CN114685900A - Dynamic vulcanization thermoplastic elastomer composite material composition and preparation method and application thereof - Google Patents
Dynamic vulcanization thermoplastic elastomer composite material composition and preparation method and application thereof Download PDFInfo
- Publication number
- CN114685900A CN114685900A CN202011612941.2A CN202011612941A CN114685900A CN 114685900 A CN114685900 A CN 114685900A CN 202011612941 A CN202011612941 A CN 202011612941A CN 114685900 A CN114685900 A CN 114685900A
- Authority
- CN
- China
- Prior art keywords
- thermoplastic elastomer
- elastomer composite
- dynamically vulcanized
- diene monomer
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000004073 vulcanization Methods 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 51
- 229920002943 EPDM rubber Polymers 0.000 claims abstract description 33
- 239000004743 Polypropylene Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 229920001971 elastomer Polymers 0.000 claims abstract description 21
- 239000005060 rubber Substances 0.000 claims abstract description 21
- 229920001155 polypropylene Polymers 0.000 claims abstract description 16
- -1 polypropylene Polymers 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims description 60
- 150000001993 dienes Chemical class 0.000 claims description 25
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 18
- 229920001400 block copolymer Polymers 0.000 claims description 16
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
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- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 3
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 claims description 3
- XWBRTYSASIVIKP-UHFFFAOYSA-N 1,3-dibutyl-5-ethenylbenzene Chemical compound CCCCC1=CC(CCCC)=CC(C=C)=C1 XWBRTYSASIVIKP-UHFFFAOYSA-N 0.000 claims description 3
- WJNKJKGZKFOLOJ-UHFFFAOYSA-N 1-dodecyl-4-ethenylbenzene Chemical compound CCCCCCCCCCCCC1=CC=C(C=C)C=C1 WJNKJKGZKFOLOJ-UHFFFAOYSA-N 0.000 claims description 3
- HVOKBODBWQEEGI-UHFFFAOYSA-N 1-ethenyl-3,5-diethylbenzene Chemical compound CCC1=CC(CC)=CC(C=C)=C1 HVOKBODBWQEEGI-UHFFFAOYSA-N 0.000 claims description 3
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- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 3
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- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
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- 238000012360 testing method Methods 0.000 description 8
- 230000003712 anti-aging effect Effects 0.000 description 6
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
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- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 6
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- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- VJIYRPVGAZXYBD-UHFFFAOYSA-N dibromosilane Chemical compound Br[SiH2]Br VJIYRPVGAZXYBD-UHFFFAOYSA-N 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- YAQXGBBDJYBXKL-UHFFFAOYSA-N iron(2+);1,10-phenanthroline;dicyanide Chemical compound [Fe+2].N#[C-].N#[C-].C1=CN=C2C3=NC=CC=C3C=CC2=C1.C1=CN=C2C3=NC=CC=C3C=CC2=C1 YAQXGBBDJYBXKL-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a dynamic vulcanization thermoplastic elastomer composite material composition, a preparation method and application thereof; the dynamically vulcanized thermoplastic elastomer composite composition comprises, by weight, 1-4: 0.8-0.97: 0.03-0.2 parts of ethylene propylene diene monomer, polypropylene and a block polymer composition; according to the invention, the third component block polymerization composition is introduced into the ethylene propylene diene monomer/polypropylene resin composite material, so that the rubber phase is uniformly distributed in the plastic phase in a small size, and the third component block polymerization composition has a high-content side group structure, so that the uniform degree of crosslinking of a vulcanizing agent on the rubber phase can be improved, and the dynamically vulcanized thermoplastic elastomer composite material with high strength and low pressure change and excellent comprehensive performance is obtained.
Description
Technical Field
The invention relates to the technical field of thermoplastic elastomer materials, in particular to a dynamically vulcanized thermoplastic elastomer composite material composition and a preparation method and application thereof.
Background
The EPDM series dynamic vulcanization thermoplastic elastomer material is a thermoplastic elastomer which firstly goes to the market, has good physical properties, can be processed by adopting thermoplastic processing equipment and technology, and is widely applied to industries such as household appliances, wires and cables, buildings, automobiles and the like. With the continuous expansion of the application range, EPDM TPV products are gradually used as third-generation rubber to replace the traditional rubber, but the application range is limited due to the inflammability and the emission of a large amount of smoke.
At present, EPDM TPV products are mainly applied to building sealing and sealing products in non-oil environments of automobiles, and EPDM dynamic vulcanized alloys are prepared by taking ethylene propylene diene monomer rubber and polypropylene as basic materials and adding filling oil, inorganic filler, a crosslinking agent and the like to obtain rubber fully vulcanized composite materials. Although EPDM TPV products are large in dosage and relatively mature in technology, the research on the process and the formula has wide space, such as generally low strength and unsatisfactory compression set performance, and numerous scientific research institutes and scientific research units are always dedicated to pursuing higher performance of EPDM vulcanized alloys.
