Process and products for generating long-chain branching in EPDM

Abstract

The present disclosure provides a process and resulting compositions. In one embodiment, the process includes providing an ethylene / propylene / non-conjugated polyene terpolymer (EPDM) having at least 3.5 wt.% of the non-conjugated polyene. The process 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) of greater than 500,000 g / mol to 10,000,000 g / mol, (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.

Description

[Background technology]

[0001] Ethylene-propylene-diene monomer terpolymers (EPDMs) with molecular structures containing long-chain branching (LCB) are known. LCB introduces side chains into the main chain of EPDM, which significantly alters the rheological and physical properties of EPDM. For example, the elasticity and shear viscosity of EPDM are improved by LCB. Advantages of high-LCB EPDM compared to unbranched EPDM include reduced cold flow, high green strength, high collapse resistance during extrusion of hollow parts, improved foaming properties, faster extrusion speeds, faster mixing, reduced energy consumption in the internal mixer, higher filler density, and reduced melt fracture.

[0002] A method is provided for adapting the LCB level in the EPDM structure by selecting the catalyst used for polymerization and polymerization process conditions. Ziegler Natta (Zn) catalysts (e.g., titanium-based or vanadium-based catalysts) can introduce LCB into EPDM during the polymerization process. However, controlling the degree of LCB is difficult, and for example, the Zn polymerization process tends to form undesirable crosslinked EPDM that leads to gel formation. The Zn polymerization process also produces EPDM with a broad compositional distribution and a broad molecular weight distribution.

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

[0004] Therefore, the field of technology recognizes the need for high LCB EPDM. The field of technology further recognizes the need for methods to increase LCB in metallocene-catalyzed EPDM. [Overview of the project]

[0005] This disclosure provides a process. In one embodiment, the process provides an ethylene / propylene / non-conjugated polyenterpolymer (EPDM) having at least 3.5 wt% non-conjugated polyene. The process comprises reacting the EPDM with a metal Lewis acid to form a rheologically modified EPDM. The rheologically modified EPDM has (i) a z-average molecular weight (Mz) of more than 500,000 g / mol and up 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 tandelta value of less than 0.1 to 1.0.

[0006] This disclosure provides compositions. In one embodiment, the composition comprises an ethylene / propylene / non-conjugated polyenterpolymer (EPDM) having at least 3.5% by weight of non-conjugated polyenes. The ethylene / propylene / non-conjugated polyenterpolymer (EPDM) has (i) a z-average molecular weight (Mz) of more than 500,000 g / mol and up 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 tandelta value of less than 0.1 to 1.0. [Brief explanation of the drawing]

[0007] [Figure 1] This is a schematic diagram of a carbocation coupling according to one embodiment of the present disclosure. [Figure 2] Table 2 is a graph showing the tandelta values ​​for EPDM1 and Invention Example 23. [Figure 3] This graph shows the GPC curves of EPDM samples before and after reaction with a metallic Lewis acid.

[0008] definition All references to the periodic table in this specification refer to the periodic table published and copyrighted by CRC Press, Inc. in 2003. Furthermore, any reference to a group(s) refers to the group(s) as they appear in the periodic table using the IUPAC system for numbering groups.

[0009] For the purposes of U.S. patent practice, the content of any referenced patent, patent application, or publication is incorporated by reference in whole (or its equivalent U.S. version is incorporated by reference) particularly with respect to definitional disclosures (to the extent that they do not contradict any definitions specifically provided herein) and general knowledge in the art.

[0010] The numerical ranges disclosed herein include all values ​​from the lower limit to the upper limit (including boundary values). In the case of a range that includes an explicit value (e.g., 1 or 2, or 3 to 5, or 6 or 7), any sub-range between any two explicit values ​​(e.g., 1 to 2, 2 to 6, 5 to 7, 3 to 7, 5 to 6, etc.) is included.

[0011] Unless otherwise stated, implied in the context, or customary in the art, all parts and percentages are based on weight, and all test methods are current as of the filing date of this disclosure.

[0012] As used herein, the term “composition” refers to a mixture of materials comprising the composition, as well as reaction products and decomposition products formed from the materials of the composition.

