CN115386022A - Hydroxyl modified ethylene propylene diene monomer rubber and preparation method thereof - Google Patents
Hydroxyl modified ethylene propylene diene monomer rubber and preparation method thereof Download PDFInfo
- Publication number
- CN115386022A CN115386022A CN202110570978.1A CN202110570978A CN115386022A CN 115386022 A CN115386022 A CN 115386022A CN 202110570978 A CN202110570978 A CN 202110570978A CN 115386022 A CN115386022 A CN 115386022A
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- CN
- China
- Prior art keywords
- diene monomer
- propylene
- modified ethylene
- rubber
- substituted
- Prior art date
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- 229920002943 EPDM rubber Polymers 0.000 title claims abstract description 179
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 239000000178 monomer Substances 0.000 claims abstract description 35
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000005977 Ethylene Substances 0.000 claims abstract description 25
- 150000001993 dienes Chemical class 0.000 claims abstract description 19
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 68
- 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 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 18
- 238000005686 cross metathesis reaction Methods 0.000 claims description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 16
- 150000001336 alkenes Chemical class 0.000 claims description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 14
- -1 halide ion Chemical class 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- QGFSQVPRCWJZQK-UHFFFAOYSA-N 9-Decen-1-ol Chemical compound OCCCCCCCCC=C QGFSQVPRCWJZQK-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 150000002461 imidazolidines Chemical class 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 claims description 4
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- LQAVWYMTUMSFBE-UHFFFAOYSA-N pent-4-en-1-ol Chemical compound OCCCC=C LQAVWYMTUMSFBE-UHFFFAOYSA-N 0.000 claims description 4
- WRYCSMQKUKOKBP-UHFFFAOYSA-N Imidazolidine Chemical compound C1CNCN1 WRYCSMQKUKOKBP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000004644 alkyl sulfinyl group Chemical group 0.000 claims description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 3
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000000304 alkynyl group Chemical group 0.000 claims description 3
- 125000005133 alkynyloxy group Chemical group 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- UIZVMOZAXAMASY-UHFFFAOYSA-N hex-5-en-1-ol Chemical compound OCCCCC=C UIZVMOZAXAMASY-UHFFFAOYSA-N 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000007942 carboxylates Chemical group 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- WXPWPYISTQCNDP-UHFFFAOYSA-N oct-7-en-1-ol Chemical compound OCCCCCCC=C WXPWPYISTQCNDP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 150000003568 thioethers Chemical class 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 2
- 239000000460 chlorine Substances 0.000 claims 2
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- 150000002500 ions Chemical class 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 abstract description 18
- 229920001971 elastomer Polymers 0.000 abstract description 13
- 239000005060 rubber Substances 0.000 abstract description 13
- 239000000243 solution Substances 0.000 description 39
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 26
- 238000012360 testing method Methods 0.000 description 17
- 239000002244 precipitate Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 229920000459 Nitrile rubber Polymers 0.000 description 8
- 238000007792 addition Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 7
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001733 carboxylic acid esters Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 229920006112 polar polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 125000004711 1,1-dimethylethylthio group Chemical group CC(C)(S*)C 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000202296 Delphinium Species 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
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- 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
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000005070 decynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000006216 methylsulfinyl group Chemical group [H]C([H])([H])S(*)=O 0.000 description 1
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- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000005069 octynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- DZQQRNFLQBSVBN-UHFFFAOYSA-N tri(butan-2-yl)phosphane Chemical compound CCC(C)P(C(C)CC)C(C)CC DZQQRNFLQBSVBN-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- FPZZZGJWXOHLDJ-UHFFFAOYSA-N trihexylphosphane Chemical compound CCCCCCP(CCCCCC)CCCCCC FPZZZGJWXOHLDJ-UHFFFAOYSA-N 0.000 description 1
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 1
- IWPNEBZUNGZQQQ-UHFFFAOYSA-N tripentylphosphane Chemical compound CCCCCP(CCCCC)CCCCC IWPNEBZUNGZQQQ-UHFFFAOYSA-N 0.000 description 1
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 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
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide 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
- C08F8/00—Chemical modification by after-treatment
-
- 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
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of rubber, and discloses hydroxyl modified ethylene propylene diene monomer rubber and a preparation method thereof. The modified ethylene-propylene-diene monomer rubber contains a first structural unit provided by ethylene, a second structural unit provided by propylene and a third structural unit provided by a non-conjugated diene monomer, and at least part of the third structural unit contains a compound grafting group derived from a structure shown in a formula (1); the modified ethylene propylene diene monomer has the characteristics of high unsaturation degree, high grafting rate and high vulcanization speed, and the preparation method has the characteristics of quick reaction, simple steps and easy implementation;
Description
Technical Field
The invention relates to the field of rubber, in particular to hydroxyl modified ethylene propylene diene monomer rubber and a preparation method thereof.
Background
The ethylene propylene diene monomer (ethylene propylene rubber) has excellent physical and chemical properties such as high elasticity, viscoelasticity, electrical insulation and the like, and is very prominent in application in aspects such as engineering plastic toughening, ozone aging resistance and the like. However, since ethylene propylene diene rubber is a nonpolar rubber, it is inferior in oil resistance, chemical resistance, self-adhesiveness and mutual adhesiveness, and it is expected that a rubber having a relatively excellent combination property can be obtained by combining with a diene rubber (e.g., natural rubber, butadiene rubber, nitrile rubber, chloroprene rubber, etc.). However, ethylene-propylene rubber has great difference with most diene rubbers in polarity and saturation, and is difficult to blend with polar polymers, so the application range of the ethylene-propylene rubber is limited to a certain extent.
The chemical modification of ethylene propylene diene monomer is to introduce other atoms or groups into the molecular chain through the chemical reaction of rubber to make the molecular chain have polarity or change the flexibility, so as to improve the compatibility of the ethylene propylene rubber and diene rubber, i.e. to introduce ester, acrylonitrile and other polar groups into the main chain of ethylene propylene rubber, and to use the modified ethylene propylene rubber as a co-used compatibilizer, so as to expand the application field of ethylene propylene rubber.
The grafting reaction mainly takes a thermo-mechanical chemical modification method and solution modification as main materials, common rubber mixing equipment in rubber processing can be used for carrying out the modification treatment, but the removal of residual monomers and initiators after the modification is finished is difficult, the obtained product has thick smell, the process condition requirement is strict, side reactions are not easy to control, the crosslinking of rubber is easy to cause, and the equipment cost is high.
The solution modification mainly comprises the step of chemically modifying ethylene propylene rubber by the initiation action of benzoyl peroxide and the like in a chemical solvent or an aqueous emulsion. However, in the existing solution modification method, various catalysts and assistants are used in the production process, the treatment after reaction is difficult, the environmental pollution is serious, the reaction process is still a free radical reaction, the initiation and reaction time is long, the reaction process is not easy to control, and side reactions such as crosslinking are easy to generate.
Therefore, it is important to modify the epdm to enhance its compatibility with polar polymers.
