CN111718555B - Sealing strip material based on partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer and preparation thereof - Google Patents
Sealing strip material based on partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer and preparation thereof Download PDFInfo
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- CN111718555B CN111718555B CN201910210363.0A CN201910210363A CN111718555B CN 111718555 B CN111718555 B CN 111718555B CN 201910210363 A CN201910210363 A CN 201910210363A CN 111718555 B CN111718555 B CN 111718555B
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- China
- Prior art keywords
- conjugated diene
- parts
- random copolymer
- partially hydrogenated
- divinylbenzene
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- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000007789 sealing Methods 0.000 title claims abstract description 65
- 150000001993 dienes Chemical class 0.000 title claims abstract description 55
- 239000000463 material Substances 0.000 title claims abstract description 41
- 229920005604 random copolymer Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 238000004073 vulcanization Methods 0.000 claims abstract description 76
- 238000001125 extrusion Methods 0.000 claims abstract description 28
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 229920001971 elastomer Polymers 0.000 claims description 95
- 239000005060 rubber Substances 0.000 claims description 84
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 37
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims description 26
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- 238000009826 distribution Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000003921 oil Substances 0.000 claims description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 13
- 239000011630 iodine Substances 0.000 claims description 13
- 229910052740 iodine Inorganic materials 0.000 claims description 13
- 239000006229 carbon black Substances 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 239000007822 coupling agent Substances 0.000 claims description 10
- 230000003712 anti-aging effect Effects 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 9
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 9
- 235000021355 Stearic acid Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 8
- 239000008117 stearic acid Substances 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- WITDFSFZHZYQHB-UHFFFAOYSA-N dibenzylcarbamothioylsulfanyl n,n-dibenzylcarbamodithioate Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)C(=S)SSC(=S)N(CC=1C=CC=CC=1)CC1=CC=CC=C1 WITDFSFZHZYQHB-UHFFFAOYSA-N 0.000 claims description 7
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 claims description 6
- 238000011925 1,2-addition Methods 0.000 claims description 5
- 125000002897 diene group Chemical group 0.000 claims description 5
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 239000012744 reinforcing agent Substances 0.000 claims description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 2
- VILGDADBAQFRJE-UHFFFAOYSA-N n,n-bis(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SN(SC=3SC4=CC=CC=C4N=3)C(C)(C)C)=NC2=C1 VILGDADBAQFRJE-UHFFFAOYSA-N 0.000 claims 2
- 230000003078 antioxidant effect Effects 0.000 claims 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims 1
- 238000007906 compression Methods 0.000 abstract description 10
- 230000006835 compression Effects 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract description 7
- 229920000642 polymer Polymers 0.000 description 56
- 239000000047 product Substances 0.000 description 35
- 238000006116 polymerization reaction Methods 0.000 description 33
- 229920002943 EPDM rubber Polymers 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 23
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- 239000004793 Polystyrene Substances 0.000 description 17
- 229920002223 polystyrene Polymers 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000003292 glue Substances 0.000 description 14
- 239000000178 monomer Substances 0.000 description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000000806 elastomer Substances 0.000 description 11
- 229920002725 thermoplastic elastomer Polymers 0.000 description 11
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000012545 processing Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000009471 action Effects 0.000 description 8
- 235000019241 carbon black Nutrition 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 239000003566 sealing material Substances 0.000 description 8
- 239000004636 vulcanized rubber Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000003825 pressing Methods 0.000 description 7
- 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 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 6
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 5
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 5
- 229960001826 dimethylphthalate Drugs 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 5
- 238000007493 shaping process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 239000011265 semifinished product Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010924 continuous production Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004606 Fillers/Extenders Substances 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920005683 SIBR Polymers 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000013013 elastic material Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- LGBYJXBCVZKJBL-UHFFFAOYSA-N 1-[(2-oxoazepan-1-yl)disulfanyl]azepan-2-one Chemical compound O=C1CCCCCN1SSN1C(=O)CCCCC1 LGBYJXBCVZKJBL-UHFFFAOYSA-N 0.000 description 1
- ZRMMVODKVLXCBB-UHFFFAOYSA-N 1-n-cyclohexyl-4-n-phenylbenzene-1,4-diamine Chemical compound C1CCCCC1NC(C=C1)=CC=C1NC1=CC=CC=C1 ZRMMVODKVLXCBB-UHFFFAOYSA-N 0.000 description 1
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 241000499895 Bloomeria Species 0.000 description 1
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920006978 SSBR Polymers 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- HASGOCLZFTZSTN-UHFFFAOYSA-N cyclohexane;hexane Chemical compound CCCCCC.C1CCCCC1 HASGOCLZFTZSTN-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 1
- 201000009240 nasopharyngitis Diseases 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
Abstract
The invention discloses a sealing strip material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer and a preparation method thereof. The formula can obtain the sealing strip with good physical and mechanical properties, strong ageing resistance, good heat resistance, low compression deformation, continuous tensile strength and long fatigue resistance time through mixing, extrusion and vulcanization, and is particularly suitable for outdoor windows.
Description
Technical Field
The invention relates to a sealing material and a preparation method thereof, in particular to a sealing strip material obtained by taking a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer with partial double bonds, long chain branching and wide molecular weight distribution as an elastomer, belonging to the technical field of sealing materials.
Background
Conventional hydrogenated polystyrene-conjugated diene copolymers are polymers initiated with butyllithium in the presence of a solvent from styrene and conjugated dienes, the molecular structure of which can be linear or star-shaped, and are used primarily for thermoplastic elastomers and other plastics materials. The preparation of elastomers prepared by hydrogenating block polystyrene-conjugated diene polymers, such as those prepared by hydrogenating block polystyrene-conjugated diene polymers, is described in patents ZL97108078.4, USP 498421 (1990), EP0471415 (1991, USP5132372 (1992), USP5206307 (1993), etc., wherein the hydrogenated elastomers or copolymers are prepared by fully hydrogenating the conjugated diene units in the hydrogenated polymers, and the double bonds in the hydrogenated polymers are fully hydrogenated, so that the polymer molecules are free of double bonds, and thus the polymer cannot be processed and vulcanized by a sulfur-accelerator system or under the action of peroxides, and the fully hydrogenated polystyrene-conjugated diene block Polymers and Polyolefin (PP) are blended and extruded to form products which show the behavior of thermoplastic elastomers, and are not suitable for use as sealing strip materials because of large compression deformation and permanent deformation; from microscopic analysis, PP and SEBS are incompatible because of phase separation at the intermolecular interface of the PP and the SEBS, and the PP and the SEBS are separated from each other to break under the action of long stress, for example, SEBS-602 and SEBS-604 which are produced by the Baling petrochemical company of China and have a hydrogenation degree of more than 98% on self production, and special materials for sealing strips prepared by mixing and granulating rib agents such as polypropylene PP, white oil and calcium carbonate, wherein the hardness of the composite material is 70-88A, the elongation at 300% is 6-8MPa, the elongation at break is 450%, but the permanent deformation is as high as 50%, and the continuous tensile time is less than 72h. In addition, researches show that the existing commercial products of SEBS and SEPS of YH are good in processing extrusion formability, but the materials are large in deformation, the compatibility of the products and softening oil is poor, and the polymer molecules have no double bonds, the molecular weight distribution is too narrow, the polymer cohesion is large, the polymer cannot be molded by adopting a common mixing and vulcanization mode of synthetic rubber, and sulfur vulcanization cannot be adopted, so that an injection molded product belongs to physical crosslinking, the product has low strength, large deformation, poor continuous stretching fatigue resistance and poor ageing resistance, and is not suitable for sealing strip materials used under high temperature and strong sunlight.
However, although the conventional BR, ESBR, NR, SSBR and SIBR and other polymers contain a large amount of unsaturated double bond units in the molecule, the raw rubber strength, melt elasticity or melt strength of the polymer are relatively low, and the polymer does not have the raw rubber behavior of an elastomer; the appearance of the product is blocky, the stiffness of the polymer is low, the polymer does not have the granular behavior exhibited by ethylene propylene rubber (raw rubber), and the polymer can be processed and vulcanized by a sulfur-accelerator system, but the vulcanized product still contains a large number of double bonds, so that the product has poor heat resistance, ageing resistance and solvent resistance, and does not have the processing behavior of ethylene propylene diene monomer and the comprehensive physical and chemical properties of the ethylene propylene diene monomer. As (Wang Nini, et al, synthesis of tin-coupled oil-extended styrene-isoprene-butadiene terpolymers [ J ], synthetic rubber industry, 2010,33 (6)), methods employing tin tetrachloride-even-biphenylethylene-isoprene-butadiene copolymers are described, wherein the solution polymerization SIBR is not hydrogenated and the polymer monomer units are randomly distributed. The raw rubber is blocky, low in raw rubber strength, large in cold flow, and poor in dimensional stability of injection molded products which are not completely vulcanized, and cannot meet the requirements of continuous production, namely, the processing technology of outdoor products such as sealing strips for windows is not suitable. In (Liu Dahua et Al, ethylene propylene rubber [ M ], handbook of synthetic rubber industry, second edition, 2006, 8) is described a conventional ethylene propylene diene monomer which is an elastic material catalytically polymerized from ethylene, propylene and a small amount of a third monomer such as DCPD or END under the action of Ziegler-Natta catalysts (such as V-Al), the polymer molecular weight distribution index of which is up to 2 to 5, a branched ethylene propylene diene monomer which is a thermoplastic elastomer interposed between a soft resin and a hard rubber at ordinary temperature, has an amorphous, low to medium iodine value. The thermoplastic elastomer is typically suitable for continuous microwave and hot air vulcanization, and vulcanized products are linear and profiled bars. If the existing solid door and window sealing strip formula is formed by ethylene propylene diene monomer, calcium carbonate, paraffin oil, a processing rib agent, zinc oxide, stearic acid, an accelerator, sulfur and the like, the Mooney viscosity is 40-80, the microwave heating is carried out, and the hot air vulcanization is carried out for 160 ℃/10-30min. The tensile strength of the vulcanized rubber is 9.8Mpa, the elongation at break is 380%, the Shore (A) is 69, the fracture strength is 29KN/m, and the compression deformation (22 h at 70 ℃) is less than 30%; after hot air ageing (70 ℃ C. For 70 h): the tensile strength retention is 99%, the elongation retention is 72%, and the hardness is improved by 2.
The sealing material has good surface finish, stability in processing and shaping, higher strength, lower deformation, heat resistance, weather resistance and the like, and the base polymer material for producing the sealing material is required to have wider molecular weight distribution and better melt fluidity, and meanwhile, the melt strength of the material is required to be large enough to ensure that the formed product is not broken and deformed in the process of extruding the sealing product (strip). In addition, the product is required to have better elasticity and stretching strength. The comprehensive performance of the existing SEBS and SEPS is far less than that of ethylene propylene diene monomer rubber, and the requirements of sealing profiles of buildings, automobiles, containers, various appliances and the like are not met.
In chinese patent CN107663342a (Gao Bingtuo et al, "weather strip-coated compound and method of making same and door weather strip and method of making same"), a weather strip-coated compound is described herein, which is made from the following components in weight proportions: ethylene propylene diene monomer rubber: 70-130 parts of zinc oxide: 6.0 to 8.0 portions of stearic acid: 0.5 to 1.5 portions of paraffin oil R2291: 50-70 parts of carbon black N550: 120-140 parts of sulfur: 1.0 to 2.0 parts of accelerator: 3.5 to 7.5 parts of auxiliary agents. Namely, the sealing strip for the vehicle door is mainly made of ethylene propylene diene monomer rubber, and is vulcanized by a sulfur-accelerator system, but a specific molding processing method is not described. In addition, for example, chinese patent CN101323693 (Wu Shu, et al, in the description of a dynamically vulcanized thermoplastic elastomer and a preparation method thereof), a dynamically vulcanized thermoplastic elastomer and a preparation method thereof are described, wherein the formula comprises 50-80 parts of high-polymerization-degree polyvinyl chloride, 20-50 parts of ethylene propylene diene monomer rubber, 10-35 parts of plasticizer, 10-30 parts of filler, 0.1-0.5 part of cross-linking agent, 0.05-1 part of cross-linking auxiliary agent, 1-5 parts of stabilizer, 0.1-1 part of lubricant, 5-20 parts of compatilizer, 1-5 parts of auxiliary agent and the like. The preparation method comprises the steps of fully mixing the components in a high-speed mixer, then carrying out melt blending, carrying out dynamic vulcanization reaction, and finally extruding and granulating. The thermoplastic elastomer is applied to the fields of wires and cables, oil-resistant rubber pipes, gas rubber pipes, sealing strips, sports goods, sole materials, conveyer belt covering rubber and the like. The Chinese patent ZL200710074252 discloses an environment-friendly SEBS thermoplastic elastomer sealing strip material which comprises the following components in parts by weight: 100 parts of SEBS resin and modified substances thereof; 150-250 parts of rubber; 0.4-0.8 part of lubricant; 0.45-0.60 part of anti-aging agent. The invention also provides a preparation method of the environment-friendly SEBS thermoplastic elastomer sealing strip material, which comprises the following steps: weighing raw materials; a mixing step; and (3) granulating. However, the molecular structure of the sealing strip material prepared by the method is non-crosslinking, and the product has poor heat resistance, fatigue resistance, oil resistance, weather resistance and the like. In (Chen Wei et al, "preparation of dynamically vulcanized SEBS/EPDM blended thermoplastic elastomer" and "Performance study [ J ] (2011 in the world rubber industry) it is described that EPDM is blended with sulfur and the like to prepare an EPDM masterbatch, which is then blended with plasticized SEBS for vulcanization. Firstly, preparing master batch by EPDM and a compounding agent on an open mill at normal temperature; the second step is to carry out dynamic vulcanization on the master batch and SEBS on an open mill at 170 ℃, the concrete method is to raise the temperature of the open mill to 170 ℃ to fully mix and plasticize the SEBS and the master batch, alternate cutting is carried out for 10min, and the rubber compound is evenly mixed and then is cut into pieces; the third step is to mould the lower piece of glue on a 25 ton/10 Mpa (190 ℃/5 min) press, then cold press the lower piece of glue on the press for 5min, and then to form pieces. Wherein the master batch comprises 100 parts of EPDM, 40 parts of carbon black, 2.5 parts of accelerator EC-4, 1.8 parts of sulfur, 1 part of anti-aging agent and 69 parts of silicon. The hardness (A) of the product is 69-77, the tensile strength is 7-9MPa, the permanent deformation is 15-20% and the elongation is 360-380%. However, in the technology, SEBS and EPDM are mixed at high temperature, so that the operation efficiency is low; the SEBS and the EPDM vulcanized rubber without double bond crosslinking points still have phase separation, so that the compatibility of the SEBS and the EPDM vulcanized rubber is poor, and the continuous tensile fatigue resistance of the product is poor.
Similarly, in the institute of the golden star of the university of south China, "research on special materials for sealing strips of environmental-friendly SEBS thermoplastic elastomer" the SEBS/filler oil KP 6030=3: 2, SEBS/PP=9:1, the filler is calcium carbonate and titanate is used as a coupling agent, and as a result, the hardness of the composite extrusion product is 54A, the tensile strength is 11.67MPa, the elongation at break is 800%, but the permanent deformation is 45%, the continuous fatigue resistance is poor, and the like.
The comprehensive performance of the existing SEBS and SEPS is far less than that of ethylene propylene diene monomer rubber, and the requirements of sealing profiles of buildings, automobiles, containers, various appliances and the like are not met. By hydrogenating the polystyrene-isoprene copolymer, the conjugated diene in the hydrogenated polymer forms a soft segment chain having a molecular structure equivalent to that of ethylene propylene rubber, whereby properties similar to those of ethylene propylene rubber can be obtained. However, by using partially hydrogenated rubber and leaving a portion of the unsaturated double bonds available for vulcanization, no corresponding literature or commercial report is currently available for use in sealing materials.
In addition, for the rubber sealing strip industry, the vulcanization time becomes a bottleneck for improving the industrial productivity, and the rapid development of the application field of the rubber sealing strip industry is limited. However, from the current market, the continuous maturation of the rapid vulcanization technology of rubber is making up for the defect of long vulcanization time in the past, and the temperature, pressure and time are three factors for combined action in the vulcanization process of rubber. How to realize continuous vulcanization and improve the vulcanization system to accelerate the vulcanization process are paid attention and paid.
Up to now, the use of partially hydrogenated polystyrene-conjugated diene elastomers with high melt elasticity, high stiffness and broad molecular weight distribution as sealing materials has not been reported in the corresponding literature.
Disclosure of Invention
Aiming at the defects of SEBS and SEPS used as sealing strips in the prior art, the invention aims to provide a sealing strip (or product) which is prepared from a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer elastomer which contains partial double bonds and has long chain branching and wide molecular weight distribution, and has good physical and mechanical properties, strong ageing resistance, good heat resistance, low compression deformation, continuous tensile strength and long fatigue resistance.
The invention also aims at providing the method for preparing the sealing strip by using the partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer as a base polymer material, which has the characteristics of good processability of the mixed composite material, heat resistance, deformation resistance of an extrusion-molded blank or semi-finished product and convenience for continuous vulcanization molding, and has the advantages of simple operation and low manufacturing cost.
In order to achieve the technical purpose, the invention provides a sealing strip material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer, which comprises the partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer, sulfur and auxiliary materials;
The partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer is obtained by partially hydrogenating a copolymer having the structure of formula 1:
S x -b-(I y /B z -D g )
1 (1)
Wherein,
S x is a styrene homo-block, I y /B z -D g Is a conjugated diene and divinylbenzene random copolymer block; the conjugated diene includes butadiene and/or isoprene;
the ratio of the mass of the styrene unit to the mass of the conjugated diene unit in the copolymer of the formula 1 is (20-40)/(80-60), and the mass of the divinylbenzene unit is 0.08-0.16% of the total mass of the conjugated diene unit.
S x Is a polystyrene block, S is a styrene unit, x is the polymerization degree of styrene, B z Is a butadiene block, B is a butadiene unit, z is the degree of polymerization of butadiene, I y Is an isoprene block, I is an isoprene unit, y is the polymerization degree of isoprene, D g Is a divinylbenzene block, b represents a block composed of styrene homo-blocks and conjugated dienes and divinylbenzeneThe phenyl random copolymer block is composed of two blocks.
In a preferred embodiment, the number average molecular weight of the copolymer of formula 1 is within the range of 100000 ～ 150000, the molecular weight distribution index is 2.0 to 5.0, and the branching distribution index is 1 to 8. The widely distributed polymer is beneficial to improving the subsequent processing performance of the rubber.
In a preferred embodiment, the number average molecular weight of the styrene homo-block is in the range of 15000 to 35000. The styrene homo-block is preferably in a suitable molecular weight range, and the prepared polymer has proper green strength and stiffness and sufficient melt strength to ensure that the semi-finished product (or blank) prepared by the polymer in the mixing, extrusion and other units has good dimensional stability; cold flow or heat flow deformation phenomenon can not be generated at the middle and low temperature of 60-120 ℃ so as to facilitate the subsequent continuous vulcanization.
In a preferred embodiment, the 1, 4-addition amount ratio of the isoprene units in the conjugated diene and divinylbenzene random copolymer block is 85% or more; the 1, 2-addition amount ratio in the butadiene unit is 20% or more.
In a preferred embodiment, the total iodine value of the butadiene units and the isoprene units of the conjugated diene and divinylbenzene binary random copolymer block after partial hydrogenation is 8 to 30g/100g of rubber. The polymers have a suitable number of double bonds in order to provide a suitable amount of cure crosslinking points (density) during the curing process of the compounds.
The preferred partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymers have a Mooney viscosity of from 40 to 80, a suitable viscosity being one which maintains adequate stiffness and shaping of the polymer.
The partially hydrogenated styrene-b-conjugated diene/divinylbenzene random copolymer is designed into a two-block structure, and aims to ensure that the polymer raw rubber has enough strength, stiffness and melt strength, and simultaneously ensures that the rubber compound has good flowability of non-Newtonian fluid during low-temperature extrusion-shearing, so that the raw rubber can be fully mixed with fillers and auxiliaries in the mixing process.
The invention selects the partially hydrogenated-b-conjugated diene/divinylbenzene random copolymer as the basic elastic material, because the polymer has wide molecular weight distribution index, good rubber mobility, is favorable for extrusion, calendaring and other molding process requirements, and increases the extrusion, calendaring, compression molding and injection rates of the rubber material along with the increase of the dosage of the inorganic filler of the compounding system in a certain range; proper long chain branching of raw rubber is beneficial to reducing the mouth expansion rate of rubber and stabilizing the shape and the stability of rubber.
The partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymers of the present invention are prepared by well known anionic polymerization and hydrogenation processes. The method comprises the following steps:
1) Polymerization reaction:
in a cyclohexane-hexane solvent system containing a structure regulator, firstly, styrene monomer is subjected to an anionic polymerization reaction by butyl lithium, after the reaction is carried out for 20-25 min at 50-85 ℃, mixed monomers consisting of divinylbenzene and conjugated diene are slowly and continuously added for random copolymerization and long chain branching, the continuous addition time is 60-90 min, after the diene monomer is added, the reaction is continued for 20-25 min, and then the molecular weight, the molecular weight distribution index and the content of isoprene segment 1, 4-addition product and/or butadiene polymerization segment 1, 2-addition product units of the polymer in the polymerization glue solution are measured.
2) Partial hydrogenation reaction:
adding a certain amount of nickel-based or titanium-based catalyst into the polymerized glue solution, carrying out hydrogenation reaction for 2-2.5 h under the conditions that the temperature is 70-85 ℃ and the hydrogen pressure is 1.0-1.5 MPa, stopping the hydrogenation reaction when the iodine value of the hydrogenated polymer meets the design requirement, condensing, extruding, drying and granulating the glue solution to obtain granular raw rubber, thus obtaining the partially hydrogenated polystyrene-b-isoprene-divinylbenzene/butadiene random copolymer raw rubber.
Nickel-based catalysts such as nickel isooctanoate/triisobutylaluminum (Ni/Al molecular ratio) =1/3.0 to 3.5; the catalyst is 3-5 mmol/100g dry polymer calculated by Ni. Titanium catalysts such as dicyclopentadiene titanium dichloride/dimethyl phthalate (molecular ratio) =1/0.5 to 1. The dosage of the dicyclopentadiene titanium dichloride catalyst is 0.12-0.15 mmol/100g dry polymer.
The structure regulator comprises at least one of tetrahydrofurfuryl alcohol ethyl ether, ditetrahydrofurfuryl propane, tetrahydrofurfuryl alcohol hexyl ether and tertiary amine compounds; the dosage of the 1,2 structure regulator is 10-50 mg/kg of solvent. Tetrahydrofuran, which is known in the industry and inexpensive, is preferred. The dosage of the solvent is 10-50 mg/kg, the content of 1, 2-addition units polymerized by butadiene in the controlled poly conjugated diene section is more than 20%, the content of 1.4-addition products polymerized by isoprene is more than 85%, and the content of 3, 4-addition products is not more than 15%.
In a preferred scheme, the auxiliary materials comprise a reinforcing agent, a filler, an extender oil, a coupling agent, an accelerator, a post-effect vulcanizing agent, zinc oxide, stearic acid and an anti-aging agent.
More preferably, the reinforcing agent comprises carbon black and/or white carbon black. Carbon blacks N220, N330, N550, N234, etc. are most suitably used.
More preferably, the filler comprises at least one of heavy calcium carbonate, barium carbonate, light calcium carbonate, precipitated barium sulfate and talcum powder. The mesh number of the filler is not less than 500 mesh, preferably light calcium carbonate, and the high-dosage inorganic filler is beneficial to maintaining the stability of the product after the rubber compound is extruded.
More preferably, the filler oil comprises mineral white oil. Such as naphthenic oils, paraffinic oils, and environmentally friendly low aromatic content rubber oils, preferably one of the commercially available 3, 5, 10, 25, 26, 46 white oils and NAP-10 naphthenic oils and mixtures thereof, so that higher amounts of extender oil are also advantageous for maintaining product stability after extrusion of the compound.
More preferably, the coupling agent comprises a silicone coupling agent. The silicone-containing compound is preferably commercially available KH-550, silicon-69, silicon-75, etc., and more preferably silicon-69 or silicon-75.
More preferably, the accelerator comprises at least one of a vulcanization accelerator DTDC, a vulcanization accelerator TBzTD, a vulcanization accelerator TBSI, a vulcanization accelerator TMTD and a vulcanization accelerator D.
More preferably, the anti-aging agent comprises phenolic and/or organic amine antioxidants. Preferred antioxidants a, D, 4010, CPPD, RD, etc.
More preferably, the post-cure agent comprises ZXK-HTS. The aim of the post-effect vulcanizing agent is to directly participate in the vulcanization reaction through the molecules, and the longer and flexible hexamethylene in the molecules is embedded into the sulfur atom bonds among rubber molecules, so that the vulcanized rubber is endowed with excellent dynamic performance or anti-bending property under the action of heat. The post-effect is that the rubber compound in the prescription component can be continuously vulcanized at a slightly lower temperature or under milder conditions after extrusion molding, and the post-effect vulcanization is the continuation of the operation process of the front section. The formula in the technical scheme of the invention uses various accelerators and super vulcanization accelerators with higher dosage, and the accelerator and the post-effect vulcanizing agent are used together, so that the vulcanized product has the advantages of good uniformity, improved heat resistance, low compression deformation and the like. This is extremely important for a weather strip product for a locomotive window.
The sealing strip material comprises the following components in parts by mass: 100 parts of partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer; 120-140 parts of carbon black; 80-100 parts of calcium carbonate; 70-90 parts of filling oil; 7-10 parts of a coupling agent; 3-5 parts of an anti-aging agent; 3-6 parts of a promoter; 1.5 to 2.5 portions of post-effect vulcanizing agent; 4-5 parts of zinc oxide; 1-2 parts of stearic acid; 0.5 to 2 portions of sulfur.
In a more preferable scheme, the accelerator consists of the following components in parts by mass: 1.0 to 1.5 portions of vulcanization accelerator DTDC; 0.5 to 1.0 part of vulcanization accelerator TBzTD; 0.5 to 1.0 part of vulcanization accelerator TBSI; 1.0 to 1.5 portions of vulcanization accelerator TMTD; 0.5 to 1.0 part of vulcanization accelerator D. The sealing material is compounded with several kinds of accelerators, and has the synergistic effect of raised cross-linking density, raised vulcanizing speed, shortened vulcanizing time and raised efficiency. The vulcanization accelerator DTDC (N, N' -dithio-biscaprolactam) has the advantages of no frosting, safe scorching and high vulcanization speed, and can partially replace sulfur, and because the DTDC can release active sulfur under the general vulcanization condition, and form a monosulfur bond and a disulfide bond with the added sulfur among rubber molecules, the vulcanized rubber can be endowed with excellent heat resistance, compression resistance and high stretching stress. The vulcanization accelerator TBzTD (tetramethylthiuram disulfide) has a longer scorch time than TMTD and acts as a rapid vulcanization accelerator of the present invention. The vulcanization accelerator TBSI (N-tert-butyl bis-2-benzoxazolyl sulfonamide) is safe at the operating temperature and does not generate carcinogenic nitrosamine. Good thermal stability compared with TBBS long scorch time, high vulcanizing speed and the like. The vulcanization accelerator TMTD has the characteristics of very strong vulcanization acceleration and extremely rapid or overspeed vulcanization. The vulcanization accelerator D has the characteristic of medium-speed vulcanization, and is used together with the accelerator TMTD, TBSI, TBzTD, DTDC in a continuous-speed vulcanization mode.
The invention also provides a preparation method of the sealing strip material based on the partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer, which comprises the steps of carrying out one-stage mixing on the partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer and auxiliary materials to obtain a mixed rubber, and carrying out two-stage mixing on the mixed rubber and sulfur to obtain master batch; tabletting, layering, extrusion molding and vulcanizing the masterbatch to obtain the finished product.
In a preferred embodiment, the one-stage mixing temperature is 145-150 ℃ and the mixing time is 200-280 s.
In a preferred scheme, the two-stage mixing temperature is 145-150 ℃ and the mixing time is 80-100 s.
Preferably, the molding conditions in the extrusion molding process are as follows: the length-diameter ratio L/D of the screw is 15-16, the set temperature of the inlet area of the screw is room temperature, the temperature of the preheating area is 90-110 ℃, and the set temperature of the forming die head is 130-140 ℃; the extrusion linear speed is 0.8-5 m/min, and the vacuum degree is 0.01-0.1 multiplied by 101.325KPa.
Preferably, the vulcanization conditions are as follows: the vulcanization temperature is 90-180 ℃ and the vulcanization time is 8-15 min.
In the preparation process of the sealing material, the mouth shape expansion rate of the mixed rubber material is reduced along with the increase of the consumption of the inorganic filler and the filler oil, which is beneficial to maintaining the stability of the product after the mixed rubber is extruded.
The preparation method of the sealing strip comprises the following steps:
the sealing strip forming method is preferably mixing, tabletting or layering, injection molding and subsequent vulcanization, and is preferably provided with an internal mixer, a tablet press, an extrusion injection molding machine and a chain transmission vulcanizing box, and the formed section bar is vulcanized in continuous vulcanizing equipment to form a forming-vulcanizing continuous production (operation) line.
Namely, the specific operation process is as follows:
1) Mixing
Firstly, partially hydrogenated polystyrene-b-conjugated diene/ethylene and benzene random copolymer rubber, carbon black, calcium carbonate, filling oil, a coupling agent, an anti-aging agent, an accelerator, a vulcanizing agent, zinc oxide, stearic acid and the like are put into an internal mixer at one time, a motor is started, a composite material generates heat through friction under the shearing action of a rotor in the internal mixer, the rubber compound is heated to 145-150 ℃ and is mixed for 240 seconds to form a section of rubber compound, the Mooney viscosity of the section of rubber compound is measured by sampling, then the rubber compound is formed by adding sulfur and mixing for 90 seconds, and then the rubber compound can be discharged and discharged, and the value of the Mooney viscosity of the rubber compound is measured by sampling.
2) Tabletting and layering of masterbatch
The masterbatch is put on a roller of an open mill, and is cut three times at the position of about 3/4 of the roller temperature of 50-60 ℃ respectively, and then the rubber compound is pressed into rectangular rubber compound sample strips with the thickness of 5-10 mm (the width is set according to the requirement).
3) Extrusion injection molding
A shear head cold feed screw extrusion injection molding machine was used. And adding the prepared mixed rubber strip with the thickness of 5-10 mm into an inlet of a screw extrusion injection molding machine in a cold feeding mode, and pressing the composite rubber material into a die head of a die of the injection molding machine for extrusion molding under the rotation driving action of the screw. Wherein, the preferable molding process conditions are as follows: the length-diameter ratio L/D of the screw is 15-16, the set temperature of the inlet area of the screw is room temperature, the temperature of the preheating area is 90-110 ℃, and the set temperature of the forming die head is 130-140 ℃; the linear speed of extrusion of the sealing strip is 0.8-5 m/min, and the vacuum degree (0.01-0.1) is 101.325Kpa. And (3) cooling the sealing strip extruded from the molding die head in a cold water bath for shaping and winding, and then storing the wound semi-finished sealing strip or product at 25-30 ℃ for 24 hours, thus being capable of performing forward vulcanization (or vulcanization). The increase in the Mooney viscosity of the extruded bars was measured.
4) Vulcanization
The iodine value of the partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene and benzene random copolymer is 8-30 g/100g rubber, and the industry is known that the vulcanization speed of the rubber is accelerated with the increase of temperature, the use amount of vulcanizing agent and the vulcanization time.
The vulcanization conditions of the sealing strip or the product extruded by the composite sizing material are as follows: the vulcanization temperature is 90-180 ℃, the vulcanization time is 8-15 min, more preferably 90-140 ℃, and the vulcanization time is 10-15 min.
The method of curing the weatherstrip for vehicle windows of the present invention is preferably a pressureless continuous cure system of a microwave heater-hot air tunnel vulcanizer combination known in modern rubber (e.g., preferably an MCV-15 door weatherstrip line, of length 18 m).
The preferred vulcanization process parameters are that the pressure of the vulcanization chamber is 0.25mpa; the temperature of a first area (sealing rubber strip inlet) of the vulcanizing chamber is 80-90 ℃, and the temperature of a final area (final area) is 140 ℃, namely the temperature of the first area to the final area increases at a proportional rate of 2.5-2.8 ℃/m; the transmission line speed of the conveyor belt is 1.0-1.5 m/min.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
compared with the existing SEBS, SEPS and other elastomers, the sealing strip has the defects of narrow molecular weight distribution, low strength, large compression and tensile deformation, poor continuous stretch fatigue resistance, poor aging resistance and the like, and the sealing strip and the product prepared by the sealing strip cannot be filled and mixed at low and medium temperatures and cannot be crosslinked and molded due to no rheological property at the low and medium temperatures.
The invention selects a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer elastomer as a basic high polymer material of a sealing strip or a product, wherein the copolymer has a polystyrene block with higher molecular weight and mass fraction at the head end of a molecular chain, proper unsaturation degree (vulcanized cross-sulfur point), wide molecular weight distribution, ethyl, ethylene or isobutyl or isopropyl contained in the molecular chain, and the like, and endows the polymer with low temperature resistance, non-crystallization and high segment flexibility, and has the similarity of ethylene propylene rubber.
The sealing strip formula is formed by matching the partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer elastomer with inorganic filler, softening oil, reinforcing carbon black, composite high-efficiency overspeed vulcanizing agent and the like, has good processing performance, and can be mixed by an internal mixer and an open type multi-roller mixer, pressed into tablets at low temperature, extruded and injection molded at medium temperature and vulcanized at slightly low temperature. The continuous production line of mixing, layering, injection molding and subsequent vulcanization shaping can be carried out on the mixture. The prepared sealing strip (product) has the characteristics of good rebound resilience, high stretching strength, low deformation, good fatigue and heat resistance in continuous stretch resistance, good ageing resistance and the like. The comprehensive physical properties of the sealing strip are seen in many aspects, and the sealing strip can be compared favorably with sealing strips (or products) prepared from ethylene propylene diene monomer. The invention can be manufactured by traditional equipment and technology, and has the characteristics of simple preparation method and low cost.
Detailed Description
The following examples illustrate the invention and are not to be construed as limiting the scope or practice of the invention.
The number average molecular weight and the molecular weight distribution index of the polymer were measured by Gel Permeation Chromatography (GPC) in the following examples; quantitatively determining the microstructure of the polymer by adopting an H-NMR spectrum; measuring the viscosity ML (ML 100 ℃ C. 1+4) of the raw rubber and the processing material by using the Mooney viscosity; measuring physical properties of vulcanized and semi-vulcanized tabletting adhesives by using an INSTRON tensile machine; measuring the continuous anti-fatigue time of the vulcanized rubber by adopting a tensile fatigue tester; adopting a Mo Xiya flexural fatigue tester to measure the continuous fatigue crack resistance times of the vulcanized rubber; measuring Rebound resilience of vulcanized rubber by adopting a Rebound 3000 rubber Rebound resilience meter; the compression set of the vulcanizate was determined using a CS3000 compression set test tool.
Examples of sources of partially hydrogenated polystyrene-conjugated diene copolymer:
example 1
Adding 3500mL of cyclohexane solution of 10% n-hexane in mass fraction into a 5-liter polymerization kettle under the protection of nitrogen, then adding 0.42mL of tetrahydrofurfuryl alcohol ethyl ether, heating to 55-60 ℃, adding 100g of styrene into the polymerization kettle, stirring, then injecting 7mL of 1.05mol/L n-butyllithium into the polymerization kettle by using a syringe, and initiating polymerization reaction for 20-25 min; then evenly and continuously adding 400g of butadiene, 21g of isoprene and 0.35mL of divinylbenzene into a polymerization kettle, and controlling the continuous feeding time of the mixed monomers to be 60 minutes in the polymerization process, wherein the polymerization temperature is 55-75 ℃, then stirring and reacting for 25 minutes, quantitatively measuring the vinyl mass content of a butadiene segment in the polymer by an H-NMR spectrum, and measuring the number average molecular weight Mn=79000 and the Mw=164000 of the polymer by a Gel Permeation Chromatograph (GPC), wherein the molecular weight distribution index D=2.07; wherein the number average molecular weight mn=15000 of the block polystyrene.
Then, pressing the polymer into a hydrogenation kettle, adding 0.15g of dicyclopentadiene titanium dichloride with the weight portion of 99 percent, 0.06g of dimethyl phthalate, controlling the hydrogen pressure to be 1.3MPa, stirring and reacting for 100min at the temperature of 70-80 ℃ to obtain the polymer with the iodine value of 29.6g/100g, stopping the hydrogenation reaction at the moment, and agglomerating, extruding, granulating and drying the glue solution to obtain the raw rubber with the Mooney viscosity ML=45.7.
Example 2
Adding 3500mL of cyclohexane solution of 10% n-hexane in mass fraction into a 5-liter polymerization kettle under the protection of nitrogen, then adding 0.5mL of ditetrahydrofurfuryl propane, heating to 55-60 ℃, adding 200g of styrene into the polymerization kettle, stirring while stirring, then injecting 7.5mL of 1.05mol/L n-butyllithium into the polymerization kettle by using a syringe, and initiating polymerization reaction for 20-25 min; then evenly and continuously adding 300g of butadiene and 0.30mL of mixed monomer which is uniformly mixed with divinylbenzene in advance into a polymerization kettle, wherein the continuous adding time of the mixed monomer is controlled to be 70min in the polymerization process, the polymerization temperature is 55-75 ℃, then stirring and reacting for 25min, the vinyl mass content of a butadiene segment in the polymer is quantitatively measured by an H-NMR spectrum, the number average molecular weight Mn=74000 and the Mw= 196000 molecular weight distribution index D=2.66 are measured by a Gel Permeation Chromatograph (GPC); wherein the number average molecular weight mn=29000 of the block polystyrene.
Then, pressing the polymer into a hydrogenation kettle, adding 0.17g of dicyclopentadiene titanium dichloride with the mass fraction of 99%, 0.08g of dimethyl phthalate, controlling the hydrogen pressure to be 1.4MPa, stirring and reacting for 110min at the temperature of 70-80 ℃ to obtain the polymer with the iodine value of 23.2g/100g, stopping the hydrogenation reaction at the moment, and agglomerating, extruding, granulating and drying the glue solution to obtain the raw rubber with the Mooney viscosity ML=42.8.
Example 3
3500mL of cyclohexane solution of 10% n-hexane in mass fraction was charged into a 5-liter polymerizer under nitrogen protection, and other relevant process conditions were the same as in example 1 except that 0.6mL of tetrahydrofurfuryl alcohol hexyl ether, 120g of styrene, 360g of butadiene, 12g of isoprene and 0.37mL of divinylbenzene were added, 6mL of butyllithium for initiation of polymerization, and the continuous addition time of the mixed monomers was 68 minutes. After the polymerization reaction was completed, the vinyl mass content of the butadiene segment in the polymer was 53.7%, and the number average molecular weight mn=88000, mw=302000, and the molecular weight distribution index d=3.43 were measured by GPC; wherein the number average molecular weight mn=22000 of the block polystyrene.
After the polymer is transferred into a hydrogenation kettle, 0.14g of dicyclopentadiene titanium dichloride with the mass fraction of 99% and 0.09g of dimethyl phthalate are added, and the mixture is stirred and reacted for 120min at the temperature of 70-80 ℃ to obtain the polymer with the iodine value of 16.7g/100g, at the moment, the hydrogenation reaction is stopped, and the glue solution is subjected to coagulation, extrusion and granulation and drying to obtain the raw rubber with the Mooney viscosity ML=54.6.
Example 4
The relevant process conditions were the same as in example 1, except that 0.7mL of tetrahydrofurfuryl alcohol ethyl ether, 140g of styrene, 300g of butadiene, 8g of isoprene and 0.38mL of divinylbenzene were added, 5mL of butyllithium was used for initiation of polymerization, and the continuous addition time of the mixed monomers was 76 minutes. After the polymerization reaction, the vinyl mass content of the butadiene segment in the polymer was 58.8%, and the number average molecular weight mn=94000, mw= 352000 and the molecular weight distribution index d=3.74 were measured by GPC; wherein the number average molecular weight mn=26000 of the block polystyrene. After the polymer is transferred into a hydrogenation kettle, 0.14g of dicyclopentadiene titanium dichloride with the mass fraction of 99% and 0.08g of dimethyl phthalate are added, and the mixture is stirred and reacted for 130min at the temperature of 70-80 ℃ to obtain the polymer with the iodine value of 14.6g/100g, at the moment, the hydrogenation reaction is stopped, and the glue solution is subjected to coagulation, extrusion and granulation and drying to obtain the raw rubber with the Mooney viscosity ML=60.4.
Example 5
Adding 3500mL of cyclohexane solution of 10% n-hexane in mass fraction into a 5-liter polymerization kettle under the protection of nitrogen, then adding 5mL of Tetrahydrofuran (THF) cyclohexane solution of 0.10mol/L, heating to 55-60 ℃, adding 100g of styrene into the polymerization kettle, stirring, then injecting 5mL of n-butyllithium of 1.05mol/L into the polymerization kettle by using a syringe, and initiating polymerization reaction for 20-25 min; then evenly and continuously adding 400g of isoprene and 0.32mL of divinylbenzene into a polymerization kettle, and controlling the continuous feeding time of the mixed monomers to be 60min in the polymerization process, wherein the polymerization temperature is 55-85 ℃, stirring and reacting for 25min, taking a glue solution sample to measure the mass content of 1, 4-addition substances of an isoprene chain segment in the polymer to be 88.7%, and measuring the number average molecular weight Mn=105000 and Mw=227000 molecular weight distribution index D=2.16 of the polymer by GPC; wherein the number average molecular weight mn=21000 of the block polystyrene.
Then, pressing the polymer into a hydrogenation kettle, adding 38mL of cyclohexane Ni/Al catalyst complex with nickel content of 0.40mol/L, controlling the hydrogen pressure to be 1.5MPa, stirring and reacting for 120min at 75-85 ℃, measuring the polymer iodine value to be 28.4g/100g of raw rubber, stopping the hydrogenation reaction at the moment, and performing condensation, extrusion granulation and drying on the glue solution to obtain the raw rubber with Mooney viscosity ML=48.6.
Example 6
The relevant process conditions in example 5 were kept unchanged except that butyllithium was added at 3.5mL, THF was used at 4mL, divinylbenzene was used at 0.4mL, and the mixed diene monomer was continuously fed for 90min. The Ni/Al catalyst added in the hydrogenation is 60mL, the hydrogen pressure is controlled to be 1.4MPa, and the hydrogenation reaction time is 140min.
Results: the mass content of the 1, 4-adduct of the isoprene segment in the polymer gel was measured to be 89.7%, the number average molecular weight mn=151800, the mw= 737700, and the molecular weight distribution index d=4.86; wherein the number average molecular weight mn=29000 of the block polystyrene; the iodine value of the raw rubber elastomer after the hydrogenation of the polymerized glue solution was 9.42g/100g raw rubber, and the mooney viscosity ml=78.8.
Example 7
The relevant process conditions in example 5 were kept unchanged except that butyllithium was added at the first polymerization stage in an amount of 4mL, THF was used in an amount of 4mL, divinylbenzene was used in an amount of 0.36mL, and the mixed diene monomer was continuously fed for 80 minutes.
The Ni/Al catalyst added in the hydrogenation is 50mL, the hydrogen pressure is controlled to be 1.5MPa, and the hydrogenation reaction time is 130min.
Results: the mass content of the 1, 4-adduct of the isoprene segment in the polymer gel was 86.4%, the number average molecular weight mn=131500, the mw= 556500, and the molecular weight distribution index d=4.23; wherein the number average molecular weight of the block polystyrene mn= 26300; the iodine value of the raw rubber elastomer after the hydrogenation of the polymerized glue solution was 16.84g/100g raw rubber, and the mooney viscosity ml=68.5.
Example 8
The relevant process conditions in example 5 were kept unchanged except that 3.5mL of butyllithium, 2.5mL of THF, 0.56mL of divinylbenzene were added, 266g of mixed monomer isoprene, 134g of butadiene, and the continuous addition time of the mixed diene monomer was 70min during the first polymerization step.
45mL of Ni/Al catalyst is added in the hydrogenation, the hydrogen pressure is controlled to be 1.4MPa, and the hydrogenation reaction time is 120min.
Results: the mass content of 1, 4-addition substances of the isoprene chain segment in the polymer dry gel is 88.6%, and the mass content of 1, 2-addition substances in the polybutadiene units is 18.7%; the number average molecular weight mn=151500, mw= 746800, and the molecular weight distribution index d=4.93 in the copolymer; wherein the number average molecular weight of the block polystyrene mn=30300; the iodine value of the raw rubber elastomer after the hydrogenation of the polymerized glue solution is 20.6g/100g raw rubber, and the Mooney viscosity ML=65.6.
Example 9
The polymers and comparative examples (EPDM 2060) of partially hydrogenated polystyrene-conjugated diene copolymer sources of examples 1 to 8 were respectively kneaded with the materials in the formulation in the process for producing a sealing tape of the present invention in a 1L internal mixer,
wherein, the composite material is mixed for 240s at 145-150 ℃, and then the Mooney viscosity of a section of mixed rubber is measured by sampling; and then adding sulfur, mixing for 90 seconds to form master batch, discharging and discharging rubber, and sampling to measure the Mooney viscosity of the master batch.
And putting the masterbatch into an open mill, cutting the masterbatch three times at the two sides of the masterbatch at the temperature of 50-60 ℃ for 3/4 of each time, and pressing the masterbatch into rectangular rubber sample strips with the thickness of 5-10 mm (the width is set according to the requirement). And adding the prepared rectangular rubber compound sample strip into an inlet of a screw extrusion injection molding machine, and pressing the composite rubber compound into a die head of the injection molding machine for extrusion molding under the action of screw rotation driving. Wherein the temperature of the inlet area of the screw is set to be room temperature, the temperature of the preheating area is set to be 90-110 ℃, and the temperature of the forming die head is set to be 130-140 ℃; the linear speed of the extrusion of the sealing strip is 1.2m/min, and the sealing strip extruded from the molding die head enters a cold water bath for cooling and shaping. And the increase in the mooney viscosity of the extruded bars was determined.
And then placing the extruded sealing strips (semi-finished products) directly or after being stored for 24 hours at the inlet of a pressureless continuous vulcanization system of a microwave heater-hot air pipeline vulcanizing machine combination, setting the temperature of a first area (sealing rubber strip inlet) of a vulcanization chamber to be 80-90 ℃, setting the temperature of a final area (sealing rubber strip outlet) to be 140 ℃, increasing the ratio of the first area to the final area to be 2.5 ℃/m, and setting the transmission line speed of a conveyor belt to be 1.5m/min and the vulcanization time to be 11 min. The physical properties of the prepared seal bars are shown in Table 1.
Remarks:
the formulations of experimental groups 1 to 9 were: 100 parts of copolymer or comparative EPDM in source examples 1-8, 130 parts of carbon black, 90 parts of light calcium carbonate, 150 parts of white oil PAO-150, 75 parts of silicon-75 parts of an anti-aging agent RD 4, 1.5 parts of DTDC, 0.5 part of TBzTD, 1.0 part of TBSI, 1.5 parts of TMTD, 1.0 part of an accelerator D, 2.0 parts of disodium hexamethylene-1, 6 dithiosulfate dihydrate, 5 parts of zinc oxide, 1.5 parts of stearic acid and 1.5 parts of sulfur.
Test sample of physical properties of sealing strip: and (3) metering the extruded sealing strip rubber sample, re-mixing on an open mill, pressing the sealing strip rubber sample into a corresponding mould, then placing the mould with the mixed rubber into a microwave heater-hot air pipeline vulcanizing machine set at 80-140 ℃, transmitting the linear speed of 1.5m/min, vulcanizing for 11min, cooling, demoulding and preparing the sample, and testing.
Table 1 physical properties of the sealing tapes prepared from the polymers and the comparative adhesive ethylene propylene diene monomer EPDM in examples 1 to 8.
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Note that the relevant data are all the highest values
* The coupon was hot air aged (100 ℃ C./70 h).
* Ozone resistance (2 μl/L, static 20% elongation, 40 ℃/70 h).
* Compression set (100 ℃/22 h).
Example 2
The molding seal strips (semi-finished products) extruded by the die head of the screw extrusion injection molding machine in example 9 and cooled by water bath are respectively and quantitatively sampled and put into an open mill for mixing at 60-70 ℃ and pressed into rubber compound sample sheets with the thickness of 2.0-2.5 mm, and the strength and hardness of the pressed rubber compound before and after the rubber compound is stored are respectively measured. The results are shown in Table 2.
Table 2 post-cure results of compounds prepared in examples 1-8 and comparative gum prior to positive cure.
Injecting, namely, storing the mixed film at 25-30 DEG C
From the results shown in Table 2, it is found that when the extrusion molding rubber (or blank) is above 25 ℃ at room temperature, the hardness and self-adhesive strength of the blank tend to increase along with the extension of the storage time, i.e. the post-effect vulcanization effect of the composite rubber or blank is reflected, which is beneficial to the fact that the extruded sealing strip or blank does not generate cold flow or thermal deformation in the initial stage (one section of the inlet area) of the continuous vulcanizing machine, i.e. the positive vulcanization of the semi-finished blank profile is facilitated, and the processing performance is improved.
Claims (11)
1. A sealing tape material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer, characterized in that: comprises partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer, sulfur and auxiliary materials; the auxiliary materials comprise reinforcing agents, filling oil, coupling agents, accelerators, post-effect vulcanizing agents, zinc oxide, stearic acid and anti-aging agents;
the partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer is obtained by partially hydrogenating a copolymer having the structure of formula 1:
S-b-(I/B-D)
1 (1)
Wherein,
s is a styrene homopolymerization block, and I/B-D is a conjugated diene and divinylbenzene random copolymerization block; the conjugated diene includes butadiene and/or isoprene;
the ratio of the mass of the styrene unit to the mass of the conjugated diene unit in the copolymer with the structure of formula 1 is (20-40)/(80-60), and the mass of the divinylbenzene unit is 0.08-0.16% of the total mass of the conjugated diene unit; the number average molecular weight of the styrene homopolymerization block is in the range of 15000-35000; the 1, 4-addition quantity proportion of isoprene units in the conjugated diene and divinylbenzene random copolymerization block is more than 85%; the 1, 2-addition amount ratio in the butadiene unit is 20% or more.
2. A sealing tape material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer according to claim 1, characterized in that: the number average molecular weight of the copolymer with the structure of the formula 1 is in the range of 100000-150000, the molecular weight distribution index is 2.0-5.0, and the branching distribution index is 1-8.
3. A sealing tape material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer according to claim 1, characterized in that: the total iodine value of the butadiene unit and the isoprene unit of the conjugated diene and divinylbenzene binary random copolymer block after partial hydrogenation is 8-30 g/100g rubber.
4. A sealing tape material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer according to claim 1, characterized in that:
the reinforcing agent comprises carbon black and/or white carbon black;
the filler comprises at least one of heavy calcium carbonate, barium carbonate, light calcium carbonate, precipitated barium sulfate and talcum powder;
the filler oil comprises mineral white oil;
the coupling agent comprises a silicone coupling agent;
the accelerator comprises at least one of a vulcanization accelerator DTDC, a vulcanization accelerator TBzTD, a vulcanization accelerator TBSI, a vulcanization accelerator TMTD and a vulcanization accelerator D;
the antioxidant comprises phenolic and/or organic amine antioxidants;
the post-effect vulcanizing agent comprises ZXK-HTS.
5. A sealing tape material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer according to any one of claims 1 to 3, characterized in that: comprises the following components in parts by mass:
100 parts of partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer;
120-140 parts of carbon black;
80-100 parts of calcium carbonate;
70-90 parts of filling oil;
7-10 parts of a coupling agent;
3-5 parts of an anti-aging agent;
3-6 parts of an accelerator;
1.5-2.5 parts of post-effect vulcanizing agent;
4-5 parts of zinc oxide;
1-2 parts of stearic acid;
0.5-2 parts of sulfur.
6. A sealing tape material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer according to claim 5, characterized in that: the accelerator consists of the following components in parts by mass:
1.0-1.5 parts of vulcanization accelerator DTDC;
0.5-1.0 part of vulcanization accelerator TBzTD;
0.5-1.0 part of vulcanization accelerator TBSI;
1.0-1.5 parts of vulcanization accelerator TMTD;
0.5-1.0 parts of vulcanization accelerator D.
7. The method for preparing a sealing strip material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer as claimed in any one of claims 1 to 6, characterized by comprising the steps of: carrying out primary mixing on the partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer and auxiliary materials to obtain a mixed rubber, and carrying out secondary mixing on the mixed rubber and sulfur to obtain a masterbatch; tabletting, layering, extrusion molding and vulcanizing the masterbatch to obtain the finished product.
8. The method for producing a sealing tape material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer according to claim 7, characterized in that: the first-stage mixing temperature is 145-150 ℃, and the mixing time is 200-280 s.
9. The method for producing a sealing tape material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer according to claim 7, characterized in that: the two-stage mixing temperature is 145-150 ℃, and the mixing time is 80-100 s.
10. The method for producing a sealing tape material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer according to claim 7, characterized in that: the molding conditions in the extrusion molding process are as follows: the length-diameter ratio L/D of the screw is 15-16, the set temperature of the inlet area of the screw is room temperature, the temperature of the preheating area is 90-110 ℃, and the set temperature of the forming die head is 130-140 ℃; the extrusion line speed is 0.8-5 m/min, and the vacuum degree is (0.01-0.1) multiplied by 101.325KPa.
11. The method for producing a sealing tape material based on a partially hydrogenated polystyrene-b-conjugated diene/divinylbenzene random copolymer according to claim 7, characterized in that: the vulcanization conditions are as follows: the vulcanization temperature is 90-180 ℃ and the vulcanization time is 8-15 min.
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