CN102020752B - Method for modifying latex containing poly-conjugated diene through silicon in-situ hybridization and grafting - Google Patents
Method for modifying latex containing poly-conjugated diene through silicon in-situ hybridization and grafting Download PDFInfo
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- CN102020752B CN102020752B CN200910092836.8A CN200910092836A CN102020752B CN 102020752 B CN102020752 B CN 102020752B CN 200910092836 A CN200910092836 A CN 200910092836A CN 102020752 B CN102020752 B CN 102020752B
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- rubber
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- 229920000126 latex Polymers 0.000 title claims abstract description 43
- 239000004816 latex Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 39
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 30
- 239000010703 silicon Substances 0.000 title claims abstract description 30
- 150000001993 dienes Chemical class 0.000 title claims abstract 6
- 238000007901 in situ hybridization Methods 0.000 title description 14
- 230000004048 modification Effects 0.000 claims abstract description 44
- 238000012986 modification Methods 0.000 claims abstract description 44
- 239000003999 initiator Substances 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 5
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 5
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims abstract description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims abstract description 4
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- -1 3-pentenyl Chemical group 0.000 claims description 48
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000000839 emulsion Substances 0.000 claims description 16
- 239000003292 glue Substances 0.000 claims description 15
- 125000005375 organosiloxane group Chemical group 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001282 organosilanes Chemical class 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 8
- 239000012966 redox initiator Substances 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 229920001519 homopolymer Polymers 0.000 claims description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 7
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 5
- 230000000977 initiatory effect Effects 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- 239000007858 starting material Substances 0.000 claims description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 5
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 claims description 4
- UNIYDALVXFPINL-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propylsilicon Chemical compound CC(=C)C(=O)OCCC[Si] UNIYDALVXFPINL-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical group CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 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 claims description 3
- 239000012874 anionic emulsifier Substances 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 claims description 2
- AGUIILSGLFUTKG-UHFFFAOYSA-N CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] Chemical compound CC(C)O.CC(C)O.CC(C)O.C=C[SiH3] AGUIILSGLFUTKG-UHFFFAOYSA-N 0.000 claims description 2
- GTZOZDOTOWNSJH-UHFFFAOYSA-N [O].CCCCCCC Chemical compound [O].CCCCCCC GTZOZDOTOWNSJH-UHFFFAOYSA-N 0.000 claims description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- YVXHZKKCZYLQOP-UHFFFAOYSA-N hept-1-yne Chemical compound CCCCCC#C YVXHZKKCZYLQOP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims 2
- 238000002156 mixing Methods 0.000 abstract description 15
- 238000003756 stirring Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 125000004432 carbon atom Chemical group C* 0.000 abstract 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000009396 hybridization Methods 0.000 abstract 1
- 239000008267 milk Substances 0.000 abstract 1
- 210000004080 milk Anatomy 0.000 abstract 1
- 235000013336 milk Nutrition 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 67
- 239000005060 rubber Substances 0.000 description 67
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 49
- 229920003048 styrene butadiene rubber Polymers 0.000 description 39
- 239000000377 silicon dioxide Substances 0.000 description 24
- 229960001866 silicon dioxide Drugs 0.000 description 20
- 235000012239 silicon dioxide Nutrition 0.000 description 20
- 238000012360 testing method Methods 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000008187 granular material Substances 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 10
- 230000001070 adhesive effect Effects 0.000 description 10
- 238000009835 boiling Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 239000004159 Potassium persulphate Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 8
- 235000019394 potassium persulphate Nutrition 0.000 description 8
- 238000010792 warming Methods 0.000 description 8
- 239000004342 Benzoyl peroxide Substances 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- 244000043261 Hevea brasiliensis Species 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- 229960003328 benzoyl peroxide Drugs 0.000 description 6
- 229920003052 natural elastomer Polymers 0.000 description 6
- 229920001194 natural rubber Polymers 0.000 description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000003377 silicon compounds Chemical class 0.000 description 5
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- SPTHWAJJMLCAQF-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000011790 ferrous sulphate Substances 0.000 description 4
- 235000003891 ferrous sulphate Nutrition 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 229920001084 poly(chloroprene) Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 3
- 239000004160 Ammonium persulphate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 229920013649 Paracril Polymers 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 235000019395 ammonium persulphate Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000003801 milling Methods 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 238000007334 copolymerization reaction Methods 0.000 description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
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- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
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- MEBONNVPKOBPEA-UHFFFAOYSA-N 1,1,2-trimethylcyclohexane Chemical class CC1CCCCC1(C)C MEBONNVPKOBPEA-UHFFFAOYSA-N 0.000 description 1
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- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 description 1
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- FZPXKEPZZOEPGX-UHFFFAOYSA-N n,n-dibutylaniline Chemical compound CCCCN(CCCC)C1=CC=CC=C1 FZPXKEPZZOEPGX-UHFFFAOYSA-N 0.000 description 1
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- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- IOZVKVQMRQRJFK-UHFFFAOYSA-N propane;quinoline Chemical compound CCC.N1=CC=CC2=CC=CC=C21 IOZVKVQMRQRJFK-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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Abstract
A method for modifying latex containing poly-conjugated diene through silicon in-situ grafting hybridization comprises the steps of adding 4-25 parts of organic siloxane monomer containing unsaturated bonds into the latex containing poly-conjugated diene, fully stirring and uniformly mixing, adding 0.20-0.36 part of initiator at the temperature of 5-85 ℃ under the stirring condition for graft polymerization reaction for 5-8 hours, and finally carrying out graft modification on the latexCoagulating and drying the milk; the structural formula of the organosilicon monomer containing unsaturated bonds is as follows:
y-an unsaturated aliphatic segment containing 2 to 18 carbons; r1An alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms or a siloxy group having 3 to 12 carbon atoms; r2And R3Is a sum of R1The same group may be a saturated chain segment containing 1 to 20 carbon atoms, or a cyclic alkane or aromatic hydrocarbon of 1 to 8 carbon atoms.
