Process and products for generating long-chain branching in EPDM

Abstract

The present invention provides ethylene / propylene / non-conjugated polyenterpolymer (EPDM) having a molecular structure including long-chain branching (LCB). [Solution] A composition is provided which contains a mixed metal Lewis acid composed of (i) Mg and Al, (ii) Ti and Al, and (iii) Ti, Al, and Mg at a concentration of 100 ppm to 23,000 ppm and has at least 3.5 wt% non-conjugated polyene in an ethylene / propylene / non-conjugated polyenterpolymer (EPDM); (i) z-average molecular weight (Mz) of more than 500,000 g / mol to 10,000,000 g / mol, (ii) Mz / Mw of 3 to 10, (v) Mooney viscosity of 50 to 150, and (vi) tan delta value of less than 0.1 to 1.0.

Description

[Background technology]

[0001] Ethylene-propyl having a molecular structure including long chain branching (LCB) Ethylene-propylene-diene monomer terpolymer LCB is known to be derived from the introduction of side chains into the main chain of EPDM, thereby... The rheological and physical properties of EPDM change significantly, for example, the elasticity and Shear viscosity reduction characteristics are improved by LCB. High LCB EPD compared to unbranched EPDM. The advantages of M include reduced cold flow, high green strength, and high collapse resistance during extrusion of hollow parts. Improved destructiveness and foaming properties, faster extrusion speed, faster mixing, and energy efficiency in the internal mixer. These include reduced consumption, a high filler filling rate, and reduced melt fracture.

[0002] By selecting the catalyst used in polymerization and polymerization process conditions, the EPDM structure can be modified. A method for adapting the LCB level is provided. Ziegler Natta, Zn) catalysts (e.g., titanium-based or vanadium-based catalysts) are used in LC during the polymerization process. B can be introduced into EPDM. However, controlling the degree of LCB is difficult. This is difficult, and for example, the Zn polymerization process results in undesirable cross-linking of EPD, leading to gel formation. The ZN polymerization process has a broad compositional distribution and a broad molecular weight distribution. It also generates EPDMs that have [specific characteristics].

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

[0004] Therefore, the technical field recognizes the need for high LCB EPDM. The field further recognizes the need for methods to increase LCB in metallocene catalyst EPDM. Yes, they are. [Overview of the project]

[0005] This disclosure provides a process. In one embodiment, the process is at least 3.5 times Ethylene / propylene / non-conjugated polyethylene polymer (E) containing % of non-conjugated polyenes This process includes providing EPDM. This process involves reacting EPDM with a metal Lewis acid. This includes forming rheologically modified EPDM. Rheologically modified EPDM is (i) z-average molecular weight (Mz) of molecules with molecular weights greater than 500,000 g / mol and up to 10,000,000 g / mol (ii) Mz / Mw of 3-10, (iii) g-value of 0.4-1.0, (iv) 1.0 (v) a z value of ~3.5, a Mooney viscosity of 50~150, and (vi) less than 0.1~1.0 It has a tan-delta value of .

[0006] This disclosure provides a composition. In one embodiment, the composition is at least 3.5% by weight Ethylene / propylene / non-conjugated polyethylene polymer (EPD) having non-conjugated polyenes M) contains. Ethylene / propylene / non-conjugated polyintrapolymer (EPDM) is (i )Having a z-average molecular weight (Mz) of more than 500,000 g / mol to 10,000,000 g / mol, (ii) Mz / Mw of 3 to 10, (iii) g value of 0.4 to 1.0, (iv) z value of 1.0 to 3 .5, (v) Mooney viscosity of 50 to 150, and (vi) a tan delta value of 0.1 to less than 1.0 .

Brief Description of the Drawings

[0007] [Figure 1] It is a schematic diagram of cationic coupling according to an embodiment of the present disclosure. [Figure 2] It is a graph showing the tan delta values for EPDM1 in Table 2 and Invention Example 23. [Figure 3] It is a graph showing the GPC curves of the EPDM sample before and after the reaction with the metal Lewis acid.