[0013] The terms “comprising,” “including,” and “having,” and their derivatives, are not intended to exclude any additional components, processes, or procedures, whether or not they are specifically disclosed herein. To avoid any doubt, all compositions claimed through the use of the term “comprising” may include any additional additives, adjuvants, or compounds (whether polymers or not), unless otherwise stated. In contrast, the term “essentially consisting of” excludes any other components, processes, or procedures from the scope of any subsequent enumeration, except those not essential to the feasibility. The term “consisting of” excludes any components, steps, or procedures not explicitly described or enumerated. The term “or” refers to the enumerated members individually and in any combination, unless otherwise specified. The use of the singular includes the use of the plural, and vice versa.

[0014] An "ethylene-based polymer" is a polymer containing more than 50 weight percent polymerizable ethylene monomers (based on the total amount of polymerizable monomers) and optionally containing 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 polymer" and "polyethylene" can be 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), multicomponent ethylene copolymers (EPE), ethylene / α-olefin multiblock copolymers (also known as olefin block copolymers (OBCs)), single-site catalyst linear low-density polyethylene (m-LLDPE), substantially linear or linear plastomers / elastomers, and high-density polyethylene (HDPE). Generally, polyethylene can be produced in gas phase, fluidized bed reactors, liquid-phase slurry process reactors, or liquid-phase solution process reactors using heterogeneous catalyst systems such as Ziegler-Natta catalysts, homogeneous catalyst systems containing ligand structures such as Group IV transition metals and metallocenes, non-metallocene metal centers, heteroaryls, heterovalent aryloxyethers, phosphine imines, and others. A combination of heterogeneous and / or homogeneous catalysts can also be used in either a single-reactor or double-reactor configuration. In one embodiment, the ethylene-based polymer does not contain aromatic comonomers polymerized within the polymer.

[0015] "Hydrocarbon" is a compound containing only hydrogen and carbon atoms. Hydrocarbons can be branched or unbranched, saturated or unsaturated, cyclic, polycyclic, or acyclic species, and combinations thereof.

[0016] The terms "interpolymer" and "copolymer" refer to polymers prepared by the polymerization of at least two different types of monomers. These general terms include both classical copolymers, i.e., polymers prepared from two different types of monomers, and polymers prepared from three or more different types of monomers, such as terpolymers, tetrapolymers, and the like.

[0017] "Lewis acid" is a substance that can accept a pair of electrons, and a Lewis acid is an electron pair acceptor. H + Cations are non-limiting examples of Lewis acids. "Lewis base" is a substance that can donate a pair of electrons, and a Lewis base is an electron pair donor. OH - Anions are non-limiting examples of Lewis bases.

[0018] As used herein, the term "long chain branch" or ("LCB") refers to the presence of side chains on an ethylene / propylene / diene - monomer terpolymer where the side chain molecular weight exceeds the entanglement molecular weight of the polymer.

[0019] The term "polymer" refers to a material prepared by reacting (i.e., polymerizing) a set of monomers, which set can be a set of the same kind (i.e., only one type) of monomers or a set of different kinds (i.e., two or more types) of monomers. The term "polymer" as used herein includes the term "homopolymer" which refers to a polymer prepared from a set of homogeneous monomers, and the term "interpolymer" as defined below.

[0020] The term "terpolymer" refers to a polymer prepared by the polymerization of three different types of monomers.

[0021] Test Methods The density is measured according to ASTM D792, Method B. The result is expressed in grams per cubic centimeter (g / cc or g / cm³). 3 Record it using ).

[0022] Mooney Viscosity Test: The Mooney viscosity of EPDM rubber is measured using a Mooney shear disk viscometer according to ASTM 1646-04. The instrument is an Alpha Technologies Mooney Viscometer 2000. The torque required to rotate the rotor at 2 rpm is measured using a torque transducer. After closing the platen, the sample is preheated for 1 minute. Then the motor is started and the torque is recorded for 4 minutes. The results are reported in Mooney Units (MU) as "ML(1+4) at 125°C". The term "ML" indicates that a large rotor, "Mooney Large," is used in the viscosity test, and this large rotor is a standard-sized rotor. Mooney viscosity (MV) measures the resistance of a polymer flowing at relatively low shear rates and indicates the fluidity of the polymer.