Description
Technical field
The present invention relates to a kind of method of modifying of latex, be specifically related to silicon situ-formed graft hybrid modification containing the method for poly-conjugated-diolefin latex.
Background technology
So-called in-situ hybridization refers in the disperse phase (reinforcement or functive) and external phase (matrix) at compound system, have at least once not existing before Compound Machining mutually, but in compound processing course, under other one condition having existed mutually, generate.The in-situ hybridization modification of rubber refer to by the techniques such as graft copolymerization or cohydrolysis by disperse phase silicon with chemical bond or nano-size dispersion in rubber matrix, improving its tear resistance, reduce heat-dissipating and can improve the binding property of sizing material and other parts in composite product.Because the rubber of silicon modification shows good low-rolling-resistance and anti-slippery after being applied to tire, so scientific worker prepared the method for silicon modified rubber in exploration in the last few years always.
At present, the preparation method of domestic and international silicon modified rubber has a variety of, can be divided on the whole two large classes: mechanically milling composite algorithm Reinforced Rubber; In-situ hybridization method.Mechanically milling composite algorithm Reinforced Rubber comprises again mixing composite strengthening after the mixing composite strengthening of improved silica, modified rubber.Generally speaking, it is higher that mechanically milling composite algorithm ubiquity mixed refining process energy consumption, and when mixing, nanoparticle is difficult to reach the problems such as desirable equidistant dispersed, reunion.And in-situ hybridization method has not only well solved particle scattering problem of (particularly nonpolar rubber) in rubber matrix, and can realize to a certain extent the controllability of silicon dioxide granule particle diameter, this process can be carried out in cross-linked rubber or unvulcanised glue simultaneously.
Document " Y.IKEDA; Y.KAMEDA.Preparation of " Green " Composites by Sol-Gel Process:InSitu Silica Filled Natural Rubber[J] .Journal of Sol-Gel Science and Technology2004; 31 (1-3): 137～142. " introduced under alkaline condition, by tetraethoxysilane (TEOS) in natural rubber after swelling, there is hydrolytic condensation, then sulfuration has obtained the rubber strengthening, compare with traditional blend, the dispersion of generated in-situ silicon-dioxide in rubber is comparatively even.Between the interface of silicon-dioxide/rubber composite prepared by this article, be to connect by physical action, rather than connect by chemical bond.
In US5665812, it is solvent that author adopts toluene, with n-Butyl Lithium, cause divinyl and styrene polymerization, then add γ-(2,3 epoxy the third oxygen) propyl trimethoxy silicane that the rubber that anionoid polymerization has obtained two ends or multiterminal functional silicon occurs at 60 ℃.This rubber shows good Static and dynamic mechanical property, also butadiene-styrene-synthetic polyisoprene has been carried out the functional silicon at two ends in patent simultaneously.In US6013718, also used similar method to use respectively pregnancy basic ring cyclotrisiloxane and γ-(2,3 epoxy the third oxygen) propyl trimethoxy silicane has carried out the functional silicon of the styrene-butadiene rubber(SBR) end of the chain, and with methyl alcohol, obtained not having the styrene-butadiene rubber(SBR) of functionalization, and reached 81% by the degree that HNMR has analyzed the functional silicon of molecular chain, the Mooney viscosity test of three kinds of rubbers shows basic not variation, and after sulfuration, the SBR of kinetic test result Presentation Function has lower heat-dissipating Δ G ' (23 ℃) and dissipation factor tan δ (23 ℃).