[0008] Definitions All references to the periodic table of the elements in this specification shall refer to the periodic table of the elements published and copyrighted in 2003 by CRC Press, Inc. Also, any reference to a group (plural possible ) shall be to the group (plural possible) reflected in that periodic table of the elements using the IUPAC system for numbering the groups.

[0009] For the purposes of U.S. patent practice, the content of any referenced patent, patent application, or publication shall be incorporated by reference in its entirety (to the extent not inconsistent with the specifically provided definitions of this disclosure and with respect to general knowledge in the relevant technical field), or the equivalent U.S. version thereof shall be incorporated as such by reference.

[0010] The numerical ranges disclosed in this specification include all values from the lower limit value to the upper limit value (including the boundary values). . For ranges that include explicit values ​​(e.g., 1, or 2, or 3-5, or 6, or 7), Any sub-range between any two explicit values ​​(e.g., 1-2, 2-6, 5-7, 3- This includes numbers 7, 5-6, etc.

[0011] Unless otherwise stated, unless implicitly stated in the context, or if it is customary in the art, To the extent that, all parts and percentages are based on weight, and all test methods are as of the filing date of this disclosure. It is the latest model.

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

[0013] The terms "comprising," "including," and "having" , and their derivatives, if any additional components, processes, or procedures are specifically used herein. Whether disclosed or not, this is not intended to exclude their existence. To avoid any doubt, the use of the term "includes" means that all claims are included. Unless otherwise stated, the composition (whether polymer or not) (Nevertheless), it may contain any additional additives, adjuvants, or compounds. The term "essentially consisting of" is used to describe something that is not essential to feasibility. Any other component, process, or procedure is excluded from the scope of any subsequent enumeration. The term "ran" does not include any component, step, or hand that is not explicitly described or enumerated. The order is excluded. The term "or" means that unless otherwise specified, the listed members are treated individually. It refers to, and any combination thereof. The use of the singular form includes the use of the plural form, and vice versa. It is the same.

[0014] "Ethylene-based polymers" make up 50% by weight (based on the total amount of polymerizable monomers). It contains polymerized ethylene monomers exceeding a certain value, and optionally contains at least one comonomer. It is a polymer that may contain ethylene. Ethylene-based polymers include ethylene homopolymers and ethylene Contains len copolymer (meaning units derived from ethylene and one or more comonomers) The terms "ethylene polymer" and "polyethylene" can be used interchangeably. Non-limiting examples of ethylene polymers (polyethylene) include low-density polyethylene (LO Examples include high-density polyethylene (LDPE) and linear polyethylene. A non-limiting example of ethylene is linear low-density polyethylene. (Thylene, LLDPE), ultra-low density polyethylene (U LDPE, very low density polyethylene (VLDPE), Multicomponent ethylene copolymer (EPE), ethylene / α-olefin multiblock copolymer Remer (also known as olefin block copolymer (OBC)) (Knowledge), single-site catalyst linear low-density polyethylene (m-LLDPE), substantially linear Chain-like or linear plastomers / elastomers, and high-density polyethylene (high densi Examples include polyethylene (HDPE). Generally, polyethylene is used in teeger nut. Heterogeneous catalytic systems such as catalysts, Group 4 transition metals and metallocenes, non-metallocene metal centers, heteroaryls, heterovalent aryloxy ethers, phosphinimines, etc. Homogeneous catalyst systems including Gund structures, and others, are used in gas phase, fluidized bed reactors, and liquid phase slurry reactors. - Can be produced in a process reactor or a liquid-phase solution process reactor. Heterogeneous catalyst and The combination of a single and / or homogeneous catalyst is also suitable for either a single reactor or a double reactor configuration. It can be used in this way. In one embodiment, the ethylene polymer is polymerized in the polymer. It does not contain aromatic comonomers.

[0015] A hydrocarbon is a compound that contains only hydrogen and carbon atoms. Hydrocarbons are branched chains. Chain-like or non-branched, saturated or unsaturated, cyclic, polycyclic or acyclic species, and combinations thereof. It could be a combination.

[0016] The terms "interpolymer" and "copolymer" refer to at least two different types This refers to polymers prepared by the polymerization of monomers. The general term encompasses both classical polymers. Copolymers, i.e., polymers prepared from two different types of monomers, and three Polymers prepared from the above different types of monomers, for example, terpolymers, tetrapolymers This includes things like rimmer.