[0023] Rubber rheology property analysis (RPA): Rubber rheology property analysis is performed according to ASTM D6204 using a rotorless vibrating shear rheometer (i.e., a rubber process analyzer, RPA). RPA frequency sweep tests are performed using Alpha Technologies RPA 2000. Test samples are cut out with Cutter 2000R. Sample size is 5-7 grams. The test specimen is considered to be of appropriate size (116-160% of the test cavity volume) if small beads of the rubber compound are uniformly extruded around the die when the die is closed. The sample is placed between two Mylar films. Frequency sweeps are performed at 125°C with a 5% strain on the neater polymer. The frequency range is 0.1 radians / second (rad / s) to 100 rad / s. The stress response was analyzed in terms of amplitude and phase, and from this, the storage shear modulus (G'), loss shear modulus (G"), complex viscosity (V), tan delta (i.e., phase angle δ), and complex shear modulus G* were calculated. The modulus values ​​are reported in kilopascals (kPa), the phase angle in degrees, and the viscosity in pascal-seconds (Pa·s).

[0024] The term "rheology ratio" (or "rheology ratio, RR") is calculated as the ratio of the complex viscosity measured at 0.1 rad / sec and 125°C (V0.1) to the complex viscosity measured at 100 rad / sec and 125°C (V100). RR is equal to V0.1 / V100 at 125°C.

[0025] As used herein, the term "tan delta" (tangent delta), tangent "phase angle δ", is the tangent phase angle lag shown between the applied stress and the resulting strain imparted by this stress. For a given dynamic mechanical study, the tan delta (phase angle δ) is measured at a shear rate of 0.1 rad / s and 125 °C. When comparing the tan delta (phase angle δ) of a group of polymers, a decreased tan delta value generally indicates that the polymer is more elastic and has more long-chain branching.

[0026] High Temperature Gel Permeation Chromatography Test ("HT GPC Test"): The HT GPC test is composed of an infrared concentration / composition detector (IR-5 detector), a PDI2040 laser light scattering detector (Agilent), and a 4-capillary bridge viscometer (Malvern Panalytical), and is performed using a Polymer Char (Valencia, Spain) HT GPC system that enables the determination of the number average molecular weight (M N ), weight average molecular weight (M W ), and zeta average molecular weight (M Z ).

[0027] The columns are four mixed A LS 20 micrometer columns (Agilent). The detector compartment is operated at 160 °C and the column compartment is operated at 150 °C. The carrier solvent is 1,2,4-trichlorobenzene (TCB) containing approximately 250 ppm of butylated hydroxytoluene (BHT) and is nitrogen-sparged.

[0028] The HT GPC system is calibrated with 21 narrow molecular weight distribution polystyrene standards. The molecular weights of the standards range from 580 to 8,400,000 and are placed in six "cocktail" mixtures with at least a 10-fold separation between individual molecular weights. The resulting molecular weight data (M ps ) of the polystyrene standards is given by Equation (1): M pe = A(M ps ) BAccording to the data, polyethylene molecular weight (M pe ) is converted to ). In the formula, the value of A is determined iteratively and is approximately 0.42, and the value of B is 1.0. Using cubic and quintic polynomials, the respective polyethylene equivalent calibration points obtained from equation (1) were applied to the observed elution volumes for each polystyrene standard.

[0029] M N M W , and M Z Calculate this according to the following equation:

number

[0030] 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'-values ​​of the same terpolymer before and after chemical treatment. The g'-values ​​of terpolymers before and after chemical treatment were determined by HT GCP testing using a triple detector. The g'-value is the ratio of the intrinsic viscosity of the terpolymer, determined 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 an ethylene homopolymer is given by the Mark-Houwink equation, IV = k*Mw α The calculation was performed using , and the k value is 4.06 × 10 -4The alpha value was 0.725 (Th.G.Scholte, NLJMeijerink, HMSchoffeleers, and AMGBrands, J.Appl.Polym.Sci., 29, 3763-3782 (1984)). The calculated g value has an accuracy of ±2%.

[0031] The ratio of the zeta-mean (or "z-mean") molecular weight to the weight-mean molecular weight (Mz / Mw) indicates the distribution at the high molecular weight end. A high Mz / Mw indicates tailing of the molecular weight distribution plot to the high molecular weight end, or an increase in the high molecular weight fraction. The z value was defined as the Mz / Mw of the resin before and after chemical treatment. A z value greater than 1 indicates that the chemical treatment increased the relative high molecular weight content, which affects the melt elasticity of the resin.

[0032] Monomer content testing: The ethylene and propylene content of the terpolymer, based on weight percentage, is determined by Fourier transform infrared (FTIR) analysis according to ASTM D3900. The ENB content of the terpolymer, based on weight percentage, is determined by Fourier transform infrared (FTIR) analysis according to ASTM D6047.