Disclosure of Invention
The invention aims to overcome the problem of low grafting rate and unsaturated degree of modified ethylene propylene diene monomer in the prior art, and provides hydroxyl modified ethylene propylene diene monomer and a preparation method thereof.
In order to achieve the above object, a first aspect of the present invention provides a hydroxyl-modified ethylene-propylene-diene rubber, wherein the hydroxyl-modified ethylene-propylene-diene rubber contains a first structural unit provided by ethylene, a second structural unit provided by propylene, and a third structural unit provided by a non-conjugated diene monomer, and at least a part of the third structural unit contains a compound graft group derived from a structure represented by formula (1);
wherein, in the formula (1), n 1 Is an integer of 1 to 20, m 1 Is an integer from 2 to 40.
The second aspect of the invention provides a preparation method of hydroxyl modified ethylene propylene diene monomer, wherein the preparation method comprises the following steps: contacting an ethylene-propylene-diene monomer rubber with a compound derived from a structure represented by formula (2) in an organic solvent in the presence of a ruthenium carbene-type catalyst under the condition of olefin cross metathesis reaction, wherein the ethylene-propylene-diene monomer rubber contains a first structural unit provided by ethylene, a second structural unit provided by propylene and a third structural unit provided by a non-conjugated diene monomer;
in the formula (2), n 2 Is an integer of 1 to 20, m 2 Is an integer of 2 to 40.
The third aspect of the invention provides the hydroxyl modified ethylene propylene diene monomer prepared by the preparation method.
Through the technical scheme, the technical scheme provided by the invention has the following beneficial effects:
the invention adopts the ruthenium carbene type catalyst with the structure shown in the formula (3) to catalyze the olefin cross metathesis reaction of the ethylene propylene diene rubber and the compound derived from the structure shown in the formula (1) to ensure that the unsaturation degree of the prepared modified ethylene propylene diene rubber is 0.56-1mol/kg.
Furthermore, the hydroxyl modified ethylene propylene diene monomer provided by the invention also has high grafting rate. Specifically, the grafting ratio of the modified ethylene propylene diene monomer provided by the invention is 1.1-13.5 wt% based on the weight of the modified ethylene propylene diene monomer.
Furthermore, compared with unmodified ethylene propylene diene monomer, the hydroxyl modified ethylene propylene diene monomer provided by the invention has a certain improvement in vulcanization speed, and the possible reason is that after the compound derived from the structure shown in the formula (1) and the ethylene propylene diene monomer are subjected to an olefin ring-opening cross metathesis reaction, the double bond content of a side chain of the ethylene propylene diene monomer can be increased, the vulcanization process is facilitated, and the vulcanization speed of the modified ethylene propylene diene monomer is improved.
Furthermore, the hydroxyl modified ethylene propylene diene monomer provided by the invention has a good compatibilization effect when ethylene propylene rubber and polar rubber are used together.
Furthermore, the preparation method of the hydroxyl modified ethylene propylene diene monomer provided by the invention has the characteristics of quick reaction, simplicity and easiness in implementation.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
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.
According to a first aspect of the present invention, there is provided a hydroxyl-modified ethylene-propylene-diene rubber, wherein the hydroxyl-modified ethylene-propylene-diene rubber contains a first structural unit provided by ethylene, a second structural unit provided by propylene, and a third structural unit provided by a non-conjugated diene monomer, and at least part of the third structural unit contains a compound graft group derived from a structure represented by formula (1);
wherein, in the formula (1), n 1 Is an integer of 1 to 20, m 1 Is an integer of 2 to 40.
Compared with unmodified ethylene propylene diene monomer, the modified ethylene propylene diene monomer provided by the invention has the main improvement that hydroxyl is introduced into the side chain of the modified ethylene propylene diene monomer, the polarity of the ethylene propylene rubber is improved, the content of double bonds in the side chain of the modified ethylene propylene diene monomer is increased, the vulcanization speed is improved, and the modified ethylene propylene rubber has a good compatibilization effect when the ethylene propylene rubber and the polar rubber are used together. In addition, in the preparation method provided by the invention, the organic solvent is used for dissolving the ethylene propylene rubber, the catalyst and the modified monomer into a homogeneous solution, so that the contact probability of the catalyst, the monomer and the ethylene propylene rubber is increased, and the grafting efficiency is improved; the ruthenium carbene catalyst has the advantages of high initiation activity and mild reaction conditions.
According to the invention, in formula (1), n 1 Is an integer of 3 to 10, m 1 Is an integer from 6 to 20; more preferably, the compound with the structure shown in the formula (1) is selected from one or more of 4-pentenyl-1-alcohol, 9-decenyl-1-alcohol, 2-propenyl-1-alcohol, 5-hexenyl-1-alcohol and 7-octenyl-1-alcohol; still more preferably, the compound of the structure represented by the formula (1) is 4-pentenyl-1-ol and, 9-decenyl-1-ol and 2-propenyl-1-ol-one or more of alcohols.
According to the invention, in view of further improving the vulcanization speed of the modified ethylene propylene diene monomer, the unsaturation degree of the hydroxyl modified ethylene propylene diene monomer is 0.56-1mol/kg, preferably 0.56-0.87mol/kg; more preferably 0.73 to 0.87mol/kg, and still more preferably 0.8 to 0.87mol/kg. In addition, in the present invention, the unsaturation degree of the modified ethylene propylene diene rubber may be, for example, any value in the range of 0.56mol/kg, 0.58mol/kg, 0.73mol/kg, 0.77mol/kg, 0.8mol/kg, 0.82mol/kg, 0.84mol/kg, 0.85mol/kg, 0.87mol/kg, and 1mol/kg, and any two of these values.
The unsaturation degree of the hydroxyl modified ethylene propylene diene monomer rubber is measured by an iodometry method.
In the present invention, the third structural unit may be a compound containing a structure derived from the compound represented by the formula (2) in its entirety, or a part of the third structural unit may be a compound containing a structure derived from the compound represented by the formula (2). From the viewpoint of further increasing the vulcanization speed of the modified ethylene-propylene-diene rubber, the graft ratio of the modified ethylene-propylene-diene rubber is preferably 1.1 to 13.5% by weight, preferably 2.5 to 13.5% by weight, more preferably 3.3 to 13.5% by weight, more preferably 4.3 to 13.5% by weight, still more preferably 7.5 to 13.5% by weight, and most preferably 10 to 13.5% by weight, based on the weight of the hydroxyl-modified ethylene-propylene-diene rubber. In the present invention, the graft ratio of the hydroxyl-modified ethylene-propylene-diene rubber may be, for example, 1.1 wt%, 2.5 wt%, 3.3 wt%, 3.9 wt%, 4.3 wt%, 4.5 wt%, 4.9 wt%, 5.1 wt%, 5.2 wt%, 7.5 wt%, 10 wt%, and 13.5 wt%, or any two of these values.
In the present invention, the graft ratio is the mass content of the compound derived from the structure represented by formula (1) in the modified ethylene-propylene-diene rubber.
