Process for producing long chain branching in epdm and products

Abstract

This disclosure provides a method and a resulting composition. In one embodiment, the method includes providing an ethylene / propylene / non-conjugated polyene terpolymer (EPDM) having at least 3.5 wt% non-conjugated polyene. The method includes reacting the EPDM with a metal Lewis acid to form a rheology-modified EPDM. The rheology-modified EPDM has (i) a z-average molecular weight (Mz) greater than 500,000 g / mol to 10,000,000 g / mol, (ii) an Mz / Mw ratio of 3 to 10, (iii) a g value of 0.4 to 1.0, (iv) a z value of 1.0 to 3.5, (v) a Mooney viscosity of 50 to 150, and (vi) a tanδ value of 0.1 to less than 1.0.

Description

Background Technology

[0001] Ethylene-propylene-diene monomer terpolymers (EPDMs) are known to have a molecular structure incorporating long-chain branched (LCB) molecules. LCBs introduce side chains into the EPDM backbone, significantly altering its rheological and physical properties; for example, the elasticity and shear-thinning characteristics of EPDM increase with increasing LCB. Compared to unbranched EPDM, the benefits of high-LCB EPDM include reduced cold flow, higher raw strength, greater resistance to collapse during hollow component extrusion, better foaming properties, faster extrusion rates, faster mixing, lower internal mixer energy consumption, higher filler loading, and reduced melt fracture.

[0002] The selection of catalysts and polymerization process conditions used in polymerization provide methods for tuning the LCB level in the EPDM architecture. Ziegler-Natta (ZN) catalysts (e.g., titanium-based or vanadium-based catalysts) can introduce LCBs into EPDM during the polymerization process. However, the degree of LCB is difficult to control; for example, ZN polymerization processes tend to form undesirable cross-linked EPDM that leads to gel formation. ZN polymerization processes also produce EPDM with broad compositional and molecular weight distributions.

[0003] Metallocene catalysts (e.g., zirconium-based catalysts) produce EPDM during solution polymerization. Compared to Zn-catalyzed EPDM, metallocene catalysts generally produce EPDM with a more uniform compositional distribution, narrower MWD, and a more linear molecular architecture. However, metallocene catalysts typically produce lower levels of LCB compared to Zn-catalyzed EPDM.

[0004] Therefore, the art recognizes the need for high LCB EPDM. The art also recognizes the need for methods to increase the LCB in metallocene-catalyzed EPDM. Summary of the Invention

[0005] This disclosure provides a method. In one embodiment, the method includes providing an ethylene / propylene / non-conjugated polyene terpolymer (EPDM) having at least 3.5 wt% non-conjugated polyene. The method includes reacting the EPDM with a metal-Lewis acid; and forming a rheology-modified EPDM. The rheology-modified EPDM has (i) a z-average molecular weight (Mz) greater than 500,000 g / mol to 10,000,000 g / mol, (ii) an Mz / Mw ratio of 3 to 10, (iii) a g value of 0.4 to 1.0, (iv) a z value of 1.0 to 3.5, (v) a Mooney viscosity of 50 to 150, and (vi) a tanδ value of 0.1 to less than 1.0.

[0006] This disclosure provides a composition. In one embodiment, the composition comprises an ethylene / propylene / non-conjugated polyene terpolymer (EPDM) having at least 3.5 wt% of a non-conjugated polyene. The ethylene / propylene / non-conjugated polyene terpolymer (EPDM) has (i) a z-average molecular weight (Mz) greater than 500,000 g / mol to 10,000,000 g / mol, (ii) an Mz / Mw ratio of 3 to 10, (iii) a g value of 0.4 to 1.0, (iv) a z value of 1.0 to 3.5, (v) a Mooney viscosity of 50 to 150, and (vi) a tanδ value of 0.1 to less than 1.0. Attached Figure Description

[0007] Figure 1 This is a schematic diagram of carbon-cation coupling according to one embodiment of the present disclosure.

[0008] Figure 2 The diagram illustrates the tanδ values ​​of EPDM1 and Embodiment 23 of the present invention in Table 2.

[0009] Figure 3 This is a diagram illustrating the GPC curves of EPDM samples before and after reaction with a metal Lewis acid.

[0010] definition

[0011] All references to the periodic table in this document refer to the periodic table published and copyrighted by CRC Press, Inc. in 2003. Furthermore, any reference to one or more groups refers to one or more groups reflected in such a periodic table that uses the IUPAC system for group numbering.

[0012] For the purposes of U.S. patent practice, any reference to the contents of a patent, patent application, or publication, particularly the disclosure of the definitions (limited to not being inconsistent with any definition specifically provided in this disclosure) and general knowledge in the art, is incorporated in its entirety by reference (or its equivalent U.S. version thereof).

[0013] The numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit and including both the lower and upper limits. For ranges containing definite values ​​(e.g., 1 or 2 or 3 to 5 or 6 or 7), any subranges between any two definite values ​​are included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6; etc.).