[0017] A Lewis acid is a substance that can accept a pair of electrons, and Lewis acids are electron pair acceptors. H + A cation is a non-limiting example of a Lewis acid. A "Lewis base" is a pair of electrons Lewis bases are substances that donate electrons; they are electron pair donors. - Anions are Lewis salts This is a non-restrictive example of the base.

[0018] As used herein, the term “long-chain branched” or ("LCB") refers to a side chain molecular weight of 1. Ethylene / propylene / diene-monomer exceeding the entanglement molecular weight of the rimer. - This refers to the presence of side chains on the polymer.

[0019] The term "polymer" refers to the reaction (i.e., polymerization) of a set of monomers. This refers to materials prepared by [method], and this set is of the same kind (i.e., only one type). A set of monomers or a set of different monomers (i.e., two or more types). The term polymer used here refers to a polymer prepared from a homogeneous set of monomers. The term "homopolymer" as used below, and the term "interpolymer" as defined below Includes the word.

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

[0021] Test method The density is measured according to ASTM D792, Method B. The result is measured per cubic centimeter. 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 according to ASTM 1646-04. Measurements are taken using a knee shear disk viscometer. The instrument is from Alpha Technologies. This is a Mooney Viscometer 2000. The rotor rotates at 2 rpm. The torque required to close the platen is measured by a torque transducer. The sample is preheated for 1 minute. Then, the motor is started and the torque is recorded for 4 minutes. The results are expressed in Mooney Units (MU) as "ML(1+4) at 125°C". It is reported as follows: The term "ML" refers to the large rotor "Mooney Large" in viscosity tests. This large rotor is a standard-sized rotor, indicating that it is intended for use. Mooney viscosity Mooney viscosity (MV) measures the resistance of a polymer flowing at relatively low shear rates. This indicates the fluidity of the polymer.

[0023] Rubber rheology property analysis (RPA): Rubber rheology Rheological characteristic analysis is performed using a rotorless vibrating shear rheometer (i.e., rubber process analyzer). Using a rubber process analyzer (RPA) in accordance with ASTM D6204 The RPA frequency sweep test will be performed using Alpha Technologies RPA 2. Perform this using 000. Cut out the test sample with Cutter 2000R. Sample The size is 5-7 grams. When the die is closed, small beads of the rubber compound are around the die. When extruded uniformly within the enclosure, the test specimen will be of the appropriate size (116-160% of the test cavity volume). ) is assumed. Place the sample between two Mylar films. Perform a frequency sweep, The process is carried out at 125°C using a 5% strain on the terpolymer. The frequency range is 0.1 The unit is radians / second (rad / s) to 100 rad / s. The stress response is measured from the perspective of amplitude and phase. From this analysis, the storage shear modulus (G'), loss shear modulus (G"), and complex viscosity were determined. (V), tandelta (i.e., phase angle δ), and complex shear modulus G* were calculated. Report the performance value in kilopascals (kPa), the phase angle in degrees, and the viscosity in pascals-seconds (P). Report using a·s).

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

[0025] The terms tandelta (tangent delta) and tangent "phase angle δ" are used herein. The term refers to the applied stress and the resulting strain that is imparted by this stress. This is the tangent phase angle lag shown between and . In a given dynamic machine study, tangent The phase delta (phase angle δ) is measured at a shear rate of 0.1 rad / s and 125°C. When comparing the tangent delta (phase angle δ) of the polymer group, the reduced tangent delta The values ​​generally indicate that the polymer is more elastic and has longer-chain branching.

[0026] High-temperature gel permeation chromatography ("HT GPC test"): The HT GPC test , infrared density / composition detector (IR-5 detector), PDI2040 laser light scattering detector ( It consists of an Agilent viscometer and a 4-capillary bridge viscometer (Malvern Panalytical). Furthermore, the number-average molecular weight (M N ), weight average molecular weight (M W ), and zeta-average molecular weight (M Z ) Enables determination of Polymer Char (Valencia, Spain) H This will be done using the T GPC system.

