CN111499788B - Ethylene-propylene-non-conjugated diene copolymer and synthesis method thereof - Google Patents
Ethylene-propylene-non-conjugated diene copolymer and synthesis method thereof Download PDFInfo
- Publication number
- CN111499788B CN111499788B CN201910092769.3A CN201910092769A CN111499788B CN 111499788 B CN111499788 B CN 111499788B CN 201910092769 A CN201910092769 A CN 201910092769A CN 111499788 B CN111499788 B CN 111499788B
- Authority
- CN
- China
- Prior art keywords
- copolymer
- ethylene
- propylene
- conjugated diene
- 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.)
- Active
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 170
- 238000001308 synthesis method Methods 0.000 title claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 16
- 239000000178 monomer Substances 0.000 claims description 60
- 239000003054 catalyst Substances 0.000 claims description 54
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 54
- 238000006116 polymerization reaction Methods 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 36
- 150000001993 dienes Chemical class 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 24
- 229930195733 hydrocarbon Natural products 0.000 claims description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 22
- 239000005977 Ethylene Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 22
- 239000004215 Carbon black (E152) Substances 0.000 claims description 20
- -1 alicyclic hydrocarbons Chemical class 0.000 claims description 20
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- 239000003381 stabilizer Substances 0.000 claims description 14
- 229910052720 vanadium Inorganic materials 0.000 claims description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012190 activator Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical group C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 150000002148 esters Chemical class 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 6
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical group CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims description 6
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 6
- 239000008116 calcium stearate Substances 0.000 claims description 6
- 235000013539 calcium stearate Nutrition 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 5
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 claims description 3
- 239000001273 butane Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- 229910001456 vanadium ion Inorganic materials 0.000 claims description 3
- 125000002897 diene group Chemical group 0.000 claims 6
- 230000015572 biosynthetic process Effects 0.000 claims 5
- 238000003786 synthesis reaction Methods 0.000 claims 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- BLXLSQIOCCHAHJ-UHFFFAOYSA-N [2,3,4-tri(nonyl)phenyl] dihydrogen phosphite Chemical compound CCCCCCCCCC1=CC=C(OP(O)O)C(CCCCCCCCC)=C1CCCCCCCCC BLXLSQIOCCHAHJ-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000010189 synthetic method Methods 0.000 claims 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 abstract description 17
- 230000002902 bimodal effect Effects 0.000 abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229920005604 random copolymer Polymers 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 235000012438 extruded product Nutrition 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000594310 Randia aculeata Species 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- CANXLAXDRLYESO-UHFFFAOYSA-N ethyl 2-(2,3-dichlorophenyl)acetate Chemical compound CCOC(=O)CC1=CC=CC(Cl)=C1Cl CANXLAXDRLYESO-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003681 vanadium Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides an ethylene-propylene-non-conjugated diene copolymer and a synthesis method thereof. The synthesis method comprises synthesizing an ethylene-propylene-non-conjugated diene copolymer with the number average molecular weight of 220,000-400,000 as a first part copolymer; synthesizing an ethylene-propylene-non-conjugated diene copolymer having a number average molecular weight of 60,000 to 200,000 as a second-part copolymer, the number average molecular weight of the second-part copolymer being smaller than that of the first-part copolymer; and mixing the first part copolymer and the second part copolymer according to the mass ratio of 3:7-9:1 to obtain the ethylene-propylene-non-conjugated diene copolymer. The invention develops the ethylene propylene rubber product with bimodal distribution, excellent mechanical property and processability.
Description
Technical Field
The invention relates to the technical field of ethylene-propylene rubber, in particular to an ethylene-propylene-non-conjugated diene copolymer and a synthesis method thereof.
Background
Due to the high saturability of molecular chains, compared with other general-purpose rubbers, the ethylene propylene rubber has excellent heat resistance, ozone resistance, weather resistance, good electrical insulation and chemical medium corrosion resistance, low relative density, large filling amount and good adaptability to various conventional rubber processing methods. At present, in the domestic market, ethylene propylene rubber is mainly used in the fields of automobile accessories, building materials, tires, waterproof coiled materials, wires and cables, polyolefin plastic modification, oil additives and the like. Other fields also include railway transportation, subway engineering, pipeline transportation and the like. With the increase of automobile demand in China and the continuous development of social public facilities such as city basic construction, high-speed railways, rail transit construction and the like, the ethylene propylene rubber in China is pulled to enter a demand peak.
The size and distribution of molecular weight have important influence on the physical and mechanical properties and processability of the ethylene propylene rubber. The ethylene propylene rubber with high molecular weight generally has good physical and mechanical properties, and the crude rubber, the mixed rubber and the vulcanized rubber have high tensile strength, constant tensile strength, tearing strength and fillability, but have poor processability such as mixing, extrusion, calendering and the like. It is therefore of interest to develop ethylene propylene rubbers with a broad or bimodal distribution. Although the widely distributed ethylene propylene rubber has low molecular weight components and can play a role in internal lubrication, thereby being beneficial to improving the processability, the physical and mechanical properties and the uniformity of the properties cannot be effectively guaranteed. Therefore, the purpose of bimodal distribution ethylene propylene rubber becomes the development direction of easily processed ethylene propylene rubber.
The main method of the preparation process of the ethylene propylene rubber with bimodal distribution at present is a double-kettle series/parallel process. In addition, a part of work adopts a single kettle polymerization process to directly synthesize the ethylene-propylene-diene copolymer with bimodal distribution, but the adjustability of the synthesized ethylene-propylene-diene copolymer monomer by the process cannot be comparable to that of a double kettle parallel process. In addition, in order to ensure good processability of the prepared ethylene-propylene rubber with bimodal distribution, a large amount of ethylene-propylene-diene copolymer with small molecular weight needs to be added, and the mechanical property of the ethylene-propylene rubber copolymer with high molecular weight needs to be greatly sacrificed.