According to the invention, the third monomer may be a non-conjugated diene commonly used in the art, based on the capability of olefin cross-metathesis reaction between the ethylene-propylene-diene monomer and the compound having the structure represented by formula (2), such as one or more of 1, 4-hexadiene, dicyclopentadiene (DCPD) and 5-ethylidene-2-norbornene, and dicyclopentadiene is preferred in order to obtain a higher grafting ratio to increase the vulcanization speed of the modified ethylene-propylene-diene monomer.
Preferably, when the third monomer is dicyclopentadiene (DCPD), at least part of the third structural units containing the grafting groups have the structure shown in the formula (I),
formula (I), n 1 Is an integer of 1 to 20, m 1 Is an integer of 2 to 40.
When the third monomer is dicyclopentadiene (DCPD), at least part of the third structural units also contain structural units shown in a formula (II) from the viewpoint of further improving the vulcanization speed of the modified ethylene propylene diene monomer,
in the present invention, the structural units in the ethylene-propylene-diene monomer rubber are mainly an ethylene structural unit having a structure represented by formula (III) and a propylene structural unit having a structure represented by formula (IV), and a structural unit derived from a third monomer is referred to as a third structural unit,
according to the modified ethylene propylene diene rubber, the modified ethylene propylene diene rubber is preferably obtained by contacting the ethylene propylene diene rubber with a compound derived from a structure shown as a formula (1) under the condition of olefin cross metathesis reaction.
According to the modified ethylene propylene diene monomer, the ethylene propylene diene monomer is subject to olefin cross metathesis reaction with a compound derived from a structure shown in a formula (1), the content of a first structural unit provided by ethylene is 50-70wt%, and the content of a third structural unit provided by a non-conjugated diene monomer is 4-8wt%; preferably, the content of the first structural unit provided by ethylene is 55-65 wt% and the content of the third structural unit provided by the non-conjugated diene monomer is 5-7 wt% based on the total weight of the modified ethylene propylene diene monomer.
According to the invention, the weight average molecular weight of the modified ethylene propylene diene monomer rubber is 10-40 ten thousand, preferably 12-30 ten thousand, and preferably 12-20 ten thousand.
The weight average molecular weight of the modified ethylene propylene diene rubber of the present invention is measured by a Gel Permeation Chromatography (GPC) method.
The modified ethylene propylene diene rubber is prepared by the method described below.
The second aspect of the invention provides a preparation method of hydroxyl modified ethylene propylene diene monomer, wherein the preparation method comprises the following steps: contacting an ethylene-propylene-diene monomer rubber with a compound derived from a structure represented by formula (2) in an organic solvent in the presence of a ruthenium carbene-type catalyst under the condition of olefin cross metathesis reaction, wherein the ethylene-propylene-diene monomer rubber contains a first structural unit provided by ethylene, a second structural unit provided by propylene and a third structural unit provided by a non-conjugated diene monomer;
in the formula (2), n 2 Is an integer of 1 to 20, m 2 Is an integer of 2 to 40.
According to the invention, n is preferably 2 Is an integer of 3 to 10, m 2 Is an integer from 6 to 20; more preferably, the compound with the structure shown in the formula (1) is selected from one or more of 4-pentene-1-ol, 9-decen-1-ol, 2-propene-1-ol, 5-hexene-1-ol and 7-octene-1-ol; still more preferably, the compound having a structure represented by formula (1) is one or more of 4-penten-1-ol and 9-decen-1-ol and 2-propen-1-ol. In addition, in the present invention, the,it is noted that 2-propen-1-ol, also known as allyl alcohol, CAS number 107-18-6.
According to the invention, the catalyst has a structure represented by formula (3);
according to the invention, in formula (3), R 1 Is hydrogen, C 2 -C 20 Substituted or unsubstituted alkenyl of, C 2 -C 20 Substituted or unsubstituted alkynyl of (A), C 1 -C 20 Substituted or unsubstituted alkyl of, C 6 -C 20 Substituted or unsubstituted aryl of (1), C 2 -C 20 Substituted or unsubstituted carboxylate group of (A), C 1 -C 20 Substituted or unsubstituted alkoxy of (1), C 2 -C 20 Substituted or unsubstituted alkenyloxy, C 2 -C 20 Substituted or unsubstituted alkynyloxy of (A), C 6 -C 20 Substituted or unsubstituted aryloxy of (A), C 1 -C 20 Substituted or unsubstituted alkylthio of (2), C 1 -C 20 Substituted or unsubstituted alkylsulfonyl or C 1 -C 20 Substituted or unsubstituted alkylsulfinyl of (a);
according to the invention, in formula (3), X 1 And X 2 Can be various anionic ligands, such as X 1 And X 2 Each independently an anionic ligand.
According to the invention, in formula (3), L 1 And L 2 Each independently is a neutral ligand, and optionally L 1 And L 2 Can be linked to each other to form bidentate neutral ligands.
According to the invention, R is preferably 1 Is C 6 -C 20 The substituted or unsubstituted aryl group of (a) is preferably a phenyl group.
According to the invention, X is preferably 1 And X 2 Each independently a halide ion, preferably chloride.
According to the bookInvention, preferably, L 1 And L 2 Each independently a phosphine, amine, thioether, carbene, or a substituted or unsubstituted imidazolidine, preferably, L 1 And L 2 Each independently a phosphine, a carbene, or a substituted or unsubstituted imidazolidine.
According to the invention, more preferably, R 1 Is phenyl, L 1 Is a substituted or unsubstituted imidazolidine, L 2 Is phosphine, X 1 And X 2 Is chloride ion.
According to the invention, the phosphine may be a compound formed by partially or totally substituting hydrogen in various phosphine molecules with an organic group, preferably a trialkylphosphine, which organic groups may be identical or different and each may be selected from alkanyl groups (e.g. C) 1 -C 10 Alkyl of (2) or substituted or unsubstituted cycloalkyl (e.g. C) 6 -C 12 Substituted or unsubstituted cycloalkyl) of (a) preferably each selected from substituted or unsubstituted cycloalkyl, more preferably cyclohexyl. Specifically, examples of the phosphine may include, but are not limited to: one or more of trimethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-sec-butylphosphine, tripropylphosphine, tripentylphosphine, trihexylphosphine, trioctylphosphine and tricyclohexylphosphine.
According to the invention, L 1 Is a substituted or unsubstituted imidazolidine, L 1 Imidazolidine having a structure represented by the formula (4),
in the formula (4), R 2 And R 3 Identical or different, each independently of the others, is C 6 -C 20 Substituted or unsubstituted aryl of (a);
preferably, R 2 And R 3 Are the same or different and are each independently
R 4 、R 5 、R 6 、R 7 And R 8 Each independently selected from hydrogen or C 1 -C 5 Substituted or unsubstituted alkyl of (a);
preferably, in formula (3), R 2 And R 3 Is composed of
More preferably, R 2 And R 3 Are each independently
In the present invention, C 1 -C 5 Specific examples of the alkyl group of (a) may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and n-pentyl.
In a preferred embodiment of the present invention, in formula (3), R 1 Is phenyl, L 1 Is a substituted or unsubstituted imidazolidine, L 2 Is a phosphine, X 1 And X 2 Is chloride ion.