CN102181101A discloses a building sealing strip based on thermoplastic ethylene propylene diene monomer material and a preparation method thereof, wherein the tensile strength of the EPDM/PP material with 65A hardness is 6.1MPa, and the strength is lower.
CN103980621A discloses a high-performance dynamic vulcanization thermoplastic elastomer and a preparation method thereof, wherein the EPDM/PP material with 65A hardness has the strength of 6.4MPa, the compression set of 30 percent, lower strength and common compression set.
Since the inherent properties of the raw material are difficult to change, it is difficult to obtain a thermoplastic elastomer material having both high strength and low permanent set.
Disclosure of Invention
The invention aims to overcome the problem that the existing thermoplastic elastomer material in the prior art is difficult to combine high strength and low permanent deformation performance, and provides a dynamically vulcanized thermoplastic elastomer composite material composition, and a preparation method and application thereof.
After research, the inventor of the present invention found that the EPDM rubber material has low hardness, while the PP resin material has high hardness, and because of the large hardness difference, when the two materials are dynamically vulcanized in a screw, the force transmission is difficult to perform, so that the rubber phase is difficult to be uniformly dispersed in the resin phase, and small-sized rubber particles are difficult to obtain, which is a main reason for poor comprehensive performance of the EPDM/PP material; the introduction of the copolymer resin with the high side group structure is beneficial to the uniform distribution of the rubber phase in the plastic phase in a small size, and the copolymer resin with the high side group structure can improve the crosslinking uniformity of a vulcanizing agent to the rubber phase, so that the EPDM dynamic vulcanized alloy with excellent performances such as high strength, low pressure change and the like is obtained.
In order to achieve the above object, a first aspect of the present invention provides a dynamically vulcanized thermoplastic elastomer composite composition comprising a thermoplastic elastomer and a thermoplastic elastomer, the thermoplastic elastomer and the thermoplastic elastomer being present in a weight ratio of 1 to 4: 0.8-0.97: 0.03-0.2 parts of ethylene propylene diene monomer, polypropylene and a block polymer composition;
the block polymeric composition comprises in a weight ratio of 1: 99 to 30: 70 of block copolymer with star structure and linear structure,
the linear structure polymeric combination comprises:
block copolymer L of Linear Structure1：S1-S2-B；
Block copolymer L of Linear Structure2：S2-B；
Homopolymer L of linear structure3：B；
The star-structured block copolymer comprises: (L)1-)m(L2-)n(L3-)p-X；
S1Being a homopolymerisation stage formed from monovinylaromatic monomers, S1The number average molecular weight of (A) is 2-30 ten thousand;
S2being a homopolymerisation stage formed from monovinylaromatic monomers, S2Has a number average molecular weight of 0.3 to 3 ten thousand, and said S2Is less than the degree of polymerization of S1Degree of polymerization of (a);
b is a homopolymerization section formed by conjugated diene monomers, and the number average molecular weight of B is 0.3-2 ten thousand;
x is a coupling agent residue, m is L1N is L2P is L3M, n, p are each independently an integer from 0 to 20, and the sum of m, n, p is selected from an integer from 0 to 20;
based on the total weight of the homopolymerization section, the content of the structural unit provided by the monovinylarene monomer is 50-95 wt%, and the content of the structural unit provided by the conjugated diene monomer is 5-50 wt%;
based on the total weight of the structural units formed by the monovinylarene monomer, S1In an amount of 51-99 wt.%, said S2In an amount of 1 to 49 wt.%;
the content of the side group structure is 40-80 wt% based on the total weight of the structural units formed by the conjugated diene monomer.
In a second aspect, the present invention provides a process for preparing said dynamically vulcanized thermoplastic elastomer composite composition, which process comprises: blending ethylene propylene diene monomer, polypropylene and the block polymerization composition in a double-screw extruder to obtain blended rubber; the blended rubber is then vulcanized in the presence of a vulcanizing agent.
The third aspect of the present invention provides the use of said dynamically vulcanised thermoplastic elastomer composite composition in the field of building seals and/or automotive seals.
By adopting the technical scheme, the third component block polymerization composition is introduced into the ethylene propylene diene monomer/polypropylene resin composite material, so that the rubber phase is uniformly distributed in the plastic phase in a small size; the third component block polymerization composition has a high-content side group structure, and can improve the crosslinking uniformity of a vulcanizing agent to a rubber phase, so that the dynamically vulcanized thermoplastic elastomer composite material with high strength, low pressure variation and excellent comprehensive performance is obtained.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously mentioned, a first aspect of the present invention provides a dynamically vulcanised thermoplastic elastomer composite composition comprising a weight ratio of 1 to 4: 0.8-0.97: 0.03-0.2 of an ethylene propylene diene monomer, polypropylene, and a block polymer composition;
the block polymeric composition comprises a weight ratio of 1: 99 to 30: 70 of block copolymer with star structure and linear structure,
the linear structure polymeric combination comprises:
block copolymer L of Linear Structure1：S1-S2-B；
Block copolymer L of Linear Structure2：S2-B；
Homopolymer L of linear structure3：B；
The star-structured block copolymer comprises: (L)1-)m(L2-)n(L3-)p-X；
S1Being a homopolymerisation stage formed from monovinylaromatic monomers, S1The number average molecular weight of (A) is 2-30 ten thousand;
S2being a homopolymerisation stage formed from monovinylaromatic monomers, S2Has a number average molecular weight of 0.3 to 3 ten thousand, and said S2Is less than the degree of polymerization of S1Degree of polymerization of (a);
b is a homopolymerization section formed by conjugated diene monomers, and the number average molecular weight of B is 0.3-2 ten thousand;
x is a coupling agent residue, m is L1N is L2P is L3M, n, p are each independently an integer from 0 to 20, and the sum of m, n, p is selected from an integer from 0 to 20;
based on the total weight of the homopolymerization section, the content of the structural unit provided by the monovinylarene monomer is 50-95 wt%, and the content of the structural unit provided by the conjugated diene monomer is 5-50 wt%.
