phr (e.g., about 1.5 phr).

[0155] Any suitable vulcanizing agent known in the art may be used. Of particular note are the curing agents described in column 19, line 35 through column 20, line 30 of U.S. Patent No. 7,915,354, the description of which is incorporated herein by reference (e.g., sulfur, peroxide-based curing agents (Vulcup 40 KE, available from Arkema of Colombes, France), resin curing agents, silane and hydrosilane curing agents). Other examples include phenolic resin curing agents (e.g., described in U.S. Patent No. 5,750,625, also incorporated herein by reference). Curing aids may also be included (e.g., zinc dimethacrylate (Dymalink 708) or those described in the incorporated description of U.S. Patent No. 7,915,354).

[0156] Additionally, the additives may be selected from any known additives that can be used in EPDM compositions, and particularly include one or more of the following substances:

[0157] • Processing oils, such as alkane and / or isoalkane processing oils (examples include Sunpar) TM 2280 (available from HollyFrontier Refining & Marketing LLC, Tulsa, Oklahoma); and Flexon TM 876, CORE TM 600 base oil, Flexon TM 815 and CORE TM2500 base oil is available from ExxonMobil Chemical Company, Baytown, Texas. Particularly in embodiments where the color of the final product may be important, white oil (e.g., API Group II or III base oil) can be used as a processing oil. Examples include alkane and / or isoalkane oils having low (less than 1 wt%, preferably less than 0.1 wt%) aromatic and heteroatom content. The compositions of this disclosure may contain processing oils of 1 phr-150 phr, for example 50 phr-100 phr, for example 60 phr-80 phr, or, for sponge grades, 50 phr-200 phr, for example 70 phr-150 phr, for example 80 phr-100 phr, and preferably processing oils having a viscosity of 80 CSt-600 CSt at 40°C.

[0158] • Vulcanization accelerators, the compositions of this disclosure may contain 0.1 phr-15 phr, for example 1 phr-5 phr, or 2 phr-4 phr, wherein examples include thiazoles such as 2-mercaptobenzothiazole or disulfide mercaptobenzothiazole (MBTS); guanidines such as diphenylguanidine; sulfinamides such as N-cyclohexylbenzothiazole sulfinamide; dithiocarbamates such as zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, zinc dibenzyl dithiocarbamate (ZBEC); and zinc dibutyl dithiocarbamate, thioureas such as 1,3-diethylthiourea, thiophosphates, etc.

[0159] • Processing aids (e.g., polyethylene glycol or zinc soap);

[0160] • Carbon black (e.g., having a particle size of 20 nm-600 nm and a structure having a DBPA (dibutyl phthalate absorbance number) of 0-150 as measured by the DBP method described in ASTM D2414). The compositions of this disclosure may contain carbon black of 1 phr-500 phr, preferably 1 phr-200 phr, for example 50 phr-150 phr;

[0161] • Mineral fillers (talc, calcium carbonate, clay, silica, aluminum trihydrate, etc.) may be present in the composition at a concentration of 1-200 phr, preferably 20-100 phr, for example 30-60 phr;

[0162] When foaming may be desired, foaming agents or foaming grade additives, such as foaming agents or foaming agents, are used, especially in embodiments with very high Mooney viscosity, such as those suitable for sponge grades. Examples of such agents include: azodicarbonamide (ADC), o-benzosulfonyl hydrazide (OBSH), p-toluenesulfonyl hydrazide (TSH), 5-phenyltetrazole (5-PT), and sodium bicarbonate in citric acid. Microcapsules can also be used, or are used as an alternative, for this foaming application. These can include thermally expandable microspheres comprising a polymer shell containing a propellant. Examples are known in the art and described, for example, in U.S. Patent Nos. 6,582,633 and 3,615,972, WIPO Publications WO 99 / 46320 and WO 99 / 43758, the contents of which are incorporated herein by reference. Examples of such thermally expandable microspheres include EXPANCEL, commercially available from Akzo Nobel NV. TM Products and ADVANCELL available from Sekisui TM

[0163] Product. In other embodiments, the sponge or foam can be achieved by directly injecting a gas and / or liquid (e.g., water, CO2, N2) into the rubber in an extruder to foam the composition after passing it through a die; and

[0164] It may also include various other additives, such as antioxidants (e.g., 1,2-dihydro-2,2,4-trimethylquinoline), stabilizers, preservatives, UV absorbers, antistatic agents, lubricants, moisture absorbers (e.g., calcium oxide), pigments, dyes and other colorants.

[0165] The at least partially crosslinked polymer compositions of this disclosure are formed as follows: the components are mixed in any suitable manner as described in the polymer blending section above, such as using a Banbury mixer. The mixing in these embodiments may include any one or more typical mixing methods for EP(D)M compositions, such as open mill mixing, mixing using an internal mixer or kneader, and extrusion (e.g., via a twin-screw extruder).