In a more preferred embodiment of the present invention, in formula (3), R 1 Is phenyl, L 1 Is composed of
L 2 Is a trialkylphosphine, X 1 And X 2 Is chloride ion.
According to the present invention, in order to provide the catalyst with a better catalytic effect, it is further preferable that the catalyst of the structure represented by formula (3) has a structure represented by formula (5):
in the above formula (5), PCy 3 Represents tricyclohexylphosphine, ph represents phenyl.
The catalyst represented by the above formula (5) can be obtained commercially.
According to the invention, substituted or unsubstituted C 2 -C 20 The alkenyl group (b) may be linear or branched, and specific examples may includeBut are not limited to: vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl.
According to the invention, substituted or unsubstituted C 2 -C 20 The alkynyl group of (a) may be linear or branched, and specific examples may include, but are not limited to: ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and decynyl.
According to the invention, substituted or unsubstituted C 1 -C 20 The alkyl group of (a) may be linear or branched, and specific examples may include, but are not limited to: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl, undecyl, dodecyl, octadecyl.
According to the invention, substituted or unsubstituted C 6 -C 20 Specific examples of the aryl group of (a) may include, but are not limited to: phenyl, methylphenyl, naphthyl.
According to the invention, substituted or unsubstituted C 2 -C 20 The carboxylic ester group means that the carboxylic ester group contains in the molecular chain
Specific examples may include, but are not limited to: methyl propionate, ethyl acetate and propyl formate.
According to the invention, substituted or unsubstituted C 1 -C 20 Specific examples of the alkoxy group of (a) may include, but are not limited to: methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, octadecyloxy.
According to the invention, substituted or unsubstituted C 2 -C 20 Specific examples of the alkenyloxy group of (a) may include, but are not limited to: 1-allyloxy, 2-alkenylbutoxy, 1-alkenylpentoxy.
According to the invention, substituted or unsubstituted C 2 -C 20 Specific examples of the alkynyloxy group of (a) may include, but are not limited to: 1-alkynylpropoxy, 2-alkynylbutoxy, 1-alkynylpentyloxy.
According to the invention, substituted or unsubstituted C 6 -C 20 Specific examples of the aryloxy group of (a) may include, but are not limited to: phenoxy, naphthyloxy.
According to the invention, substituted or unsubstituted C 1 -C 20 Alkylthio of (C) is a straight-chain or branched C bonded through a sulfur atom 1 -C 20 Alkyl groups, specific examples include, but are not limited to: methylthio (CH) 3 -S-), ethylthio, propylthio, butylthio, pentylthio, 1-methylpropylthio, 2-methylpropylthio and 1, 1-dimethylethylthio.
According to the invention, substituted or unsubstituted C 1 -C 20 Specific examples of the alkylsulfonyl group of (a) may include, but are not limited to: methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, nonylsulfonyl.
According to the invention, substituted or unsubstituted C 1 -C 20 Specific examples of the alkylsulfinyl group of (a) may include, but are not limited to: methylsulfinyl, ethylsulfinyl.
According to the invention, the third monomer may be a non-conjugated diene commonly used in the art, such as one or more of 1, 4-hexadiene, dicyclopentadiene (DCPD) and 5-ethylidene-2-norbornene, to enable the ethylene-propylene-diene monomer to undergo olefin cross-metathesis with the compound having the structure shown in formula (2), and preferably dicyclopentadiene (DCPD) in order to obtain higher grafting ratio to increase the vulcanization speed and the compatibilization of the modified ethylene-propylene-diene monomer.
According to the invention, the amounts of the ethylene-propylene-diene rubber, the compound of formula (2) and the catalyst may vary within wide limits, as long as the aim of achieving a rapid reaction and obtaining a modified ethylene-propylene-diene rubber having a high target saturation and grafting yield is achieved, the amount of the compound derived from formula (2) being 0.05 to 40 parts by weight, preferably 1 to 25 parts by weight, more preferably 9 to 18 parts by weight, relative to 100 parts by weight of the ethylene-propylene-diene rubber; the catalyst is used in an amount of 0.05 to 10 parts by weight, preferably 0.2 to 5 parts by weight, more preferably 0.5 to 5 parts by weight.
According to the invention, the ethylene-propylene-diene monomer rubber is subject to olefin cross metathesis reaction with a compound with a structure shown in a formula (2), wherein the ethylene-propylene-diene monomer rubber contains 50-70wt% of ethylene structural units and 4-8wt% of structural units derived from a third monomer; preferably, the ethylene-propylene-diene monomer contains the first structural unit provided by ethylene in an amount of 55 to 65 wt% and the third structural unit provided by a non-conjugated diene monomer in an amount of 5 to 7 wt%, based on the total weight of the ethylene-propylene-diene monomer.
In the invention, the total content of a first structural unit provided by ethylene, a second structural unit provided by propylene and a third structural unit provided by a non-conjugated diene monomer in the modified ethylene propylene diene monomer is 100wt% based on the weight of the modified ethylene propylene diene monomer.
Preferably, the weight average molecular weight of the ethylene propylene diene monomer is 10-40 ten thousand, preferably 12-30 ten thousand, and more preferably 12-20 ten thousand.
According to the invention, the cross-metathesis reaction of the olefins is preferably carried out under an inert atmosphere. The inert atmosphere refers to a gas that does not participate in the reaction, such as: nitrogen and a gas of a group zero element of the periodic table, such as argon.
According to the invention, the conditions of the cross-metathesis reaction of the olefins comprise: the reaction temperature is 0 to 150 ℃, preferably 20 to 100 ℃, more preferably 70 to 100 ℃. The reaction time can be suitably selected depending on the reaction temperature, and for example, the reaction time is 0.1 to 5 hours, preferably 0.1 to 3 hours.
In the invention, the reaction is carried out under the temperature and time conditions, and the advantages are that the grafting efficiency is higher, if the temperature is too high, the stability of the catalyst is reduced, and the grafting efficiency is reduced; if the temperature is too low, the catalyst initiation is slow and the grafting efficiency decreases.
According to the present invention, the manner of adding the catalyst is not particularly limited, and the catalyst may be added to the reaction system of the ethylene propylene diene monomer and the compound having the structure represented by formula (2) in a single addition manner or in a plurality of additions. In view of the fact that the addition of the catalyst at one time is likely to cause a side reaction of the compound having the structure represented by formula (2) in the reaction system, it is preferable to add the catalyst in divided portions. More preferably, the catalyst is added into the reaction system for 2 to 6 times, the time interval between two adjacent times of addition is 3 to 15min, and the difference between the catalyst addition amount of any two times accounts for less than 5 weight percent of the total catalyst addition amount, so that the addition of the catalyst is beneficial to improving the grafting rate of the modified ethylene propylene diene rubber. Further preferably, in order to make the catalyst have better catalytic effect, the catalyst is added into the reaction system in a solution form (preferably, the catalyst is dissolved in the organic solvent) in 2-6 times, the adding time interval of two adjacent times is 3-15min, and the difference of the adding amount of the catalyst in any two times accounts for less than 5 wt% of the total adding amount of the catalyst, so that the adding of the catalyst is favorable for improving the grafting rate and the unsaturation degree of the modified ethylene propylene diene rubber.