Disclosure of Invention
The invention mainly aims to provide an ethylene-propylene-non-conjugated diene copolymer and a synthesis method thereof, so as to solve the problem of low mechanical property of the ethylene-propylene-non-conjugated diene copolymer in the prior art.
In order to achieve the above object, according to an aspect of the present invention, there is provided a method for synthesizing an ethylene-propylene-non-conjugated diene copolymer, the method comprising: synthesizing an ethylene-propylene-non-conjugated diene copolymer having a number average molecular weight of 220,000 to 400,000 as a first partial copolymer; synthesizing an ethylene-propylene-non-conjugated diene copolymer having a number average molecular weight of 60,000 to 200,000 as a second-part copolymer, the number average molecular weight of the second-part copolymer being smaller than that of the first-part copolymer; and mixing the first part copolymer and the second part copolymer according to the mass ratio of 3:7-9:1 to obtain the ethylene-propylene-non-conjugated diene copolymer.
Further, the step of obtaining the first partial copolymer comprises: hydrogen gas: ethylene: propylene is mixed according to the molar ratio (0.005-0.15): 1: (1.0-3.0) to obtain a first mixed gas; in an inert hydrocarbon medium solvent, carrying out polymerization reaction on the first mixed gas, the third monomer and the fourth monomer under the catalysis of a catalyst to obtain a first part of copolymer; wherein, the third monomer is dialkene containing one polymerizable double bond, and the fourth monomer is dialkene containing two polymerizable double bonds.
Further, the step of obtaining a second partial copolymer comprises: hydrogen gas: ethylene: propylene is mixed according to a molar ratio (0.5-2.0): 1: (3.0-5.0) to obtain a second mixed gas; in an inert hydrocarbon medium solvent, carrying out polymerization reaction on a second mixed gas, a third monomer and a fourth monomer under the catalysis of a catalyst to obtain a second part of copolymer; wherein, the third monomer is dialkene containing one polymerizable double bond, and the fourth monomer is dialkene containing two polymerizable double bonds.
Further, the inert hydrocarbon medium solvent is selected from aliphatic hydrocarbon and/or alicyclic hydrocarbon, preferably the aliphatic hydrocarbon is selected from any one or more of propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene; the alicyclic hydrocarbon is selected from one or more of cyclopentane, cyclohexane and methyl cyclopentane, and more preferably, the inert hydrocarbon medium solvent is hexane with water content less than 10 μ g/g.
Further, the catalyst comprises a main catalyst and a cocatalystThe catalyst is a vanadium catalyst with a general formula of VOL n X m N = 1-3,m = 1-3,n + m =3, wherein V is a vanadium ion having a valence of 5; l is a ligand, the ligand is an acidic phosphate, and the preferred organic phosphate is 2-ethylhexyl phosphate; x is halogen; the molar ratio of L to V is 1-3; the cocatalyst is an alkylaluminum, and preferably the alkylaluminum is any one of triisobutylaluminum, diisobutylaluminum monochloride, diethylaluminum monochloride, triethyldialuminum trichloride, monoethylaluminum dichloride and triethylaluminum.
Furthermore, the addition amount of the main catalyst is 0.05 mmol/L-1.0 mmol/L, preferably 0.1 mmol/L-0.6 mmol/L, and more preferably 0.2 mmol/L-0.4 mmol/L measured by the volume of the inert hydrocarbon medium solvent; preferably, the molar ratio of Al in the cocatalyst to V in the main catalyst is 5-100: 1, more preferably 5 to 40:1, more preferably 6 to 15:1.
further, the third monomer is selected from any one or more of vinyl norbornene, ethylidene norbornene, dicyclopentadiene and 1, 4-hexadiene; the fourth monomer is vinyl norbornene and/or 1, 4-hexadiene; preferably, the addition amount of the third monomer is 20g/L to 50g/L of solvent, more preferably 25g/L to 45g/L of solvent; preferably, the molar ratio of the third monomer to the fourth monomer is 5 to 25:1, more preferably 10 to 20:1.
further, carrying out polymerization reaction on the second mixed gas, the third monomer, the fourth monomer and an activating agent under the catalysis of a catalyst to obtain a second part of copolymer; preferably, the activator is a chlorinated ester having 2 to 5 chlorine atoms, the chlorinated ester being a saturated or unsaturated chlorinated ester; or the activating agent is ester chlorinated hydrocarbon with 2-5 carbon atoms and 5-8 chlorine atoms, and the ester chlorinated hydrocarbon is saturated or unsaturated ester chlorinated hydrocarbon; more preferably, the activator is 2,3-dichlorophenyl ethyl acetate; preferably, the molar ratio of the activator to V in the main catalyst is 0.5 to 20:1, more preferably 1 to 10:1, more preferably 1 to 5:1.
further, the polymerization reaction is carried out in an oxygen-free atmosphere, preferably, the temperature of the polymerization reaction is 10-35 ℃, and the pressure is 0.3-1.0 MPa; the time for the polymerization reaction is more preferably 10 to 60min.
Further, after the polymerization reaction and before the first part of copolymer is obtained, the method also comprises the steps of sequentially carrying out water washing inactivation, flash evaporation concentration, mixing with a stabilizer and extrusion drying on the polymerization product.
Further, after the polymerization reaction and before the second part of copolymer is obtained, the method also comprises the steps of sequentially carrying out water washing inactivation, flash evaporation concentration, mixing with a stabilizer and extrusion drying on the polymerization product.
Further, the stabilizer is a mixture of calcium stearate, antioxidant 1010 and trisnonylphenyl phosphite antioxidant, preferably calcium stearate is HA-stabilizer, trisnonylphenyl phosphite antioxidant is TNP, more preferably HA-stabilizer: antioxidant 1010: the mass ratio of TNP is 1.5-2.5.
According to another aspect of the present invention, there is provided an ethylene-propylene-non-conjugated diene copolymer comprising a mixture of a first copolymer portion and a second copolymer portion, the mass ratio of the mixture of the first copolymer portion to the second copolymer portion being 3:7-9:1, the number average molecular weight of the first copolymer portion being 220,000-400,000, and the number average molecular weight of the second copolymer portion being 60,000-200,000.