[0014] Unless otherwise stated, implied by the context or customary in the art, all parts and percentages are by weight, and all test methods are current methods as of the date of this disclosure.

[0015] As used herein, the term "composition" refers to a mixture of materials comprising the composition and reaction and decomposition products formed from the materials of the composition.

[0016] The terms “comprising,” “including,” “having,” and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether or not they are specifically disclosed. For the avoidance of any doubt, unless stated to the contrary, all compositions claimed using the term “comprising” may contain any additional additives, auxiliaries, or compounds (whether polymeric or otherwise). In contrast, the term “consistently composed of” excludes any other components, steps, or procedures from the scope of any subsequent description, except those not essential for operability. The term “composed of” excludes any components, steps, or procedures not specifically described or listed. Unless otherwise stated, the term “or” refers to the listed members individually and in any combination. Use of the singular includes use of the plural, and vice versa.

[0017] "Ethylene-based polymers" are polymers containing more than 50% by weight of polymerizable ethylene monomers (based on the total amount of polymerizable monomers) and optionally may contain at least one comonomer. Ethylene-based polymers include ethylene homopolymers and ethylene copolymers (meaning units derived from ethylene and one or more comonomers). The terms "ethylene-based polymers" and "polyethylene" are used interchangeably. Non-limiting examples of ethylene-based polymers (polyethylene) include low-density polyethylene (LDPE) and linear polyethylene. Non-limiting examples of linear polyethylene include linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), very low-density polyethylene (VLDPE), multi-component ethylene-based copolymers (EPE), ethylene / α-olefin multi-block copolymers (also known as olefin block copolymers (OBC)), single-point catalytic linear low-density polyethylene (m-LLDPE), substantially linear or linear plastisol / elastomers, and high-density polyethylene (HDPE). Generally, polyethylene can be produced in gas-phase fluidized bed reactors, liquid-phase slurry reactors, or liquid-phase solution reactors using heterogeneous catalyst systems (such as Ziegler-Natta catalysts) or homogeneous catalyst systems containing Group 4 transition metals and ligand structures (such as metallocenes, non-metallocene metal centers, heteroaryl groups, isovalent aryloxy ethers, phosphine imides, etc.). Combinations of heterogeneous and / or homogeneous catalysts can also be used in single-reactor or dual-reactor configurations. In one embodiment, the ethylene-based polymer does not contain aromatic comonomers polymerized therein.

[0018] Hydrocarbons are compounds containing only hydrogen and carbon atoms. Hydrocarbons can be branched or unbranched, saturated or unsaturated, cyclic, polycyclic, or acyclic, as well as combinations thereof.

[0019] The terms “interpolymer” and “copolymer” refer to polymers prepared by polymerizing at least two different types of monomers. These general terms include both: classic copolymers, i.e., polymers prepared from two different types of monomers, and polymers prepared from more than two different types of monomers, such as terpolymers, tetrpolymers, etc.

[0020] A Lewis acid is a substance that can accept a pair of electrons; a Lewis acid is an electron docking acceptor. H + Non-limiting examples of Lewis acids as cations. A "Lewis base" is a substance that donates a pair of electrons; a Lewis base is an electron pair donor. Non-limiting examples of Lewis bases as OH- anions.

[0021] As used herein, the term “long-chain branching” or (“LCB”) refers to the presence of side chains on an ethylene / propylene / diene monomer terpolymer, wherein the molecular weight of the side chains is greater than the molecular weight of the polymer entanglement.

[0022] The term "polymer" refers to a material prepared by reacting (i.e., polymerizing) a group of monomers, wherein the group of monomers is either a homogeneous (i.e., only one type) group of monomers or a heterogeneous (i.e., more than one type) group of monomers. As used herein, the term polymer includes the term "homogeneous polymer" and the term "interpolymer" as defined below, where "homogeneous polymer" refers to a polymer prepared from a homogeneous group of monomers.

[0023] The term "terpolymer" refers to a polymer prepared by polymerizing three different types of monomers.

[0024] Test methods

[0025] density Measured according to ASTM D792, Method B. Results are expressed in grams per cubic centimeter (g / cc or g / cm³). 3 Records are kept in units of ).

[0026] Mooney viscosity testThe Mooney viscosity of EPDM rubber was measured in a Mooney shear disk viscometer according to ASTM 1646-04. The instrument was an Alpha Technologies Mooney Viscometer 2000. The torque was measured by rotating the rotor at 2 rpm via a torque transducer. After the pressure plate was closed, the sample was preheated for 1 minute (min). The motor was then started, and the torque was recorded over a 4-minute period. The results were reported in Mooney units (MU) as “ML(1+4) at 125°C”. The term “ML” indicates the use of a large rotor, “Mooney Large,” in the viscosity test, where the large rotor is a standard-sized rotor. Mooney viscosity (MV) measures the flow resistance of a polymer at relatively low shear rates and indicates the polymer’s flowability.