[0027] The column is 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 ) of the polystyrene standards is converted to polyethylene molecular weight data (M ps ) using Equation (1): M pe = A(M ps ) B pe ) where the value of A is determined iteratively and is approximately 0.42, and the value of B is 1.0. A third-order and a fifth-order polynomial are used to fit each polyethylene equivalent calibration point obtained from Equation (1) to their observed elution volumes for each polystyrene standard.

[0029] M N W Z

Equation

[0030] The g-value is used to characterize the amount of long-chain branching introduced by chemical treatment. The value is the ratio of the g' values ​​of the same terpolymer before and after chemical treatment. The g' value of the rimer was determined by HT GCP testing using a triple detector. The g' value was: The intrinsic viscosity of the terpolymer, determined using a calibrated viscometer and concentration detector, and the same This is the ratio of the weight-average molecular weight of an ethylene homopolymer to its calculated intrinsic viscosity. The intrinsic viscosity of a homopolymer is given by the Mark-Houwink equation, IV = k * Mw α of The calculation was performed using the formula, and the k value is 4.06 × 10⁻⁶. -4 The alpha value was 0.725 (Th. G.Scholte,NLJMeijerink,HMSchoffelee rs,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-average molecular weight (Mz / Mw) is: This shows the distribution at the high molecular weight end. A high Mz / Mw ratio indicates a molecular weight distribution plot towards the high molecular weight end. This indicates tailing or an increase in the high molecular weight fraction. The z value is the Mz of the resin before and after chemical treatment. Defined as / Mw. A z value greater than 1 indicates that chemical treatment increased the relative content of high molecular weight molecules. This indicates that it affects the melt elasticity of the resin.

[0032] Monomer content test: Ethylene and propylene content of terpolymers on a weight percentage basis. The content is measured using the Fourier Transform Infrared according to ASTM D3900. Determined by FTIR analysis. ENB content of the polymer on a weight percentage basis. This is determined by Fourier transform infrared (FTIR) analysis according to ASTM D6047.

[0033] Residual element analysis test: Residual element analysis is performed using inductively coupled plasma atomic emission spectroscopy. Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) and X-ray fluorescence (X- This is performed using both ray fluorescence and XRF techniques. In the case of ICP-AES analysis, Weigh the sample into a quartz tube and add 1 mL of water and 3 mL of nitric acid to the sample. Place the sample in a 115°C hot block for 30 minutes. Then, transfer the sample to UltraWav. Place in a microwave oven and decompose at 250°C. After decomposition in the microwave, dilute the sample. According to Perkin Elmer ICP, aluminum (Al), magnesium Regarding magnesium (Mg), titanium (Ti), vanadium (V), and zirconium (Zr): Analyze. In the case of XRF analysis, the sample is formed in a plaque within a hot press at 127°C. Then, rinse the sample with distilled water, then with acetone, and measure the chlorine content using XRF. Measure using [specific method / method]. Report the results in parts per million (ppm). [Modes for carrying out the invention]

[0034] process This disclosure provides a process. In one embodiment, this process is Ethylene / propylene / non-conjugated polyene having at least 3.5% by weight of non-conjugated polyene To provide enterpolymer (EPDM), Reacting EPDM with a metal Lewis acid, Rheologically modified EPDM, (i) z-average molecular weight (M) of molecules with molecular weights greater than 500,000 g / mol and up to 10,000,000 g / mol z), (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) Formation of rheologically modified EPDM having a tandelta value of 0.1 to less than 1.0 This includes doing something.

[0035] This process includes providing a terpolymer. The terpolymer is a polymerized form of ter - Based on the total weight of the polymer, ethylene, propylene, and at least 3.5% by weight Ethylene / α-olefin / non-conjugated polyethylene polymer composed of non-conjugated polyenes Yes. A non-limiting example of a suitable non-conjugated polyene is C4-C 40 Non-conjugated dienes are cited. It is possible.