Based on the total weight of the structural units formed by the monovinylarene monomer, S1In an amount of 51-99 wt.%, S2In an amount of 1 to 49 wt.%;
the content of the side group structure is 40-80 wt% based on the total weight of the structural units formed by the conjugated diene monomer.
In the present invention, under the preferable conditions, based on the total weight of the homopolymerization section, the content of the structural unit provided by the monovinylarene monomer is 65-85 wt%, and the content of the structural unit provided by the conjugated diene monomer is 15-35 wt%.
In the present invention, S is preferably S based on the total weight of the structural units formed from the monovinyl aromatic hydrocarbon monomer1In an amount of 65-85 wt.%, S2Is present in an amount of 15-35 wt.%.
In the invention, the content of the side group structure in the structural unit formed by the conjugated diene monomer is up to 40-80 wt%, so that the block polymerization composition has high reactivity, and the star structure introduced into the block polymerization composition can effectively improve the processing fluidity of the block polymerization composition, so that the block polymerization composition has high impact resistance and elongation at break, and simultaneously has excellent light transmittance, preferably, the content of the side group structure is 50-70 wt% based on the total weight of the structural unit formed by the conjugated diene monomer.
In the present invention, under the preferred conditions, S1The number average molecular weight of (A) is 2-30 ten thousand; s2Has a number average molecular weight of 0.7 to 1.5 ten thousand, and S2Is less than the degree of polymerization of S1Degree of polymerization of (a); the number average molecular weight of B is 0.5-1.5 ten thousand.
According to the present invention, it is preferable that the monovinylarene monomer is at least one selected from styrene, vinyl toluene, α -methyl styrene, 4-tert-butyl styrene, 4-methyl styrene, 3, 5-diethyl styrene, 3, 5-di-n-butyl styrene, 4-n-propyl styrene and 4-dodecyl styrene; preferably, the monovinylarene monomer is a styrene monomer.
According to the invention, under preferred conditions, the conjugated diene monomer is selected from at least one of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene; further preferably, the conjugated diene monomer is butadiene and/or isoprene.
In a preferred embodiment of the present invention, the monovinylarene monomer is a styrene monomer and the conjugated diene monomer is butadiene and/or isoprene.
According to the invention, the ethylene-propylene-diene monomer rubber preferably contains 40 to 80 wt.%, preferably 50 to 70 wt.%, of ethylene structural units.
According to the invention, the content of unsaturated double bonds in the ethylene-propylene-diene rubber is preferably from 1 to 10% by weight, preferably from 3 to 6% by weight.
In a preferred embodiment of the invention, the ethylene-propylene-diene monomer rubber has a content of ethylene structural units of 50 to 70 wt.% and the ethylene-propylene-diene monomer rubber has a content of unsaturated double bonds of 3 to 6 wt.%.
According to the invention, preferably, the polypropylene is a homo-and/or co-polypropylene.
In the present invention, in order to further optimize the comprehensive performance of the dynamically vulcanized thermoplastic elastomer composite composition, preferably, the dynamically vulcanized thermoplastic elastomer composite composition further comprises auxiliary materials, and the auxiliary materials comprise at least one of extender oil, anti-aging agent and inorganic filler; further preferably, the extender oil is a saturated alkane, preferably a saturated alkane having a flash point of not less than 190 ℃, and may be, for example, a paraffin oil; more preferably, the extender oil is present in an amount of from 10 to 60 wt%, preferably from 20 to 45 wt%, based on the total amount of the dynamically vulcanised thermoplastic elastomer composite composition.
In a preferred embodiment of the present invention, the inorganic filler is selected from at least one of talc, calcium carbonate, white carbon and carbon black; more preferably, the inorganic filler is present in an amount of from 0 to 20 wt%, preferably from 5 to 15 wt%, based on the total amount of the dynamically vulcanised thermoplastic elastomer composite composition.