[0027] Rheological property analysis of rubber (RPA) Rubber rheological properties were analyzed using a rotorless oscillating shear rheometer (i.e., a rubber processing analyzer (RPA)) according to ASTM D6204. RPA frequency sweep tests were performed using an Alpha Technologies RPA2000. Test samples were cut using a 2000R cutter. Sample sizes ranged from 5 to 7 grams. A suitable sample size (116% to 160% of the test chamber volume) was considered to be achieved when a small particle of rubber compound was uniformly extruded around the perimeter of the die while the die was closed. The sample was placed between two polyester films. For pure terpolymers, frequency sweeps were performed at 125°C using 5% strain. The frequency range was from 0.1 radians / second (rad / s) to 100 rad / s. The stress response is analyzed using amplitude and phase, from which the storage shear modulus (G'), loss shear modulus (G”), complex viscosity (V), tanδ (i.e., phase angle δ), and complex shear modulus G* are calculated. Modulus values ​​are reported in kilopascals (kPa), phase angles in degrees, and viscosity in pascals-seconds (Pa·s).

[0028] the term" Rheological ratio The (or “RR”) is calculated as the ratio of the measured complex viscosity (V0.1) at 0.1 rad / s and 125 °C to the measured complex viscosity (V100) at 100 rad / s and 125 °C; RR is equal to V0.1 / V100 at 125 °C.

[0029] As used in this article, terminology Tanδ (tangent δ) The tangent "phase angle δ" is the tangential phase hysteresis exhibited between the applied stress and the resulting strain. For a given dynamic mechanical study, the tangent δ (phase angle δ) is measured at a shear rate of 0.1 rad / s and 125 °C. When comparing the tangent δ (phase angle δ) of a group of polymers, a decreasing tanδ value generally indicates that the polymer is more elastic and has more long-chain branching.

[0030] High-temperature gel permeation chromatography Testing (“HT GPC Testing”): HT GPC testing was performed using a Polymer Char (Valencia, Spain) HT GPC system, which consists of an infrared concentration / composition detector (IR-5 detector), a PDI 2040 laser scattering detector (Agilent), and four capillary bridge viscometers (Malvern Panalytical), allowing for the determination of number-average molecular weight (M). N ), weight-average molecular weight (M W ), and zeta average molecular weight (M Z ).

[0031] The column consists of four mixed ALS 20-micron columns (Agilent). The detector compartment operates at 160°C, and the column compartment operates at 150°C. The support solvent is 1,2,4-trichlorobenzene (TCB) containing approximately 250 ppm butylated hydroxytoluene (BHT) and aerated with nitrogen.

[0032] The HT GPC system was calibrated using 21 polystyrene standards with narrow molecular weight distributions. The standards ranged in molecular weight from 580 to 8,400,000 and were arranged in six "cocktail" mixtures, with individual molecular weights separated by at least tenfold. The molecular weight data (M0) of the resulting polystyrene standards were expressed using Equation (1). ps ) converted into polyethylene molecular weight data (M pe ):M pe =A(M ps ) B The value of A is determined iteratively and is approximately 0.42, and the value of B is 1.0. The corresponding polyethylene equivalent calibration points obtained from equation (1) are fitted to the elution volumes observed for each polystyrene standard using a third or fifth order polynomial.

[0033] Calculate M according to the following equation. N M W and M Z :

[0034]

[0035]

[0036] Among them, Wf i It is the weight fraction of the i-th eluted component, and M iThis is the molecular weight of the i-th eluted component. The molecular weight distribution (MWD) is expressed as M. W Relative to M N The ratio; M W / M N The value of A is determined by adjusting the value of A in equation (1) until the value of Mw in equation (3) and the corresponding retained volume polynomial, based on Mw having a known value of 120,000. W The Mw value was determined in consistency with the independently determined value obtained from a linear homopolymer reference with an intrinsic viscosity of 1.873 dL / g. The same linear homopolymer reference was used to determine the response factors of the IR-5 detector, laser scattering detector, and viscometer. The determination of response factors and detector offsets was carried out in a manner consistent with that published in the following literature: “A Strategy for Interpreting Multidetector Size-Exclusion Chromatography Data I” in “Chromatography of Polymers (ACS Seminar Series, #521)”, TH Mouryy and ST Balke, Chapter 12, p. 180, (1993); and “A Strategy for Interpreting Multidetector Size-Exclusion Chromatography Data II” in “Chromatography of Polymers (ACS Seminar Series, #521)”, ST Balke, R. Thitiratsakul, R. Lew, P. Cheung, TH Mouryy, Chapter 13, p. 199, (1993), the entire contents of which are incorporated herein by reference.