[0166] Additionally, in some embodiments, additives may be introduced into the polymer blend directly or as part of a masterbatch (i.e., an additive package containing several additives to be added at once in a predetermined proportion). The masterbatch may be added in any suitable amount. For example, a masterbatch containing additives may be used in amounts of about 0.1 to about 10 wt%, or about 0.25 to about 7.5 wt%, or about 0.5 to about 5 wt%, or about 1 to about 5 wt%, or about 2 to about 4 wt%, based on the total weight of the polymer blend and the masterbatch. This is a common practice in polymer processing, typically used to add pigments, additives, and fillers to the final composition. The dispersion (or "thinning") of the masterbatch may be carried out as part of a process step used to manufacture the article, such as in an extruder on an injection molding machine or a continuous extrusion line, or during a separate compounding step.

[0167] Drive belt

[0168] The compositions disclosed herein can be used as one or more components of a drive belt.

[0169] Figure 1 This is a perspective view of a segment of a transmission belt according to some embodiments of this disclosure. For example... Figure 1 As shown, the timing belt 100 includes an elastomer body portion 102 and pulley contacts 104 arranged along the inner edge of the body portion 102. The body portion 102 contains a composition comprising one or more PEDM materials as disclosed herein. The pulley contacts 104 are configured to form alternating lateral protrusions 106 and grooves 108, which are configured to couple with a lateral pulley or sprocket. A tension layer 110 is arranged within the body portion 102 to provide support and strength to the belt 100. The tension layer 110 includes a plurality of tension cables 112 arranged longitudinally along the length of the body portion 112. The cables 112 contain one or more of any suitable material, such as cotton, rayon, polyamide, polyester, aramid, steel, glass, carbon, polyketone, basalt, boron, or discontinuous fibers oriented for low load capacity. Reinforcing fabric 114 is arranged on the protrusions 106 and grooves 108 and forms the pulley contacts. The reinforcing fabric 114 can have any suitable configuration, such as a conventional textile composed of warp and weft threads at an angle, or may include warp threads joined together by spatial pick-up threads, or a knitted or woven configuration, or a nonwoven fabric. Suitable fabrics include one or more of cotton, polyester, polyamide, acrylic resins, aramid, polyketone, hemp, jute, or glass fiber.

[0170] Figure 2 This is a perspective view of a segment of a transmission belt according to other embodiments of this disclosure. (e.g.) Figure 2As shown, the toothed V-belt 200 includes an elastomer portion 202 and a tension layer 204 comprising a cable 206. The body portion 202 comprises one or more compositions of the present disclosure (compositions containing PEDM). The cable 206 comprises one or more of any suitable material, such as cotton, rayon, polyamide, polyester, aramid, steel, glass, carbon, polyketone, basalt, boron, or discontinuous fibers oriented for low load capacity. The V-belt 200 includes a pulley contact portion 208 having two side-by-side sides of the belt designed to be inserted into a V-shaped pulley. The V-belt 200 includes grooves 210 and protrusions 212. Included in the category of V-belts are those designed for continuously variable transmission (“CVT”) applications, which typically exhibit a belt body that is relatively wider than the belt thickness.

[0171] Figure 3 This is a perspective view of a segment of a transmission belt according to one embodiment of this disclosure. Figure 3 As shown, the multi-V ribbed belt 300 includes a body portion 302 and a tensile reinforcing member 304 comprising a cable 306. The body portion 302 comprises one or more compositions of the present disclosure (compositions containing PEDM). The longitudinal grooved pulley contact portion 308 includes a plurality of protrusions 310 alternating with a plurality of grooves 312, which together define the drive surface 314 of the belt 300. Figure 1 , Figure 2 and Figure 3 In each of these examples, the corresponding pulley contact portion is coupled / coupled with the corresponding body portion and can be formed of the same material or layered with different materials.

[0172] exist Figure 1 , Figure 2 and 3 In each of the three exemplary tape embodiments shown, the present disclosure composition (containing the PEDM composition) forming the tape body may further comprise any suitable polymer. Suitable additional polymers include polyurethane elastomers (including polyurethane / urea elastomers and so-called ground rubber) (PU), polychloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), hydrogenated NBR (HNBR), styrene-butadiene rubber (SBR), alkylated chlorosulfonated polyethylene (ACSM), polyepoxychloropropane, polybutadiene rubber (BR), natural rubber (NR), and ethylene α-olefin elastomers such as ethylene propylene copolymer (EPM), ethylene propylene diene terpolymer (EPDM), ethylene octene copolymer (EOM), ethylene butene copolymer (EBM), ethylene octene terpolymer (EODM); ethylene butene terpolymer (EBDM); ethylene vinyl acetate elastomer (EVM); ethylene methyl acrylate (EAM); and siloxane rubbers.