[0036] In one embodiment, the non-conjugated polyene is an acyclic diene or a cyclic diene. Non-limiting examples of ions include linear acyclic dienes, such as 1,4-hexadiene and 1,5- Heptadienes, as well as branched 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-deca Examples include mixed isomers of dienes and dihydromyrcenes. Non-restrictive examples of cyclic dienes. Examples include 1,4-cyclohexadiene, 1,5-cyclooctadiene, and 1,5-cyclohexadiene. Polycyclic lipids such as clododecadiene, tetrahydroindene, and methyltetrahydroindene Cyclic condensation and crosslinked ring dienes, 5-methylene-2-norbornene (MNB), 5-ethyl Den-2-norbornene (ENB), 5-vinyl-2-norbornene, 5-propenyl- 2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentene Al(nyl)-2-norbornene and 5-cyclohexylidene-2-norbornene are examples of Examples include kenyl, alkylidene, cycloalkenyl, and cycloalkylidene norbornene. It is possible.

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

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

[0039] In one embodiment, the terpolymer is ethylene / propylene / norbornene terpolymer. In further embodiments, the terpolymer is ethylene / propylene / ENB terpolymer. It is a polymer. The term "EPDM" as used herein refers to a polymer containing only three monomers. It is an ethylene / propylene / ENB terpolymer, and ENB is the only one in the terpolymer. This is the Jien.

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

[0041] In one embodiment, the n-EPDM used herein is entirely as referred to herein. Produced using a metallocene catalyst described in U.S. Patent No. 8,101,696, which is incorporated into the product. It will be done.

[0042] In one embodiment, EPDM is n-EPDM, (i) 40-70% by weight, or 45-65% by weight, or 50-60% by weight Particle ethylene, (ii) 35% to 65% by weight, or 40 to 60% by weight, or 45 to 55% by weight Amount % of polymerized propylene, (iii) 3.5% to 8.5% by weight, or 3.6% to 7% by weight, or 4% to 6% by weight % polymerized ENB (where the total amount of (i), (ii), and (iii) is 10% of n-EPDM) Composed of 0% by weight, n-EPDM possesses one or more of the following properties, or It possesses everything. (iv) Mooney viscosity of 10 MU to 40 MU, or 20 MU to 30 MU, and / or teeth (v) 0.86g / cc to 0.89g / cc, or 0.86g / cc to 0.88g density / cc

[0043] This process involves reacting a terpolymer (e.g., n-EPDM) with a metal Lewis acid. This includes. As used herein, "metallic Lewis acid" (or "mLA") refers to one or more different It is a Lewis acid containing a certain type of metal atom. ("Single-metal Lewis acid" or "Single-mL") A) is a metal Lewis acid containing one type of metal. Lewis acids (or "mixed mLAs") are Lewis acids containing two or more different types of metal atoms. It is isic acid. This process involves adding n-EPDM at a concentration of 100 ppm to 23,000 ppm, or mLA and reaction between 200 ppm and 10,000 ppm, or 300 ppm and 3,000 ppm. This includes making them respond.

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

[0045] In one embodiment, the mLA is a single mLA containing 300 ppm to 1000 ppm of Al This includes. In further embodiments, the mLA contains 300 ppm to 1000 ppm of Al metal. It is a single mLA containing AlCl3.

[0046] In one embodiment, the mLA is a mixed mLA, and at least one of Mg and / or Ti It also includes at least one of Al, V, Zr, Sn, and / or B in combination with another. nothing.

[0047] In one embodiment, the process involves melting and mixing EPDM and then melting and mixing mLA. This includes introducing into EPDM to form rheologically modified EPDM. The process involves melt mixing (using a Banbury mixer and / or a Haacke mixer) and melt extrusion. (Single-screw extruder, twin-screw extruder, multi-screw extruder, continuous mixer) This is achieved by a (or kneading) machine, or a combination thereof.

[0048] In one embodiment, this process involves dissolving EPDM in a solvent to form a mixture. This process includes introducing a metal Lewis acid into a mixture and rheological modification E This involves forming PDM. The solvent is C6-C, such as decane. 20 With hydrocarbon solvents Yes, EPDM is C6~C 20 It is added to a hydrocarbon solvent to form a mixture. (Metal Lewis) Add the acid to the mixture. Heat the mixture to a temperature of 60°C to 170°C, or 95°C to 160°C. Heat to form rheologically modified EPDM. Rheologically modified EPDM from the reaction mixture. Collect it.