[0037] The g-value is used to characterize the amount of long-chain branching introduced by chemical treatment. The g-value is the ratio of the g' value of the same terpolymer after chemical treatment to that before. The g' value of the terpolymer before and after chemical treatment is determined by HT GCP testing using a triple detector. The g' value is the ratio of the determined intrinsic viscosity of the terpolymer using a calibrated viscometer and concentration detector to the calculated intrinsic viscosity of an ethylene homopolymer with the same weight-average molecular weight. The intrinsic viscosity of the ethylene homopolymer is calculated using the Mark-Houwink Equation, IV = k * Mw. α Calculate, where the value of k is 4.06 × 10-4 And the α value is 0.725 (Th.G. Scholte, NLJ Meijerink, HMSchoffeleers, and AMG Grands, Journal of Applied Polymer Science, 29, 3763-3782 (1984)). The calculated g value has an accuracy of ≤+ / -2%.

[0038] The zeta average (or "z-average") molecular weight ratio (Mz / Mw) indicates the distribution at the high molecular weight end. A high Mz / Mw indicates that the molecular weight distribution curve tails to the high molecular weight end, or that there is an increased fraction of high molecular weight. The z-value is defined as the Mz / Mw of the resin after chemical treatment compared to before. A z-value greater than 1 indicates that chemical treatment increased the relative content of high molecular weight, which affects the melt elasticity of the resin.

[0039] Monomer content test According to ASTM D3900, the ethylene and propylene content of the terpolymer was determined by Fourier Transform Infrared (FTIR) analysis, expressed as a weight percentage. According to ASTM D6047, the ENB content of the terpolymer was determined by Fourier Transform Infrared (FTIR) analysis, expressed as a weight percentage.

[0040] Residual element analysis test Residual elemental analysis was performed using inductively coupled plasma-atomic emission spectrometry (ICP-AES) and X-ray fluorescence (XRF). For ICP-AES analysis, the sample was weighed into a quartz tube, and 1 mL of water and 3 mL of nitric acid were added. The sample was placed in a hot block at 115 °C for 30 minutes. The sample was then placed in an UltraWave microwave oven, where it was digested at 250 °C. After microwave digestion, the sample was diluted and analyzed for aluminum (Al), magnesium (Mg), titanium (Ti), vanadium (V), and zirconium (Zr) by Perkin Elmer ICP. For XRF analysis, the sample was formed into a thin plate in a hot press at 127 °C. The sample was then rinsed with distilled water and then with acetone, and the chlorine content was measured by XRF. Results are reported in parts per million (ppm). Detailed Implementation

[0041] method

[0042] This disclosure provides a method. In one embodiment, the method includes:

[0043] Provide ethylene / propylene / non-conjugated polyene ternary copolymers with at least 3.5 wt% non-conjugated polyene.

[0044] Polymer (EPDM);

[0045] The EPDM is reacted with a metal Lewis acid; and

[0046] EPDM with the following rheological modifications is formed:

[0047] (i) z-average molecular weight (Mz) greater than 500,000 g / mol to 10,000,000 g / mol,

[0048] (ii) Mz / Mw from 3 to 10,

[0049] (iii) g values ​​from 0.4 to less than 1.0,

[0050] (iv) z values ​​from 1.0 to 3.5,

[0051] (v) Mooney viscosity of 50 to 100, and

[0052] (vi) tanδ values ​​from 0.1 to less than 1.0.

[0053] The method includes providing a terpolymer. The terpolymer is an ethylene / α-olefin / non-conjugated polyene terpolymer, said terpolymer consisting of polymerized ethylene, propylene, and at least 3.5 wt% non-conjugated polyene based on the total weight of the terpolymer. Non-limiting examples of suitable non-conjugated polyenes include C4-C. 40 Non-conjugated dienes.

[0054] In one embodiment, the non-conjugated polyene is an acyclic diene or a cyclic diene. Non-limiting examples of acyclic dienes include straight-chain acyclic dienes such as 1,4-hexadiene and 1,5-heptadiene; and branched-chain acyclic dienes such as 5-methyl-1,4-hexadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, 5,7-dimethyl-1,7-octadiene, and 1,9-decadiene, as well as mixed isomers of dihydromyrcene. Non-limiting examples of cyclic dienes include monocyclic dienes such as 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,5-cyclododecadiene; polycyclic alicyclic fused and bridged cyclic dienes such as tetrahydroindene and methyltetrahydroindene; alkenyl norbornene, alkylene norbornene, cycloalkenyl norbornene, and cycloalkylene norbornene, such as 5-methylene-2-norbornene (MNB), 5-ethylene-2-norbornene (ENB), 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, and 5-cyclohexylene-2-norbornene.

[0055] In one embodiment, the non-conjugated polyene is ENB.

[0056] In one embodiment, the terpolymer contains only one type of non-conjugated polyene. The single type of non-conjugated polyene has no or no heteroatoms.

[0057] In one embodiment, the terpolymer is an ethylene / propylene / norbornene terpolymer. In another embodiment, the terpolymer is an ethylene / propylene / ENB terpolymer. As used herein, the term "EPDM" refers to an ethylene / propylene / ENB terpolymer having only three monomers, with ENB being the only diene in the terpolymer.