[0033] Residual Element Analysis Test: Residual element analysis is performed using both inductively coupled plasma atomic emission spectroscopy (ICP-AES) and X-ray fluorescence (XRF) techniques. For ICP-AES analysis, the sample is weighed into a quartz tube, and 1 mL of water and 3 mL of nitric acid are added to the sample. The sample is placed in a 115°C hot block for 30 minutes. Then, the sample is placed in an UltraWave microwave oven and decomposed at 250°C. After decomposition in the microwave, the sample is diluted and analyzed for aluminum (Al), magnesium (Mg), titanium (Ti), vanadium (V), and zirconium (Zr) using Perkin Elmer ICP. For XRF analysis, the sample is formed in a plaque in a 127°C hot press. Then, the sample is rinsed with distilled water, then with acetone, and the chlorine content is measured by XRF. The results will be reported in parts per million (ppm). [Modes for carrying out the invention]

[0034] process This disclosure provides a process. In one embodiment, this process is To provide an ethylene / propylene / non-conjugated polyethylene polymer (EPDM) having at least 3.5% by weight of non-conjugated polyene, Reacting EPDM with a metal Lewis acid, Rheologically modified EPDM, (i) z-average molecular weight (Mz) for molecules greater than 500,000 g / mol and up to 10,000,000 g / mol, (ii) 3-10 Mz / Mw, (iii) g values ​​between 0.4 and less than 1.0, (iv) z values ​​from 1.0 to 3.5, (v) Mooney viscosity of 50-100, (vi) Forming rheologically modified EPDM having a tandelta value of 0.1 to less than 1.0.

[0035] This process involves providing a terpolymer. The terpolymer is an ethylene / α-olefin / non-conjugated polyene terpolymer, in polymerization form, composed of ethylene, propylene, and at least 3.5% by weight of non-conjugated polyenes, based on the total weight of the terpolymer. A non-limiting example of a suitable non-conjugated polyene is C4-C 40 Non-conjugated dienes are an example.

[0036] In one embodiment, the non-conjugated polyene is an acyclic diene or a cyclic diene. Non-limiting examples of acyclic dienes include linear acyclic dienes, e.g., 1,4-hexadiene and 1,5-heptadiene, and branched acyclic dienes, e.g., 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 polycyclic alicyclic condensates such as 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,5-cyclododecadiene, tetrahydroindene and methyltetrahydroindene, as well as cross-linked cyclic dienes, alkenyls, alkylides, cycloalkenyls, and cycloalkylidene norbornene such as 5-methylene-2-norbornene (MNB), 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, and 5-cyclohexylidene-2-norbornene.

[0037] In one embodiment, the non-conjugated polyene is ENB.

[0038] In one embodiment, the terpolymer contains only one type of non-conjugated polyene. This single type of non-conjugated polyene is either inactive or does not contain heteroatoms.

[0039] In one embodiment, the terpolymer is an ethylene / propylene / norbornene terpolymer. In a further 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, where ENB is the only diene in the terpolymer.

[0040] In one embodiment, the terpolymer is a neat terpolymer. As used herein, the term “neat” refers to a material that does not contain oil in or on its structure. As used herein, the term “neat” interchangeably refers to a material that is “oil-free.” In one embodiment, the EPDM is neat EPDM (i.e., “n-EPDM”).

[0041] In one embodiment, the n-EPDM used herein is produced using a metallocene catalyst described in U.S. Patent No. 8,101,696, the entirety of which is incorporated herein by reference.

[0042] In one embodiment, EPDM is n-EPDM, (i) 40-70% by weight, or 45-65% by weight, or 50-60% by weight of polymerized ethylene, (ii) 35% to 65% by weight, or 40 to 60% by weight, or 45 to 55% by weight of polymerized propylene, (iii) comprising 3.5 to 8.5% by weight, or 3.6 to 7% by weight, or 4 to 6% by weight of polymerized ENB (where the total amount of (i), (ii), and (iii) is 100% by weight of n-EPDM), the n-EPDM having one, some, or all of the following properties: (iv) Mooney viscosity of 10 MU to 40 MU, or 20 MU to 30 MU, and / or (v) Density of 0.86 g / cc to 0.89 g / cc, or 0.86 g / cc to 0.88 g / cc

[0043] This process involves reacting a terpolymer (e.g., n-EPDM) with a metallic Lewis acid. As used herein, “metallic Lewis acid” (or “mLA”) is a Lewis acid containing one or more different types of metal atoms. “Single-metallic Lewis acid” (or “single mLA”) is a metallic Lewis acid containing one type of metal. As used herein, “mixed-metallic Lewis acid” (or “mixed mLA”) is a Lewis acid containing two or more different types of metal atoms. This process involves reacting n-EPDM with mLA in concentrations of 100 ppm to 23,000 ppm, 200 ppm to 10,000 ppm, or 300 ppm to 3,000 ppm.