[0049] Although not bound by any particular theory, the reaction between metal Lewis acids and EPDM is in EPDM It is thought to result in carbocation coupling between polyene moieties. The reaction sequence for on-coupling is as shown in Figure 1, with the polyene moiety being... H bonds are formed between EPDM polymer chains over moieties (ENB).

[0050] This process involves forming rheologically modified EPDM. M is (a) 40-70% by weight, or 45-65% by weight, or 50-60% by weight of polymerized esters. (b) 35% to 65% by weight, or 40% to 60% by weight, or 45% to 55% by weight Polymerized propylene, (c) 3.5 to 8.5% by weight, or 3.6 to 7% by weight, or 4 to 6% by weight Polymerized ENB by weight % (where the total amount of (i), (ii), and (iii) is rheologically modified) Rheologically modified EPDM, which contains 100% by weight of EPDM, has the following properties: To have one, some, or all of them. (i) Over 500,000 g / mol ~ 10,000,000 g / mol, or 700 000g / mol to 8,000,000g / mol, or 1,000,000g / m³ z-average molecular weight (Mz) of ol~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 ​​between 1.0 and 3.5, or between 1.5 and 3.5, or between 2.0 and 3.5 and / or (v) Mooney viscosity of 50-100 or 60-90, and / or (vi) 0.1 to less than 1.0, or 0.1 to 0.5, or 0.1 to 0.3 Delta.

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

[0052] composition This disclosure provides compositions. In one embodiment, the composition is rheologically modified EPDM , comprising an optional oil and one or more optional additives. Rheologically modified EPDM is (a) 40-70% by weight, or 45-65% by weight, or 50-60% by weight of polymerized ethylene (b) polymerization of 35% to 65% by weight, or 40 to 60% by weight, or 45 to 55% by weight. Propylene, (c) greater than 3.5% to 8.5% by weight, or 3.6% to 7% by weight, or 4% to 6% by weight Polymerized ENB (where the total amount of (i), (ii), and (iii) is rheologically modified EPD) Rheology-modified EPDM contains 100% by weight of M, and one of the following properties is To have one, several, or all of them. (i) Over 500,000 g / mol ~ 10,000,000 g / mol, or 700 000g / mol to 8,000,000g / mol, or 1,000,000g / m³ z-average molecular weight (Mz) of ol~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 ​​between 1.0 and 3.5, or between 1.5 and 3.5, or between 2.0 and 3.5 and / or (v) Mooney viscosity of 50-100 or 60-90, and / or (vi) 0.1 to less than 1.0, or 0.1 to 0.5, or 0.1 to 0.3 Delta.

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

[0054] In one embodiment, the composition comprises rheologically modified EPDM and oil. The oil is limited to Not specified, but petroleum such as aromatic oils and naphthenic oils; polyalkylbenzene oil; alkyl and organic acid monoesters such as alkoxyalkyl oleates and stearates; phthalates Dialkyl and dialkoxy forms of acids, terephthalic acid, sebacic acid, adipic acid, and glutaric acid. Organic acid diesters such as alkyl and alkylaryl; tri-, tetra-, and poly Glycol diesters such as ethylene glycol dialkanoates; trialkyl trimeth Litate; trialkyl, trialkoxyalkyl, alkyldiaryl, and trial phosphate; chlorinated paraffin oil; coumaron-indene resin; pine tar; castor oil Oils of the oak tree, tall oil, rapeseed oil, and soybean oil, as well as their esters and epoxidized derivatives. Examples include vegetable oils such as; and combinations thereof. In further embodiments, the oil is S UNPAR 2280, PARALUX 6001, HYDROBRITE 550, and The selection is made from the group consisting of and CALSOL 5550.

[0055] In one embodiment, the composition comprises rheologically modified EPDM and oil. The oil is part of the composition. Based on the total weight, 5% by weight, or 15% by weight, or 20% to 30% by weight, or 4 It is present in an amount of 0% by weight or 70% by weight. In further embodiments, the composition is Based on the total weight, 5-70% by weight, or 15-40% by weight, or 20-30% by weight Contains a certain amount of oil.