[0058] In one embodiment, the terpolymer is a pure terpolymer. As used herein, the term "pure" indicates a material that is free of oil within or in its structure. As used herein, the term "pure" may interchangeably indicate an "oil-free" material. In one embodiment, the EPDM is pure EPDM (i.e., "n-EPDM").

[0059] In one embodiment, the n-EPDM used herein is produced using a metallocene catalyst as described in U.S. Patent No. 8,101,696, the entire contents of which are incorporated herein by reference.

[0060] In one implementation, the EPDM is an n-EPDM and consists of the following:

[0061] (i) 40 wt% to 70 wt%, or 45 wt% to 65 wt%, or 50 wt% to 60 wt% of polymerized ethylene,

[0062] (ii) 35 wt% to 65 wt%, or 40 wt% to 60 wt%, or 45 wt% to 55 wt% polymerized propylene,

[0063] (iii) Greater than 3.5 wt% to 8.5 wt%, or 3.6 wt% to 7 wt%, or 4 wt% to 6 wt% of polymerized ENB (where the total amount of (i), (ii), and (iii) is 100 wt% n-EPDM), and the n-EPDM has one, some, or all of the following characteristics:

[0064] (iv) Mooney viscosity of 10 MU to 40 MU, or 20 MU to 30 MU, and / or

[0065] (v) Density from 0.86 g / cc to 0.89 g / cc, or from 0.86 g / cc to 0.88 g / cc

[0066] The method involves reacting a terpolymer (e.g., n-EPDM) with a metal Lewis acid. As used herein, a “metal Lewis acid” (or “mLA”) is a Lewis acid containing one or more different types of metal atoms. A “monometal Lewis acid” (or “mono-mLA”) is a metal Lewis acid containing a single type of metal. As used herein, a “mixed metal Lewis acid” (or “mixed mLA”) is a Lewis acid containing two or more different types of metal atoms. The method involves reacting n-EPDM with 100 ppm to 23,000 ppm, or 200 ppm to 10,000 ppm, or 300 ppm to 3,000 ppm mLA.

[0067] In one embodiment, the mLA is a single mLA and contains metal atoms selected from Al, V, Zr, tin (Sn), or boron (B).

[0068] In one embodiment, the mLA is a single mLA containing 300 ppm to 1000 ppm Al. In another embodiment, the mLA is a single mLA of AlCl3 containing 300 ppm to 1000 ppm of Al metal.

[0069] In one embodiment, the mLA is a mixture of mLA and comprises at least one of Al, V, Zr, Sn, and / or B combined with at least one of Mg and / or Ti.

[0070] In one embodiment, the method includes melt-blending EPDM and introducing mA into the melt-blended EPDM to form rheology-modified EPDM. The melt-blending of EPDM is achieved by means of melt mixing (using a Banbury mixer and / or a Haake mixer), melt extrusion (single-screw extruder, twin-screw extruder, multi-screw extruder, continuous mixer, or kneader), and combinations thereof.

[0071] In one embodiment, the method includes dissolving EPDM in a solvent to form a mixture. The method further includes introducing a metal Lewis acid into the mixture and forming rheology-modified EPDM. The solvent is C6-C. 20 Hydrocarbon solvents, such as decane. Add EPDM to C6-C... 20 A mixture is formed in a hydrocarbon solvent. A metal Lewis acid is added to the mixture. The mixture is heated to a temperature of 60°C to 170°C, or 95°C to 160°C, to form rheology-modified EPDM. The rheology-modified EPDM is obtained from the reaction mixture.

[0072] Unbound by any specific theory, it is believed that the reaction between a metal Lewis acid and EPDM induces carbocation coupling between the polyene moieties in EPDM. The reaction procedure for carbocation coupling involves the formation of H-bonds between the EPDM polymer strands within the polyene moieties (ENB), such as... Figure 1 As shown in the image.

[0073] The method includes forming rheology-modified EPDM. The rheology-modified EPDM contains (a) 40 wt% to 70 wt%, or 45 wt% to 65 wt%, or 50 wt% to 60 wt% polymerized ethylene, (b) 35 wt% to 65 wt%, or 40 wt% to 60 wt%, or 45 wt% to 55 wt% polymerized propylene, and (c) greater than 3.5 wt% to 8.5 wt%, or 3.6 wt% to 7 wt%, or 4 wt% to 6 wt% polymerized ENB (wherein the total amount of (i), (ii), and (iii) is 100 wt% of the rheology-modified EPDM), and the rheology-modified EPDM has one, some, or all of the following properties:

[0074] (i) z-average molecular weight (Mz) greater than 500,000 g / mol to 10,000,000 g / mol, or 700,000 g / mol to 8,000,000 g / mol, or 1,000,000 g / mol to 6,000,000 g / mol; and / or

[0075] (ii) 3 to 10, or 3.4 to 8.0 Mz / Mw; and / or

[0076] (iii) g values ​​of 0.4 to 1.0, or 0.5 to 0.9, or 0.6 to 0.8; and / or

[0077] (iv) z-values ​​from 1.0 to 3.5, or 1.5 to 3.5, or 2.0 to 3.5; and / or

[0078] (v) Mooney viscosity of 50 to 100, or 60 to 90; and / or

[0079] (vi) tanδ from 0.1 to less than 1.0, or from 0.1 to 0.5, or from 0.1 to 0.3.