The functionalization that in US7141622, the people such as Daniel Edward Bowen has adopted TEOS to carry out the chain end group of styrene-butadiene rubber(SBR), then the silicon-dioxide that has added silane coupling agent to process has carried out modification, compare with mechanical mixing, show better tensile strength and Young's modulus, particularly reduced energy consumption when mixing, the price of TEOS is also comparatively cheap, this is important in industrialization, the rubber strengthening by the method is owing to will adding a large amount of solvents, so for industrialization, will inevitably increase production cost.
In US4381377, author adopts two-step approach to obtain the polybutadiene rubber of functional silicon, the first step is the isomerization of polyhutadiene, second step is under high temperature (190～250 ℃), vinyltriethoxysilane is reacted to the rubber that 4h obtains functional silicon with polyhutadiene, but when by the method modified rubber latex, need on the one hand very high energy consumption, under hot conditions, also can cause breakdown of emulsion simultaneously.
US4822587 discloses under the condition existing at zinc oxide, and the method that adopts reaction to extrude is carried out the graft modification of organosilane to segmented copolymer.Concrete technical scheme is: first the mixture of segmented copolymer and zinc oxide is mixed in forcing machine with organosilane, then at 140 ℃, utilize peroxide degradation polymkeric substance and cause Silanization reaction being not less than, the last graft reaction of whole silane that completes after the mixing through after a while, the method operating process is complicated, simultaneously under hot conditions, graft modification agent is autohemagglutination and affect graft polymerization reaction probably.
Graft modification for emulsion polymerized rubber, the monomer that is usually used in grafting has ST (vinylbenzene), MMA (methyl methacrylate), MA (maleic acid), MAH (MALEIC ANHYDRIDE), MAA (methacrylic acid), AA (vinylformic acid) etc., yet for the grafted monomer of organosilicon alkanes, because organosilane is easily hydrolyzed and causes the unstable of emulsion in mutually, seldom, the method that this patent adopts organosilane to drip has realized organosilane graft modification rubber to present research report.
Summary of the invention
In order to overcome, the prepared rubber/silicon compound matrix material disperse phase of prior art is easily reunited, the problems such as reactive force is low between organic/inorganic interface, the invention provides a kind ofly from containing the latex of poly-conjugated-diolefin, in latex phase original position, prepare the preparation method of rubber/silicon compound matrix material.
The technical solution adopted in the present invention is (dry glue quality of take containing the latex of poly-conjugated-diolefin is 100 parts): by 4～25 parts of the organo-siloxane monomers that contains unsaturated link(age), preferably 10～15 parts, join in the latex that contains poly-conjugated-diolefin, fully be uniformly mixed, under 5～85 ℃ of temperature and agitation condition, add 0.20～0.36 part of initiator to carry out graft polymerization reaction 5～8h, finally that the emulsion condensation of graft modification is dry; Its structural formula of organo-siloxane monomer that contains unsaturated link(age) is:
Wherein:
The unsaturated aliphatic segment that Y-contains 2～18 carbon, can be vinyl, propenyl, allyl group, sec.-propyl, pseudoallyl, isopentene group, 3-pentenyl, 6-octenyl, tetramethyl-ethylene base, ethynyl, 1-proyl, ethyl acetylene base, 1-pentynyl, 1-heptyne base, methacryloxypropyl, methacryloxy, preferred vinyl, methacryloxypropyl;
R
1-the alkoxyl group that contains 1～12 carbon, the aryloxy of 6～12 carbon, the siloxy of 3～12 carbon, can be methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, hexyloxy, pentyloxy, positive heptan oxygen base, different octyloxy, positive ninth of the ten Heavenly Stems oxygen base, phenoxy group, chlorophenoxy, allyloxy, benzyloxy, acetoxyl group, trimethylsiloxy group, preferred methoxyl group, oxyethyl group, isopropoxy;
R
2and R
3can be and R
1identical group, can also be the saturated segment that contains 1～20 carbon, 1～8 cyclic alkane, aromatic hydrocarbon; Preferable methyl, ethyl, methoxyl group, oxyethyl group.
The organo-siloxane monomer that contains unsaturated link(age) of the present invention can be vinyl siloxanes, one or more in methyl acrylic ester siloxanes, preferred vinyl triethoxyl silane (VTES), vinyltrimethoxy silane (VTMS), vinyl three ('beta '-methoxy oxyethyl group) silane, vinyltriacetoxy silane, vinyl tributyl ketoximyl silane, methyl tributanoximo silane, vinyl silane triisopropoxide, vinyl trimethoxysilane oligomer, γ-methacryloxypropyl trimethoxy silane (MPS), one or more in three (trimethylsiloxy group) methacryloxypropyl silane (MPTS), more preferably one or more in vinyltriethoxysilane, vinyltrimethoxy silane, three (trimethylsiloxy group) methacryloxypropyl silane.