[0044] In one embodiment, the mLA is a single mLA containing a metal atom selected from Al, V, Zr, tin (Sn), or boron (B).

[0045] In one embodiment, the mLA is a single mLA containing 300 ppm to 1000 ppm of Al. In a further embodiment, the mLA is a single mLA that is AlCl3 containing 300 ppm to 1000 ppm of Al metal.

[0046] In one embodiment, the mLA is a mixed mLA comprising at least one of Al, V, Zr, Sn, and / or B in combination with at least one of Mg and / or Ti.

[0047] In one embodiment, the process includes melting and mixing EPDM and introducing mLA into the melted EPDM to form rheologically modified EPDM. The melting and mixing of EPDM is achieved by melt mixing (by a Banbury mixer and / or Haacke mixer), melt extrusion (by a single-screw extruder, twin-screw extruder, multi-screw extruder, continuous mixer, or kneader), and combinations thereof.

[0048] In one embodiment, the process includes dissolving EPDM in a solvent to form a mixture. The process also includes introducing a metallic Lewis acid into the mixture and forming rheologically modified EPDM. The solvent is, for example, C6-C such as decane. 20 It is a hydrocarbon solvent. EPDM is C6~C 20 The mixture is added to a hydrocarbon solvent to form a mixture. A metallic 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 rheologically modified EPDM. The rheologically modified EPDM is recovered from the reaction mixture.

[0049] While not bound by any specific theory, the reaction between metal Lewis acids and EPDM is thought to result in carbocation coupling between polyene moieties in EPDM. The reaction sequence of carbocation coupling is as shown in Figure 1, forming hydrogen bonds between EPDM polymer chains across polyene moieties (ENBs).

[0050] The process involves forming rheologically modified EPDM. The rheologically modified EPDM contains (a) 40-70% by weight, or 45-65% by weight, or 50-60% by weight of polymerized ethylene, (b) 35-65% by weight, or 40-60% by weight, or 45-55% by weight of polymerized propylene, and (c) more than 3.5-8.5% by weight, or 3.6-7% by weight, or 4-6% by weight of polymerized ENB (where the total amount of (i), (ii), and (iii) is 100% by weight of the rheologically modified EPDM), and the rheologically modified EPDM has one, some, or all of the following properties. (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 (ii) Mz / Mw of 3-10 or 3.4-8.0, and / or (iii) g values ​​of 0.4 to 1.0, or 0.5 to 0.9, or 0.6 to 0.8, and / or (iv) z values ​​of 1.0 to 3.5, or 1.5 to 3.5, or 2.0 to 3.5, and / or (v) Mooney viscosity of 50-100 or 60-90, and / or (vi) Tandelta between 0.1 and less than 1.0, or between 0.1 and 0.5, or between 0.1 and 0.3.

[0051] This process may include two or more embodiments disclosed herein.

[0052] composition This disclosure provides compositions. In one embodiment, the composition comprises rheologically modified EPDM, an optional oil, and one or more optional additives. The rheologically modified EPDM contains (a) 40-70% by weight, or 45-65% by weight, or 50-60% by weight of polymerized ethylene, (b) 35-65% by weight, or 40-60% by weight, or 45-55% by weight of polymerized propylene, (c) more than 3.5-8.5% by weight, or 3.6-7% by weight, or 4-6% by weight of polymerized ENB (where the total amount of (i), (ii), and (iii) is 100% by weight of the rheologically modified EPDM), and the rheologically modified EPDM has one, some, or all of the following properties: (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 (ii) Mz / Mw of 3-10 or 3.4-8.0, and / or (iii) g values ​​of 0.4 to 1.0, or 0.5 to 0.9, or 0.6 to 0.8, and / or (iv) z values ​​of 1.0 to 3.5, or 1.5 to 3.5, or 2.0 to 3.5, and / or (v) Mooney viscosity of 50-100 or 60-90, and / or (vi) Tandelta between 0.1 and less than 1.0, or between 0.1 and 0.5, or between 0.1 and 0.3.