[0080] The method may include two or more embodiments disclosed herein.

[0081] Composition

[0082] This disclosure provides a composition. In one embodiment, the composition comprises rheology-modified EPDM, an optional oil, and one or more optional additives. The rheology-modified EPDM contains (a) 40 wt% to 70 wt%, or 45 wt% to 65 wt%, or 50 wt% to 60 wt% polymeric ethylene, (b) 35 wt% to 65 wt%, or 40 wt% to 60 wt%, or 45 wt% to 55 wt% polymeric propylene, and (c) greater than 3.5 wt% to 8.5 wt%, or 3.6 wt% to 7 wt%, or 4 wt% to 6 wt% polymeric ENB (wherein the total amount of (i), (ii), and (iii) is 100 wt% of the rheology-modified EPDM), and the rheology-modified EPDM has one, some, or all of the following properties:

[0083] (i) z-average molecular weight (Mz) greater than 500,000 g / mol to 10,000,000 g / mol, or 700,000 g / mol to 8,000,000 g / mol, or 1,000,000 g / mol to 6,000,000 g / mol; and / or

[0084] (ii) 3 to 10, or 3.4 to 8.0 Mz / Mw; and / or

[0085] (iii) g values ​​of 0.4 to 1.0, or 0.5 to 0.9, or 0.6 to 0.8; and / or

[0086] (iv) z-values ​​from 1.0 to 3.5, or 1.5 to 3.5, or 2.0 to 3.5; and / or

[0087] (v) Mooney viscosity of 50 to 100, or 60 to 90; and / or

[0088] (vi) tanδ values ​​from 0.1 to less than 1.0, or from 0.1 to 0.5, or from 0.1 to 0.3.

[0089] additive

[0090] The compositions of the present invention may optionally contain one or more additives.

[0091] In one embodiment, the composition comprises rheology-modified EPDM and an oil. The oil includes, but is not limited to, petroleum products such as aromatic and cycloalkane oils; polyalkylbenzene oils; organic acid monoesters such as alkyl / alkoxyalkyl oleates and alkyl / alkoxyalkyl stearates; and organic acid diesters such as dialkyl / dialkoxyalkyl / alkylaryl phthalates, dialkyl / dialkoxyalkyl / alkylaryl terephthalates, dialkyl / dialkoxyalkyl / alkylaryl sebacate, dialkyl / dialkoxyalkyl / alkylaryl adipate, and dialkyl / dialkoxyalkyl / alkylaryl glutarate. Alkyl / dialkoxyalkyl / alkylaryl esters; diol esters, such as polyethylene glycol dialkylate, polyethylene glycol dialkylate, and polyethylene glycol dialkylate; trimellitic acid trialkyl esters; trialkyl phosphates, trialkoxyalkyl phosphates, alkyl diaryl phosphates, and triaryl phosphates; chlorinated paraffin oils; coumarone-indene resins; pine tar; vegetable oils, such as castor oil, tall oil, rapeseed oil, and soybean oil, and their esters and epoxidized derivatives; and combinations thereof. In another embodiment, the oil is selected from the group consisting of: SUNPAR 2280, PARALUX 6001, HYDROBRITE 550, and CALSOL 5550.

[0092] In one embodiment, the composition comprises rheology-modified EPDM and oil. The oil is present in an amount of 5 wt%, or 15 wt%, or 20 wt% to 30 wt%, or 40 wt%, or 70 wt% based on the total weight of the composition. In another embodiment, the composition comprises an amount of oil of 5 wt% to 70 wt%, or 15 wt% to 40 wt%, or 20 wt% to 30 wt% based on the total weight of the composition.

[0093] The oil may include a combination of two or more embodiments as described herein.

[0094] In one embodiment, the composition comprises rheology-modified EPDM and additives (alone or in combination with oil). Suitable additives include, but are not limited to, fillers, antioxidants and anti-ozone agents, UV stabilizers, flame retardants, colorants or pigments, curing agents (e.g., sulfur, peroxides), accelerators, auxiliaries, processing aids, foaming agents, plasticizers, and combinations thereof.

[0095] Fillers include, but are not limited to, carbon black; silicates of aluminum, magnesium, calcium, sodium, and potassium, and mixtures thereof; carbonates of calcium and magnesium, and mixtures thereof; oxides of silicon, calcium, zinc, iron, titanium, and aluminum; sulfates of calcium, barium, and lead; polyethylene glycol (PEG); sulfur; stearic acid; sulfonamide; aluminum hydroxide; magnesium hydroxide; precipitated silica; fumed silica; natural fibers; synthetic fibers; and combinations thereof.

[0096] Antioxidants and anti-ozone agents include, but are not limited to, hindered phenols, bisphenols, and thiobisphenols; as well as substituted hydroquinones.

[0097] In one embodiment, the composition comprises rheology-modified EPDM and calcium carbonate. In one embodiment, calcium carbonate is present in an amount of 5 wt%, or 15 wt%, or 20 wt% to 30 wt%, or 40 wt%, or 70 wt% based on the total weight of the composition. In another embodiment, calcium carbonate is present in an amount of 5 wt% to 70 wt%, or 15 wt% to 40 wt%, or 20 wt% to 30 wt% based on the total weight of the composition.

[0098] In one embodiment, the composition comprises rheology-modified EPDM and carbon black. In one embodiment, the carbon black is present in an amount of 5 wt%, or 15 wt%, or 20 wt% to 30 wt%, or 40 wt%, or 70 wt% based on the total weight of the composition. In another embodiment, the carbon black is present in an amount of 5 wt% to 70 wt%, or 15 wt% to 40 wt%, or 20 wt% to 30 wt% based on the total weight of the composition.

[0099] In one embodiment, the composition comprises an aggregate additive support, said support excluding calcium carbonate and carbon black. In one embodiment, the aggregate additive support is present in an amount of 0.5 wt%, or 1 wt%, or 2 wt% to 4 wt%, or 5 wt%, or 10 wt% based on the total weight of the composition. In another embodiment, the aggregate additive support is present in an amount of 0.5 wt% to 10 wt%, or 1 wt% to 5 wt%, or 2 wt% to 4 wt% based on the total weight of the composition.

[0100] The additive may include two or more embodiments disclosed herein.

[0101] The aggregate additive loading may include two or more embodiments disclosed herein.

[0102] The composition can be used to form articles. Non-limiting examples of articles that can be formed from the composition include automotive parts (car door seals, car seat belts, car hoses), harnesses, building materials, cables, computer parts, extruder profiles, foams, footwear, gaskets, hoses, diaphragms, molded goods, roofing sheets, sponges, tires, weatherstripping, and wires.

[0103] Some embodiments of this disclosure will now be described by way of example and not limitation in the following examples.

[0104] Example

[0105] The raw materials used to prepare the comparative samples (“CS”) and the embodiments of the present invention (“IE”) are provided in Table 1 below.

[0106] Table 1

[0107]

[0108] In a drying oven under a nitrogen atmosphere, EPDM1 was dissolved in decane to form a 10 wt% solution in a glass vial equipped with a magnetic stir bar. Samples were prepared by introducing varying amounts of different m-Lewis acids (mLA) into individual portions of the dissolved EPDM1 solution. After the addition of mA, each mixture was heated to temperatures ranging from 95°C to 160°C. After 30 minutes, each mixture was precipitated in methanol, filtered, and dried in a vacuum oven at 70°C for 5 hours. The properties of the rheology-modified EPDM1 are shown in Table 2 below.

[0109]

[0110]

[0111] Table 3. Rheological data from RPA testing

[0112] V0.1 (Pa·s) V100 (Pa·s) RR tanδ at 0.1 Rad / s EPDM1 (control) 77,806 3,880 20 1.94 IE23 535,966 4,100 131 0.47

[0113] Table 2 presents the results of carbocation coupling of EPDM1 resin (NORDEL 4520 from Table 1) in solutions of various mono-mLA or mixed-mLA. The controls in Table 2 are the base resin, EPDM1, which underwent the same dissolution and heating processes as the comparative samples and examples of the invention; however, the controls were not treated with Lewis acids. Al was used as the mono-mLA in CS1, IE2, IE3, CS4, and CS5. At low Al doses (less than 300 ppm) in CS1 (CS1 67 ppm Al), no changes in molecular weight and / or branching were observed in EPDM1. At high Al doses or greater than 1000 ppm Al, CS4 (CS4 2680 ppm Al) and CS5 (CS5 6750 ppm Al) produced insoluble polymers. The applicant found that an unexpected range of 300 ppm to 1000 ppm Al can be used to produce acceptable rheologically modified EPDM for mono-mLAs that are AlCl3. As the Al dose increased to 330 ppm in IE2 and 675 ppm in IE3, monomLA AlCl3 produced rheologically modified EPDM1 with a high molecular weight tail (IE2 Mz 566,533 g / mol, IE3 Mz 1,576,535 g / mol).

[0114] TiCl4, with Ti as the single metal, is unsuitable as a single mA. Comparative samples CS6 to CS8 are those treated with TiCl4. Surprisingly, TiCl4 does not induce a coupling reaction even at high doses. This is unexpected because TiCl4 is a known initiator for cationic polymerization.

[0115] Similarly, MgCl2, with Mg as the single metal, is unsuitable as a single mLA. MgCl2 is ineffective for carbocation coupling even at extremely high doses (CS11).

[0116] EtAlCl2 is an effective Lewis acid as shown in Example IE9 of this invention, but requires a higher dosage to achieve the same level of branching as AlCl3. Without being bound by any particular theory, EtAlCl2 is considered a milder Lewis acid than AlCl3. While stronger Lewis acids offer the advantages of higher effectiveness and lower dosage requirements, milder Lewis acids offer the advantage of easier methodological control, thereby avoiding excessive crosslinking and improper gel formation.

[0117] The Lewis acidity of a metal Lewis acid can be modified by mixing it with one or more other metals. In this embodiment, IE12 was treated with a mixture of mA MgCl2-EtAlCl2 at 5400 ppm Al. Compared to IE9 (IE9 Mw: 266, 150 Mz: 1,246, 557) with an Al content of 2160 ppm, IE12 exhibited a lower degree of coupling, as indicated by lower Mw and Mz (IE12 Mw: 213, 690 Mz: 1,000, 443), suggesting that MgCl2 further reduces the Lewis acidity of EtAlCl2. Without being bound by any theory, it is believed that Mg donates electrons to Al through the Mg→Cl→Al bridge, thus reducing the acidity of the Al sites.

[0118] Comparative sample CS13 was treated with a mixed mLA Ti(OiPr)4-AlCl3 containing 877 ppm Al. For CS13, the Mw and Mz values ​​remained unchanged, indicating no coupling occurred. This forms an interesting comparison with IE3, in which significant coupling was observed only at 675 ppm Al in AlCl3. Increasing the Al-Ti ratio produced more efficient coupling (IE14 to 15). Without being bound by any theory, it is believed that some isopropoxy groups migrate to Al via ligand exchange, resulting in a decrease in the Lewis acidity of the Al sites. The applicant found that using a mixed metal system unexpectedly provided a way to achieve balanced Lewis acidity. Larger samples (IE23) were prepared using a trimetallic system for rheological testing.

[0119] It is particularly desirable that this disclosure is not limited to the embodiments and descriptions contained herein, but includes modifications of those embodiments, including portions of the embodiments as described in the scope of the following claims and combinations of elements of different embodiments.

Claims

1. A method comprising: providing an ethylene / propylene / non-conjugated polyene terpolymer (EPDM) having at least 3.5 wt% non-conjugated polyene; reacting the EPDM with 100 ppm to 23,000 ppm of a metal Lewis acid, the metal Lewis acid being a mixed metal Lewis acid composed of at least two different types of metal atoms selected from: (i) Mg and Al, (ii) Ti and Al, and (iii) Ti, Al, and Mg; and forming a rheology-modified EPDM having: (i) a z-average molecular weight (Mz) of greater than 500,000 g / mole to 10,000,000 g / mole, (ii) an Mz / Mw of 3 to 10, (iii) a g value of 0.4 to 1.0, (iv) a z value of 1.0 to 3.5, (v) a Mooney viscosity of 50 to 150, and (vi) a tan delta value of 0.1 to less than 1.

0.

2. The method of claim 1, wherein the reacting comprises melt mixing the EPDM; introducing the metal Lewis acid to the melt mixed EPDM; and forming the rheology-modified EPDM.

3. The method of claim 1, comprising: dissolving the EPDM in a solvent to form a mixture; introducing the metal Lewis acid to the mixture; and forming the rheology-modified EPDM.

4. The method of claim 3, comprising: heating the mixture to a temperature of 90 °C to 170 °C; and The EPDM is added to C6-C 20 hydrocarbon solvent; 5. A composition comprising: dissolved in the C6-C 20 hydrocarbon solvent. an ethylene / propylene / non-conjugated polyene terpolymer (EPDM) having at least 3.5 wt% non-conjugated polyene; (i) a z-average molecular weight (Mz) of greater than 500,000 g / mole to 10,000,000 g / mole, (ii) an Mz / Mw of 3 to 10, (iii) a g value of 0.4 to 1.0, (iv) a z value of 1.0 to 3.5, (v) a Mooney viscosity of 50 to 150, and (vi) a tan delta value of 0.1 to less than 1.

0.

6. The composition of claim 5, wherein the EPDM is neat.

7. The composition of claim 5 or 6, wherein the EPDM comprises: (i) 35 wt% to 75 wt% ethylene; (ii) 25 wt% to 65 wt% propylene; and (iii) greater than 3.5 wt% to 8.5 wt% polyene.

8. The composition of claim 5 or 6, wherein the polyene is 5-ethylidene-2- norbornene (ENB).

9. The composition of claim 5 or 6, wherein the composition comprises at least one of Al, V, Zr, Sn, or B in combination with at least one of Mg or Ti.

10. The composition of claim 9, wherein the composition comprises a metal combination selected from the group consisting of: (i) Mg and Al, (ii) Ti and Al, and (iii) Ti, Al, and Mg. ​

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