Further, the number average molecular weight of the first copolymer fraction is 220,000 to 380,000, and the number average molecular weight of the second copolymer fraction is 80,000 to 150,000.
Further, the first part copolymer comprises ethylene units, propylene units and non-conjugated diene units, wherein the content of ethylene units in the first part copolymer is from 50wt% to 85wt%, preferably from 60wt% to 75wt%, the content of propylene units in the first part copolymer is from 15wt% to 50wt%, preferably from 25wt% to 40wt%, and the content of non-conjugated diene units in the first part copolymer is from 2wt% to 9wt%, preferably from 4wt% to 6wt%.
Further, the second part copolymer comprises ethylene units, propylene units and non-conjugated diene units, wherein the content of the ethylene units in the second part copolymer is 40wt% to 65wt%, preferably 45wt% to 60wt%, the content of the propylene units in the second part copolymer is 35wt% to 60wt%, preferably 40wt% to 55wt%, and the content of the non-conjugated diene units in the second part copolymer is 4wt% to 12wt%, preferably 5wt% to 10wt%.
Further, the ethylene-propylene-non-conjugated diene copolymer has a phase angle difference of a long chain branching degree at 125 ℃ of from delta (0.1 Hz) to delta (100 Hz) of 5 to 20, preferably from 8 to 16.
Further, the molecular weight distribution of the first part copolymer and the second part copolymer is 1.8-2.5.
By applying the technical scheme of the invention, two ethylene propylene rubber copolymers with long chain branched structures, different molecular weights and narrow molecular weight distribution are synthesized and blended to prepare the ethylene propylene rubber copolymer, and on the premise of ensuring good processability, the addition amount of ethylene-propylene-diene with small molecular weight is reduced, so that a bimodal ethylene propylene rubber product with bimodal distribution, excellent mechanical property and processability is developed.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
The invention aims to provide a bimodal distribution ethylene-propylene-non-conjugated diene copolymer with simple process and easily obtained raw materials and a synthesis method thereof. The synthesis method comprises the following steps: synthesizing an ethylene-propylene-non-conjugated diene copolymer having a number average molecular weight of 220,000 to 400,000 as a first partial copolymer; synthesizing an ethylene-propylene-non-conjugated diene copolymer having a number average molecular weight of 60,000 to 200,000 as a second-part copolymer, the number average molecular weight of the second-part copolymer being smaller than that of the first-part copolymer; and mixing the first part copolymer and the second part copolymer according to the mass ratio of 3:7-9:1 to obtain the ethylene-propylene-non-conjugated diene copolymer.
The prepared ethylene-propylene-non-conjugated diene copolymer with bimodal distribution has the characteristics of long-chain branched structure, low content of low molecular weight part, excellent mechanical property and processability and the like, and meets the use requirements in the fields of high-grade sealing strips, high-hardness extruded products, high-grade sponge extruded products and the like.
In a preferred embodiment, the step of obtaining the high molecular weight first partial copolymer comprises: hydrogen gas: ethylene: propylene is mixed according to a molar ratio (0.005-0.15): 1: (1.0-3.0) to obtain a first mixed gas; in an inert hydrocarbon medium solvent, carrying out polymerization reaction on the first mixed gas, the third monomer and the fourth monomer under the catalysis of a catalyst to obtain a first part of copolymer; wherein, the third monomer is dialkene containing one polymerizable double bond, and the fourth monomer is dialkene containing two polymerizable double bonds.
In a preferred embodiment, the step of obtaining the above-mentioned low molecular weight second partial copolymer comprises: hydrogen gas: ethylene: propylene is mixed according to a molar ratio (0.5-2.0): 1: (3.0-5.0) to obtain a second mixed gas; in an inert hydrocarbon medium solvent, carrying out polymerization reaction on a second mixed gas, a third monomer and a fourth monomer under the catalysis of a catalyst to obtain a second part of copolymer; wherein, the third monomer is dialkene containing a polymerizable double bond, and the fourth monomer is dialkene containing two polymerizable double bonds.
Specifically, the steps of preparing the first part copolymer and the second part copolymer are all prepared by adopting a solution polymerization method, taking an inert hydrocarbon medium as a solvent, taking ethylene, propylene and diene containing one polymerizable double bond as a third monomer, and taking diene containing two polymerizable double bonds as a fourth monomer in the presence of a catalyst for olefin polymerization.
Preferably, the polymerization reaction is carried out in an oxygen-free atmosphere in a reactor, a certain amount of inert hydrocarbon medium is added into the reactor, the reactor is heated to 10-35 ℃, then mixed gas of ethylene, propylene and hydrogen is continuously introduced into the reactor through a compressor, the gas inlet speed is controlled to keep the pressure in the reactor at 0.3-1.0 MPa, after the mixed gas dissolved in the inert medium is saturated, the inert medium, the main catalyst, the cocatalyst, the third monomer, the fourth monomer and other raw materials are continuously added through a metering pump, and the residence time of the polymerization reaction is controlled to be 10-60 min.
In the step of preparing the first partial copolymer and the second partial copolymer, the inert hydrocarbon medium solvent may be independently selected from aliphatic hydrocarbons and/or alicyclic hydrocarbons, preferably, the aliphatic hydrocarbons may be selected from any one or more of propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and the alicyclic hydrocarbons may be selected from any one or more of cyclopentane, cyclohexane, and methylcyclopentane; more preferably, the inert hydrocarbon medium solvent is hexane having a water content of less than or equal to 10. Mu.g/g.
In the step of preparing the first partial copolymer and the second partial copolymer, the catalyst may comprise a main catalyst and a cocatalyst, and specifically, the narrow distribution of the high molecular weight ethylene-propylene-non-conjugated diene random copolymer and the narrow distribution of the low molecular weight ethylene-propylene-non-conjugated diene random copolymer are synthesized by homogeneous continuous polymerization with the modified soluble vanadium complex as the main catalyst and the alkyl aluminum halide as the cocatalyst.