According to the invention, the organic solvent for preparing the modified ethylene-propylene-diene rubber is selected from toluene, xylene, chlorobenzene, C 6 -C 12 Cycloalkane of (C) 5 -C 10 Further preferably, the organic solvent is one or more of toluene, xylene, chlorobenzene, cyclohexane, n-hexane, tetrahydrofuran, acetone and 1, 4-dioxane; most preferred is toluene and/or xylene. These solvents may be used alone or in combination.
According to the invention, the amount of the organic solvent is 85-3000mL relative to 100 parts by weight of the ethylene propylene diene monomer.
In addition, in the present invention, the organic solvent defined above is used, which has the effect of promoting the modified grafting reaction, and if the organic solvent of the present invention is not used, the grafting efficiency is lowered.
According to the invention, the preparation method of the modified ethylene propylene diene monomer further comprises a purification step. The purification step may be a conventional purification step in the art, for example, a reaction solution obtained after the reaction is filtered with a nickel mesh, and acetone is added to the filtrate to form a precipitate, and then the resulting precipitate is filtered, washed and dried.
The third aspect of the invention provides a hydroxyl modified ethylene propylene diene monomer prepared by the method.
The following preparations and examples relate to the following measurements of properties:
(1) The graft ratio was determined as follows:
the ethylene-propylene rubber (W1/g) and xylene are metered into a reaction flask protected by nitrogen, after the ethylene-propylene rubber is completely dissolved, the compound derived from the structure shown in formula (2) is added, and then the catalyst solution of formula (5) is added in portions. After the reaction is finished, precipitating the reaction product by acetone, dissolving residual reactants in a reaction bottle by a proper amount of dimethylbenzene, precipitating by acetone, performing Soxhlet extraction on all precipitates by DMF, and drying in vacuum at 60 ℃ to obtain the grafted product. The graft product was weighed (W2/g) and the graft ratio was calculated according to the following formula:
(2) The unsaturation degree of the modified ethylene propylene diene monomer is measured by an iodometry method, and the specific method is as follows: accurately weighing 2 g of modified ethylene propylene diene monomer sample, placing the sample in a 250mL conical flask with a ground opening, and adding 50mL of LCCl 4 Dissolving the sample, adding 20mL of iodine bromide (IBr) solution by a pipette, fully shaking, standing in the dark for 1h, then adding 10mL of 10 wt% potassium iodide solution, shaking up, titrating with 0.1N sodium thiosulfate standard solution until the solution is yellow, adding 5mL of starch indicator, and continuing to titrate until the blue color disappears to obtain the end point. And simultaneously performing a blank test. The unsaturation is calculated as follows:
in the formula, V 0 : the blank test consumes the volume, mL, of the sodium thiosulfate standard solution; v: the sample consumed the volume of sodium thiosulfate standard solution, mL; c: concentration of sodium thiosulfate standard solution, mol/L; m: sample mass, g. The unit of unsaturation in the formula is mol/kg.
(3) The weight average molecular weight of the modified ethylene propylene diene rubber was determined by means of Gel Permeation Chromatography (GPC) using a Waters 1515 Isocratic HPLC gel chromatograph.
Ethylene-propylene-diene monomer ESPRENE 305, available from sumitomo, having an ethylene structural unit content of 65 wt%, a third structural unit content of 7 wt% provided by a non-conjugated diene monomer, which is dicyclopentadiene (DCPD), and a weight average molecular weight of 12 ten thousand;
ethylene propylene diene monomer 3280, available from Yanshan petrochemical company, having an ethylene structural unit content of 55 wt%, a third structural unit content provided by a non-conjugated diene monomer of 5 wt%, and a weight average molecular weight of 30 ten thousand, wherein the non-conjugated diene monomer is ENB;
catalyst I: having the structure shown below, commercially available from lark technologies ltd;
catalyst II: having the structure shown below, commercially available from carbofuran technologies ltd;
catalyst III: having the structure shown below, commercially available from carbofuran technologies ltd;
wherein L is
PCy 3 Represents tricyclohexylphosphine;
carbon black N550, available from Shanghai Kabot chemical Co., ltd;
ASTM103# oil, available from ningbo co-evolution chemical ltd;
accelerator TMTD, available from shanghai essence-rubber science ltd;
sulfur, purchased from Shijiazhuang Ruiton chemical technology, inc.;
nitrile rubber: 3945, available from Langshen;
ethylene propylene rubber: 2450, available from Langshen;
examples and comparative examples all other materials were commercially available.
Example 1
This example is used to illustrate the modified ethylene propylene diene monomer and the preparation method thereof provided by the present invention.
9 g of ethylene-propylene-diene monomer (ESPRENE 305, available from Sumitomo Japan, having an ethylene structural unit content of 65% by weight and a structural unit derived from a third monomer of dicyclopentadiene (DCPD), 1.1 g of 2-propen-1-ol (commercially available from Bailingwei Tech., ltd., the same applies hereinafter) was mixed in N, to give a mixture having a weight average molecular weight of 12 ten thousand 2 Under protection, dissolving the mixture in 100mL of dimethylbenzene solution until the mixture is completely dissolved to form a reaction system; 0.045 g of a catalyst having a structure represented by formula (5) (commercially available from carbofuran technologies, ltd., the same applies hereinafter) was weighed and dissolved in 10mL of a xylene solution to obtain a catalyst solution C1.
Heating the obtained reaction system to 70 ℃, adding 2mL of catalyst solution C1 into the reaction system, after 5min of reaction, uniformly dividing the rest 8mL of catalyst solution C1 into 4 parts, adding into the reaction system in a manner of adding one part every 5min, and after the last part of catalyst solution C1 is added into the reaction system for 5min, stopping the reaction, wherein the total reaction time is 30min. After the reaction, the reaction solution was filtered with a nickel screen while it was hot, and acetone was added to the filtrate to remove impurities and precipitate. Separating out the precipitate, washing the precipitate with acetone until the filtrate is clear, and drying the precipitate in a vacuum oven at 60 ℃ for 14h to obtain the modified ethylene propylene diene monomer A1. The properties of the modified ethylene propylene diene rubber were analyzed and determined, and the results are shown in table 1.
Example 2
Modified ethylene-propylene-diene monomer was prepared in the same manner as in example 1, except that the reaction system was heated to 70 ℃ and then 10mL of the catalyst solution C1 was added to the reaction system at a time, followed by reaction for 30min. Obtaining the modified ethylene propylene diene monomer A2. The properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
Example 3
The modified ethylene propylene diene monomer was prepared in the same manner as in example 2, except that the reaction system was heated to 70 ℃ and then 10mL of the catalyst solution C1 was added to the reaction system in two portions, the addition time was 5mL each time when the reaction system was heated to 70 ℃ i.e. when the reaction started and after the reaction proceeded for 15min, and the reaction was stopped after 30min of reaction. Obtaining the modified ethylene propylene diene monomer A3. The properties of the modified ethylene propylene diene rubber were analyzed and determined, and the results are shown in table 1.