In a preferred embodiment of the present invention, in order to further optimize the performance of the dynamically vulcanized thermoplastic elastomer composite composition, the dynamically vulcanized thermoplastic elastomer composite composition further comprises an activator, the activator comprises zinc oxide and/or stearic acid, and further preferably, the zinc oxide is contained in an amount of 0 to 2 wt%, preferably 0.4 to 0.5 wt%, and the stearic acid is contained in an amount of 0 to 2 wt%, preferably 0.2 to 0.3 wt%, based on the total amount of the dynamically vulcanized thermoplastic elastomer composite composition.
In a preferred embodiment of the present invention, the kind of the antioxidant may be known to those skilled in the art, and may be, for example, antioxidant 1076, antioxidant 1010, or the like; further preferably, the antioxidant is present in an amount of 1 to 6 wt%, preferably 2 to 5 wt%, based on the total amount of the dynamically vulcanized thermoplastic elastomer composite composition.
In a preferred embodiment of the present invention, the block polymeric composition is prepared by anionic polymerization, which has the following characteristics: (1) the active center simultaneously initiates growth, and no chain termination and chain transfer exist, namely, the anionic polymerization does not generate chain termination and chain transfer reaction under proper conditions, and the extended chain still has reaction activity until all monomers are exhausted; (2) chain growth starts simultaneously, and the growth probability is equal; (3) the molecular weight is linearly increased along with the conversion rate and is controllable; (4) the molecular distribution is close to monodispersion; (5) the reaction yield can reach 100%; further preferably, the method comprises:
(1) in the presence of a structure regulator, a first initiator and a nonpolar solvent, carrying out a first polymerization reaction on a first part of monovinyl aromatic hydrocarbon monomers to obtain a monomer containing S1The first polymerization system of (1);
(2) in the presence of a second initiator, carrying out a second polymerization reaction on the first polymerization system and a second part of monovinyl aromatic hydrocarbon monomer to obtain a product containing S1-S2And S2The second polymerization system of (1);
(3) in the presence of a third initiator, carrying out a third polymerization reaction on the second polymer system and a conjugated diene monomer to obtain a polymer containing S1-S2-B、S2-a third polymerization system of B and B;
(4) carrying out coupling reaction on the third polymerization system and a coupling agent to obtain a segmented copolymer L containing a linear structure1Block copolymer L of linear structure2Homopolymer L of linear structure3And a block copolymer (L) of star structure1-)m(L2-)n(L3-)p-a block polymeric composition of X;
wherein the content of the first and second substances,
the block copolymer L having a linear structure1Comprises the following steps: s1-S2-B；
The block copolymer L having a linear structure2Comprises the following steps: s2-B；
The linear structure homopolymer L3Comprises the following steps: b;
S1、S2b, X, m, n and p are as defined in the first aspect and S2Is less than the degree of polymerization of S1Degree of polymerization of (2).
According to the present invention, preferably, the amount of the first portion of the monovinylarene monomer is 60 to 85 wt%, and the amount of the second portion of the monovinylarene monomer is 15 to 40 wt%, based on the total weight of the monovinylarene monomers, preferably, the amount of the first portion of the monovinylarene monomer is 65 to 75 wt%, and the amount of the second portion of the monovinylarene monomer is 25 to 35 wt%.
According to the invention, under the preferred conditions, the amount of the monovinylarene monomer is 50-95 wt% and the amount of the conjugated diene monomer is 5-50 wt% based on the total weight of the monovinylarene monomer and the conjugated diene monomer; preferably, the monovinylarene monomer is used in an amount of 65 to 85 weight percent and the conjugated diene monomer is used in an amount of 15 to 35 weight percent.
According to the present invention, it is preferable that the monovinylarene monomer is at least one selected from styrene, vinyl toluene, α -methyl styrene, 4-tert-butyl styrene, 4-methyl styrene, 3, 5-diethyl styrene, 3, 5-di-n-butyl styrene, 4-n-propyl styrene and 4-dodecyl styrene; preferably, the monovinylarene monomer is a styrene monomer.
According to the invention, under preferred conditions, the conjugated diene monomer is selected from at least one of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene and 2, 3-dimethylbutadiene; further preferably, the conjugated diene monomer is butadiene and/or isoprene.
According to the present invention, preferably, the amount of the first initiator is 15 to 25 wt%, the amount of the second initiator is 55 to 70 wt%, and the amount of the third initiator is 5 to 30 wt%, based on the total weight of the first initiator, the second initiator, and the third initiator.
According to the present invention, under the preferable conditions, in the step (1), the nonpolar solvent is selected from at least one of benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, o-xylene, p-xylene, m-xylene, cyclohexane, n-hexane; more preferably, the non-polar solvent is cyclohexane and/or n-hexane.
According to the present invention, it is preferable that in the step (1), the molecular structure of the structure regulator contains at least one of an oxygen atom, a nitrogen atom, a sulfur atom and a phosphorus atom, and specifically, the structure regulator is at least one selected from the group consisting of ether compounds, amine compounds, sulfonate compounds and alkali metal alcohol compounds; further preferably, the structure regulator is at least one selected from the group consisting of diethyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofurfuryl alcohol diethyl ether, tetrahydrofurfuryl alcohol butyl ether, dioxane, crown ether, triethylamine, tetramethylethylenediamine, hexamethylphosphoric triamide, potassium tert-butoxide, potassium laurate, potassium alkylbenzene sulfonate and sodium alkylbenzene sulfonate, and more preferably, the structure regulator is tetrahydrofurfuryl alcohol diethyl ether and/or tetrahydrofurfuryl alcohol butyl ether.