[0173] In order to form the elastomeric belt body of a transmission belt according to at least one embodiment of the present disclosure, the polymer may be blended according to known mixing methods and blended with general rubber compounding components as described above, including but not limited to fillers, plasticizers, stabilizers, vulcanizing agents / curing agents, additives and accelerators in conventionally used amounts.

[0174] Example

[0175] Molecular weights (number-average molecular weight (Mn), weight-average molecular weight (Mw), and Z-average molecular weight (Mz)) were determined using a Polymer Laboratories Model 220 high-temperature GPC-SEC equipped with online differential refractive index (DRI), light scattering (LS), and viscometer (VIS) detectors. Three Polymer Laboratories PLgel 10 m Mixed-B columns were used for separation at a flow rate of 0.54 ml / min and a nominal injection volume of 300 μL. The detectors and columns were housed in an oven maintained at 135°C. The feed stream exiting the SEC column was directed into a miniDAWN (Wyatt Technology, Inc.) optical flow channel and then into the DRI detector. The DRI detector is an integrated component of the Polymer Laboratories SEC. The viscometer is located within the SEC oven, downstream of the DRI detector. A detailed description of these detectors and their calibration has been provided, for example, by T. Sun, P. Brant, RR Chance, and W.W. Graessley in Macromolecules, Vol. 34, No. 19, pp. 6812-6820 (2001).

[0176] Polymer formation:

[0177] The second polymer (an ethylene-based copolymer) was purchased from a commercial source. The first polymer (PEDM) was synthesized as follows: The reactor is a 0.15-liter reactor. The reactor is a stainless steel autoclave reactor manufactured by Autoclave Engineers, Erie PA, equipped with a stirrer, water-cooled / steam-heated elements (with temperature controllers), and a pressure controller. The reactor is designed to operate at maximum pressures and temperatures of 2000 bar (30 kpsi) and 225°C, but for the current experiment, the nominal reactor pressure is lower, ranging from 1600 to 1700 psig. The nominal reactor vessel volume is 150 mL. Pressure sensors measure the pressure in the reactor. Reactor temperature is measured using type K thermocouples. A flush-mounted rupture diaphragm on the reactor side provides protection against catastrophic pressure failure. All product lines are heated to ~120°C to prevent scaling. The reactor body has electrically heated belts controlled by a programmable logic controller (PLC). The reactor has no cooling except for heat loss to the environment (approaching adiabatic operation).

[0178] The solvent (isohexane) and comonomers (propylene, ethylene, and ENB) were first purified using a three-column purification system. This system consisted of Oxiclear columns (Labclear model #RGP-Rl-500) followed by 5 Å and 3 Å molecular sieve columns. The purification columns were periodically regenerated whenever there was evidence of reduced polymerization activity. The 3 Å and 5 Å molecular sieve columns were internally regenerated under a nitrogen atmosphere at set temperatures of 260 °C and 315 °C, respectively. The molecular sieve material was purchased from Aldrich. Ethylene was transported as a gas dissolved in a cryogenic solvent / monomer mixture. The purified solvent and monomers were then cooled to -15 °C via a cooler before being fed into the reactor through a manifold. The solvent and monomers were mixed in the manifold and fed into the reactor via a single tube. Contact between the catalyst and monomers took place in the reactor. All liquid flow rates were measured using a mass flow controller.

[0179] All catalyst solutions were kept under an inert atmosphere and fed into the reactor using an ISCO injection pump. A tri-n-octylaluminum (TNOAL) solution (available from Sigma Aldrich, Milwaukee, WI) was further diluted in isohexane and used as a scavenger. The scavenger feed rate was adjusted to maximize catalyst efficiency. The catalyst was dimethyl-1,1'-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tert-butylfluorene-9-yl)hafnium. Other Cs-symmetric metallocene precursors with good diene introduction and MW capacity, such as those described herein, can also be used. The activator was N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate. Other noncoordinate anionic activators or methylaluminoxane (MAO) can also be used.

[0180] The reactor was first prepared as follows: It was continuously purged with N2 at the maximum permissible temperature, and then isohexane and a scavenging agent solution were pumped through the reactor system for at least one hour. The monomer and catalyst solution were then fed into the reactor for polymerization. Once activity was established and the system reached steady state, the system was continuously operated under established conditions for a period of at least five times the average residence time, then samples were collected, and the reactor was shut down. The conversion in the reactor was monitored by simultaneously sampling the feed and effluent using an online gas chromatograph (GC). The GC analysis used propane impurities present in the propylene feed as an internal standard. The reactor temperature and temperature difference along the reactor wall were maintained constant by adjusting the reactor heater output (surface temperature) and the catalyst feed rate.

[0181] The resulting mixture, primarily containing solvent, polymer, and unreacted monomers, was collected in a collection box. The collected samples (PEDM A, PEDM B, and PEDM C) were washed with xylene to remove unreacted macromonomers, then air-dried in a hood to evaporate most of the solvent, followed by drying in a vacuum oven at 90°C for 12 hours. The oven-dried samples were weighed to obtain the product. All reactions were carried out at a gauge pressure of 2.4 MPa.