The latex that contains poly-conjugated-diolefin in described method is that its homopolymer is content of polybutadiene rubber latex, chloroprene rubber latex, natural rubber latex etc. by conventional emulsion polymerization prepared homopolymer or multipolymer containing conjugated diolefine hydrocarbon compound, its multipolymer is conjugated diolefine hydrocarbon compound and aryl ethylene compounds, monoene compounds, acrylic compounds, the binary of acrylic ester compound or terpolymer, described aryl ethylene compounds can be vinylbenzene, alpha-methyl styrene, 2-phenylallene, 1-bromobenzene propylene, ethyl styrene and their derivative, described monoene compounds can be ethene, vinylchlorid, propylene, 1-butylene, 2-amylene, vinyl cyanide and their derivative, described acrylic compounds can be vinylformic acid, methacrylic acid and their derivative, described acrylic ester compound can be methyl methacrylate, β-dimethyl-aminoethylmethacrylate, methyl acrylate, ethyl propenoate and their derivative, multipolymer can be styrene butadiene rubber latex, paracril latex, carboxy nitrile rubber latex, carboxylic styrene-butadiene rubber latex etc.Homopolymer or multipolymer containing polymerized conjugated diene hydrocarbon compound of the present invention, take homopolymer or copolymer quality as 100%, and its conjugated diolefine hydrocarbon content is 50%～100%, and preferably 60%～80%.
In described method, initiator can be thermal decomposition initiating, can be also redox initiator, and initiator is that those of ordinary skills are known.Thermal decomposition initiating can be oil-soluble initiator, can be also water soluble starter, oil-soluble initiator can be acyl peroxide class initiator or azo-initiator, preferred benzoyl peroxide, peroxidized t-butyl perbenzoate, isopropyl benzene hydroperoxide, 1, 1-dual-tert-butyl peroxidation-3, 3, 5 trimethyl-cyclohexanes, ditertiary butyl peroxide, peroxidation-2-ethylhexyl tert-pentyl ester, tert-butyl peroxy acetate, tertbutyl peroxide, 2, 5-dimethyl-2, 5 di-t-butyl peroxy hexanes, dilauroyl peroxide, di-isopropylbenzene hydroperoxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), 2,2'-Azobis(2,4-dimethylvaleronitrile), azo two isocapronitriles, dinitrogen (2, 5-dimethyl-6-carboxyl) one or more in own nitrile, more preferably benzoyl peroxide, peroxidized t-butyl perbenzoate, isopropyl benzene hydroperoxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), water soluble starter can be persulphate or azo salt initiator, ammonium persulphate, Potassium Persulphate, Sodium Persulfate, 2, two (the 2-amidine azoles quinoline propane) hydrochlorides, 2 of 2-azo, 2-azo [2-(2-tetrahydroglyoxaline-2-yl) propane] dihydrochloride.Redox initiator can be persulphate-mercaptan, persulphate-hydrosulphite, oxymuriate-hydrosulphite, hydrogen peroxide-ferrous salt, one or more in organic hydroperoxide-ferrous salt redox initiation system, preferred Potassium Persulphate/S-WAT, lauroyl peroxide amine/N, N-dibutyl aniline, benzoyl peroxide/N, N-dimethyl-para-totuidine, hydrop diisopropylbenzene(DIPB)/tetraethylene pentamine, di-isopropylbenzene hydroperoxide/ferrous sulfate redox initiation system, more preferably ammonium persulphate/sodium bisulfite, Potassium Persulphate/sodium bisulfite, Sodium Persulfate/sodium bisulfite, Potassium Persulphate/S-WAT and di-isopropylbenzene hydroperoxide/ferrous sulfate redox initiation system.In the redox initiator adopting, oxygenant and reductive agent mass ratio are 2～10: 1.
When adopting oil-soluble initiator, preferably first oil-soluble initiator is dissolved in emulsifier solution, emulsifier solution and initiator mass ratio are 60～70: 1, described emulsifying agent is one or more in anionic emulsifier; If water soluble starter is preferably dissolved in deionized water, deionized water and initiator mass ratio are 60～70: 1.Anionic emulsifier is that those of ordinary skills are known, for example metal carboxylate emulsifying agent or Sulfates emulsifying agent.
The present invention's advantage is compared to existing technology: directly adopt the method for chemical situ-formed graft hydridization to prepare rubber/silicon compound matrix material, organosilane monomer is grafted on latex, organosilane monomer with chemical bond or nano-size dispersion in rubber matrix, interface between organic rubber phase and silicon compound is combining tightr like this, avoided the problem that in direct mixing method, the easy agglomeration of silicon dioxide granule and white carbon black pollute, and the phenomenon that needs greater energy consumption, also avoided between rubber/silicon compound matrix material prepared by sol-gel method interface in conjunction with untight phenomenon simultaneously.