According to the present invention, it is preferred that the structural regulator is used in such an amount that the concentration of the structural regulator at the start of the reaction system in which the first polymerization reaction is carried out is 50 to 1000ppm, preferably 100 to 600 ppm.
According to the present invention, under preferred conditions, the first initiator, the second initiator and the third initiator are each independently selected from at least one of methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-hexyllithium and tert-octyllithium; further preferably, the first initiator, the second initiator, and the third initiator are each independently selected from at least one of n-butyllithium, sec-butyllithium, and tert-butyllithium.
According to the invention, under the preferable conditions, in the step (4), the coupling agent is at least one selected from silicon tetrachloride, tin tetrachloride, epoxidized soybean oil, epoxidized castor oil, divinylbenzene, methoxysilane, dibromosilane and dichlorosilane, and is preferably epoxidized soybean oil or epoxidized castor oil.
According to the invention, under the preferable conditions, the weight ratio of the total usage amount of the first initiator, the second initiator and the third initiator to the usage amount of the coupling agent is 1: 1.2-4, preferably 1: 1.5-3.
According to the invention, in step (1), the reaction conditions of the first polymerization reaction are at least such that: the temperature is 20-100 deg.C, and the time is 5-40 min; preferably, the reaction conditions of the first polymerization reaction are at least: the temperature is 40-70 deg.C, and the time is 10-20 min.
According to the invention, in step (2), the reaction conditions of the second polymerization reaction at least satisfy: the temperature is 20-100 deg.C, and the time is 5-40 min; preferably, the reaction conditions of the second polymerization reaction at least satisfy: the temperature is 40-70 deg.C, and the time is 10-20 min.
According to the invention, in step (3), the reaction conditions of the third polymerization reaction at least satisfy: the temperature is 40-100 deg.C, and the time is 30-90 min; preferably, the reaction conditions of the third polymerization reaction at least satisfy: the temperature is 60-80 deg.C, and the time is 45-60 min.
According to the invention, in step (4), the reaction conditions of the coupling reaction at least satisfy: the temperature is 20-120 deg.C, and the time is 10-50 min; further preferably, the reaction conditions of the coupling reaction at least satisfy: the temperature is 60-100 deg.C, and the time is 15-30 min.
According to the present invention, the method further comprises adding a terminator to the reaction system of the coupling reaction in step (4) to terminate the coupling reaction; preferably, the terminator is selected from at least one of water, alcohol and acid, for example, the alcohol may be at least one of ethanol, propanol, butanol, hexanol, 2-methylpentanol, n-heptanol, 2-ethylhexanol, n-octanol and isooctanol; the acid can be acetic acid, oxalic acid, propionic acid, malonic acid, butyric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, and dodecanedioic acidAt least one of a dicarboxylic acid, a tridecanoic acid, a tetradecanoic acid, a pentadecanoic acid, a hexadecanoic acid, a heptadecanoic acid, and an octadecanoic acid; more preferably, the terminating agent is selected from C4-C12For example, at least one of the fatty acids of (a) may be at least one of butyric acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid and dodecanedioic acid, most preferably C6-C8For example, at least one of adipic acid, pimelic acid and suberic acid may be used as at least one of the fatty acids of (a).
According to the present invention, in order to optimize the performance of the block polymerization composition, an anti-aging agent is preferably added to the block polymerization composition under the preferred conditions, wherein the anti-aging agent is a compound agent known to those skilled in the art, such as TNPP (trinonylphenyl phosphite) and/or antioxidant 1076, preferably TNPP and antioxidant 1076, and more preferably, the anti-aging agent is added in an amount of 0.8 to 1.2 wt% of the total amount of the block polymerization composition.
As previously mentioned, a second aspect of the present invention provides a process for preparing said dynamically vulcanized thermoplastic elastomer composite composition, the process comprising: blending ethylene propylene diene monomer, polypropylene and the block polymerization composition in a double-screw extruder to obtain blended rubber; the blended rubber is then vulcanized in the presence of a vulcanizing agent.
In a preferred embodiment of the present invention, the vulcanizing agent is selected from at least one of peroxides, phenol resins, and azo-based compounds; preferably, the vulcanizing agent is selected from at least one of peroxides, more preferably, the peroxide is selected from at least one of dibenzoyl peroxide, cumene hydroperoxide, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane, di- (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, dicyclohexyl peroxydicarbonate and tert-butyl peroxyisopropyl formate.
According to the present invention, preferably, the blending conditions at least satisfy: the temperature is 130 ℃ and 220 ℃, and the rotating speed of the double-screw extruder is 100 ℃ and 600 rpm; further preferably, the blending conditions at least satisfy: the temperature is 150 ℃ and 190 ℃, and the rotating speed of the double-screw extruder is 150 rpm and 400 rpm.