Comparative example 1
Ethylene propylene diene monomer (ESPRENE 305, available from sumitomo, having an ethylene structural unit content of 65 wt%, a structural unit derived from a third monomer of dicyclopentadiene (DCPD), i.e., unmodified ethylene propylene diene monomer, was used as a reference ethylene propylene diene monomer D1, and a weight average molecular weight of 12 ten thousand, and the results of the analytical measurement were performed on the reference ethylene propylene diene monomer D1, as shown in table 1.
Example 4
This example is used to illustrate the modified ethylene propylene diene monomer and the preparation method thereof provided by the present invention.
A modified ethylene-propylene-diene monomer was prepared in the same manner as in example 1, except that the reaction time was 1 hour, that is, the reaction was stopped 35 minutes after the last portion of the catalyst solution was added to the reaction system. Obtaining the modified ethylene propylene diene monomer A4. The properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
Example 5
Modified ethylene propylene diene monomer was prepared in the same manner as in example 1, except that the reaction system was heated to 40 ℃ to obtain modified ethylene propylene diene monomer A5. The properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
Example 6
A modified ethylene-propylene-diene rubber was produced in the same manner as in example 1, except that 0.82 g of 2-propen-1-ol was added to give a modified ethylene-propylene-diene rubber A6. The properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
Example 7
Modified ethylene-propylene-diene monomer rubber was prepared in the same manner as in example 1, except that 0.08 g of the catalyst having the structure represented by formula (5) was weighed and dissolved in 10mL of a xylene solution, and the solution was divided into 5 parts, and the manner of adding each part was the same as in example 1, to obtain modified ethylene-propylene-diene monomer rubber A7. The properties of the modified ethylene propylene diene rubber were analyzed and measured, and the results are shown in table 1.
Example 8
This example is used to illustrate the modified ethylene propylene diene monomer and the preparation method thereof provided by the present invention.
9 g of ethylene-propylene-diene rubber (ESPRENE 305, available from Sumitomo, japan) having an ethylene structural unit content of 65% by weight and a structural unit derived from a third monomer of dicyclopentadiene (DCPD) in an amount of 7% by weight and a weight-average molecular weight of 12 ten thousand, 0.1 g of 2-propen-1-ol in N 2 Under protection, dissolving the mixture in 100mL of dimethylbenzene solution until the mixture is completely dissolved to form a reaction system; 0.45 g of the catalyst having the structure represented by the formula (5) was weighed out and dissolved in 10mL of xyleneTo the solution, a catalyst solution C8 was obtained.
Heating the reaction system to 20 ℃, adding 2mL of catalyst solution C8 into the reaction system, after reacting for 5min, uniformly dividing the rest 8mL of catalyst solution C8 into 4 parts, adding one part of catalyst solution C8 into the reaction system every 5min, and stopping the reaction after the last part of catalyst solution C8 is added into the reaction system for 5min, wherein the total reaction time is 1h. After the reaction is finished, filtering the reaction solution with a nickel screen while the reaction solution is hot, adding acetone into the filtrate to remove impurities, and precipitating. Separating out the precipitate, washing the precipitate with acetone until the filtrate is clear, and drying the precipitate in a vacuum oven at 60 ℃ for 14h to obtain the modified ethylene propylene diene monomer A8. The properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
Example 9
This example is used to illustrate the modified ethylene propylene diene monomer and the preparation method thereof provided by the present invention.
9 g of ethylene propylene diene monomer (3280, available from Yanshan petrochemical company, containing 55 wt.% of ethylene structural units and 5 wt.% of structural units derived from a third monomer (ENB), 0.55 g of 2-propen-1-ol in N, and a weight average molecular weight of 30 ten thousand 2 Under protection, dissolving the mixture in 100mL of dimethylbenzene solution until the mixture is completely dissolved to form a reaction system; at the same time, 0.018 g of the catalyst having a structure represented by formula (5) was weighed and dissolved in 10mL of a xylene solution to obtain a catalyst solution C9.
Heating the reaction system to 100 ℃, adding 2mL of catalyst solution C9 into the reaction system, after reacting for 15min, uniformly dividing the rest 8mL of catalyst solution into 4 parts, adding one part of catalyst solution into the reaction system every 15min, and stopping the reaction after the last part of catalyst solution is added into the reaction system for 105min, wherein the total reaction time is 3h. After the reaction, the reaction solution was filtered with a nickel screen while it was hot, and acetone was added to the filtrate to remove impurities and precipitate. Separating out the precipitate, washing the precipitate with acetone until the filtrate is clear, and drying the precipitate in a vacuum oven at 60 ℃ for 14h to obtain the modified ethylene propylene diene monomer A9. The properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
Comparative example 2
Ethylene propylene diene monomer (3280, available from Yanshan petrochemical company, in which the content of ethylene structural units is 55 wt%, the content of structural units derived from a third monomer is 5 wt%, and the weight average molecular weight is 30 ten thousand) i.e., unmodified ethylene propylene diene monomer was used as reference ethylene propylene rubber D2, and the analysis and determination were performed on the reference ethylene propylene diene monomer D2, and the results are shown in Table 1.
Example 10
A modified ethylene-propylene-diene monomer rubber was produced in the same manner as in example 1, except that a catalyst having a structure represented by formula (6) (commercially available from carbofuran technologies ltd.) was used in place of the catalyst having a structure represented by formula (5), to obtain a modified ethylene-propylene-diene monomer rubber a10. The properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
In the above formula (6), PCy 3 Represents tricyclohexylphosphine, ph represents phenyl.
Example 11
A modified ethylene-propylene-diene rubber was prepared in the same manner as in example 1, except that a catalyst having a structure represented by formula (7) (commercially available from Bailingwei science and technology Co., ltd.) was used in place of the catalyst having a structure represented by formula (5), to obtain a modified ethylene-propylene-diene rubber A11. The properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
In the above formula (7), L is
PCy 3 Represents tricyclohexylphosphine.
Example 12
A modified ethylene-propylene-diene rubber was prepared in the same manner as in example 1, except that 1.3 g of 4-penten-1-ol (commercially available from carbofuran technologies, ltd.) was added to obtain a modified ethylene-propylene-diene rubber A12. The properties of the modified ethylene propylene diene monomer rubber were analyzed and determined, respectively, and the results are shown in table 1.
Example 13
A modified ethylene-propylene-diene rubber was prepared in the same manner as in example 1, except that 2.2 g of 9-decen-1-ol (commercially available from carbofuran technologies, ltd.) was added to obtain a modified ethylene-propylene-diene rubber A13. The properties of the modified ethylene propylene diene rubber were analyzed and measured, and the results are shown in table 1.
TABLE 1
As can be seen from Table 1, the compound derived from the structure represented by the formula (2) can be grafted onto ethylene-propylene-diene rubber by cross-metathesis reaction using olefin, and the grafting ratio is relatively high and the reaction is rapid.