[0053] additives This composition may optionally contain one or more additives.

[0054] In one embodiment, the composition comprises rheologically modified EPDM and oil. Examples of oils include, but are not limited to, petroleum oils such as aromatic oils and naphthenic oils; polyalkylbenzene oils; organic acid monoesters such as alkyl and alkoxyalkyl oleates and stearates; organic acid diesters such as dialkyl, dialkoxyalkyl, and alkylaryl of phthalic acid, terephthalic acid, sebacic acid, adipic acid, and glutaric acid; glycol diesters such as tri-, tetra-, and polyethylene glycol dialkanoates; trialkyl trimellitates; trialkyl, trialkoxyalkyl, alkyldiaryl, and triaryl phosphates; chlorinated paraffinic 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 further embodiments, the oil is selected from the group consisting of SUNPAR 2280, PARALUX 6001, HYDROBRITE 550, and CALSOL 5550.

[0055] In one embodiment, the composition comprises rheologically modified EPDM and oil. The oil is present in an amount of 5% by weight, or 15% by weight, or 20% to 30% by weight, or 40% by weight, or 70% by weight, based on the total weight of the composition. In a further embodiment, the composition contains an amount of oil of 5 to 70% by weight, or 15 to 40% by weight, or 20 to 30% by weight, based on the total weight of the composition.

[0056] The oil may include a combination of two or more embodiments described herein.

[0057] In one embodiment, the composition comprises rheologically modified EPDM and additives (alone or in combination with oil). Suitable additives include, but are not limited to, fillers, antioxidants and ozone inhibitors, UV stabilizers, flame retardants, colorants or pigments, curing agents (e.g., sulfur, peroxides), accelerators, auxiliary agents, processing aids, foaming agents, plasticizers, and combinations thereof.

[0058] Fillers include, but are not limited to, carbon black; silicates of aluminum, magnesium, calcium, sodium, 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; alumina trihydrate; magnesium hydroxide; precipitated silica; fumed silica; natural fibers; synthetic fibers; and combinations thereof.

[0059] Examples of antioxidants and ozone inhibitors include, but are not limited to, hindered phenols, bisphenols, and thiobisphenols, as well as substituted hydroquinones.

[0060] In one embodiment, the composition comprises rheologically modified EPDM and calcium carbonate. In one embodiment, calcium carbonate is present in an amount of 5% by weight, or 15% by weight, or 20% to 30% by weight, or 40% by weight, or 70% by weight, based on the total weight of the composition. In further embodiments, calcium carbonate is present in an amount of 5 to 70% by weight, or 15 to 40% by weight, or 20 to 30% by weight, based on the total weight of the composition.

[0061] 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% by weight, or 15% by weight, or 20% to 30% by weight, or 40% by weight, or 70% by weight, based on the total weight of the composition. In a further embodiment, the carbon black is present in an amount of 5 to 70% by weight, or 15 to 40% by weight, or 20 to 30% by weight, based on the total weight of the composition.

[0062] In one embodiment, the composition comprises a total additive filling excluding calcium carbonate and carbon black. In one embodiment, the total additive filling is present in an amount of 0.5% by weight, or 1% by weight, or 2% to 4% by weight, or 5% by weight, or 10% by weight, based on the total weight of the composition. In a further embodiment, the amount of total additive filling is present in an amount of 0.5 to 10% by weight, or 1 to 5% by weight, or 2 to 4% by weight, based on the total weight of the composition.

[0063] The additive may include two or more embodiments disclosed herein.

[0064] Total additive filling may include two or more embodiments disclosed herein.

[0065] This composition can be used to form articles. Non-limiting examples of articles that can be formed using this composition include automotive parts (automotive door sealants, automotive belts, automotive hoses), belts, building materials, cables, computer components, extruder outlines, foams, footwear, gaskets, hoses, membranes, molded articles, roofing panels, sponges, tires, sealants, and wires.