[0182] Characterization of PEDM A, PEDM B, and PEDM C samples is provided in Table 1 below. All three samples are amorphous with approximately zero crystallinity.

[0183] polymer:

[0184] Table 1 shows the polymer properties of the EP(D)M and PEDM polymers in the examples. Reference polymer Vistalon TM 706 is an ethylene-propylene copolymer with a Mooney viscosity of 42 MU (ML, 1+4 @ 125°C) and an ethylene content of 65 wt%. Vistalon TM 9301 is more powerful than Vistalon. TM706 is a higher Mooney viscosity (specifically, 67 MU (ML, 1+4 @ 125 °C)) and an EP(D)M terpolymer with ENB as the diene. The PEDM polymers (A, B, and C) in Table 1 have ethylene contents of 35 wt% (PEDM A)–15 wt% (PEDM C), ENB contents of 3 wt%, and MFR of 7.5 g / 10 min (230 °C, 2.16 kg), determined using a Dynisco Kayeness Polymer Test Systems Series 4003 instrument following ASTM D1238. The glass transition temperature (Tg) of the PEDM terpolymers was measured using differential scanning calorimetry (DSC) according to the previously described procedure. The Tg of the PEDM samples decreased with increasing ethylene content. PEDM polymers were synthesized using a metallocene catalyst: dimethyl-1,1'-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(2,7-di-tert-butyl-fluorene-9-yl)hafnium and an activator: N,N-dimethylphenylammonium tetra(pentafluorophenyl)borate.

[0185] Table 1

[0186]

[0187] Composition:

[0188] Compositions comprising EP(D)M polymer, carbon black, oil, and curing agent were prepared in a 410 cc Banbury® mixer. Table 2 shows representative compositions. Mixing was performed using a 70% fill factor. At the start of mixing, the polymer, carbon black, and additives were introduced at a speed of 50 rpm. The piston (ram) was raised three times during the mixing cycle. Mixing continued for 5 minutes, at which point the batch was discharged. The average temperature of the discharged batch was approximately 250°C. o F. Approximately 5 grams of the mixture masterbatch was separated for rheological measurements.

[0189] Table 2

[0190]

[0191] A curing agent was added to the masterbatch (329 gm) on a two-roll mill. The batch was then passed through the mill several times to ensure uniform dispersion of the curing agent. The batch containing the curing agent was then cured in an electric thermoforming press, and various physical and mechanical properties were tested.

[0192] In Table 2, “polymer” indicates Vistalon included in the composition. TMThe appropriate amounts of 706 polymer (plus PEDM polymer, as in Examples 2-7); Black 330 is carbon black (in granular form); Sunpar 2280 is alkyl processing oil; zinc stearate and ZnO (zinc oxide) are vulcanization activators; Agerite resin D antioxidant 1,2-dihydro-2,2,4-trimethylquinoline; Dymalink 708 (ZDMA) (zinc dimethacrylate) and Dymalink 719 are each vulcanization activators; and Vulcup 40 KE is an organic peroxide vulcanizing / crosslinking agent. The composition is considered a useful composition of EP(D)M compounds and is therefore taken as a means to test the processability of Examples 2-7 compared to Comparative Example C1.

[0193] The composition was mixed according to the following procedure to form an elastomer composition. The polymer and other components from the “First Pass” section of Table 2 were added to a 410 cc Banbury tangential mixer (available from Farrel Corporation) at 0’00” and 0’30” respectively, and the mixer was operated for 3 minutes (specifically, at 90 RPM, 70°C) as shown in Table 3 for the “First Pass” parameters. The piston was then raised, and mixing continued for another 15 seconds. The “First Pass” component was then discharged and ground in a 2-roll mill. The mixed and ground “First Pass” component was allowed to cool. The cooled “First Pass” component and the “Grinding Addition” component from Table 2 were then added to the mixer, and the mixer was operated for another 1 minute using the “Grinding Addition” parameters (70 RPM, 30°C) in Table 3. After a second pass of 1 minute, the mixed compound is discharged, ground and allowed to cool, then collected for further analysis / rheological testing (uncured), and then pressed and cured at 180°C to form a composition that is at least partially cured (suitable for evaluation, e.g., tack and raw rubber properties).

[0194] Table 3

[0195] Mixer operation of mixtures formed in Examples C1 and 2-7

[0196]

[0197] Based on Vistalon TM Curing properties of 706 formulation:

[0198] Figure 4 This is a graphical representation of the curing state in relation to the ethylene content of PEDM. The curing state is defined as the difference between the highest torque value (MH) and the lowest torque value (ML) indicated during curing in a moving-die rheometer at 180°C and 0.5° arc. For example... Figure 4As shown, the formulation labeled "PEDM-free" is made with Vistalon. TM The control blends formulated with 706 copolymer. The curves correspond to the levels of PEDM (at 5 phr and 10 phr, respectively, as substitutes for EP copolymer in the composition).