Comparing example 1 and example 9 with comparative example 1 and comparative example 2 (unmodified ethylene propylene diene monomer), the modified ethylene propylene diene monomer obtained in example 1 and example 9 of the present invention has an unsaturation degree of 0.85mol/kg and 0.58mol/kg, and the unsaturation degree is significantly improved compared with the unmodified ethylene propylene diene monomer, because the present invention increases the side chain double bonds of the ethylene propylene diene monomer after the 2-propylene-1-ol and the ethylene propylene diene monomer are subjected to olefin cross metathesis reaction.
Comparing example 1 with example 2, it can be seen that the grafting ratio of the modified ethylene propylene diene rubber obtained by the method of dropping the catalyst in several times is higher, which is probably because the catalyst concentration in the system is higher after the catalyst is added once, and the 2-propylene-1-alcohol is easy to generate cross metathesis side reaction, so that the amount of the 2-propylene-1-alcohol participating in the grafting reaction is reduced, and finally the grafting ratio is reduced. Further, from examples 2 to 13, it can be seen that the degree of reaction can be effectively controlled by adjusting the reaction conditions, so that a modified ethylene-propylene-diene rubber having a desired graft ratio can be obtained.
Test example 1
The modified ethylene-propylene-diene rubbers A1 to A13 prepared in examples 1 to 13 of the present invention were subjected to vulcanization property measurement in accordance with the following methods.
100 parts by weight of the modified ethylene propylene diene monomer A1 prepared in the examples of the present invention was placed on a two-roll kneader, and 5 parts by weight of active zinc oxide, 1 part by weight of stearic acid, 80 parts by weight of carbon black (N550, shanghai Kabot chemical Co., ltd.), 50 parts by weight of ASTM103# oil (Ningbo Co. Evolution chemical Co., ltd.), 1 part by weight of accelerator TMTD (Shanghai Fine-rubber science Co., ltd.), and 1.5 parts by weight of sulfur (Shijiazhuang Sha Tou chemical science Co., ltd.) were sequentially added at a temperature of 35. + -. 5 ℃ to the two-roll kneader, and the mixture was uniformly mixed and kneaded for 21 minutes to obtain a blend. And vulcanizing the blend for 15 minutes on a hydraulic flat vulcanizing machine with the temperature of 160 ℃ and the pressure of 15MPa to obtain the vulcanized ethylene propylene diene monomer rubber sheet.
The vulcanized ethylene propylene diene monomer rubber sheets were tested according to the method in GB/T16584-1996, and the positive vulcanization time TC90 as a vulcanization speed parameter was recorded, and the test results are shown in Table 2.
The modified ethylene propylene diene monomer rubber A1-A13 is subjected to vulcanization performance measurement according to the method, and the test results are shown in Table 2.
Comparative test example 1
An ethylene-propylene-diene rubber sheet was prepared in the same manner as in test example 1, except that a commercially available ethylene-propylene-diene rubber D1 (ESPRENE 305, available from sumitomo, japan) having an ethylene structural unit content of 65% by weight, an ethylene structural unit content derived from a third monomer which is dicyclopentadiene (DCPD) of 7% by weight and a weight average molecular weight of 12 ten thousand was used in place of the modified ethylene-propylene-diene rubber. The test results are shown in Table 2.
Comparative test example 2
An ethylene propylene diene rubber sheet was prepared in the same manner as in test example 1, except that a modified ethylene propylene diene rubber was replaced with a commercially available ethylene propylene diene rubber D2 (3280, available from delphinium petrochemical company, having an ethylene structural unit content of 55 wt%, a structural unit derived from a third monomer having a weight average molecular weight of 30 ten thousand, which was ENB). The test results are shown in Table 2.
TABLE 2
Remarking: the unit of TC90 is min.
As can be seen from the data in Table 2, compared with the unmodified EPDM, the vulcanization speed of the modified EPDM provided by the invention is obviously improved, mainly because the hydroxyl-containing compound shown in formula (1) is introduced into the modified EPDM, and the unsaturation degree is also improved to a certain degree.
Test example 2
The modified ethylene-propylene-diene rubbers A1 to A13 prepared in examples 1 to 13 of the present invention were subjected to compatibilization measurement according to the following methods.
Taking the use of the ethylene propylene rubber and the nitrile rubber as an example, a carbon black master batch method mixing process is adopted, the compatibilization effect of the ethylene propylene rubber/nitrile rubber combined rubber derived from the grafting of the ethylene propylene rubber by the structural compound shown in the formula (2) is preliminarily examined, and the basic formula (parts by mass) is as follows: nitrile rubber (3945, langer) 70, ethylene-propylene rubber (2450, langer) 30, modified ethylene-propylene rubber 5, anti-aging agent (commercially available) MB 1, stearic acid (commercially available) 0.5, paraffin wax (commercially available) 1, carbon black (brand N330, product of shanghai cabot chemical limited) 40, polystyrene (commercially available) 10, dioctyl phthalate (commercially available) 12, dicumyl peroxide (commercially available) 3, trimethylolpropane trimethacrylate 1 (commercially available), trimethylolmethylamine (commercially available) 0.5, triallylisocyanurate (commercially available) 2.
Tensile strength was measured according to the method in GB 528-1998, and the results are shown in Table 3.
The vulcanized ethylene propylene diene monomer and the vulcanized nitrile rubber are tested by using a rubber sheet according to the method in GB/T16584-1996, and the vulcanization speed parameter, namely the positive vulcanization time TC90 is recorded, and the test results are shown in Table 3.
Comparative test example 3
A blend of ethylene propylene rubber and nitrile rubber was prepared in the same manner as in test example 2, except that no modified ethylene propylene rubber was added during the test, and the test results are shown in Table 3.
TABLE 3
| Examples | A1 | D3 | A2 | A3 | A4 | A5 | A6 | A7 | A8 | A9 | A10 | A11 | A12 | A13 |
| Intensity a | 12.9 | 10.1 | 11.8 | 12.5 | 13 | 12.2 | 12.6 | 13.1 | 11 | 11.3 | 12.4 | 12.6 | 12.8 | 12.9 |
| TC90 | 10.5 | 13.5 | 11.5 | 10.9 | 10.4 | 11.1 | 10.8 | 10.3 | 12.8 | 12 | 10.9 | 10.8 | 10.7 | 10.8 |
The unit of strength (tensile strength at break) is MPa; the unit of TC90 is min.
As can be seen from the data in Table 3, the vulcanization speed is obviously improved and the breaking strength of the vulcanized rubber is also obviously improved by adding a small amount of the modified graft copolymer into the ethylene propylene rubber and nitrile rubber blended rubber. This shows that the modified ethylene propylene diene rubber provided by the invention has better compatibilization effect.
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 various technical features being combined 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 (17)
1. A hydroxyl-modified ethylene-propylene-diene monomer rubber, characterized in that the hydroxyl-modified ethylene-propylene-diene monomer rubber contains a first structural unit provided by ethylene, a second structural unit provided by propylene and a third structural unit provided by a non-conjugated diene monomer, and at least part of the third structural unit contains a compound graft group derived from a structure represented by formula (1);
wherein, in the formula (1), n 1 Is an integer of 1 to 20, m 1 Is an integer from 2 to 40.