[0066] Without limiting ourselves to any particular example, some embodiments of this disclosure will be described in the following examples. [Examples]

[0067] The raw materials used to formulate the comparative sample ("CS") and the inventive example ("IE") are shown in Table 1 below. [Table 1]

[0068] Under a nitrogen atmosphere in a dry box, EPDM1 was dissolved in decane to form a 10% by weight solution in a glass vial equipped with a magnetic stirring rod. Samples were prepared by introducing different amounts of various m-Lewis acids (mLA) into individual parts of the dissolved EPDM1 solution. After the addition of mLA, each mixture was heated to a temperature of 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 rheologically modified EPDM1 are shown in Table 2 below. [Table 2] CS = Comparative Sample, IE = Invention Example Et = ethyl group OiPr = isopropoxy group, (CH3)2CH-O- The g-value is the ratio of the g'-value (the intrinsic viscosity of the polymer to the intrinsic viscosity of homopolyethylene having the same weight-average molecular weight) before and after chemical treatment. The Z value is the ratio of the Mz / Mw values ​​before and after chemical treatment. [Table 3]

[0069] Table 2 shows the results of carbocation coupling of EPDM1 resin (NORDEL4520 from Table 1) in solution using various single mLAs or mixed mLAs. The control in Table 2 is the base resin EPDM1, which is subjected to the same dissolution and heating processes as the comparative samples and inventive examples. However, the control was not treated with Lewis acid. In CS1, IE2, IE3, CS4, and CS5, Al was used as the single mLA. At low Al doses (less than 300 ppm) in CS1 (67 ppm Al for CS1), no change in molecular weight and / or branching in EPDM1 was observed. At high Al doses, or Al greater than 1000 ppm, CS4 (2680 ppm Al for CS4) and CS5 (6750 ppm Al for CS5) resulted in insoluble polymers. The applicant discovered an unexpected range of Al (300 ppm to 1000 ppm) for a single mLA of AlCl3 for the production of acceptable rheologically modified EPDM. Increasing the Al dose to 330 ppm in IE2 and to 675 ppm in IE3 resulted in a single mLA of AlCl3 producing rheologically modified EPDM1 with a high molecular weight tail (IE2 Mz 566,533 g / mol, IE3 Mz 1,576,535 g / mol).

[0070] TiCl4, which has Ti as the single metal, does not function as a suitable single mLA. Comparative samples CS6-CS8 are samples treated with TiCl4. Surprisingly, TiCl4 did not induce a coupling reaction even at high doses. This is unexpected, as TiCl4 is a known initiator for cationic polymerization.

[0071] Similarly, MgCl2, which has Mg as the single metal, does not function as a suitable single mLA. MgCl2 was not effective for carbocation coupling even at extremely high doses (CS11).

[0072] EtAlCl2 was an effective metallic Lewis acid, as shown in Invention Example IE9, but required a higher dose to achieve the same level of branching compared to AlCl3. While not bound by any particular theory, EtAlCl2 is considered a weaker Lewis acid than AlCl3. Stronger Lewis acids offer the benefits of higher efficacy and lower dose requirements, while weaker Lewis acids offer the benefits of easier process control to avoid excessive crosslinking and undesirable gel formation.

[0073] The Lewis acidity of a metallic Lewis acid can be adjusted by mixing it with a specific other metal(s). Example IE12 was treated with a mixed mLA of MgCl2-EtAlCl2 containing 5400 ppm Al. IE12 showed a lower degree of coupling, as indicated by lower Mw and Mz values ​​(IE12 Mw: 213, 690 Mz: 1,000, 443) compared to IE9 (IE9 Mw: 266, 150 Mz: 1,246, 557) with an Al content of 2160 ppm, suggesting that MgCl2 further reduced the Lewis acidity of EtAlCl2. While not bound by any theory, it is thought that Mg donated electrons to Al via the Mg→Cl→Al bridge, thereby reducing the acidity of the Al moiety.

[0074] Comparative sample CS13 was treated with Ti(OiPr)4-AlCl3, a mixed mLA containing 877 ppm Al. In the case of CS13, the Mw and Mz values ​​remained unchanged, indicating that no coupling occurred. This is an interesting comparison with IE3, where significant coupling with AlCl3 was observed with only 675 ppm Al. Increasing the Al-Ti ratio resulted in more effective coupling (IE14-15). While not bound by any theory, it is thought that some isopropoxy groups migrated to Al through ligand exchange, reducing the Lewis acidity of the Al moiety. The applicant found that using a mixed metal system unexpectedly provides a way to achieve balanced Lewis acidity. For rheological testing, a larger sample (IE23) was prepared using three metal systems.