The method is directly carried out graft copolymerization by unsaturated organosilicon oxygen alkane and rubber and is obtained organosilicon grafted and modified rubber, only need a small amount of unsaturated organosilicon oxygen alkane just can make the tensile strength of rubber improve 20%～25%, and the mooney viscosity of silicon modified rubber rubber is not compared with former rubber significantly to be increased, and the utilization ratio of organosilane can reach 87%～95%; SEM test result shows not occur illustrating that organosilicon does not have a large amount of hydrolysis in emulsion by oarse-grained silicon dioxide granule in modified adhesive material; The thermotolerance of rubber has also had raising to a certain extent simultaneously.
Accompanying drawing explanation
Fig. 1 does not adopt the infrared spectrum of SBR1500 after the SBR1500 of silicon modification and embodiment 1 silicon in-situ hybridization modification, wherein: 1-does not adopt the SBR1500 of silicon modification, and the SBR1500 after 2-embodiment 1 silicon in-situ hybridization modification; At 1050cm
-1and 1137cm
-1place, after the modification of silicon in-situ hybridization there is strong peak, 1050cm in SBR1500
-1for the feature stretching vibration peak of Si-O key, 1137cm
-1for the feature stretching vibration peak of Si-O-C key, illustrate that unsaturated organosilicon oxygen alkane successfully grafts in styrene butadiene rubber latex, and generate siloxane bond at styrene-butadiene rubber(SBR) situ, this is the key point of the increase of rubbery intensity.
Fig. 2 does not adopt the SBR1500 of silicon modification and the ash content infrared spectrum of embodiment 1 silicon in-situ hybridization modification SBR1500, wherein: 1-does not adopt the SBR1500 of silicon modification, and the SBR1500 after 2-embodiment 1 silicon in-situ hybridization modification.After silicon in-situ hybridization modification SBR1500 rubber, ash content is at 1050cm
-1there is SiO
2typical characteristic infrared absorption, illustrate that equally unsaturated organosilicon oxygen alkane graft modification styrene butadiene rubber latex is successful.
Fig. 3 does not adopt the weightless temperature curve of SBR1500 after the SBR1500 of silicon modification and embodiment 1 silicon in-situ hybridization modification, wherein: 1-does not adopt the SBR1500 of silicon modification, and the SBR1500 after 2-embodiment 1 silicon in-situ hybridization modification.T in Fig. 3
dcfor the fastest temperature section of thermal weight loss, it has embodied the thermotolerance of material.As seen from Figure 3, grafting unsaturated organosilicon oxygen alkane meets the T that can make rubber
dcimprove, this explanation latex grafting unsaturated organosilicon monomer can make the thermotolerance of material improve.
Embodiment
For effect of the present invention is described, enumerate embodiment the present invention is described in further detail, but the present invention is not limited in these embodiment.
1, analytical procedure:
The mensuration of mooney viscosity: shear with disk the mensuration that viscometer is measured part 1 mooney viscosity according to GB/T 1232.1-2000 unvulcanized rubber.
Properties testing method: after X for rubber (S) K-160 type (Shanghai rubber manufacturing machinery one factory) open refining glue (moulding) machine is at room temperature mixing, at 45 ℃, 150kgf/cm
2temperature and pressure under, with 45 tons of vulcanizing presses of G53-445D type, be pressed into the thin slice that about 2mm is thick, after 30min, take out, owing to not having the rubber of sulfuration to have the ability that can recover deformation, therefore the rubber pressing is discharged under certain weight to 24h left and right, then by standard dumbbell shape cut-off knife, be cut into standard mechanics sample, finally adopt the CMT5104 type microcomputer controlled electronic tension testing machine of Shenzhen Sans Material Detection Co., Ltd to carry out the mensuration of tensile strength, instrument parameter is 500mm/min.
Infrared testing method: the SBR latex after modification, product and the responseless organo-siloxane monomer of the homopolymer that contains some organo-siloxanes after cohesion, a small amount of hydrolysis of organo-siloxane, adopt Soxhlet to extract to remove these products, with acetone as extraction agent, Soxhlet is extracted 24h, the product of removing unreacted monomer and organo-siloxane auto-polymerization and being certainly hydrolyzed, and the SBR of SBR and graft modification is insoluble to acetone.Respectively the SBR sample of the SBR after Soxhlet is extracted and modification is dissolved with toluene, be then added drop-wise on KBr sheet, KBr is placed under ultraviolet lamp and is dried except toluene 30min, then test.Simultaneously by rubber in retort furnace, after the residuum that calcination 10h obtains at 800 ℃ is washed with 5% dilute hydrochloric acid, after dry 2h, adopt the infrared spectra of KBr pressed disc method testing rubber ash content.
The stable on heating analysis of rubber: adopt SDTQ600 (the being Simultaneous DSC-TGA) thermal analyzer of the U.S. TA company sample to be carried out to thermogravimetric analysis, test condition: 20 ℃-800 ℃ of temperature, 20 ℃/min of temperature rise, nitrogen flow 100ml/min.