The main catalyst used in the present invention is a vanadium catalyst, preferably the vanadium catalyst has the general formula VOL n X m N = 1-3,m = 1-3,n + m =3, wherein V is a 5-valent vanadium ion; l is a ligand selected from the group consisting of acidic phosphates, preferably 2-ethylhexyl phosphate; x is halogen, wherein the molar ratio of L to V is 1 to 3. More preferably, the amount of the main catalyst added is 0.05 to 1.0mmol/L, still more preferably 0.1 to 0.6mmol/L, most preferably 0.2 to 0.4mmol/L, based on the volume of the inert hydrocarbon medium solvent.
The cocatalyst used in the present invention is an alkylaluminum halide, and the alkylaluminum halide is preferably any one selected from the group consisting of alkylaluminum such as triisobutylaluminum, diisobutylaluminum monochloride, diethylaluminum monochloride, triethyldialuminum trichloride, ethylaluminum dichloride and triethylaluminum. More preferably, the molar ratio of Al in the cocatalyst to V in the main catalyst is 5 to 100:1, more preferably 5 to 40:1, most preferably 6 to 15:1.
in the step of preparing the above first partial copolymer and the above second partial copolymer, preferably, the above third monomer is selected from any one or more of vinyl norbornene, ethylidene norbornene, dicyclopentadiene and 1, 4-hexadiene, and more preferably, ethylidene norbornene; the fourth monomer is vinyl norbornene and/or 1, 4-hexadiene, and more preferably vinyl norbomene. Also, the amount of the third monomer added is preferably 20 to 50g/L solvent, more preferably 25 to 45g/L solvent; preferably, the molar ratio of the third monomer to the fourth monomer is 5 to 25:1, more preferably 10 to 20:1.
in the above step of preparing the second partial copolymer, in order to increase the polymerization activity, it is preferable that the second mixed gas, the third monomer, the fourth monomer and the activator (low molecular weight ethylene-propylene-nonconjugated diene random copolymer) are subjected to a polymerization reaction under catalysis of a catalyst to obtain the second partial copolymer. More preferably, the activator used is a chlorinated saturated or unsaturated ester having from 2 to 5 chlorine atoms or a chlorinated saturated or unsaturated aliphatic hydrocarbon having from 2 to 5 carbon atoms and from 5 to 8 chlorine atoms, more preferably 2,3-dichlorophenylacetic acid ethyl ester (DCPAE). Preferably, the molar ratio of V in the activator to the main catalyst is 0.5 to 20:1, more preferably 1 to 10, most preferably 1 to 5:1.
In the step of preparing the first part copolymer and the second part copolymer, after the polymerization reaction, the polymerization product may be sequentially subjected to water washing for deactivation, flash evaporation for concentration, mixing with a stabilizer, extrusion drying and other treatment steps to obtain a finished product. Preferably, the stabilizer is a mixture of calcium stearate, an antioxidant 1010 and a trisnonylphenylphosphite antioxidant, the calcium stearate is preferably an HA-stabilizer, the trisnonylphenylphosphite antioxidant is preferably TNP, and more preferably, the HA-stabilizer: antioxidant 1010: the mass ratio of TNP is 1.5-2.5.
After narrow-distribution high molecular weight ethylene-propylene-non-conjugated diene random copolymer and low molecular weight ethylene-propylene-non-conjugated diene random copolymer are respectively synthesized, the high molecular weight ethylene-propylene-non-conjugated diene random copolymer and the low molecular weight ethylene-propylene-non-conjugated diene random copolymer are proportionally mixed to synthesize the ethylene-propylene-non-conjugated diene random copolymer with bimodal distribution. The technological process mainly comprises the working procedures of raw material preparation, polymerization, blending, catalyst removal, monomer and solvent recovery, refining, condensation, drying and the like.
According to another aspect of the present invention, there is also provided an ethylene-propylene-non-conjugated diene copolymer comprising a mixture of a first copolymer portion and a second copolymer portion, the mass ratio of the mixture of the first copolymer portion to the second copolymer portion being 3:7 to 9:1, the number average molecular weight of the first copolymer portion being 220,000 to 400,000, and the number average molecular weight of the second copolymer portion being 60,000 to 200,000.
The bimodal distribution ethylene-propylene-non-conjugated diene copolymer has the characteristics of long chain branching structure, low content of low molecular weight part, excellent mechanical property and processability and the like, and meets the use requirements in the fields of high-grade sealing strips, high-hardness extruded products, high-grade sponge extruded products and the like.
The data molecular weight (Mn) and molecular weight distribution (Mw/Mn) of the above ethylene-propylene-nonconjugated diene copolymer of the present invention can be determined by Gel Permeation Chromatography (GPC) using single dispersed phase polystyrene as a standard. The number average molecular weight of the ethylene-propylene-nonconjugated diene random copolymer of the high molecular weight portion measured by the method satisfies 220,000 to 400,000, preferably 220,000 to 380,000; the number average molecular weight of the ethylene-propylene-non-conjugated diene random copolymer of the low molecular weight portion satisfies 60,000 to 200,000, preferably 80,000 to 150,000. Also, it is preferable that the molecular weight distribution of the first partial copolymer and the second partial copolymer in the above ethylene-propylene-non-conjugated diene copolymer are each 1.8 to 2.5.
In the above ethylene-propylene-non-conjugated diene copolymer of the present invention, preferably, the first copolymer fraction comprises ethylene units, propylene units and non-conjugated diene units, wherein the content of the ethylene units in the first copolymer fraction is from 50 to 85wt%, preferably from 60 to 75wt%, the content of the propylene units in the first copolymer fraction is from 15 to 50wt%, preferably from 25 to 40wt%, and the content of the non-conjugated diene units in the first copolymer fraction is from 2 to 9wt%, preferably from 4 to 6wt%.