2. The modified ethylene-propylene-diene rubber according to claim 1, wherein in formula (1), n is 1 Is an integer of 3 to 10, m 1 Is an integer from 6 to 20;
preferably, the compound graft group having the structure represented by formula (1) is selected from one or more of 4-pentenyl-1-ol, 9-decenyl-1-ol, 2-propenyl-1-ol, 5-hexenyl-1-ol and 7-octenyl-1-ol.
3. The modified ethylene-propylene-diene rubber of claim 1, wherein the non-conjugated diene monomer is selected from one or more of 1, 4-hexadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene.
4. The modified ethylene propylene diene monomer according to claim 1, wherein the third monomer is dicyclopentadiene, at least a part of the third structural units containing the grafting groups have a structure represented by formula (I),
formula (I), n 1 Is an integer of 1 to 20, m 1 Is an integer of 2 to 40. .
5. The modified ethylene propylene diene monomer according to claim 1, wherein the unsaturation degree of the modified ethylene propylene diene monomer is 0.56-1mol/kg, preferably 0.56-0.87mol/kg;
preferably, the grafting ratio of the modified ethylene propylene diene monomer is 1.1-13.5 wt% based on the weight of the modified ethylene propylene diene monomer.
6. The modified ethylene-propylene-diene rubber of any one of claims 1 to 5, wherein ethylene provides from 50 to 70wt% of first structural units and the non-conjugated diene monomer provides from 4 to 8wt% of third structural units, based on the weight of the modified ethylene-propylene-diene rubber;
preferably, the weight average molecular weight of the modified ethylene propylene diene monomer is 10-40 ten thousand, and preferably 12-30 ten thousand.
7. A preparation method of hydroxyl modified ethylene propylene diene monomer is characterized by comprising the following steps: contacting an ethylene-propylene-diene monomer rubber with a compound derived from a structure represented by formula (2) in an organic solvent in the presence of a ruthenium carbene-type catalyst under the condition of olefin cross metathesis reaction, wherein the ethylene-propylene-diene monomer rubber contains a first structural unit provided by ethylene, a second structural unit provided by propylene and a third structural unit provided by a non-conjugated diene monomer;
in the formula (2), n 2 Is an integer of 1 to 20, m 2 Is an integer of 2 to 40.
8. The method according to claim 7, wherein n is 2 Is an integer of 3 to 10, m 2 Is an integer from 6 to 20;
preferably, the compound having the structure represented by formula (2) is selected from one or more of 4-penten-1-ol, 9-decen-1-ol, 2-propen-1-ol, 5-hexen-1-ol and 7-octen-1-ol.
9. The production method according to claim 7, wherein the catalyst has a structure represented by formula (3);
in the formula (3), R 1 Is hydrogen, C 2 -C 20 Substituted or unsubstituted alkenyl of, C 2 -C 20 Substituted or unsubstituted alkynyl of (A), C 1 -C 20 Substituted or unsubstituted alkyl of, C 6 -C 20 Substituted or unsubstituted aryl of (1), C 2 -C 20 Substituted or unsubstituted carboxylate group of (A), C 1 -C 20 Substituted or unsubstituted alkoxy of (A), C 2 -C 20 Substituted or unsubstituted alkenyloxy of (A), C 2 -C 20 Substituted or unsubstituted alkynyloxy of (A), C 6 -C 20 A substituted or unsubstituted aryloxy group of,C 1 -C 20 Substituted or unsubstituted alkylthio of (A), C 1 -C 20 Substituted or unsubstituted alkylsulfonyl or C 1 -C 20 Substituted or unsubstituted alkylsulfinyl of (a);
X 1 and X 2 Each independently an anionic ligand;
L 1 and L 2 Each independently is a neutral ligand, and optionally L 1 And L 2 Can be linked to each other to form bidentate neutral ligands.
10. The method of claim 9, wherein R 1 Is C 6 -C 20 Substituted or unsubstituted aryl of (a), preferably phenyl;
X 1 and X 2 Each independently a halide ion, preferably chloride;
L 1 and L 2 Each independently a phosphine, amine, thioether, carbene, or a substituted or unsubstituted imidazolidine, preferably, L 1 And L 2 Each independently a phosphine, a carbene, or a substituted or unsubstituted imidazolidine.
11. The method of claim 9 or 10, wherein R 1 Is phenyl, L 1 Is a substituted or unsubstituted imidazolidine, L 2 Is phosphine, X 1 And X 2 Is the ion of chlorine, and the ion of chlorine,
preferably, the phosphine is a trialkylphosphine.
12. The production method according to claim 10 or 11, wherein the imidazolidine is an imidazolidine having a structure represented by the formula (4),
in the formula (4), R 2 And R 3 Each independently is C 6 -C 20 Substituted or unsubstituted aryl of (a); preferably, it is，R 2 And R 3 Each independently is
R 4 、R 5 、R 6 、R 7 And R 8 Each independently selected from hydrogen or C 1 -C 5 Substituted or unsubstituted alkyl of (a); r 2 And R 3 More preferably
13. The method according to claim 7, wherein the non-conjugated diene monomer is selected from one or more of 1, 4-hexadiene, dicyclopentadiene and 5-ethylidene-2-norbornene, preferably dicyclopentadiene.
14. The production method according to any one of claims 7 to 13, wherein the compound derived from the structure represented by formula (1) is used in an amount of 0.05 to 40 parts by weight and the catalyst is used in an amount of 0.05 to 10 parts by weight, relative to 100 parts by weight of the ethylene-propylene-diene rubber;
preferably, the ethylene-propylene-diene monomer has an ethylene structural unit content of 50 to 70wt% and a structural unit derived from a third monomer content of 4 to 8wt%;
preferably, the weight average molecular weight of the ethylene propylene diene monomer is 10-40 ten thousand.
15. The method of claim 7, wherein the olefin cross-metathesis conditions comprise: the olefin cross metathesis reaction is carried out in inert atmosphere, the reaction temperature is 0-150 ℃, and the reaction time is 0.1-5h.
16. The preparation method according to any one of claims 7, 9 and 14, wherein the catalyst is added into the reaction system in a one-time mode or in a multi-time mode, preferably, the catalyst is added into the reaction system in 2-6 times, the time interval between two adjacent times of addition is 3-15 minutes, and the difference between the amounts of the catalyst added in any two times accounts for less than 5 wt% of the total amount of the catalyst added;
more preferably, the organic solvent is toluene, xylene, chlorobenzene, C 6 -C 12 Cycloalkane of (C) 5 -C 10 One or more of linear alkane, tetrahydrofuran, acetone and 1, 4-dioxane.
17. A hydroxyl-modified ethylene-propylene-diene monomer rubber prepared by the preparation method of any one of claims 7 to 16.
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| CN112409523A (en) * | 2019-08-22 | 2021-02-26 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer and preparation method thereof |
| CN112457435A (en) * | 2019-09-06 | 2021-03-09 | 中国石油化工股份有限公司 | Modified ethylene propylene diene monomer rubber and preparation method thereof |
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