[0199] Figure 5 This is a graph showing the effect of curing rate on PEDM ethylene content. The curing rate is measured as [(MH-ML)]. 0.9-2] / (Tc 90 -Ts2), where the cured state is the difference between MH and ML, Tc 90 It is the time to reach 90% of the maximum MH, and Ts2 is the curing time increased by 2 torque units. For example... Figure 5 As shown, the formulation labeled "PEDM-free" is made with Vistalon. TM A control blend formulated with 706 copolymer. The curves correspond to the levels of PEDM (at 5 phr and 10 phr, respectively), as the EP copolymer Vistalon in the composition. TM (A partial substitute for 706).

[0200] Each as Figure 4 and Figure 5 As shown, the curing state and curing rate are relative to Vistalon. TM The 706 control sample was increased up to 20 wt% ethylene content in PEDM; beyond this point, it was lower than the control blend. At higher ethylene contents in PEDM, the formulation containing 10 phr PEDM showed a greater reduction in curing properties.

[0201] Figure 6 This is a graph showing the tensile strength at break (ASTM D638) versus the ethylene content of PEDM. For example... Figure 6 As shown, in all embodiments, the tensile strength was higher compared to the control composition without PEDM. Figure 7 This is a graph showing the elongation at break (%) against the ethylene content of PEDM (also determined according to ASTM D638). For example... Figure 7 As shown, the elongation at break decreases with the addition of PEDM, especially at higher 10 phr levels and with increasing ethylene content of the PEDM polymer.

[0202] Based on Vistalon TM Properties of formulations containing 706:

[0203] The tackiness of uncured (raw) rubber compound was measured using a Tel-Tak apparatus (Monsanto Company, TT-1 model). A description of this test can be found in publication JR Beatty, Rubber Chem and Tech., 42, 1041 (1969). The test measures the force required to separate the specimen from a metal surface (polished stainless steel). The specimen was cut into 0.31″ × 1″ strips reinforced with a fabric lining. These strips were placed in the instrument at right angles to the metal strips, thus defining the contact area. The contact time was 30 seconds and the contact pressure was 16 ounces. As the dwell time interval was completed, a small geared motor automatically provided a 1-inch / minute movement of the lower pressure plate. The force required to separate the two surfaces was measured using a force gauge with a built-in stop that kept the pointer at its maximum reading. The tackiness was reported as the maximum force required to separate two identical rubber specimens.

[0204] Instron TM The raw rubber strength and raw rubber tear of the uncured masterbatch composition were measured in a tensile testing apparatus (using a dumbbell body cut according to ASTM D412 die C) according to ASTM D6746.

[0205] Mooney scorch is measured according to ASTM D1646. The Mooney scorch values ​​given in Table 5 are essentially measurements of the rate at which the rubber compound sets up during the Mooney test. For example, t1 indicates the time it takes for the compound viscosity to increase by one Mooney unit from its minimum; t5 indicates the time it takes to increase by five Mooney units, and so on. The faster the compound cures, the lower its Mooney scorch time.

[0206] Table 4 shows the composition properties of the reference composition Example C1 and the compositions of the present invention in Examples 2 to 7, formulated with PEDM at different ethylene contents and phr levels in the composition. Table 4 shows the viscosity of the compositions containing PEDM polymer at 5 phr and 10 phr levels, respectively, dependent on the PEDM ethylene content. Compared with the reference composition (with 100 phr Vistalon) TM Compared to 706), viscosity was higher in all formulations. For compositions containing 15 wt% ethylene PEDM at a 5 phr level, viscosity increased from 3.3 kPa to 5.5 kPa (an increase of 67%). A similar increase was seen in PEDM containing 21 wt% ethylene in the mixture at a 10 phr level.

[0207] Table 4 further shows that the 100% and 300% moduli of the cured compositions in Examples 2-7 are higher than those of the control composition C1. Moduli (100% and 300%), stress at fracture, and strain at fracture (ultimate elongation) were determined at 23°C using an Instron testing machine at 50 mm / min, according to ISO 37. A graph of torque vs. time at isothermal conditions was plotted using an oscillating disk rheometer (ODR) and a moving die rheometer (MDR) to illustrate how curing proceeds. These results can be used to determine the curing time (e.g., t90), which is calculated as the time it takes for the torque to reach its maximum and for 90% of the maximum torque to be achieved.