According to the invention, preferably, the conditions of the vulcanization at least satisfy: the temperature is 150-230 ℃, and the rotating speed of the double-screw extruder is 100-600 rpm; further preferably, the vulcanization conditions at least satisfy: the temperature is 180 ℃ and 200 ℃; the rotation speed of the double-screw extruder is 200-400 rpm.
In a third aspect, the present invention provides a use of the dynamically vulcanized thermoplastic elastomer composite composition provided in the first aspect in the fields of building sealing and/or vehicle sealing.
The present invention will be described in detail below by way of examples.
In the following examples, homopolypropylene F401 is a commercial product from the Tacroupy group and has a melt index of 3g/10min at 230 ℃; the copolymer polypropylene 5090T is a commercially available product from Taiwan corporation, and has a melt index of 15g/10min at 230 ℃.
The ethylene propylene diene monomer 3092PM is a commercial product of petrochemical three-well chemical industry Co., Ltd, and has an ethylene content of 65 wt%, an unsaturated double bond content of 4.6 wt% and a Mooney viscosity of 61.
The ethylene propylene diene monomer 3072EPM is a commercial product of petrochemical three-well chemical industry limited company in Shanghai, 3072EPM is an oil-extended product, the Mooney viscosity is 51, the ethylene content is 64 weight percent, the unsaturated double bond content is 5.4 weight percent, and 40 parts of oil is extended.
The flash point of the paraffin oil is more than or equal to 230 ℃; di- (t-butylperoxyisopropyl) benzene (curing agent F40P), t-butylperoxyisopropyl formate (curing agent M75) are all commercial products from Acoma, France;
the cyclohexane/n-hexane mixed solvent is provided by a rubber synthesis factory of Beijing Yanshan division of petrochemical China, wherein the mass ratio of cyclohexane to n-hexane is 5: 1.
styrene is provided by a synthetic rubber factory of China petrochemical Beijing Yanshan, and the water content is less than or equal to 10 ppm; butadiene was supplied from a rubber synthesis plant of Beijing Yanshan division, petrochemical, China, and has a water content of 10ppm or less.
The anti-aging agent consists of TNPP and an antioxidant 1076 according to the weight ratio of 2: 1; the antioxidant 1076 is a commercial product available from Gaoyi county Li and chemical Co.
Preparation example 1
Preparation of block polymeric composition 1:
adding 2000g of cyclohexane/n-hexane mixed solvent, 265g of styrene and 0.2g of tetrahydrofurfuryl alcohol ether into a 5L stainless steel stirring kettle under the protection of high-purity nitrogen, adding 2.9mmol of n-butyllithium at 55 ℃ for initiating reaction, and then carrying out first polymerization reaction for 15min under the heat tracing of 70 ℃ circulating water bath until the styrene is polymerized completely to obtain the product containing S1The first polymerization system of (1);
9.5mmol of n-butyllithium was added to the first polymerization system, followed by addition of 115g of styrene, and a second polymerization was carried out at 70 ℃ for 15min until styrene was completely converted to obtain a polymer containing S1-S2And S2The second polymerization system of (1);
2.9mmol n-butyllithium, followed by 120g butadiene, were added to the second polymerization system, and a third polymerization reaction was carried out at 70 ℃ for 50min to obtain a polymer containing S1-S2-B、S2-a third polymerization system of B and B;
adding 1.8g of epoxidized soybean oil into the third polymerization system, carrying out coupling reaction at 70 ℃ for 20min, then adding 1.6g of adipic acid terminator, and continuing the reaction for 15min to obtain the block copolymer L containing the linear structure1Block copolymer L of linear structure2Homopolymer L of linear structure3The coupling efficiency of the glue solution of the block polymerization composition of the block copolymer with the star structure is 70.1 percent;
and then adding an anti-aging agent TNPP/1076 (the weight ratio of TNPP to the antioxidant 1076 is 2:1, the adding amount is 0.9 percent of the weight of dry glue), stirring for 10min, drying the glue solution by using a vacuum oven, cutting into strips, and granulating by using a Haak single-screw extruder to obtain the block polymerization composition 1.
The properties of the block polymer composition 1 are shown in table 1, wherein the microstructure of the block polymer composition 1 is measured by an AVANCE DRX 400MHz nuclear magnetic resonance spectrometer of Bruker, switzerland, and the solvent is deuterated chloroform.
The molecular weight and coupling efficiency of block polymeric composition 1 were determined using a WATERS ALLIANCE model 2690 Gel Permeation Chromatograph (GPC) with THF as the mobile phase, narrow distribution polystyrene as the standard and a temperature of 25 ℃.
The impact strength of block polymeric composition 1 was measured using a pendulum impact tester, Ceast resin Impactor, test standard ASTM D256-2010.
Tensile break strength and tensile elongation at break of block polymeric composition 1 were measured using a Material tensile tester INSTRON 5567, according to ASTM D638-2014.