[0075] This disclosure is not limited to the embodiments and examples contained herein, and is specifically intended to include modifications of embodiments, including parts of embodiments and combinations of elements of different embodiments included in the following claims. The present invention may provide the following embodiments. [1] It is a process, To provide an ethylene / propylene / non-conjugated polyethylene polymer (EPDM) having at least 3.5% by weight of non-conjugated polyene, The EPDM is reacted with a metal Lewis acid, Rheologically modified EPDM, (i) z-average molecular weight (Mz) for molecules greater than 500,000 g / mol and up to 10,000,000 g / mol, (ii) 3-10 Mz / Mw, (iii) g values ​​of 0.4 to 1.0, (iv) z values ​​from 1.0 to 3.5, (v) Mooney viscosity of 50-150, (vi) A process comprising forming rheologically modified EPDM having a tandelta value of less than 0.1 to 1.0. [2] The aforementioned reaction involves melting and mixing the EPDM, Introducing the aforementioned metal Lewis acid into the molten mixed EPDM, The process according to [1] above, comprising forming the rheologically modified EPDM. [3] The EPDM is dissolved in a solvent to form a mixture, Introducing the aforementioned metal Lewis acid into the mixture, The process according to [1] above, comprising forming the rheologically modified EPDM. [4] The aforementioned EPDM is C 6 ~C 20 Adding to hydrocarbon solvents, The mixture is heated to a temperature of 90°C to 170°C, The aforementioned EPDM is C 6 ~C 20 The process according to [3] above, comprising dissolving in a hydrocarbon solvent. [5] The process according to any one of the above [1] to [4], comprising providing a single-metal Lewis acid having a metal selected from the group consisting of Al, V, Zr, Sn, B, and combinations thereof. [6] The process according to any one of the above [1] to [4], comprising providing a mixed metal Lewis acid comprising at least one of Al, V, Zr, Sn, or B in combination with at least one of Mg or Ti. [7] A composition, Ethylene / propylene / non-conjugated polyethylene polymer (EPDM) having at least 3.5% by weight of non-conjugated polyene; (i) z-average molecular weight (Mz) for molecules greater than 500,000 g / mol and up to 10,000,000 g / mol, (ii) 3-10 Mz / Mw, (iii) g values ​​of 0.4 to 1.0, (iv) z values ​​from 1.0 to 3.5, (v) Mooney viscosity of 50-150, (vi) A composition containing a tandelta value between 0.1 and less than 1.0. [8] The composition according to [7] above, wherein the EPDM is neat. [9] The aforementioned EPDM, (i) 35% to 75% by weight of ethylene, (ii) 25% to 65% by weight of propylene, (iii) The composition according to any one of the above [6] to [8], comprising more than 3.5% by weight and up to 8.5% by weight of a polyene.

[10] The composition according to any one of the above [6] to [9], wherein the polyene is 5-ethylidene-2-norbornene (ENB).

Claims

1. It is a process, To provide an ethylene / propylene / non-conjugated polyethylene polymer (EPDM) having at least 3.5% by weight of non-conjugated polyene, The EPDM is reacted with a metal Lewis acid which is a mixed metal Lewis acid containing at least two different metal atoms selected from the group consisting of (i) Mg and Al, (ii) Ti and Al, and (iii) Ti, Al, and Mg. Rheologically modified EPDM, (i) z-average molecular weight (Mz) greater than 500,000 g / mol to 10,000,000 g / mol, (ii) 3 to 10 MHz / MW, (iii) g values ​​of 0.4 to 1.0, (iv) z values ​​from 1.0 to 3.5, (v) Mooney viscosity of 50 to 150, and (vi) A process comprising forming a rheologically modified EPDM having a tandelta value of 0.1 to less than 1.

0.

2. The aforementioned reaction involves melting and mixing the EPDM, Introducing the aforementioned metal Lewis acid into the molten mixed EPDM, The process according to claim 1, comprising forming the rheologically modified EPDM.

3. The EPDM is dissolved in a solvent to form a mixture, Introducing the aforementioned metal Lewis acid into the mixture, The process according to claim 1, comprising forming the rheologically modified EPDM.

4. The aforementioned EPDM is C ６ ~C ２０ Adding to hydrocarbon solvents, The mixture is heated to a temperature of 90°C to 170°C. The EPDM is C ６ ~C ２０ The process according to claim 3, comprising dissolving in a hydrocarbon solvent.

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