[0208] Table 4

[0209]

[0210]

[0211] Figure 8 This is a graph showing the Tel-Tak peak force versus ethylene content in PEDM. (Example) Figure 8 As shown, each composition having PEDMA A, PEDMA B, and PEDMA C has a higher Tel-Tak peak power compared to the control composition C1. Figure 9 This is a graph showing the 25% modulus of raw rubber strength versus the ethylene content of PEDM. (Example) Figure 9 As shown, the compositions containing PEDMA A and PEDMA B have a 25% lower raw rubber strength modulus than the comparative composition C1. It is expected that increased tackiness is generally accompanied by a corresponding decrease in raw rubber strength, as observed in the compositions containing PEDMA A and PEDMA B. However, for the compositions containing PEDMA A (35 wt% ethylene content), both tackiness and raw rubber strength are higher than those of the composition without the PEDM component (composition C1).

[0212] Composition Rheology: Small-Angle Vibratory Shear:

[0213] Small-angle vibrational shear (SAOS) measurements were performed using an ATD® 1000 rubber processing analyzer from Alpha Technologies. Samples weighing approximately 4.5 gm were mounted between parallel plates of the ATD® 1000. The test temperature was 66°C, the applied strain was 6.95%, and the frequency ranged from 0.21 rad / s to 210 rad / s. The elastic modulus (G') and phase angle (δ) were measured at each frequency.

[0214] Figure 10A , Figure 10B and Figure 10CThis is a graph showing the phase tangent (tanδ) versus frequency for compositions containing PEDMA A, PEDMA B, and PEDMA C at 5 phr and 10 phr, respectively. For example... Figure 10A , Figure 10B and Figure 10C As shown, the dynamic properties of the composition can be inferred from the tanδ response over the frequency range. For comparison, Vistalon will be referenced. TM The tanδ response of composition 706 (C1) is shown in Figure 10A , Figure 10B and Figure 10C In each of the following. The tanδ curves of the reference composition (C1) are compared with those of PEDMA (10 phr) respectively. Figure 10A ), according to 5 phr PEDM B ( Figure 10B ) and PEDM C (at 5 phr) Figure 10B (matches)

[0215] Figure 11A , Figure 11B and Figure 11C This is a graph showing the elastic modulus (G') versus frequency for compositions containing PEDMA A, PEDMA B, and PEDMA C at 5 phr and 10 phr, respectively. Figure 11A , Figure 11B and Figure 11C As shown, for comparison purposes, refer to Vistalon. TM The elastic modulus of composition 706 (C1). In some cases, at low frequencies (0.207 rad / s), the elastic modulus of the PEDM-containing composition is slightly lower than that of the reference (C1) composition. The correlation between viscosity and elastic modulus is described in GR Hamed's paper Rubber Chem. And Tech., 54, 578 (1981), where a lower elastic modulus at low frequencies is associated with higher viscosity properties.

[0216] Based on Vistalon TM Elastomer formulations of 706 and PEDMC:

[0217] It also forms PEDM C with 20 phr and Vistalon with 80 phr. TM The composition of 706. The EP(D)M polymer (Vistalon) was mixed in a 4300 cc Farrel OOC Banbury® mixer. TM706), Elastomer formulations of carbon black, oil, and curing agent are mixed. Table 5 shows representative EP(D)M formulations. Conventional mixing is used with a 70% fill factor. At the start of mixing, the polymer, carbon black, and additives are introduced at a speed of 50 rpm. During the mixing cycle, the piston is raised three times to complete three scans to ensure no material remains on the piston. The first batch or masterbatch mixing continues until the temperature reaches 300°C. o F (~148.9℃) and discharge the batch. In the final or second pass, pre-add the masterbatch, curing agent, and retardant at time 0 using a mixer speed of 50 rpm. Raise the piston twice to perform two scans to check for any material remaining on the piston. At approximately 210 o Each batch is discharged at F (~98.9℃). The probed temperature for rubber is approximately 250℃. o F (~121.1℃).

[0218] Table 5

[0219]

[0220] Based on Vistalon TM Performance of formulations of 706 and PEDMC:

[0221] There is still a need to improve the construction tack of EP(D)M formulations without added tackifying resins, particularly in the room temperature and feasible manufacturing temperature range. In at least one aspect, the compositions of this disclosure have a higher tack at room temperature than Vistalon by including PEDM C within the composition. TM The 706 control sample showed higher rubber-to-rubber tack. The polychloroprene and natural rubber system is known to have room temperature tack. Figure 14 This is a graph showing the rubber-to-rubber adhesion force versus temperature according to one embodiment of this disclosure. For example... Figure 14 As shown, Vistalon TM The 706 control composition lacked viscosity at room temperature. Vistalon TM 706:PEDM C (80 phr: 20 phr) sample at room temperature (23℃ (72) o F)) produces an average rubber-to-rubber tack of 67 g force / inch width. Vistalon TM The viscosity of the 706:PEDM C (80 phr:20 phr) composition is similar to that of Vistalon. TMThe 706 control sample showed a significant increase in temperature from 23°C to 60°C. Rubber-to-rubber adhesion tests were conducted based on a modified ASTM D3330 method F. Specifically, the following modifications to the ASTM method were used: (1) instead of the 2μ topcoat stainless steel substrate as per the ASTM method, an uncured sheet of rubber was used; (2) for conditioning, instead of 24 hours at 23°C as per the ASTM method, the sample was conditioned for 1 minute at the test temperature; and (3) the test temperature was in the range of 40°C–60°C, instead of 23°C as per the ASTM method. This approach provides the benefit of a wider test range and longer dwell time, thus allowing for a larger-scale testing of samples against the Tel-Tak method. Figure 15 This is a diagram showing the modulus (MPa) of the composition of the present invention. Figure 15 Table 5 shows the corresponding raw rubber strength (tensile stress at 10%, 25%, and 100% elongation) properties of the formulations shown. As mentioned above, an increase in viscosity is expected to be accompanied by a slight decrease in raw rubber strength. However, Vistalon... TM The raw rubber strength of the 706:PEDM C (80 phr:20 phr) composition was not reduced due to the presence of 20 phr PEDM C.