In the above ethylene-propylene-non-conjugated diene copolymer of the present invention, preferably, the second partial copolymer comprises an ethylene unit, a propylene unit and a non-conjugated diene unit, wherein the content of the ethylene unit in the second partial copolymer is from 40wt% to 65wt%, preferably from 45wt% to 60wt%, the content of the propylene unit in the second partial copolymer is from 35wt% to 60wt%, preferably from 40wt% to 55wt%, and the content of the non-conjugated diene unit in the second partial copolymer is from 4wt% to 12wt%, preferably from 5wt% to 10wt%.
The long chain branching degree of the ethylene-propylene-non-conjugated diene copolymer is characterized by adopting a dynamic mechanical analyzer, the constant temperature is 125 ℃, the test frequency is 0.01 Hz-100 Hz, and the difference of phase angles (loss angles) between 0.1Hz and 100Hz is calculated. The phase angle difference delta (0.1 Hz) -delta (100 Hz) of the long-chain branching degree of the ethylene-propylene-non-conjugated diene copolymer at 125 ℃ is measured by the method to be 5-20, and the preferred range is 8-16.
The ethylene-propylene-non-conjugated diene copolymer and the method for synthesizing the same according to the present invention will be further illustrated with reference to the following examples.
Example 1
The preparation method of the vanadium catalyst provided by the embodiment comprises the following steps:
taking 200mL cavel bottle with air inlet pipe at bottom, performing anhydrous and anaerobic treatment under vacuum and heating state, adding 100mL of refined hexane, introducing high-purity nitrogen gas for bubbling, adding 0.031mol of vanadium oxychloride into the dry medical glass syringe,stirring for 10min, slowly dropping 0.031mol 2-ethylhexyl phosphate diluted with 50mL hexane while bubbling high purity nitrogen gas, and stopping reaction after 30min to obtain VOLCl with concentration of 0.2mol/L 2 Modifying the vanadium catalyst solution, and storing the reaction container in the dark under the protection of high-purity nitrogen.
Example 2
Taking 200mL goat horn bottle with an air inlet pipe at the bottom, carrying out anhydrous and anaerobic treatment under vacuum and heating conditions, then adding 100mL of hexane refined in advance, introducing high-purity nitrogen for bubbling, then adding 0.031mol of vanadium oxychloride by using a dry medical glass syringe, stirring for 10min, slowly dripping 0.062mol of 2-ethylhexyl phosphate diluted by 50mL of hexane while dripping high-purity nitrogen, stopping reaction after 30min to obtain the solution with the concentration of 0.2mol/L VOL 2 And (3) Cl modifying the vanadium catalyst solution, and storing the reaction container in the dark under the protection of high-purity nitrogen.
Example 3
Taking 200mL goat horn bottle with an air inlet pipe at the bottom, carrying out anhydrous and anaerobic treatment under vacuum and heating conditions, then adding 100mL of hexane which is refined in advance, introducing high-purity nitrogen for bubbling, then adding 0.031mol of vanadium oxychloride by using a dry medical glass syringe, stirring for 10min, slowly dripping 0.096mol of 2-ethylhexyl phosphate diluted by 50mL of hexane while dripping high-purity nitrogen, stopping reaction after 30min to obtain the liquid with the concentration of 0.2mol/L VOL 3 Modifying the vanadium catalyst solution, and storing the reaction container in the dark under the protection of high-purity nitrogen.
Example 4
The method for synthesizing the ethylene-propylene-non-conjugated diene copolymer provided in this example includes the following steps:
in the first reactor, hydrogen, ethylene and propylene are mixed by a mixing device according to the weight ratio of 0.01:1:2.5, then fully and uniformly mixing the materials by a circulating compressor, carrying out polymerization in a 5L overflow type polymerization kettle, carrying out anhydrous and oxygen-free treatment on the 5L polymerization kettle for 1h in a vacuum state, wherein the used inert gas is high-purity nitrogen. Adding dry hexane into a polymerization kettle in advance through a metering pump, enabling the polymerization kettle to overflow, starting a circulating compressor, introducing mixed gas into the polymerization kettle, enabling the mixed gas dissolved in the hexane to reach saturation, and then sequentially starting the metering pumps of the hexane, the cocatalyst, the main catalyst, the third monomer and the fourth monomer, wherein the polymerization reaction temperature is 45 ℃. The polymerization pressure is 0.4MPa, and the polymerization residence time is 0.5h, so as to obtain the first part of copolymer.
In the second reactor, hydrogen, ethylene and propylene were mixed by a mixing device in a ratio of 0.6. Adding dry hexane into a polymerization kettle in advance through a metering pump, enabling the polymerization kettle to overflow, starting a circulating compressor, introducing mixed gas into the polymerization kettle, enabling the mixed gas dissolved in the hexane to reach saturation, and then sequentially starting metering pumps of the hexane, a cocatalyst, a main catalyst, a third monomer, a fourth monomer and an activator, wherein the polymerization reaction temperature is 45 ℃. The polymerization pressure is 0.4MPa, and the polymerization residence time is 0.5h, so as to obtain a second part of copolymer.
Wherein, the cocatalyst added in the first reactor and the second reactor are triisobutylaluminum, the main catalyst is the vanadium catalyst prepared in the embodiment 1, the third monomer is Ethylidene Norbornene (ENB), and the fourth monomer is Vinyl Norbornene (VNB).
Mixing the first part of copolymer and the second part of copolymer according to a mass ratio of 4:1, stirring for 1h, removing the catalyst and water from the glue solution through alkali washing and water washing, condensing out the glue solution through ethanol, and drying the condensed polymer in vacuum at 65 ℃ for 24h.
Example 5
The difference between the method for synthesizing the ethylene-propylene-non-conjugated diene copolymer provided in this example and example 4 is that:
the main catalysts added in the first reactor and the second reactor are all the vanadium catalysts prepared in example 2.
Example 6
The difference between the method for synthesizing the ethylene-propylene-non-conjugated diene copolymer provided in this example and that of example 4 is that:
the main catalysts added in the first reactor and the second reactor are all the vanadium catalysts prepared in example 3.