2, raw material sources:
Styrene-butadiene rubber(SBR) (SBR1500) latex: CNPC Lanzhou Petrochemical is produced, divinyl 77.5% (wt) wherein, mooney viscosity 56;
Polybutadiene rubber (EBR) latex: CNPC's Lanzhou Petrochemical is produced, and cis-Isosorbide-5-Nitrae-configuration content is 10%～20%, anti-form-1,4-configuration content 58%～75%, 1,2-configuration content is less than 25%, mooney viscosity 99.
Paracril (N32) latex: CNPC Lanzhou Petrochemical is produced, divinyl 66.5% (wt) wherein, mooney viscosity 45.
Chloroprene rubber (CR244) latex: Changshou, Chongqing Chemical Co., Ltd. produces, divinyl 50% (wt) wherein, mooney viscosity 70.
Natural rubber (NR) latex, Yunnan Natural Rubber industry limited-liability company, mooney viscosity 66.
To join in four-hole boiling flask containing the dry glue SBR1500 of 50g latex, 8gVTES, fully be uniformly mixed, be warming up to 68 ℃, then drip RA rosin acid (concentration the is 22%) mixing solutions of 0.1g benzoyl peroxide and 50g, under agitation condition, react 350 minutes; After reaction finishes, system is lowered the temperature, then by emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 90.4%, compares with mooney viscosity (56) with unmodified rubber tensile strength (196.2kpa), rubber tensile strength 238.8kpa after modification, improved 21.7%, mooney viscosity 62.9, has only improved 12.7%.SEM test shows not occur in modified adhesive material oarse-grained silicon dioxide granule.
To join in four-hole boiling flask containing the dry glue SBR1500 of 45g latex, 2.5gMPTS, fully be uniformly mixed, be warming up to 65 ℃, then add 0.13g benzoyl peroxide, under agitation condition, react 420 minutes; After reaction finishes, system is lowered the temperature, then by emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 88.0%, compares with mooney viscosity (56) with unmodified rubber tensile strength (196.2kpa), rubber tensile strength 236.9kpa after modification, improved 20.7%, mooney viscosity 61.2, has only improved 9.7%.SEM test shows not occur in modified adhesive material oarse-grained silicon dioxide granule.
Embodiment 3
To join in four-hole boiling flask containing the dry glue SBR1500 of 56g latex, 12gVTMS, fully be uniformly mixed, be cooled to 8 ℃, then add 0.15g di-isopropylbenzene hydroperoxide and 0.015g ferrous sulfate, under agitation condition, react 400 minutes; Reaction finishes emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 92.0%, compares with mooney viscosity (56) with unmodified rubber tensile strength (196.2kpa), rubber tensile strength 241.6kpa after modification, improved 23.1%, mooney viscosity 64.4, has improved 15.5%.SEM test shows not occur in modified adhesive material oarse-grained silicon dioxide granule.
Embodiment 4
To join in four-hole boiling flask containing the dry glue SBR1500 of 52g latex, 13gVTES, fully be uniformly mixed, be warming up to 80 ℃, add 0.15g ammonium persulphate, under agitation condition, react 350 minutes; After reaction finishes, system is lowered the temperature, then by emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 94.3%, compares with mooney viscosity (56) with unmodified rubber tensile strength (196.2kpa), rubber tensile strength 251.1kpa after modification, improved 28.0%, mooney viscosity 66, has only improved 17.8%.SEM test shows not occur in modified adhesive material oarse-grained silicon dioxide granule.
Embodiment 5
To join in four-hole boiling flask containing the dry glue SBR1500 of 48g latex, 10gVTES, fully be uniformly mixed, be warming up to 85 ℃, add the mixing solutions of 0.12g Potassium Persulphate and 8g deionized water, under agitation condition, react 360 minutes; After reaction finishes, system is lowered the temperature, then by emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 92.9%, compares with mooney viscosity (56) with unmodified rubber tensile strength (196.2kpa), rubber tensile strength 245.2kpa after modification, improved 25.0%, mooney viscosity 65.7, has only improved 17.7%.SEM test shows not occur in modified adhesive material oarse-grained silicon dioxide granule.
Embodiment 6
To join in four-hole boiling flask containing the dry glue SBR1500 of 60g latex, 12gVTES, fully be uniformly mixed, be warming up to 50 ℃, add 0.15g Potassium Persulphate and 0.03g sodium bisulfite, under agitation condition, react 360 minutes; After reaction finishes, system is lowered the temperature, then by emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 93.6%, compares with mooney viscosity (56) with unmodified rubber tensile strength (196.2kpa), rubber tensile strength 251.1kpa after modification, improved 28.0%, mooney viscosity 66.2, has only improved 18.3%.SEM test shows not occur in modified adhesive material oarse-grained silicon dioxide granule.