[0222] Table 6 shows only those with Vistalon TM Performance of the mixture of the control formulation of 706 and the formulation of the present invention having a concentration of PEDM C of 20 phr. Vistalon TM The curing agent in the 706:PEDM C (80 phr:20 phr) composition showed comparable tensile strength and elongation after 7 days of aging at 150°C to that of 100 phr Vistalon. TM The 706 composition is less affected compared to other compositions, as follows: Figure 16 and Figure 17 As shown.

[0223] Table 6

[0224]

[0225] Based on Vistalon TM Properties of formulations containing 9301:

[0226] Figure 12 This is a graph showing the Tel-Tak peak force versus ethylene content in PEDM according to one embodiment of this disclosure. (e.g.) Figure 12 As shown, the viscosity of the composition depends on the PEDM ethylene content of the formulations containing PEDM polymer at 5 phr and 10 phr levels, respectively. (Compared to Vistalon) TMCompared to the reference mixture without PEDM, 9301 showed higher viscosity in all formulations. For formulations containing 15 wt% ethylene PEDM at a 10 phr level, viscosity increased from 3.3 kPa to 5.0 kPa.

[0227] Figure 13 This is a graph showing the 100% modulus of raw rubber strength versus PEDM ethylene content according to one embodiment of this disclosure. It is anticipated that the increase in viscosity is generally accompanied by a slight decrease in raw rubber strength, which is indeed the case for formulations containing PEDM polymers.

[0228] Table 7 shows the properties of the formulations of the present invention, namely, reference formulation C2, and formulations of PEDM of Examples 8 to 14, which were formulated with different ethylene contents and phr levels in the mixtures. The cured formulations in the examples of the present invention have higher tensile strength and elongation compared with control formulation C2.

[0229] Table 7

[0230]

[0231] Overall, the compositions of this disclosure comprise 5 phr-30 phr of a PEDM terpolymer containing 1-10 wt% diene, 15-40 wt% ethylene, and 13-85 wt% propylene, the wt% being based on the weight of the PEDM terpolymer; and 70 phr-95 phr of an ethylene-based copolymer containing an ethylene content (based on the weight of the ethylene-based copolymer) different from that of the first polymer, and C3-C... 12 α-olefins and, optionally, one or more dienes. The compositions of this disclosure may have a raw rubber strength of about 1.7 MPa or greater, with a 25% modulus. The compositions of this disclosure may have a tensile strength at break of 21.4 MPa or greater. The compositions of this disclosure may have a viscous property of at least about 3.4 kPa, for example, at least about 5.5 kPa. The drive belts of this disclosure comprise one or more compositions of this disclosure having one or more advantageous properties described herein to provide novel and improved drive belts and novel and improved drive belt formation.

[0232] All documents described herein, including any priority documents and / or experimental procedures, are incorporated herein by reference to all rights, without prejudice to the present invention. It will be apparent from the foregoing overview and specific embodiments that, while some embodiments have been illustrated and described, various modifications may be made without departing from the spirit and scope of this disclosure. Therefore, it is not intended that this disclosure be limited thereto. Similarly, the term "comprising" is considered synonymous with the term "including." Likewise, whenever a composition, element, or group of elements precedes the transitional term "comprising," it should be understood that the same composition or group of elements preceding the enumerated composition, element, or element, and vice versa, is also considered to have the transitional terms "consistently composed of," "composed of," "selected from," or "is" preceding the listed composition, element, or elements.