Example 7
The difference between the method for synthesizing the ethylene-propylene-non-conjugated diene copolymer provided in this example and that of example 4 is that:
the polymerization reaction is carried out in an oxygen-free atmosphere, the temperature of the polymerization reaction is 10 ℃, and the pressure is 0.3MPa; the polymerization time was 60min.
Example 8
The difference between the method for synthesizing the ethylene-propylene-non-conjugated diene copolymer provided in this example and example 4 is that:
the polymerization reaction is carried out in an oxygen-free atmosphere, the temperature of the polymerization reaction is 35 ℃, and the pressure is 1.0MPa; the polymerization time was 10min.
The differences between examples 9 to 17 and comparative examples 1 to 2 and example 4 are shown in table 1, wherein the differences between examples 11 to 17 and example 4 further comprise the addition of an activator-2,3-dichlorophenylacetic acid ethyl ester (DCPAE) to the reactor 2.
TABLE 1
The above examples 4 to 17 and comparative examples 1 to 2 were subjected to the copolymerization composition analysis, the Mooney viscosity test, the high temperature gel chromatography analysis and the dynamic mechanical property test, and the test results are shown in tables 2 and 3, wherein the analysis results are shown in Table 2 and the blending results are shown in Table 3.
TABLE 2
TABLE 3
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
the invention synthesizes the ethylene-propylene-non-conjugated diene random copolymer with a long-chain branched structure and bimodal distribution by adopting a soluble modified vanadium catalytic system and a double-kettle parallel mixing process. The introduction of the long-chain branched structure can greatly improve the processing performance of the copolymer, reduce the addition of the ethylene-propylene-non-conjugated diene copolymer with small molecular weight and improve the physical and mechanical properties of the copolymer. The random copolymer meets the use requirements in the fields of high-grade sealing strips, high-hardness extruded products, high-grade sponge extruded products and the like.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (46)
1. A method for synthesizing an ethylene-propylene-non-conjugated diene copolymer, which is characterized by comprising the following steps:
synthesizing an ethylene-propylene-non-conjugated diene copolymer with the number average molecular weight of 220,000 to 400,000 as a first part copolymer;
synthesizing an ethylene-propylene-non-conjugated diene copolymer with the number average molecular weight of 60,000-200,000 as a second part copolymer, wherein the number average molecular weight of the second part copolymer is less than that of the first part copolymer;
mixing the first part of copolymer and the second part of copolymer according to a mass ratio of 3 to 9, so as to obtain the ethylene-propylene-non-conjugated diene copolymer;
the step of obtaining the first partial copolymer comprises:
hydrogen gas: ethylene: propylene was added in a molar ratio of (0.005 to 0.15): 1: (1.0-3.0) to obtain a first mixed gas;
in an inert hydrocarbon medium solvent, carrying out polymerization reaction on the first mixed gas, the third monomer and the fourth monomer under the catalysis of a catalyst to obtain the first part of copolymer;
the third monomer is non-conjugated diene containing one polymerizable double bond, and the fourth monomer is non-conjugated diene containing two polymerizable double bonds;
the step of obtaining the second partial copolymer comprises:
hydrogen gas: ethylene: propylene is mixed according to a molar ratio (0.5 to 2.0): 1: (3.0-5.0) to obtain a second mixed gas;
in an inert hydrocarbon medium solvent, carrying out a polymerization reaction on the second mixed gas, the third monomer and the fourth monomer under the catalysis of a catalyst to obtain a second part of copolymer;
the third monomer is non-conjugated diene containing one polymerizable double bond, and the fourth monomer is non-conjugated diene containing two polymerizable double bonds.
2. The synthesis process according to claim 1, characterized in that the inert hydrocarbon medium solvent is chosen from aliphatic and/or alicyclic hydrocarbons.
3. A synthesis method according to claim 2, characterized in that the aliphatic hydrocarbon is selected from any one or more of propane, butane, pentane, hexane, heptane, octane, decane and dodecane.
4. The method of claim 2, wherein the alicyclic hydrocarbon is selected from any one or more of cyclopentane, cyclohexane, and methylcyclopentane.
5. The synthesis process according to claim 2, characterized in that the inert hydrocarbon medium solvent is hexane with a water content of 10 μ g/g or less.
6. The method of claim 1, wherein the catalyst comprises a main catalyst and a co-catalyst, wherein the main catalyst is a vanadium catalyst having a general formula of VOL n X m N =1 to 3,m =1 to 3,n + m =3, wherein,
v is a 5-valent vanadium ion;
l is a ligand, and the ligand is an acidic phosphate;
x is halogen;
the molar ratio of L to V is 1~3;
the cocatalyst is aluminum alkyl.
7. The method of claim 6, wherein the acidic phosphate is 2-ethylhexyl phosphate.
8. The method according to claim 6, wherein the alkyl aluminum is any one of triisobutylaluminum, diisobutylaluminum chloride, diethylaluminum chloride, triethyldialuminum chloride, ethylaluminum dichloride and triethylaluminum.
9. The synthesis method according to claim 6, wherein the addition amount of the main catalyst is 0.05mmol/L to 1.0mmol/L based on the volume of the inert hydrocarbon medium solvent.
10. The synthesis method according to claim 9, wherein the addition amount of the main catalyst is 0.1mmol/L to 0.6mmol/L.
11. The synthesis method according to claim 10, wherein the addition amount of the main catalyst is 0.2mmol/L to 0.4mmol/L.
12. The synthesis method according to claim 6, wherein the molar ratio of Al in the cocatalyst to V in the main catalyst is 5-100: 1.
13. the synthesis method of claim 12, wherein the molar ratio of Al in the cocatalyst to V in the main catalyst is 5-40: 1.
14. the synthesis method of claim 13, wherein the molar ratio of Al in the cocatalyst to V in the main catalyst is 6-15: 1.
15. the method of synthesis of claim 1, wherein the third monomer is selected from the group consisting of ethylidene norbornene; the fourth monomer is vinyl norbornene and/or 1, 4-hexadiene.