Embodiment 7
To be added in four-hole boiling flask containing the dry glue latex of 50gEBR and 5gMPTS, and fully be uniformly mixed, and then be warming up to 80 ℃, and add 0.10g Potassium Persulphate, and stir, reaction 350min, after reaction finishes lowers the temperature system, then by emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 88.0% to be compared with crude rubber Mooney viscosity (99) with unmodified tensile strength (210kpa), and after modification, rubber tensile strength 260kpa, has improved 23.8%, and mooney viscosity 112.9 improves 14.3%.SEM test shows not occur in modified adhesive material oarse-grained silicon dioxide granule.
Embodiment 8
To join in four-hole boiling flask containing the dry glue paracril of 50g latex, 4gVTES, and fully be uniformly mixed, normal temperature (25 ℃), adds 0.10g hydrogen peroxide and 0.05g ferrous sulfate, reacts 360 minutes under agitation condition; After reaction finishes, system is lowered the temperature, then by emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 89.3%, compares with mooney viscosity (45) with unmodified rubber tensile strength (201.3kpa), rubber tensile strength 242.3kpa after modification, improved 20.3%, mooney viscosity 51, has only improved 13.3%.SEM test shows not occur in modified adhesive material oarse-grained silicon dioxide granule.
Embodiment 9
To join in four-hole boiling flask containing the dry glue chloroprene rubber of 52g latex, 7.8gVTES, fully be uniformly mixed, be warming up to 58 ℃, add 0.12g Potassium Persulphate and 0.025g sodium bisulfite, under agitation condition, react 360 minutes, after reaction finishes, system is lowered the temperature, then by emulsion condensation, and vacuum-drying.After tested, the utilization ratio of VTES can reach 88.4%, compares with mooney viscosity (70) with unmodified rubber tensile strength (284.6kpa), rubber tensile strength 345.7kpa after modification, improved 21.5%, mooney viscosity 82, has only improved 17.1%.SEM test shows not occur in modified adhesive material oarse-grained silicon dioxide granule.
To add in four-hole boiling flask containing the dry glue NR of 50g latex, 6gVTES, fully be uniformly mixed, be warming up to 72 ℃, then add 0.18g benzoyl peroxide, under agitation condition, react 380 minutes; Then emulsion breaking is condensed, mixing vacuum-drying, after tested, the utilization ratio of VTES can reach 89%, do not compare with mooney viscosity (66) with there is no the rubber tensile strength (981.0kpa) of modification, rubber tensile strength 1180.7kpa after modification, provides high 20.4%, mooney viscosity brings up to 79, has improved 19.7%.
Comparative example 1
The styrene-butadiene rubber(SBR) (method is with reference to CN96107364.0) of mechanical blending legal system prepared silicon dioxide modification
By two-step approach, obtained silica modified styrene-butadiene rubber(SBR), the one: wet processing silicon-dioxide, take 3.55g aerosil and 1.21gVTES, the toluene (120ml) of take is solvent, back flow reaction 24h, remove that to obtain the silicon-dioxide processed after solvent stand-by, the 2nd, by the silicon-dioxide 3.00g after processing (in silica volume, identical with theoretical silicone content in embodiment) obtain the mixing enhancing modified of silicon-dioxide after the dry glue of 96.46gSBR1500 is mixing, compare with pure SBR1500, the tensile strength 210.3kpa of rubber after modification, only improves 7.2%.And in embodiment 1, under the condition that in rubber, theoretical silicone content is the same, modified rubber back draft intensity can improve 21.7%.
Claims (13)
1. a silicon situ-formed graft hybrid modification is containing the method for poly-conjugated-diolefin latex, it is characterized in that: the dry glue quality of take containing the latex of poly-conjugated-diolefin is 100 parts, 10～15 parts of the organo-siloxane monomers that contains unsaturated link(age) are joined in the latex that contains poly-conjugated-diolefin, fully be uniformly mixed, under 5～85 ℃ of temperature and agitation condition, add 0.20～0.36 part of initiator to carry out graft polymerization reaction 5～8h, the utilization ratio of organosilane reaches 87%～95%, finally that the emulsion condensation of graft modification is dry; The organo-siloxane monomer structure formula that contains unsaturated link(age) is:
The unsaturated aliphatic segment that Y-contains 2～18 carbon;
R
1the siloxy of-the alkoxyl group that contains 1～12 carbon, the aryloxy of 6～12 carbon or 3～12 carbon;
R
2the siloxy of-the alkoxyl group that contains 1～12 carbon, the aryloxy of 6～12 carbon, 3～12 carbon; The saturated segment of 1～20 carbon, cyclic alkane or the aromatic hydrocarbon of 1～8 carbon;
R
3the siloxy of-the alkoxyl group that contains 1～12 carbon, the aryloxy of 6～12 carbon, 3～12 carbon; The saturated segment of 1～20 carbon, cyclic alkane or the aromatic hydrocarbon of 1～8 carbon.