Claims

1. A composition comprising: A propylene-α-olefin-diene PEDM terpolymer comprising 5-30 parts by weight / 100 parts by weight of rubber PHR, comprising 1-10 wt% diene, 21-40 wt% α-olefin and 50-82.1 wt% propylene, wherein the wt% is based on the weight of the PEDM terpolymer, and wherein the PEDM terpolymer has a atactic propylene sequence; and 70 to 95 phr of an ethylene-based copolymer comprising ethylene, one or more C3-C12 α-olefins, and optionally one or more dienes; wherein the ethylene content of the ethylene-based copolymer is different from the α-olefin content of the PEDM terpolymer, wherein the amount of the ethylene content of the ethylene-based copolymer is in wt% based on the total weight of the ethylene-based copolymer; and the amount of the α-olefin content of the PEDM terpolymer is in wt% based on the total weight of the PEDM terpolymer. 12 an α-olefin and optionally one or more dienes; wherein the ethylene content of the ethylene-based copolymer is different from the α-olefin content of the PEDM terpolymer, wherein the amount of the ethylene content of the ethylene-based copolymer is in wt% based on the total weight of the ethylene-based copolymer; and the amount of the α-olefin content of the PEDM terpolymer is in wt% based on the total weight of the PEDM terpolymer.

2. The composition of claim 1, wherein the PEDM is formed as follows: propylene, one or more α-olefins and one or more dienes are polymerized in the presence of a bridged fluorenyl-cyclopentadienyl Group 4 catalyst that has been activated by an activator; The catalyst is represented by the following formula (I): Where J is a binary bridge basis; M is a group 4 transition metal; Each X is independently a monovalent anionic ligand, or two Xs are joined together to form a metal cyclic ring with M, or two Xs are joined to form a chelate ligand, diene ligand, or alkylidene ligand. each R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are independently hydrogen, C1-C 50 substituted or unsubstituted alkyl, provided that R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , R 6 and R 7 , R 8 and R 9 , and R 9 and R 10 any one or more pairs of the pairings are optionally linked together to form a saturated or partially saturated cyclic or fused ring structure; and The activator is a noncoordinate anionic activator.

3. The composition of claim 2, wherein the bridged fluorenyl-cyclopentadienyl Group 4 catalyst is dimethyl-1,1'-bis(4-triethylsilylphenyl)methylene(cyclopentadienyl)(2,7-di-tert-butyl-fluoren-9-yl)hafnium.

4. The composition of claim 2 or claim 3, wherein the activator is N,N-dimethylphenylammonium tetra(pentafluorophenyl)boronic acid.

5. The composition of claim 1, wherein the PEDM terpolymer has an Hf of less than 1 J / g.

6. The composition of claim 1, wherein the PEDM terpolymer has a crystallinity of 0.1%-5% as determined by differential scanning calorimetry.

7. The composition of claim 1, wherein the PEDM terpolymer has an α-olefin of ethylene and an ethylene content of 30 wt%-40 wt%.

8. The composition of claim 1, wherein the diene of the PEDM terpolymer is one or more of the following substances: 5-ethide-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 1,4-hexadiene, alkyl dicyclopentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-heptadiene, 2-methyl-1,5-hexadiene, cyclooctadiene, 1,4-octadiene, 1,7-octadiene, 5-n-propylidene-2-norbornene, 5-(2-methyl-2-butenyl)-2-norbornene, and norbornene.

9. The composition according to claim 8, wherein the diene of the PEDM terpolymer is 5-ethylidene-2-norbornene.

10. The composition of claim 1, wherein the PEDM terpolymer has a diene content of 2 wt% to 4 wt%.

11. The composition of claim 1, wherein the ethylene-based copolymer comprises 40 to 95 wt% ethylene, 0 to 10 wt% of one or more dienes, and C3 to C12 α-olefins, the wt% based on the total weight of the ethylene-based copolymer. 12 α-olefins, the wt% based on the total weight of the ethylene-based copolymer.

12. The composition of claim 1, wherein the C3-C of the ethylene-based copolymer is... 12 The α-olefin is propylene or 1-butene.

13. The composition of claim 1, wherein the C3-C of the ethylene-based copolymer 12 The α-olefin is propylene.

14. An elastomer composition that is at least partially crosslinked, wherein the elastomer is a reaction product of the following substances: The composition according to any one of claims 1-13; One or more vulcanization activators; and One or more vulcanizing agents.

15. The composition of claim 14 further comprises one or more additives containing at least one of carbon black and / or processing oil.

16. The composition of claim 15, wherein the composition comprises an alkane processing oil of 1 phr to 150 phr, the alkane processing oil having a viscosity of 80-600 CSt at 40°C.

17. The composition of claim 15 or 16 further comprises a mineral filler.

18. The composition of claim 14, wherein the composition has a viscosity of 4,000 Pa or greater and a raw rubber strength of 1.7 MPa or greater 25% modulus.

19. The composition of claim 14, wherein the composition has a tensile strength at break of 21.4 MPa or greater.

20. The composition of claim 14, wherein the composition has a viscosity of at least 3.4 kPa.

21. The composition of claim 20, wherein the composition has a viscosity of at least 5.5 kPa.

22. A transmission belt, comprising: The composition according to any one of claims 1-21.

23. The drive belt of claim 22 further comprises at least one of a filler, a plasticizer, or a stabilizer.

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