The Melt Flow properties of the block polymer composition 1 were measured using a Melt index apparatus, Ceast Melt Flow Tester, with the test standard GB/T3682.1-2018.
TABLE 1
| Performance of | Block polymerization composition 1 |
| S1Number average molecular weight per ten thousand | 9.2 |
| S2Number average molecular weight/ten thousand | 0.93 |
| B number average molecular weight/ten thousand | 0.8 |
| Content of pendant group Structure/weight% | 52.1 |
| Coupling efficiency/% | 70.1 |
| Random styrene content/weight% | 0.1 |
| Melt index/g/10 min | 9.0 |
| Transmittance (a) | 89.5 |
| Haze/% | 4.2 |
| Impact Strength/kJ/m2 | 21.5 |
| Elongation at break/% | 188 |
| Tensile breaking strength/MPa | 16.5 |
Example 1
(1) Respectively adding a mixture of the homopolymerized polypropylene F401 and the copolymerization resin 1 (the feeding speed is 4.1kg/h), the ethylene propylene diene monomer 3072EPM (the feeding speed is 2.4kg/h) and the paraffin oil (the feeding speed is 3.5kg/h) into a double-screw extruder (a product of Kedouong machinery Co., Ltd., the length-diameter ratio of 56 and the diameter of a screw of 35mm, and an underwater pelletizing system), blending at the temperature of 190 ℃ and the rotating speed of 200rpm to obtain blended rubber, and then carrying out underwater pelletizing on the blended rubber to obtain blended rubber-plastic master batches;
(2) adding a vulcanizing agent F40P and a vulcanizing agent M75 into the blended rubber-plastic master batch to obtain a mixed master batch; and then vulcanizing the mixed master batch (with the feeding speed of 6.5kg/h) and paraffin oil (with the feeding speed of 3.5kg/h) in a double-screw extruder to obtain vulcanized rubber, and then carrying out underwater dicing on the vulcanized rubber to obtain granules of the dynamically vulcanized thermoplastic elastomer composite material composition, wherein in the vulcanizing process, the temperature of the double screws is as follows: the first section is 160 ℃, the second section is 180 ℃, the 3-14 sections are 200 ℃, and the screw rotating speed is 300 rpm/min;
the properties of the dynamically vulcanized thermoplastic elastomer composite composition obtained in this example are shown in table 2.
Examples 2 to 7
The process of example 1 was followed except that: the specific formulation and processing and material properties are shown in table 2.
Comparative example 1
The process of example 1 was followed except that: the specific formulation and processing and material properties without addition of copolymeric resin are shown in table 2.
Test example
The mechanical property of the dynamically vulcanized thermoplastic elastomer composite material composition is detected according to GB/T528-2009 and is measured by an AG-20KNG type tensile machine; wherein, the length of the effective part of the sample is 25mm, and the width is 6 mm; the stretching rate is 500mm/min, the testing temperature is 23 ℃, and the testing results are shown in table 2;
the compression set of the dynamically vulcanized thermoplastic elastomer composite composition was tested according to GB/T7759.1-2015 at 70 ℃ in an oven for 22h with a standard block height of 9.4mm, and the test results are shown in Table 2;
the melt index of the dynamically vulcanized thermoplastic elastomer composite material composition is detected according to GB/T3682.1-2018 and is measured by a JW-203A type melt index meter of Jinan instruments and provides a test result shown in Table 2;
the hardness of the dynamically vulcanized thermoplastic elastomer composite composition was measured according to GB/T531-2008 using a DSAS001 durometer from Gaoteville instruments, Inc., and the test results are shown in Table 2.
TABLE 2
In combination with the performance test data in table 1, it is evident that by introducing the block polymer composition 1 of the third component into the EPDM and PP system, the strength and elongation at break of the dynamically vulcanized thermoplastic elastomer composite composition (EPDM-based vulcanized alloy) are greatly improved, and the compression set of the alloy material is greatly reduced.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (12)
1. A dynamically vulcanized thermoplastic elastomer composite composition, wherein said dynamically vulcanized thermoplastic elastomer composite composition comprises, by weight, 1 to 4: 0.8-0.97: 0.03-0.2 parts of ethylene propylene diene monomer, polypropylene and a block polymer composition;
the block polymeric composition comprises in a weight ratio of 1: 99 to 30: 70 of block copolymer with star structure and linear structure,
the linear structure polymeric combination comprises:
block copolymer L of Linear Structure1：S1-S2-B；
Block copolymer L of Linear Structure2：S2-B；
Homopolymer L of linear structure3：B；
The star-structured blockThe copolymer comprises: (L)1-)m(L2-)n(L3-)p-X；
S1Being a homopolymerisation stage formed from monovinylaromatic monomers, S1The number average molecular weight of (A) is 2-30 ten thousand;
S2being a homopolymeric stage formed by monovinylaromatic monomers, S2Has a number average molecular weight of 0.3 to 3 ten thousand, and said S2Is less than the degree of polymerization of S1Degree of polymerization of (a);
b is a homopolymerization section formed by conjugated diene monomers, and the number average molecular weight of B is 0.3-2 ten thousand;
x is a coupling agent residue, m is L1N is L2P is L3M, n, p are each independently an integer from 0 to 20, and the sum of m, n, p is selected from an integer from 0 to 20;
based on the total weight of the homopolymerization section, the content of the structural unit provided by the monovinylarene monomer is 50-95 wt%, and the content of the structural unit provided by the conjugated diene monomer is 5-50 wt%;
based on the total weight of the structural units formed by the monovinylarene monomer, S1In an amount of 51-99 wt.%, S2In an amount of 1 to 49 wt.%;
the content of the side group structure is 40-80 wt% based on the total weight of the structural units formed by the conjugated diene monomer.