2. method according to claim 1, it is characterized in that the latex that contains poly-conjugated-diolefin is homopolymer or multipolymer containing conjugated diene structural unit, take homopolymer or copolymer quality as 100%, and conjugated diene structural unit content is 50%～100%.
3. method according to claim 2, in the latex that it is characterized in that containing poly-conjugated-diolefin, conjugated diene structural unit content is 60%～80%.
4. method according to claim 1, in the organo-siloxane monomer that it is characterized in that containing unsaturated link(age), Y is vinyl, propenyl, allyl group, sec.-propyl, pseudoallyl, isopentene group, 3-pentenyl, 6-octenyl, tetramethyl-ethylene base, ethynyl, 1-proyl, ethyl acetylene base, 1-pentynyl, 1-heptyne base, methacryloxypropyl or methacryloxy.
5. method according to claim 1, R in the organo-siloxane monomer that it is characterized in that containing unsaturated link(age)
1for methoxyl group, oxyethyl group, propoxy-, isopropoxy, n-butoxy, hexyloxy, pentyloxy, positive heptan oxygen base, different octyloxy, positive ninth of the ten Heavenly Stems oxygen base, phenoxy group, chlorophenoxy, benzyloxy or trimethylsiloxy group.
6. method according to claim 1, in the organo-siloxane monomer that it is characterized in that containing unsaturated link(age), Y is vinyl or methacryloxypropyl, R
1for methoxyl group, oxyethyl group or isopropoxy, R
2for methyl, ethyl, methoxy or ethoxy, R
3for methyl, ethyl, methoxy or ethoxy.
7. method according to claim 1, is characterized in that the organo-siloxane monomer that contains unsaturated link(age) is one or more in vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane, vinyl silane triisopropoxide, γ-methacryloxypropyl trimethoxy silane, three (trimethylsiloxy group) methacryloxypropyl silane.
8. method according to claim 7, is characterized in that the organo-siloxane monomer that contains unsaturated link(age) is one or more in vinyltriethoxysilane, vinyltrimethoxy silane, three (trimethylsiloxy group) methacryloxypropyl silane.
9. method according to claim 1, is characterized in that initiator is thermal decomposition initiating or redox initiator.
10. method according to claim 9, while it is characterized in that thermal decomposition initiating is oil-soluble initiator, is first dissolved in oil-soluble initiator in emulsifier solution, and emulsifier solution and initiator mass ratio are 60～70:1.
11. methods according to claim 10, is characterized in that emulsifying agent is anionic emulsifier.
12. methods according to claim 9, while it is characterized in that thermal decomposition initiating is water soluble starter, are first dissolved in water soluble starter in deionized water, and deionized water and initiator mass ratio are 60～70:1.
13. methods according to claim 9, is characterized in that in redox initiator that oxygenant and reductive agent mass ratio are 2～10:1.
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| TWI471335B (en) * | 2011-12-13 | 2015-02-01 | Tsrc Corp | Conjugated diene rubber modified with polar alkoxysilane, method and composition thereof |
| EP2799454B1 (en) | 2011-12-28 | 2017-07-12 | Zeon Corporation | Method for producing modified conjugated diene rubber |
| CN105732689B (en) * | 2014-12-11 | 2018-08-14 | 中国石油天然气股份有限公司 | Rubber reinforcing agent, preparation method thereof and preparation method of reinforced nitrile rubber |
| CN105778000B (en) * | 2014-12-16 | 2019-02-15 | 中国石油天然气股份有限公司 | Isoprene rubber grafted maleic anhydride and preparation method thereof |
| CN107641228B (en) * | 2016-07-20 | 2022-10-21 | 中国石油化工股份有限公司 | Use of organosilanes and rubber compositions and vulcanizates and process for their preparation |
| CN110746543B (en) * | 2018-07-23 | 2023-04-07 | 中国石油化工股份有限公司 | Middle-end functionalized high cis-1, 4BR of molecular chain, synthetic method thereof and application thereof in tire rubber |
| CN110872368B (en) * | 2018-09-03 | 2022-09-06 | 中国石油化工股份有限公司 | Formula of multi-double-bond polar compound modified semi-steel radial tire tread rubber |
| CN110952323B (en) * | 2019-12-30 | 2022-02-08 | 中国科学院上海应用物理研究所 | Polyester industrial yarn-based tire cord and preparation method thereof |
| CN113388119B (en) * | 2021-06-04 | 2022-03-22 | 诚展（清远）鞋业有限公司 | Preparation method of polyhydroxysilane modified butadiene rubber and ozone aging resistant rubber |
| CN114716969A (en) * | 2022-04-26 | 2022-07-08 | 江苏金贸科技发展有限公司 | High-displacement modified silicone adhesive |
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