[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 (either alone or in combination with oil). (Including) 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, peracids) Examples include chemical compounds, accelerators, auxiliary agents, processing aids, foaming agents, plasticizers, and combinations thereof. It can be done.

[0058] Fillers include, but are not limited to, carbon black; aluminum, magnesium, Silicates of calcium, sodium, potassium, and mixtures thereof; calcium, ma Gnesium carbonates and mixtures thereof; silicon, calcium, zinc, iron, titanium Aluminum oxides; calcium, barium, and lead sulfates; polyethylene Glycols (polyethylene glycol, PEG); sulfur; stearic acid; sulfonamides; Alumina trihydrate; magnesium hydroxide; precipitated silica; fumed silica; natural fibers; compound Fibers; and combinations thereof.

[0059] Antioxidants and ozone inhibitors include, but are not limited to, hindered phenols, bisphosphonates, and others. Examples include sphenols, thiobisphenols, and substituted hydroquinones.

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

[0061] In one embodiment, the composition comprises rheologically modified EPDM and carbon black. In one embodiment, carbon black is present in an amount of 5% by weight, or 1% by weight, based on the total weight of the composition. It is present in amounts of 5% by weight, or 20% to 30% by weight, or 40% by weight, or 70% by weight. In further embodiments, the carbon black is 5 to 70 based on the total weight of the composition. It exists in amounts of weight percent, or 15-40% by weight, or 20-30% by weight.

[0062] In one embodiment, the composition is a total additive-free mixture excluding calcium carbonate and carbon black. Includes filling. In one embodiment, the total additive filling is 0.5 by weight based on the total weight of the composition. It exists in amounts of %, or 1% by weight, or 2% to 4% by weight, or 5% by weight, or 10% by weight. In further embodiments, the total amount of additives loaded is 0.5 to 0.5 based on the total weight of the composition. It is present in amounts of 10% by weight, or 1–5% by weight, or 2–4% by weight.

[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-exclusive examples of items that can be used include automotive parts (automotive door sealant, automotive belts, etc.) Automotive hoses, belts, building materials, cables, computer components, extruder casings, foam Body, footwear, gaskets, hoses, membranes, molded products, roofing panels, sponges, tires, sealants, and Wires are one example.

[0066] Without limiting ourselves, we will now describe some embodiments of this disclosure as examples. This will be described in the examples. [Examples]

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

[0068] In a dry box under a nitrogen atmosphere, EPDM1 is dissolved in decane, and a magnetic stirring rod is used. A 10% by weight solution was formed in a glass vial. By introducing different amounts of various m-Lewis acids (mLAs) into the sample, Prepared. After adding 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 g' value before and after chemical treatment (homopolyesters with the same weight-average molecular weight). This is the ratio of the intrinsic viscosity of the polymer to the intrinsic viscosity of ethylene. 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 EPDM1 resin in solutions using various single mLAs or mixed mLAs (Table 1 The results of carbocation coupling of NORDEL4520 (from) are shown. Table 2 shows the controls. This is the base resin EPDM1, which has the same dissolution and properties as the comparative sample and the embodiment of the invention. Subjected to a heating process. However, the control was not treated with Lewis acid. CS1 In IE2, IE3, CS4, and CS5, Al was used as a single mLA. CS1 (For CS1, 67 ppm Al) In low Al doses (less than 300 ppm), EP No changes were observed in the molecular weight and / or branching of DM1. High Al dose, or 100 For Al above 0 ppm, CS4 (for CS4, 2680 ppm Al) and CS5 ( For CS5, 6750 ppm of Al resulted in an insoluble polymer. The applicant stated, For the production of acceptable rheologically modified EPDM, a single mLA which is AlCl3... An unexpected range of Al was discovered, from 300 ppm to 1000 ppm. The dose was increased to 330 ppm, and the Al dose was increased to 675 ppm in IE3. Then, AlCl3, which is a single mLA, becomes rheologically modified EPDM1 with a high molecular weight tail. This was produced (IE2 Mz 566,533 g / mol, IE3 Mz 1,576,5 (35 g / mol).