16. The synthesis method according to claim 15, wherein the third monomer is added in an amount of 20-50 g/L solvent.
17. The method of claim 16, wherein the third monomer is added in an amount of 25g/L solvent to 45g/L solvent.
18. The synthesis method according to claim 15, wherein the molar ratio of the third monomer to the fourth monomer is 5 to 25:1.
19. the synthesis method according to claim 18, wherein the molar ratio of the third monomer to the fourth monomer is 10 to 20:1.
20. the synthesis method according to claim 1, wherein the second mixed gas, the third monomer, the fourth monomer and an activator are polymerized under catalysis of a catalyst to obtain the second partial copolymer.
21. The synthesis method according to claim 20, wherein the activator is a chlorinated ester having 2 to 5 chlorine atoms, the chlorinated ester being a saturated or unsaturated chlorinated ester; or the activating agent is ester chlorinated hydrocarbon with 2-5 carbon atoms and 5-8 chlorine atoms, and the ester chlorinated hydrocarbon is saturated or unsaturated ester chlorinated hydrocarbon.
22. The method of synthesis of claim 21, wherein the activator is 2,3-dichlorophenyl ethyl acetate.
23. The synthesis method according to any one of claims 20 to 22, wherein the molar ratio of the activator to V in the main catalyst is from 0.5 to 20:1.
24. the synthesis method according to claim 23, wherein the molar ratio of the activating agent to V in the main catalyst is 1-10: 1.
25. the synthesis method according to claim 24, wherein the molar ratio of the activating agent to V in the main catalyst is 1 to 5:1.
26. the synthesis method according to claim 1, wherein the polymerization reaction is carried out in an oxygen-free atmosphere.
27. The synthesis method of claim 26, wherein the polymerization reaction is carried out at a temperature of 10 ℃ to 35 ℃ and at a pressure of 0.3MPa to 1.0MPa.
28. The method of claim 26, wherein the polymerization reaction time is 10min to 60min.
29. The synthesis method of claim 1, further comprising the steps of sequentially deactivating the polymerization product by water washing, performing flash concentration, mixing with a stabilizer, and performing extrusion drying after the polymerization reaction and before the first part of the copolymer is obtained.
30. The method of claim 1, further comprising the steps of sequentially deactivating the polymerization product with water, flash concentrating, mixing with a stabilizer, and drying by extrusion after the polymerization reaction and before the second portion of the copolymer is obtained.
31. A synthesis process according to claim 29 or claim 30, characterised in that the stabiliser is a mixture of calcium stearate, antioxidant 1010 and a trisnonylphenyl phosphite antioxidant.
32. The method as in claim 31, wherein the calcium stearate is a HA-stabilizer and the tris-nonylphenyl phosphite antioxidant is TNP.
33. The synthetic method of claim 32 wherein the HA-stabilizer: the antioxidant is 1010: the mass ratio of the TNP is 1.5-2.5.
34. An ethylene-propylene-non-conjugated diene copolymer, characterized in that it is a copolymer prepared by the synthesis method according to any one of claims 1 to 33.
35. The ethylene-propylene-nonconjugated diene copolymer according to claim 34, wherein the number average molecular weight of the copolymer in the first part is from 220,000 to 380,000, and the number average molecular weight of the copolymer in the second part is from 80,000 to 150,000.
36. The ethylene-propylene-non-conjugated diene copolymer of claim 34, wherein the first portion copolymer comprises ethylene units, propylene units, and non-conjugated diene units, wherein the ethylene units are present in the first portion copolymer in an amount of 50wt% to 85wt%, the propylene units are present in the first portion copolymer in an amount of 15wt% to 50wt%, and the non-conjugated diene units are present in the first portion copolymer in an amount of 2wt% to 9wt%.
37. The ethylene-propylene-non-conjugated diene copolymer of claim 36, wherein the content of the ethylene units in the first partial copolymer is from 60wt% to 75wt%.
38. The ethylene-propylene-non-conjugated diene copolymer of claim 36, wherein the propylene units are present in the first portion copolymer in an amount of from 25wt% to 40wt%.
39. The ethylene-propylene-non-conjugated diene copolymer of claim 36, wherein the content of the non-conjugated diene units in the first partial copolymer is from 4wt% to 6wt%.
40. The ethylene-propylene-non-conjugated diene copolymer of claim 34, wherein the second part copolymer comprises ethylene units, propylene units and non-conjugated diene units, wherein the ethylene units are present in the second part copolymer in an amount of 40wt% to 65wt%, the propylene units are present in the second part copolymer in an amount of 35wt% to 60wt%, and the non-conjugated diene units are present in the second part copolymer in an amount of 4wt% to 12wt%.
41. The ethylene-propylene-non-conjugated diene copolymer according to claim 40, wherein the content of the ethylene unit in the second partial copolymer is 45wt% to 60wt%.
42. The ethylene-propylene-non-conjugated diene copolymer of claim 40, wherein the content of the propylene unit in the second partial copolymer is from 40wt% to 55wt%.
43. The ethylene-propylene-non-conjugated diene copolymer according to claim 40, wherein the content of the non-conjugated diene unit in the second partial copolymer is 5 to 10% by weight.
44. The ethylene-propylene-non-conjugated diene copolymer according to any one of claims 34 to 43, wherein the ethylene-propylene-non-conjugated diene copolymer has a long-chain branching degree characterized by a phase angle difference δ (0.1 Hz) - δ (100 Hz) measured at 125 ℃ of 5 to 20.
45. The ethylene-propylene-non-conjugated diene copolymer according to claim 44, wherein the ethylene-propylene-non-conjugated diene copolymer has a long chain branching degree characterized by a phase angle difference δ (0.1 Hz) - δ (100 Hz) measured at 125 ℃ of 8 to 16.