2. The dynamically vulcanized thermoplastic elastomer composite composition according to claim 1, wherein the monovinylarene monomer provides structural units in an amount of 65 to 85 weight percent and the conjugated diene monomer provides structural units in an amount of 15 to 35 weight percent, based on the total weight of the homopolymerization stage;
preferably, S is based on the total weight of structural units formed by the monovinylarene monomer1In an amount of 65-85 wt.%, S2In an amount of 15-35 wt.%;
preferably, the pendant structure is present in an amount of from 50 to 70 weight percent, based on the total weight of structural units formed from the conjugated diene monomer.
3. The dynamically vulcanized thermoplastic elastomer composite composition of claim 1 or 2, wherein S1The number average molecular weight of (A) is 6-13 ten thousand;
preferably, S2The number average molecular weight of (A) is 0.7-1.5 ten thousand;
preferably, B has a number average molecular weight of 0.5 to 1.5 ten thousand.
4. The dynamically vulcanized thermoplastic elastomer composite composition according to any one of claims 1 to 3, wherein the monovinylarene monomer is selected from at least one of styrene, vinyltoluene, alpha-methylstyrene, 4-tert-butylstyrene, 4-methylstyrene, 3, 5-diethylstyrene, 3, 5-di-n-butylstyrene, 4-n-propylstyrene, 4-dodecylstyrene;
preferably, the monovinylarene monomer is a styrene monomer.
5. The dynamically vulcanized thermoplastic elastomer composite composition according to any one of claims 1 to 4, wherein the conjugated diene monomer is selected from at least one of butadiene, isoprene, 1, 3-pentadiene, 1, 3-hexadiene, 2, 3-dimethylbutadiene;
preferably, the conjugated diene monomer is butadiene and/or isoprene.
6. The dynamically vulcanized thermoplastic elastomer composite composition according to any one of claims 1 to 5, wherein the ethylene propylene diene rubber has an ethylene structural unit content of 40 to 80 wt%, preferably 50 to 70 wt%;
preferably, the content of unsaturated double bonds in the ethylene-propylene-diene monomer rubber is 1 to 10 wt%, preferably 3 to 6 wt%.
7. The dynamically vulcanized thermoplastic elastomer composite composition of any one of claims 1-6, wherein the polypropylene is a homo-and/or co-polypropylene.
8. The dynamically vulcanized thermoplastic elastomer composite composition according to any one of claims 1 to 7, further comprising at least one of an extender oil, an antioxidant and an inorganic filler;
preferably, the extender oil is saturated alkane, preferably saturated alkane with the flash point of not lower than 190 ℃;
preferably, the inorganic filler is selected from at least one of talc, calcium carbonate, white carbon and carbon black.
9. A method of preparing the dynamically vulcanized thermoplastic elastomer composite composition of any one of claims 1 to 8, comprising:
blending ethylene propylene diene monomer, polypropylene and the block polymerization composition in a double-screw extruder to obtain blended rubber; the blended rubber is then vulcanized in the presence of a vulcanizing agent.
10. The method according to claim 9, wherein the vulcanizing agent is selected from at least one of a peroxide, a phenol resin, and an azo-based compound;
preferably, the peroxide is at least one selected from the group consisting of dibenzoyl peroxide, cumene hydroperoxide, 1-di-tert-butylperoxy-3, 3, 5-trimethylcyclohexane, di- (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, dicyclohexyl peroxydicarbonate and tert-butylperoxyisopropyl formate.
11. The method of claim 9 or 10, wherein the blending conditions at least satisfy: the temperature is 130 ℃ and 220 ℃, and the rotating speed of the double-screw extruder is 100 ℃ and 600 rpm; preferably, the blending conditions at least satisfy: the temperature is 150-190 ℃, and the rotating speed of the double-screw extruder is 150-400 rpm;
preferably, the conditions of the vulcanization at least satisfy: the temperature is 150-230 ℃, and the rotating speed of the double-screw extruder is 100-600 rpm; preferably, the vulcanization conditions at least satisfy: the temperature is 180 ℃ and 200 ℃; the rotation speed of the double-screw extruder is 200-400 rpm.
12. Use of the dynamically vulcanized thermoplastic elastomer composite composition according to any one of claims 1 to 8 in the field of building sealing and/or vehicle sealing.
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