[0070] TiCl4, which has Ti as the single metal, does not function as a suitable single mLA. (Comparison) Samples CS6-CS8 are samples treated with TiCl4. Amazingly... Furthermore, TiCl4 did not induce a coupling reaction even at high doses. This is unexpected, as it 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, even at extremely high doses (CS11), is involved in carbocation coupling. It was not effective.

[0072] EtAlCl2 was an effective metallic Lewis acid, as shown in Invention Example IE9. However, compared to AlCl3, a higher dose is required to achieve the same level of branching. Although not bound by any particular theory, EtAlCl2 is a weaker Lewis acid than AlCl3. It is believed that stronger Lewis acids have higher efficacy and lower dose requirements. While this offers the benefit of a weaker Lewis acid, it avoids excessive crosslinking and undesirable gel formation. This provides the benefit of easier process control.

[0073] The Lewis acidity of a metallic Lewis acid is determined by mixing it with a specific other metal(s). It can be adjusted. Invention Example IE12 is a mixture of 5400 ppm Al mLA It was treated with MgCl2-EtAlCl2. IE12 has an Al content of 2160 ppm. Compared to IE9 (IE9 Mw:266, 150Mz:1,246,557), lower By Mw and Mz (IE12 Mw: 213,690 Mz: 1,000,443) As shown, it exhibits a lower degree of coupling, with MgCl2 being a ligature of EtAlCl2. This suggests a further reduction in the acidity of the solution. It is not bound by any particular theory. However, Mg donates electrons to Al through the Mg→Cl→Al bridge, making the Al site acidic. It is believed that the degree was reduced.

[0074] The comparative sample CS13 is a mixed mLA containing 877 ppm Al, which is Ti(OiP r) Treated with 4-AlCl3. In the case of CS13, the Mw and Mz values ​​do not change. This remained unchanged, indicating that no coupling occurred. This was at only 675 ppm. This provides an interesting comparison with IE3, where significant coupling with AlCl3 was observed in Al. An increase in the Al-to-Ti ratio resulted in more effective coupling (IE1). 4-15). Not bound by any theory, but several isopropoxy groups It is thought that the ligand moved to Al through ligand exchange, reducing the Lewis acidity of the Al site. The applicant has achieved a balanced Lewis acidity by using a mixed metal system. We discovered that an unexpected method was provided for this. For rheological testing, three metals A larger sample (IE23) was prepared using the system.

[0075] This disclosure is not limited to the embodiments and examples contained herein, but includes portions of the embodiments and Modification of an embodiment including a combination of elements of different embodiments included in the following claims It is specifically intended to include the correct form.

Claims

1. It is a process, Ethylene / propylene / non-conjugated polyene having at least 3.5% by weight of non-conjugated polyene To provide enterpolymer (EPDM), The EPDM is reacted with a metal Lewis acid, Rheologically modified EPDM, (i) z-average molecular weight (M) of over 500,000 g / mol to 10,000,000 g / mol z), (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) Formation of rheologically modified EPDM having a tandelta value of 0.1 to less than 1.0 A process that includes doing something.

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 A claim comprising dissolving in a hydrocarbon solvent. The process described in section 3.

5. A metal selected from the group consisting of Al, V, Zr, Sn, B, and combinations thereof. The present invention provides a single metal Lewis acid according to any one of claims 1 to 4. Rothes.

6. AI, V, Zr, Sn, or B in combination with at least one of Mg or Ti Claims 1 to 1 include providing a mixed metal Lewis acid composed of at least one of the above. The process described in any one of item 4.

7. A composition, Ethylene / propylene / non-conjugated polyene having at least 3.5% by weight of non-conjugated polyene Enterpolymer (EPDM); (i) z-average molecular weight (M) of over 500,000 g / mol to 10,000,000 g / mol z), (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 composition containing a tandelta value between 0.1 and less than 1.

0.

8. The composition according to claim 7, 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) any of claims 6 to 8, comprising more than 3.5% by weight to 8.5% by weight of polyene. The composition described in any one of the items.

10. Claims 6-9, wherein the polyene is 5-ethylidene-2-norbornene (ENB). A composition according to any one of the items.

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