46. The ethylene-propylene-non-conjugated diene copolymer according to any one of claims 34 to 43, wherein the molecular weight distribution of the first copolymer and the second copolymer is 1.8 to 2.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910092769.3A CN111499788B (en) | 2019-01-30 | 2019-01-30 | Ethylene-propylene-non-conjugated diene copolymer and synthesis method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910092769.3A CN111499788B (en) | 2019-01-30 | 2019-01-30 | Ethylene-propylene-non-conjugated diene copolymer and synthesis method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111499788A CN111499788A (en) | 2020-08-07 |
| CN111499788B true CN111499788B (en) | 2022-11-04 |
Family
ID=71873924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910092769.3A Active CN111499788B (en) | 2019-01-30 | 2019-01-30 | Ethylene-propylene-non-conjugated diene copolymer and synthesis method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111499788B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09241449A (en) * | 1996-03-06 | 1997-09-16 | Toyo Tire & Rubber Co Ltd | Heat-resistant rubber composition for vibration-proof rubber |
| US5677382A (en) * | 1994-12-19 | 1997-10-14 | Japan Synthetic Rubber Co., Ltd. | Ethylene-α-olefin-non-conjugated diene copolymer rubber composition |
| US5973017A (en) * | 1996-11-20 | 1999-10-26 | Toyoda Gosei Co., Ltd. | Foamed rubber blend containing and ethylene-propylene-diene polymer blend and an article formed from a sulfur-vulcanized foamed rubber blend |
| EP1186631A1 (en) * | 2000-09-08 | 2002-03-13 | JSR Corporation | Rubber composition of high and low molecular weight EPDM |
| JP2005255824A (en) * | 2004-03-11 | 2005-09-22 | Sumitomo Chemical Co Ltd | ETHYLENE-alpha-OLEFIN-NONCONJUGATED DIENE COPOLYMER RUBBER |
| CN101838365A (en) * | 2009-03-18 | 2010-09-22 | 中国石油天然气股份有限公司 | Synthesis method of bimodal distribution ethylene-alpha-olefin-non-conjugated diene random copolymer |
-
2019
- 2019-01-30 CN CN201910092769.3A patent/CN111499788B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5677382A (en) * | 1994-12-19 | 1997-10-14 | Japan Synthetic Rubber Co., Ltd. | Ethylene-α-olefin-non-conjugated diene copolymer rubber composition |
| JPH09241449A (en) * | 1996-03-06 | 1997-09-16 | Toyo Tire & Rubber Co Ltd | Heat-resistant rubber composition for vibration-proof rubber |
| US5973017A (en) * | 1996-11-20 | 1999-10-26 | Toyoda Gosei Co., Ltd. | Foamed rubber blend containing and ethylene-propylene-diene polymer blend and an article formed from a sulfur-vulcanized foamed rubber blend |
| EP1186631A1 (en) * | 2000-09-08 | 2002-03-13 | JSR Corporation | Rubber composition of high and low molecular weight EPDM |
| JP2005255824A (en) * | 2004-03-11 | 2005-09-22 | Sumitomo Chemical Co Ltd | ETHYLENE-alpha-OLEFIN-NONCONJUGATED DIENE COPOLYMER RUBBER |
| CN101838365A (en) * | 2009-03-18 | 2010-09-22 | 中国石油天然气股份有限公司 | Synthesis method of bimodal distribution ethylene-alpha-olefin-non-conjugated diene random copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111499788A (en) | 2020-08-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105189578B (en) | Sponge polymer with controlled long chain branched and wide molecular weight distribution | |
| CN101709105B (en) | Ethylene-propylene-diene methylene using liquid-state oligomers of diolefin as third monomer and method for preparing same | |
| CN105985472B (en) | A kind of preparation method of rare earth catalyst and preparation method thereof and polyisoprene | |
| CN102532368B (en) | Rare earth catalyst and method for polymerizing conjugated diene by using same | |
| CN102863590A (en) | Preparation method of EPDM (Ethylene-Propylene-Diene Monomer) rubber | |
| CN108864348A (en) | A kind of ethylene-alpha-olefin-non-conjugated diene hydrocarbon polymer and preparation method thereof | |
| CN111499788B (en) | Ethylene-propylene-non-conjugated diene copolymer and synthesis method thereof | |
| Passaglia et al. | Functionalization of polyolefins by reactive processing: influence of starting reagents on content and type of grafted groups | |
| US6887956B2 (en) | Catalyst system for high-cis polybutadiene | |
| CN105330773A (en) | Composition for rare earth catalyst, rare earth catalyst, and preparation method and application thereof | |
| CN111087499B (en) | Ziegler-Natta catalyst system and use thereof and polyolefin and olefin polymerization | |
| CN102558414A (en) | Synthesis Method of Bimodal Distribution Ethylene-Propylene-Non-conjugated Diene Random Copolymer | |
| CN109836524B (en) | Catalyst composition, ethylene-alpha-olefin polymer and preparation method thereof | |
| CN110938157B (en) | Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof | |
| CN105330763A (en) | Composition for rare earth catalyst, rare earth catalyst, preparation method and application thereof, and olefin polymerization method | |
| WO2003102041A1 (en) | A two-step butadiene polymerization process for manufacturing high-cis 1,4-ploybutadiene | |
| JP2014031403A (en) | Method for producing polymerization catalyst composition and polymerization catalyst composition | |
| CN110938160B (en) | Catalyst system for olefin polymerization and prepolymerized catalyst composition and use thereof | |
| CN106519094B (en) | It is branched cis-1,4-polyisoprene and collateralization cis-1,4-polyisoprene composition and preparation method thereof | |
| RU2500689C1 (en) | Method of producing cis-1,4-polydienes | |
| JPH11193308A (en) | Polybutadiene and preparation thereof | |
| RU2432365C1 (en) | Method of producing catalyst for (co) | |
| Akhmetov et al. | The modification of cis-1, 4-polybutadiene with copolymers of maleic anhydride and α-olefin: the influence of the nature of the α-olefin | |
| KR100403090B1 (en) | A process for preparation of high 1,4-cis polybutadiene | |
| CN106749780A (en) | Preparation method of rare earth polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |