CN114874520B - Preparation method of anti-aging chloroprene rubber - Google Patents
Preparation method of anti-aging chloroprene rubber Download PDFInfo
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- CN114874520B CN114874520B CN202210543433.6A CN202210543433A CN114874520B CN 114874520 B CN114874520 B CN 114874520B CN 202210543433 A CN202210543433 A CN 202210543433A CN 114874520 B CN114874520 B CN 114874520B
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- chloroprene rubber
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- 229920001084 poly(chloroprene) Polymers 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000003712 anti-aging effect Effects 0.000 title claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 46
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 45
- 239000007822 coupling agent Substances 0.000 claims abstract description 43
- 239000000945 filler Substances 0.000 claims abstract description 27
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 23
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 23
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims abstract description 23
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920001800 Shellac Polymers 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000004208 shellac Substances 0.000 claims abstract description 16
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 claims abstract description 16
- 229940113147 shellac Drugs 0.000 claims abstract description 16
- 235000013874 shellac Nutrition 0.000 claims abstract description 16
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001577 copolymer Polymers 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 56
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 48
- 238000010438 heat treatment Methods 0.000 claims description 38
- -1 aminopropyl Chemical group 0.000 claims description 35
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 23
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 19
- WHSQATVVMVBGNS-UHFFFAOYSA-N 4-[4,6-bis(4-aminophenyl)-1,3,5-triazin-2-yl]aniline Chemical compound C1=CC(N)=CC=C1C1=NC(C=2C=CC(N)=CC=2)=NC(C=2C=CC(N)=CC=2)=N1 WHSQATVVMVBGNS-UHFFFAOYSA-N 0.000 claims description 18
- NGJJZCPADSICRI-UHFFFAOYSA-N 4-[[4,6-bis(4-carboxyanilino)-1,3,5-triazin-2-yl]amino]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1N=C(NC(=NC=1C=CC(=CC=1)C(O)=O)N1)NC1=NC1=CC=C(C(O)=O)C=C1 NGJJZCPADSICRI-UHFFFAOYSA-N 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 16
- FKIOYBLZUCCLTL-UHFFFAOYSA-N 4-butyl-2-tert-butyl-5-methylphenol Chemical compound CCCCC1=CC(C(C)(C)C)=C(O)C=C1C FKIOYBLZUCCLTL-UHFFFAOYSA-N 0.000 claims description 15
- 239000003607 modifier Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims description 13
- 239000013067 intermediate product Substances 0.000 claims description 12
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 9
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 16
- 230000003993 interaction Effects 0.000 abstract description 7
- 239000011734 sodium Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000003063 flame retardant Substances 0.000 description 7
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000036541 health Effects 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 230000001629 suppression Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 description 2
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- MIIBUHIQXLFJFP-UHFFFAOYSA-N 3-methyl-1-[[3-[(3-methyl-2,5-dioxopyrrol-1-yl)methyl]phenyl]methyl]pyrrole-2,5-dione Chemical compound O=C1C(C)=CC(=O)N1CC1=CC=CC(CN2C(C(C)=CC2=O)=O)=C1 MIIBUHIQXLFJFP-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- NEILRVQRJBVMSK-UHFFFAOYSA-N B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C NEILRVQRJBVMSK-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 101100537779 Homo sapiens TPM2 gene Proteins 0.000 description 1
- XGULBQUJRQPLOG-OOOULUNWSA-N O([C@@H]1[C@@H](C)[C@H](O)CC(=O)O[C@@H]([C@H](/C=C(\C)/C=C/C(=O)[C@H](C)C[C@@H]1CC=O)COCC=1C=CC=CC=1)CC)[C@@H]1O[C@H](C)[C@@H](O)[C@H](N(C)C)[C@H]1O Chemical compound O([C@@H]1[C@@H](C)[C@H](O)CC(=O)O[C@@H]([C@H](/C=C(\C)/C=C/C(=O)[C@H](C)C[C@@H]1CC=O)COCC=1C=CC=CC=1)CC)[C@@H]1O[C@H](C)[C@@H](O)[C@H](N(C)C)[C@H]1O XGULBQUJRQPLOG-OOOULUNWSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 102100036471 Tropomyosin beta chain Human genes 0.000 description 1
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZJIPHXXDPROMEF-UHFFFAOYSA-N dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O ZJIPHXXDPROMEF-UHFFFAOYSA-N 0.000 description 1
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical compound [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate Drugs 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
- C08L11/00—Compositions of homopolymers or copolymers of chloroprene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses an aging-resistant neoprene and a preparation method thereof. The anti-aging chloroprene rubber takes chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene segmented copolymer, trioctyl trimellitate, functional auxiliary agents, fillers, coupling agents and triallyl isohydrourea acid ester as raw materials, and the interaction among all substances improves the heat resistance, ageing resistance, mechanical property and flame retardance of the chloroprene rubber.
Description
Technical Field
The invention relates to the technical field of plastic products, in particular to a preparation method of ageing-resistant chloroprene rubber.
Background
The chloroprene rubber is synthetic rubber generated by alpha-polymerization of chloroprene, has the characteristics of high elasticity, solvent resistance and the like, and has excellent performances of weather resistance, ozone resistance and the like. Neoprene is widely used in the fields of manufacturing automobile parts, adhesives, coatings, adhesive soles and the like, and in recent years, the demands for neoprene in the fields of industrial products, automobile parts and the like are increasing.
However, unsaturated rubber using diene as a molecular main chain has defects of aging resistance, poor heat resistance and the like, and in order to further improve the application and performance of the chloroprene rubber, a plurality of students search for the chloroprene rubber, for example: filling modification, blending modification, grafting modification and chemical modification.
CN105419029a discloses a heat-resistant and aging-resistant neoprene pipe, which comprises the following raw materials: neoprene, chlorinated butyl rubber, polyoctene rubber, polyisoprene rubber, polyether polyurethane, zinc oxide, bis (2, 4-dichlorobenzoyl) peroxide, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane, stearic acid, nano calcium carbonate, hollow glass microspheres, nano montmorillonite, basic sodium aluminum carbonate, a silane coupling agent, an anti-aging agent DFC-34, an anti-aging agent A, dipentaerythritol diphosphite, hexaphenoxy cyclotriphosphazene, vinyl silicone oil, an accelerator, zinc ricinoleate, aluminum dihydrogen phosphate, and 1, 3-bis (citraconimidomethyl) benzene. The heat-resistant aging-resistant chloroprene rubber pipe provided by the invention has the advantages of high strength, good heat resistance and aging resistance, excellent storage stability, capability of meeting the use requirements of various fields, and long service life. But neoprene has poor aging resistance, mechanical, and flame retardant properties.
Accordingly, the invention discloses an anti-aging neoprene and a preparation method thereof.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides an anti-aging neoprene and a method for preparing the same.
An anti-aging neoprene comprises the following raw materials: neoprene, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, triallyl isohydrourea.
Further, the aging-resistant chloroprene rubber comprises the following raw materials in parts by weight: 35-50 parts of neoprene, 5-15 parts of lac resin, 20-35 parts of polymethyl methacrylate, 6-12 parts of styrene-butadiene-styrene block copolymer, 3-8 parts of trioctyl trimellitate and 1-5 parts of triallyl isohydrourea.
Unsaturated chloroprene rubber using diene as a molecular main chain has problems of aging resistance and poor heat resistance.
In order to improve the heat resistance and ageing resistance of neoprene, 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate, 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, POSS containing carboxyl and isopropanol are used as raw materials to prepare an intermediate substance with a triazine and three-dimensional network structure through high-temperature reaction, and ZrSP-Na, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane are further added to treat the intermediate substance to prepare a functional auxiliary agent, wherein the functional auxiliary agent has good heat resistance, ageing resistance, flame retardance and mechanical property.
Further preferably, the aging-resistant chloroprene rubber comprises the following raw materials in parts by weight: 35-50 parts of neoprene, 5-15 parts of lac resin, 20-35 parts of polymethyl methacrylate, 6-12 parts of styrene-butadiene-styrene block copolymer, 3-8 parts of trioctyl trimellitate, 5-15 parts of functional auxiliary agent, 3-10 parts of filler, 4-8 parts of coupling agent and 1-5 parts of triallyl isohydrourea.
The filler is one or more than two of montmorillonite and precipitated silica; preferably, the filler is prepared from montmorillonite and precipitated silica according to the mass ratio of (1-3): (1-3) and mixing.
The coupling agent is one or two of a silane coupling agent, a titanate coupling agent and a borate coupling agent.
The coupling agent is one or more than two of 3- (methacryloxy) propyl trimethoxy silane, vinyl triethoxy silane, vinyl t-butyl triperoxide silane, vinyl trimethoxy silane, gamma-aminopropyl triethoxy silane, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, gamma-mercaptopropyl trimethoxy silane and 3-isocyanatopropyl triethoxy silane.
The titanate coupling agent is one or a mixture of more than two of a titanate coupling agent TMC-201, a titanate coupling agent TMC-102 and a titanate coupling agent TMC-101;
the borate coupling agent is one or more than two of tri (trimethylsilane) borate TMSB, distearoyl oxygen isopropyl borate, borate coupling agent PRA-20 and alkyl borate coupling agent FRT 90.
The preparation method of the functional auxiliary agent comprises the following steps:
(1) Adding 5-10 parts by weight of aminopropyl heptyl-cage polysilsesquioxane into 80-100 parts by weight of N, N-dimethylformamide, stirring for 5-15min at 100-300r/min, then adding 8-10 parts by weight of maleic anhydride, heating to 55-75 ℃, stirring for 6-10h at 100-300r/min, and after the completion, distilling under reduced pressure to remove the N, N-dimethylformamide, and drying to obtain POSS containing carboxyl;
(2) Uniformly mixing 4-7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 3-7 parts by weight of melamine cyanurate, 5-8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine and 1-5 parts by weight of carboxyl-containing POSS prepared in the step (1) and 30-50 parts by weight of isopropanol, heating to 200-225 ℃ under nitrogen atmosphere for reaction for 2 hours, heating to 250-270 ℃ for reaction for 2-4 hours, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain an intermediate product;
(3) Adding 5-10 parts by weight of the intermediate product prepared in the step (2) into 30-80 parts by weight of dimethylacetamide, stirring for 10-30min at 100-300r/min, heating to 70-90 ℃ for reaction for 1-5h, adding 4-6 parts by weight of ZrSP-Na and 2-4 parts by weight of modifier, heating to 120-160 ℃ for reaction for 6-12h, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain the functional auxiliary agent.
The modifier is one or two of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane. Preferably, the modifier is prepared by mixing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane according to the mass ratio of (1-3).
The invention adopts maleic anhydride to treat aminopropyl heptyl-cage polysilsesquioxane to prepare POSS containing carboxyl, and further introduces POSS containing carboxyl into 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine to participate in the reaction, so that on one hand, the dispersibility of POSS is improved, and the heat resistance is improved; on the other hand, POSS containing carboxyl reacts with 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine to generate a network structure containing triazine, so that the carbon forming rate of the network structure is improved under the high-temperature condition, a silicon oxide continuous oxide framework and a heat-resistant graphite structure are formed under the high-temperature combustion condition of POSS, the flame retardant and smoke suppression performance of the network structure are obviously improved, and meanwhile, the materials are nontoxic and easy to prepare and do not harm human health; finally, zrSP-Na, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane are adopted for crosslinking and modification treatment, so that the ageing resistance, heat resistance and mechanical property of the neoprene are improved; meanwhile, the migration of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane from chloroprene rubber is avoided, so that the ageing resistance is reduced, and the environmental pollution is reduced. Beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid stearyl alcohol ester and 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane are synergistic, and the ageing resistance and mechanical properties are obviously improved.
The invention also discloses a preparation method of the aging-resistant chloroprene rubber, which comprises the following steps: according to the formula, chloroprene rubber, lac resin, polymethyl methacrylate, styrene-butadiene-styrene segmented copolymer, trioctyl trimellitate, functional auxiliary agents, fillers, coupling agents and triallyl isohydrourea are put into an internal mixer for banburying for 5-10min, and then are put into a double-screw extruder for granulation and cooling, thus obtaining the ageing-resistant chloroprene rubber.
The invention takes chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene segmented copolymer, trioctyl trimellitate, functional auxiliary agents, fillers, coupling agents and triallyl isohydrourea acid ester as raw materials, and the interaction among all substances improves the heat resistance, ageing resistance, mechanical property and flame retardance of the chloroprene rubber; the lac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer and triallyl isohydrourea are introduced into the chloroprene rubber, so that the distribution of the chloroprene rubber is obviously promoted, and the mechanical property and the processing property of the chloroprene rubber are improved. The filler is further added to endow the neoprene with mechanical property and heat resistance, and the coupling agent is added to improve the dispersion property of the filler, strengthen the combination capability with the machine body and improve the mechanical property of the neoprene; finally, functional auxiliary agents are added, the dispersibility of the functional auxiliary agents is improved under the interaction of the coupling agent and the triallyl isohydrourea, meanwhile, the organism interaction force of the functional auxiliary agents and the chloroprene rubber is further increased, the flame retardance, the heat resistance, the ageing resistance and the mechanical properties of the chloroprene rubber are further improved, the service life of the chloroprene rubber is prolonged, the special use environment condition can be adapted, and the market application prospect is wide.
The invention has the beneficial effects that: 1. the invention takes chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene segmented copolymer, trioctyl trimellitate, functional auxiliary agents, fillers, coupling agents and triallyl isohydrourea acid ester as raw materials, and the interaction among all substances improves the heat resistance, ageing resistance, mechanical property and flame retardance of the chloroprene rubber.
2. The invention adds functional auxiliary agents, 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate, 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, POSS containing carboxyl and isopropanol are used as raw materials to prepare intermediate substances with triazine and three-dimensional network structures through high-temperature reaction, and ZrSP-Na, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane are further added to process the intermediate substances to prepare the functional auxiliary agents, wherein the functional auxiliary agents have good heat resistance, ageing resistance, flame retardance and mechanical property.
Detailed Description
The above summary of the present invention is described in further detail below in conjunction with the detailed description, but it should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples.
Chloroprene rubber, model: M130H, japanese electric chemistry, purchased from Dingguan Xin plastic materials Co., ltd.
Shellac resin, molecular weight: 964-1100, melting point: 115-120 ℃, density: 1.035-1.140, purchased from Jinan Leihe commercial Co., ltd.
Polymethyl methacrylate, brand: 8803 purchased from Ying Xiang Plastic materials Co., ltd.
Styrene-butadiene-styrene block copolymer, brand: CH1302-1HE, purchased from Dongguan city, inc. of plasticizing Co., ltd.
Montmorillonite, particle size: 325 mesh, purchased from inner Mongolia, avermeris chemical Co.
Precipitation method silicon dioxide, model: E-200A purchased from Shanghai electric International trade company, inc.
Titanate coupling agent TMC-201, model: KR-38S, kennecky, USA.
Distearoyl oxyisopropyl borate, model: PEA, purchased from magnesian biochemical engineering limited.
Aminopropyl heptyl-cage polysilsesquioxane, cat: 9502028 from fosman technologies (beijing).
Melamine cyanurate, cat No.: r054415, purchased from Shanghai Yi En chemical technologies limited.
The preparation method of ZrSP-Na in the embodiment comprises the following steps: s1, adding 10g of 1, 3-propane sultone into 30mL of toluene, stirring for 10min at 180r/min, then adding 15mL of 0.0087mol/L of triethyl phosphite toluene solution and 30mL of toluene, heating to 111 ℃ for reaction for 24h, then adding 10mL of petroleum ether for repeated extraction treatment, repeatedly extracting for 3 times, taking a lower layer of substance, and drying to obtain a substance a; s2, adding 12g of a substance a into 150mL of concentrated hydrochloric acid, uniformly mixing, heating to 120 ℃ for reaction for 72 hours, then distilling under reduced pressure to remove the concentrated hydrochloric acid, adding 100mL of ethyl acetate for extraction treatment, repeatedly extracting for 3 times, taking a lower layer of the substance, and drying to obtain a substance b; adding 4g of a substance b into 20mL of water, stirring for 10min at 180r/min, then adding 30mL of an octahydrated zirconium oxychloride mixed solution, continuously stirring for 12h, centrifuging to obtain a precipitate after the reaction is finished, washing the precipitate to be neutral, and drying to obtain ZrSP, wherein the preparation method of the octahydrated zirconium oxychloride mixed solution comprises the following steps: adding 3.2g of zirconium oxychloride octahydrate into 50mL of 0.1mol/L hydrochloric acid, and uniformly mixing to obtain the mixed solution of zirconium oxychloride octahydrate; s3, adding 1.6g of NaOH into 160mL of water, uniformly mixing, adding 10g of ZrSP, stirring at 180r/min for 6h at room temperature, evaporating water after the reaction is finished, and drying to obtain ZrSP-Na.
Example 1
An anti-aging chloroprene rubber comprises the following raw materials in parts by weight: 50 parts by weight of neoprene, 15 parts by weight of shellac resin, 35 parts by weight of polymethyl methacrylate, 12 parts by weight of styrene-butadiene-styrene block copolymer, 6 parts by weight of trioctyl trimellitate, and 5 parts by weight of triallyl isohydrourea.
The preparation method of the aging-resistant chloroprene rubber comprises the following steps: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene segmented copolymer, trioctyl trimellitate and triallyl isohydrourea are put into an internal mixer to be banburying for 10min, and then are sent into a double-screw extruder to be granulated and cooled, thus obtaining the ageing-resistant chloroprene rubber.
Example 2
An anti-aging chloroprene rubber comprises the following raw materials in parts by weight: 50 parts by weight of neoprene, 15 parts by weight of shellac resin, 35 parts by weight of polymethyl methacrylate, 12 parts by weight of styrene-butadiene-styrene block copolymer, 6 parts by weight of trioctyl trimellitate, 5 parts by weight of filler, 6 parts by weight of coupling agent, and 5 parts by weight of triallyl isohydrourea.
The filler is prepared from montmorillonite and precipitated silica according to a mass ratio of 2:1, and mixing.
The coupling agent is prepared by mixing 3-isocyanatopropyl triethoxysilane, titanate coupling agent TMC-201 and distearoyl oxygen isopropyl borate according to a mass ratio of 2:1:1.
The preparation method of the aging-resistant chloroprene rubber comprises the following steps: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene segmented copolymer, trioctyl trimellitate, filler, coupling agent and triallyl isohydrourea are put into an internal mixer for banburying for 10min, and then are sent into a double-screw extruder for granulation and cooling, thus obtaining the ageing-resistant chloroprene rubber.
Example 3
An anti-aging chloroprene rubber comprises the following raw materials in parts by weight: 50 parts of neoprene, 15 parts of shellac resin, 35 parts of polymethyl methacrylate, 12 parts of styrene-butadiene-styrene block copolymer, 6 parts of trioctyl trimellitate, 10 parts of functional auxiliary agents, 5 parts of fillers, 6 parts of coupling agents and 5 parts of triallyl isohydrourea.
The filler is prepared from montmorillonite and precipitated silica according to a mass ratio of 2:1, and mixing.
The coupling agent is prepared by mixing 3-isocyanatopropyl triethoxysilane, titanate coupling agent TMC-201 and distearoyl oxygen isopropyl borate according to a mass ratio of 2:1:1.
The preparation method of the functional auxiliary agent comprises the following steps:
(1) Adding 5 parts by weight of aminopropyl heptyl-cage polysilsesquioxane into 100 parts by weight of N, N-dimethylformamide, stirring for 10min at 180r/min, adding 10 parts by weight of maleic anhydride, heating to 60 ℃, stirring for 10h at 180r/min, and after the completion, distilling under reduced pressure to remove the N, N-dimethylformamide, and drying to obtain carboxyl-containing POSS;
(2) Uniformly mixing 7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 7 parts by weight of melamine cyanurate, 8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, 5 parts by weight of POSS containing carboxyl prepared in the step (1) and 50 parts by weight of isopropanol, heating to 225 ℃ in a nitrogen atmosphere for reaction for 2 hours, heating to 270 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain precipitate, washing and drying to obtain an intermediate product;
(3) Adding 8 parts by weight of the intermediate product prepared in the step (2) into 30 parts by weight of dimethylacetamide, stirring for 10min at 180r/min, heating to 80 ℃ for reaction for 3h, adding 4 parts by weight of ZrSP-Na and 2 parts by weight of modifier, heating to 160 ℃ for reaction for 6h, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain the functional auxiliary agent.
The modifier is prepared by mixing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane according to a mass ratio of 2:1.
The preparation method of the aging-resistant chloroprene rubber comprises the following steps: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene segmented copolymer, trioctyl trimellitate, filler, coupling agent, functional auxiliary agent and triallyl isohydrourea are put into an internal mixer for banburying for 10min, and then are put into a double-screw extruder for granulation and cooling, thus obtaining the ageing-resistant chloroprene rubber.
Example 4
An anti-aging chloroprene rubber comprises the following raw materials in parts by weight: 50 parts of neoprene, 15 parts of shellac resin, 35 parts of polymethyl methacrylate, 12 parts of styrene-butadiene-styrene block copolymer, 6 parts of trioctyl trimellitate, 10 parts of functional auxiliary agents, 5 parts of fillers, 6 parts of coupling agents and 5 parts of triallyl isohydrourea.
The filler is prepared from montmorillonite and precipitated silica according to a mass ratio of 2:1, and mixing.
The coupling agent is prepared by mixing 3-isocyanatopropyl triethoxysilane, titanate coupling agent TMC-201 and distearoyl oxygen isopropyl borate according to a mass ratio of 2:1:1.
The preparation method of the functional auxiliary agent comprises the following steps:
(1) Adding 5 parts by weight of aminopropyl heptyl-cage polysilsesquioxane into 100 parts by weight of N, N-dimethylformamide, stirring for 10min at 180r/min, adding 10 parts by weight of maleic anhydride, heating to 60 ℃, stirring for 10h at 180r/min, and after the completion, distilling under reduced pressure to remove the N, N-dimethylformamide, and drying to obtain carboxyl-containing POSS;
(2) Uniformly mixing 7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 7 parts by weight of melamine cyanurate, 8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, 5 parts by weight of POSS containing carboxyl prepared in the step (1) and 50 parts by weight of isopropanol, heating to 225 ℃ in a nitrogen atmosphere for reaction for 2 hours, heating to 270 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain precipitate, washing and drying to obtain an intermediate product;
(3) Adding 8 parts by weight of the intermediate product prepared in the step (2) into 30 parts by weight of dimethylacetamide, stirring for 10min at 180r/min, heating to 80 ℃ for reaction for 3h, adding 4 parts by weight of ZrSP-Na and 2 parts by weight of modifier, heating to 160 ℃ for reaction for 6h, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain the functional auxiliary agent.
The modifier is beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) stearyl propionate.
The preparation method of the aging-resistant chloroprene rubber comprises the following steps: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene segmented copolymer, trioctyl trimellitate, filler, coupling agent, functional auxiliary agent and triallyl isohydrourea are put into an internal mixer for banburying for 10min, and then are put into a double-screw extruder for granulation and cooling, thus obtaining the ageing-resistant chloroprene rubber.
Example 5
An anti-aging chloroprene rubber comprises the following raw materials in parts by weight: 50 parts of neoprene, 15 parts of shellac resin, 35 parts of polymethyl methacrylate, 12 parts of styrene-butadiene-styrene block copolymer, 6 parts of trioctyl trimellitate, 10 parts of functional auxiliary agents, 5 parts of fillers, 6 parts of coupling agents and 5 parts of triallyl isohydrourea.
The filler is prepared from montmorillonite and precipitated silica according to a mass ratio of 2:1, and mixing.
The coupling agent is prepared by mixing 3-isocyanatopropyl triethoxysilane, titanate coupling agent TMC-201 and distearoyl oxygen isopropyl borate according to a mass ratio of 2:1:1.
The preparation method of the functional auxiliary agent comprises the following steps:
(1) Adding 5 parts by weight of aminopropyl heptyl-cage polysilsesquioxane into 100 parts by weight of N, N-dimethylformamide, stirring for 10min at 180r/min, adding 10 parts by weight of maleic anhydride, heating to 60 ℃, stirring for 10h at 180r/min, and after the completion, distilling under reduced pressure to remove the N, N-dimethylformamide, and drying to obtain carboxyl-containing POSS;
(2) Uniformly mixing 7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 7 parts by weight of melamine cyanurate, 8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, 5 parts by weight of POSS containing carboxyl prepared in the step (1) and 50 parts by weight of isopropanol, heating to 225 ℃ in a nitrogen atmosphere for reaction for 2 hours, heating to 270 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, centrifuging to obtain precipitate, washing and drying to obtain an intermediate product;
(3) Adding 8 parts by weight of the intermediate product prepared in the step (2) into 30 parts by weight of dimethylacetamide, stirring for 10min at 180r/min, heating to 80 ℃ for reaction for 3h, adding 4 parts by weight of ZrSP-Na and 2 parts by weight of modifier, heating to 160 ℃ for reaction for 6h, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain the functional auxiliary agent. The modifier is 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
The preparation method of the aging-resistant chloroprene rubber comprises the following steps: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene segmented copolymer, trioctyl trimellitate, filler, coupling agent, functional auxiliary agent and triallyl isohydrourea are put into an internal mixer for banburying for 10min, and then are put into a double-screw extruder for granulation and cooling, thus obtaining the ageing-resistant chloroprene rubber.
Example 6
Substantially the same as in example 5, the only difference is that: the preparation method of the functional auxiliary agent comprises the following steps:
(1) Uniformly mixing 7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 7 parts by weight of melamine cyanurate, 8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine and 50 parts by weight of isopropanol, heating to 225 ℃ under nitrogen atmosphere for reaction for 2 hours, heating to 270 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, washing, centrifuging to obtain precipitate, and drying to obtain an intermediate product;
(2) Adding 8 parts by weight of the intermediate product prepared in the step (1) into 30 parts by weight of dimethylacetamide, stirring for 10min at 180r/min, heating to 80 ℃ for reaction for 3h, adding 4 parts by weight of ZrSP-Na and 2 parts by weight of modifier, heating to 160 ℃ for reaction for 6h, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain the functional auxiliary agent. The modifier is 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
Example 7
Substantially the same as in example 5, the only difference is that: the preparation method of the functional auxiliary agent comprises the following steps:
(1) Adding 5 parts by weight of aminopropyl heptyl-cage polysilsesquioxane into 100 parts by weight of N, N-dimethylformamide, stirring for 10min at 180r/min, adding 10 parts by weight of maleic anhydride, heating to 60 ℃ and reacting for 10h at 180r/min, and after the reaction is finished, distilling under reduced pressure to remove the N, N-dimethylformamide and drying to obtain carboxyl-containing POSS;
(2) Adding 8 parts by weight of POSS containing carboxyl prepared in the step (1) into 30 parts by weight of dimethylacetamide, stirring for 10min at 180r/min, heating to 80 ℃ for reaction for 3h, adding 4 parts by weight of ZrSP-Na and 2 parts by weight of modifier, heating to 160 ℃ for reaction for 6h, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain the functional auxiliary agent. The modifier is 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane.
Example 8
Substantially the same as in example 5, the only difference is that: the preparation method of the functional auxiliary agent comprises the following steps:
(1) Adding 5 parts by weight of aminopropyl heptyl-cage polysilsesquioxane into 100 parts by weight of N, N-dimethylformamide, stirring for 10min at 180r/min, adding 10 parts by weight of maleic anhydride, heating to 60 ℃ and reacting for 10h at 180r/min, and after the reaction is finished, distilling under reduced pressure to remove the N, N-dimethylformamide and drying to obtain carboxyl-containing POSS;
(2) Uniformly mixing 7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 7 parts by weight of melamine cyanurate, 8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, 5 parts by weight of POSS containing carboxyl and 50 parts by weight of isopropanol, heating to 225 ℃ under nitrogen atmosphere for reaction for 2 hours, heating to 270 ℃ for reaction for 3 hours, cooling to room temperature after the reaction is finished, washing, centrifuging, taking precipitate, and drying to obtain the functional auxiliary agent.
Example 9
Substantially the same as in example 5, the only difference is that: the preparation method of the functional auxiliary agent comprises the following steps: adding 5 parts by weight of aminopropyl heptyl-cage polysilsesquioxane into 100 parts by weight of N, N-dimethylformamide, stirring for 10min at 180r/min, adding 10 parts by weight of maleic anhydride, heating to 60 ℃, reacting for 10h at 180r/min, and after the reaction is finished, distilling under reduced pressure to remove the N, N-dimethylformamide and drying to obtain the functional auxiliary agent.
Example 10
Substantially the same as in example 5, the only difference is that: the preparation method of the functional auxiliary agent comprises the following steps:
7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 7 parts by weight of melamine cyanurate and 8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine and 50 parts by weight of isopropanol are uniformly mixed, and then heated to 225 ℃ to react for 2 hours in a nitrogen atmosphere, then heated to 270 ℃ to react for 3 hours, cooled to room temperature after the reaction is finished, washed, centrifugally precipitated and dried to obtain the functional auxiliary agent.
Test example 1
Mechanical property test:
the aging-resistant neoprene rubber prepared in examples 1-10 was prepared into standard samples by a 25t press vulcanizer (Shanghai Jiujia hydraulic machinery Co., ltd.) under sample vulcanization conditions: and (5) preserving the temperature at 160 ℃ for 10min, and pressing the plate for molding. The tensile strength test was performed on the test specimen with reference to GB/T528-2009 "determination of tensile stress Strain Properties of vulcanized rubber or thermoplastic rubber".
Table 1 results of mechanical properties test of neoprene
| Tensile Strength/MPa | |
| Example 1 | 6.1 |
| Example 2 | 8.4 |
| Example 3 | 27.6 |
| Example 4 | 25.2 |
| Example 5 | 23.5 |
| Example 6 | 20.7 |
| Example 7 | 16.3 |
| Example 8 | 18.1 |
| Example 9 | 10.8 |
| Example 10 | 13.5 |
As can be seen from table 1, the neoprene prepared in example 3 has good mechanical properties, which may be due to: the neoprene, lac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer, trioctyl trimellitate, functional auxiliary agents, fillers, coupling agents and triallyl isohydrourea acid ester are used as raw materials, and all substances interact with each other to improve the mechanical property of the neoprene; the lac resin, polymethyl methacrylate, styrene-butadiene-styrene block copolymer and triallyl isohydrourea are introduced into the chloroprene rubber, so that the distribution of the chloroprene rubber is obviously promoted, and the mechanical property and the processing property of the chloroprene rubber are improved. The filler is further added to endow the neoprene with mechanical property and heat resistance, and the coupling agent is added to improve the dispersion property of the filler, strengthen the combination capability with the machine body and improve the mechanical property of the neoprene; finally, functional auxiliary agents are added, the dispersibility of the functional auxiliary agents is improved under the interaction of the coupling agent and the triallyl isohydrourea, meanwhile, the organism interaction force of the functional auxiliary agents and the chloroprene rubber is further increased, the flame retardance, the heat resistance, the ageing resistance and the mechanical properties of the chloroprene rubber are further improved, the service life of the chloroprene rubber is prolonged, the special use environment condition can be adapted, and the market application prospect is wide.
Test example 2
The neoprene produced in examples 1-10 was tested with reference to GB/T2408-2008 "determination of Plastic Combustion Performance horizontal and vertical".
TABLE 2 flame retardant Property test results of Neoprene
| L-94 | |
| Example 1 | V-2 |
| Example 2 | V-2 |
| Example 3 | V-0 |
| Example 4 | V-0 |
| Example 5 | V-0 |
| Example 6 | V-0 |
| Example 7 | V-1 |
| Example 8 | V-0 |
| Example 9 | V-1 |
| Example 10 | V-1 |
As can be seen from table 2, the neoprene prepared in example 3 has good flame retardant properties, and the properties are remarkable for the reasons that may be attributed to examples 6-8: the maleic anhydride is adopted to treat the aminopropyl heptyl-cage polysilsesquioxane to prepare POSS containing carboxyl, and the POSS containing carboxyl is further introduced into 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine to participate in the reaction, so that on one hand, the dispersibility of the POSS is improved, and the heat resistance is improved; on the other hand, POSS containing carboxyl reacts with 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine to generate a network structure containing triazine, so that the carbon forming rate of the network structure is improved under the high-temperature condition, a silicon oxide continuous oxide framework and a heat-resistant graphite structure are formed under the high-temperature combustion condition of POSS, the flame retardant and smoke suppression performance of the network structure are obviously improved, and meanwhile, the materials are nontoxic and easy to prepare and do not harm human health; finally, zrSP-Na, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane are adopted for crosslinking and modification treatment, so that the ageing resistance, heat resistance, flame retardance and mechanical property of the neoprene are improved.
Test example 3
Aging resistance test:
the test piece of test example 1 was left at 120℃for 150 hours, and then taken out, and its tensile strength retention was measured.
TABLE 3 results of ageing resistance test of Neoprene
| Tensile strength retention/% | |
| Example 1 | 56.8 |
| Example 2 | 60.3 |
| Example 3 | 86.2 |
| Example 4 | 83.6 |
| Example 5 | 82.3 |
| Example 6 | 79.5 |
| Example 7 | 74.1 |
| Example 8 | 76.3 |
| Example 9 | 66.7 |
| Example 10 | 71.4 |
As can be seen from table 3, the ageing resistance of the neoprene prepared in example 3 is significantly better than that of examples 4-5, probably due to the following: the maleic anhydride is adopted to treat the aminopropyl heptyl-cage polysilsesquioxane to prepare POSS containing carboxyl, and the POSS containing carboxyl is further introduced into 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine to participate in the reaction, so that on one hand, the dispersibility of the POSS is improved, and the heat resistance is improved; on the other hand, POSS containing carboxyl reacts with 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine to generate a network structure containing triazine, so that the carbon forming rate of the network structure is improved under the high-temperature condition, a silicon oxide continuous oxide framework and a heat-resistant graphite structure are formed under the high-temperature combustion condition of POSS, the flame retardant and smoke suppression performance of the network structure are obviously improved, and meanwhile, the materials are nontoxic and easy to prepare and do not harm human health; finally, zrSP-Na, beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane are adopted for crosslinking and modification treatment, so that the ageing resistance, heat resistance and mechanical property of the neoprene are improved; meanwhile, the migration of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane from chloroprene rubber is avoided, so that the ageing resistance is reduced, and the environmental pollution is reduced. Beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanoic acid stearyl alcohol ester and 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane are synergistic, and the ageing resistance and mechanical properties are obviously improved.
The ageing resistance of example 3 is significantly better than examples 6-8, probably due to: the maleic anhydride is adopted to treat the aminopropyl heptyl-cage polysilsesquioxane to prepare POSS containing carboxyl, and the POSS containing carboxyl is further introduced into 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine to participate in the reaction, so that on one hand, the dispersibility of the POSS is improved, and the heat resistance is improved; on the other hand, POSS containing carboxyl reacts with 2,4, 6-tri (4-aminophenyl) -1,3, 5-triazine, melamine cyanurate and 2,4, 6-tri [ (p-carboxyphenyl) amino ] -1,3, 5-triazine to generate a network structure containing triazine, so that the carbon forming rate of the POSS is improved under the high temperature condition, a silicon oxide continuous oxide framework and a heat-resistant graphite structure are formed under the high temperature combustion condition of the POSS, the flame retardant and smoke suppression performance of the POSS are obviously improved, and the substances are nontoxic and easy to prepare and do not harm the health of human bodies.
Claims (4)
1. An anti-aging neoprene, characterized by: the material comprises the following raw materials in parts by weight: 35-50 parts of neoprene, 5-15 parts of lac resin, 20-35 parts of polymethyl methacrylate, 6-12 parts of styrene-butadiene-styrene block copolymer, 3-8 parts of trioctyl trimellitate, 3-10 parts of filler, 4-8 parts of coupling agent and 1-5 parts of triallyl isohydrourea;
also comprises 5-15 parts by weight of functional auxiliary agent;
the preparation method of the functional auxiliary agent comprises the following steps:
(1) Adding 5-10 parts by weight of aminopropyl heptyl-cage polysilsesquioxane into 80-100 parts by weight of N, N-dimethylformamide, stirring for 5-15min, then adding 8-10 parts by weight of maleic anhydride, heating to 55-75 ℃ and stirring for 6-10h, and after the completion, distilling under reduced pressure to remove the N, N-dimethylformamide and drying to obtain POSS containing carboxyl;
(2) Uniformly mixing 4-7 parts by weight of 2,4, 6-tris (4-aminophenyl) -1,3, 5-triazine, 3-7 parts by weight of melamine cyanurate, 5-8 parts by weight of 2,4, 6-tris [ (p-carboxyphenyl) amino ] -1,3, 5-triazine, 1-5 parts by weight of POSS containing carboxyl and 30-50 parts by weight of isopropanol, heating to 200-225 ℃ under nitrogen atmosphere for reaction for 2 hours, heating to 250-270 ℃ for reaction for 2-4 hours, cooling to room temperature after the reaction is finished, washing, centrifuging to obtain precipitate, and drying to obtain an intermediate product;
(3) Adding 5-10 parts by weight of the intermediate product prepared in the step (2) into 30-80 parts by weight of dimethylacetamide, stirring for 10-30min, heating to 70-90 ℃ for reaction for 1-5h, adding 4-6 parts by weight of ZrSP-Na and 2-4 parts by weight of modifier, heating to 120-160 ℃ for reaction for 6-12h, cooling to room temperature after the reaction is finished, centrifuging, taking precipitate, washing and drying to obtain a functional auxiliary agent;
the modifier is prepared by mixing beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) octadecyl propionate and 1, 3-tri (2-methyl-4-hydroxy-5-tert-butylphenyl) butane according to a mass ratio of 2:1.
2. The aging-resistant neoprene of claim 1, wherein: the filler is one or more than two of montmorillonite and precipitated silica.
3. The aging-resistant neoprene of claim 1, wherein: the coupling agent is one or two of a silane coupling agent, a titanate coupling agent and a borate coupling agent.
4. A method of preparing an aging-resistant neoprene rubber as claimed in any one of claims 1 to 3 comprising the steps of: according to the formula, chloroprene rubber, shellac resin, polymethyl methacrylate, styrene-butadiene-styrene segmented copolymer, trioctyl trimellitate, functional auxiliary agents, fillers, coupling agents and triallyl isohydrourea acid ester are put into an internal mixer for banburying, and then are sent into a double-screw extruder for granulation and cooling, so that the ageing-resistant chloroprene rubber is prepared.
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| JP2003082238A (en) * | 2001-09-11 | 2003-03-19 | Asahi Kasei Corp | Excellent flame-retardant polymer composition |
| CN105315527A (en) * | 2015-11-23 | 2016-02-10 | 苏州盖德精细材料有限公司 | Neoprene-based UL yellow adhesive and preparation method thereof |
| CN110655652A (en) * | 2019-09-02 | 2020-01-07 | 厦门大学 | Metal hybrid POSS flame retardant, preparation method and application |
| EP3885401A1 (en) * | 2020-03-25 | 2021-09-29 | Avanzare Innovacion Tencologica S.L. | Self-sensing flame resistant polymeric materials |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003082238A (en) * | 2001-09-11 | 2003-03-19 | Asahi Kasei Corp | Excellent flame-retardant polymer composition |
| CN105315527A (en) * | 2015-11-23 | 2016-02-10 | 苏州盖德精细材料有限公司 | Neoprene-based UL yellow adhesive and preparation method thereof |
| CN110655652A (en) * | 2019-09-02 | 2020-01-07 | 厦门大学 | Metal hybrid POSS flame retardant, preparation method and application |
| EP3885401A1 (en) * | 2020-03-25 | 2021-09-29 | Avanzare Innovacion Tencologica S.L. | Self-sensing flame resistant polymeric materials |
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