CN103261245B - 含有酸单体单元的苯乙烯基共聚物及其分散体、制备和用途 - Google Patents
含有酸单体单元的苯乙烯基共聚物及其分散体、制备和用途 Download PDFInfo
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- CN103261245B CN103261245B CN201180059738.XA CN201180059738A CN103261245B CN 103261245 B CN103261245 B CN 103261245B CN 201180059738 A CN201180059738 A CN 201180059738A CN 103261245 B CN103261245 B CN 103261245B
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- Prior art keywords
- multipolymer
- bituminous composition
- styrene
- polymer modification
- butadiene
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- 239000006185 dispersion Substances 0.000 title claims abstract description 94
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- 239000000178 monomer Substances 0.000 title claims abstract description 61
- 229920001577 copolymer Polymers 0.000 title claims abstract description 44
- 239000002253 acid Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 86
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 90
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- 238000012986 modification Methods 0.000 claims description 44
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- 238000004073 vulcanization Methods 0.000 claims description 23
- 239000007787 solid Substances 0.000 claims description 20
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- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
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- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
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- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 150000003949 imides Chemical class 0.000 description 4
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 3
- YXGOYRIWPLGGKN-UHFFFAOYSA-N 2,3-ditert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=C(O)C=CC(O)=C1C(C)(C)C YXGOYRIWPLGGKN-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- UEZWYKZHXASYJN-UHFFFAOYSA-N cyclohexylthiophthalimide Chemical compound O=C1C2=CC=CC=C2C(=O)N1SC1CCCCC1 UEZWYKZHXASYJN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
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- 239000011115 styrene butadiene Substances 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- QWQNFXDYOCUEER-UHFFFAOYSA-N 2,3-ditert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C QWQNFXDYOCUEER-UHFFFAOYSA-N 0.000 description 2
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- JHWGFJBTMHEZME-UHFFFAOYSA-N 4-prop-2-enoyloxybutyl prop-2-enoate Chemical compound C=CC(=O)OCCCCOC(=O)C=C JHWGFJBTMHEZME-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 150000004982 aromatic amines Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
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- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
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- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
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- NBGTWXBPCIHUQD-UHFFFAOYSA-N diethylcarbamodithioic acid;n-ethylethanamine Chemical compound CCNCC.CCN(CC)C(S)=S NBGTWXBPCIHUQD-UHFFFAOYSA-N 0.000 description 1
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- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- ILXWFJOFKUNZJA-UHFFFAOYSA-N ethyltellanylethane Chemical group CC[Te]CC ILXWFJOFKUNZJA-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- WHDGWKAJBYRJJL-UHFFFAOYSA-K ferbam Chemical compound [Fe+3].CN(C)C([S-])=S.CN(C)C([S-])=S.CN(C)C([S-])=S WHDGWKAJBYRJJL-UHFFFAOYSA-K 0.000 description 1
- QJQZEJFUIOWFMS-UHFFFAOYSA-N formaldehyde;sulfanediol Chemical compound O=C.OSO QJQZEJFUIOWFMS-UHFFFAOYSA-N 0.000 description 1
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- 238000007710 freezing Methods 0.000 description 1
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- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
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- 238000005658 halogenation reaction Methods 0.000 description 1
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- ZGCHATBSUIJLRL-UHFFFAOYSA-N hydrazine sulfate Chemical compound NN.OS(O)(=O)=O ZGCHATBSUIJLRL-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-M hydrosulfide Chemical compound [SH-] RWSOTUBLDIXVET-UHFFFAOYSA-M 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- CKFMJXZQTNRXGX-UHFFFAOYSA-L iron(2+);diperchlorate Chemical compound [Fe+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O CKFMJXZQTNRXGX-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
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- 229940049920 malate Drugs 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- BLCKKNLGFULNRC-UHFFFAOYSA-L n,n-dimethylcarbamodithioate;nickel(2+) Chemical compound [Ni+2].CN(C)C([S-])=S.CN(C)C([S-])=S BLCKKNLGFULNRC-UHFFFAOYSA-L 0.000 description 1
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 description 1
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- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
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- 229920003192 poly(bis maleimide) Polymers 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- TVPFLPJBESCUKI-UHFFFAOYSA-M potassium;n,n-dimethylcarbamodithioate Chemical compound [K+].CN(C)C([S-])=S TVPFLPJBESCUKI-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 238000005070 sampling Methods 0.000 description 1
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- 239000004332 silver Substances 0.000 description 1
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- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- VYGBQXDNOUHIBZ-UHFFFAOYSA-L sodium formaldehyde sulphoxylate Chemical class [Na+].[Na+].O=C.[O-]S[O-] VYGBQXDNOUHIBZ-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- IRZFQKXEKAODTJ-UHFFFAOYSA-M sodium;propan-2-yloxymethanedithioate Chemical class [Na+].CC(C)OC([S-])=S IRZFQKXEKAODTJ-UHFFFAOYSA-M 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XDLNRRRJZOJTRW-UHFFFAOYSA-N thiohypochlorous acid Chemical compound ClS XDLNRRRJZOJTRW-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- RKQOSDAEEGPRER-UHFFFAOYSA-L zinc diethyldithiocarbamate Chemical compound [Zn+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S RKQOSDAEEGPRER-UHFFFAOYSA-L 0.000 description 1
- PGNWIWKMXVDXHP-UHFFFAOYSA-L zinc;1,3-benzothiazole-2-thiolate Chemical compound [Zn+2].C1=CC=C2SC([S-])=NC2=C1.C1=CC=C2SC([S-])=NC2=C1 PGNWIWKMXVDXHP-UHFFFAOYSA-L 0.000 description 1
- NEYNBSGIXOOZGZ-UHFFFAOYSA-L zinc;butoxymethanedithioate Chemical class [Zn+2].CCCCOC([S-])=S.CCCCOC([S-])=S NEYNBSGIXOOZGZ-UHFFFAOYSA-L 0.000 description 1
- JGSUMMPGKPITGK-UHFFFAOYSA-L zinc;n,n-dipentylcarbamodithioate Chemical compound [Zn+2].CCCCCN(C([S-])=S)CCCCC.CCCCCN(C([S-])=S)CCCCC JGSUMMPGKPITGK-UHFFFAOYSA-L 0.000 description 1
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 description 1
- SZNCKQHFYDCMLZ-UHFFFAOYSA-L zinc;propan-2-yloxymethanedithioate Chemical class [Zn+2].CC(C)OC([S-])=S.CC(C)OC([S-])=S SZNCKQHFYDCMLZ-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
- C08L95/005—Aqueous compositions, e.g. emulsions
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2676—Polystyrenes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/26—Bituminous materials, e.g. tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/10—Copolymers of styrene with conjugated dienes
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Abstract
本发明提供了含有酸单体单元的苯乙烯基共聚物及其分散体、制备方法和用途。所述苯乙烯基共聚物通过在40°C或更高的温度下聚合苯乙烯、一种或多种酸单体和任选地丁二烯并且然后硫化而制备。所得的苯乙烯基共聚物用于沥青基体系中。
Description
相关申请的交叉引用
本申请要求于2010年10月14日提交的美国临时专利申请61/393,189的优先权,该申请全文以引用的方式纳入本申请。
背景技术
苯乙烯-丁二烯聚合物分散体用于制备多种产品,包括汽车轮胎、地毯背衬、粘合剂、泡沫、纸张涂料和沥青乳液。制备苯乙烯-丁二烯共聚物分散体有两种常用的方法:低温法(即,冷聚合)和高温法(即,热聚合)。生产苯乙烯-丁二烯共聚物分散体的低温法包括在表面活性剂存在及不使用羧化酸共聚单体条件下,在通常为5°C-25°C的温度下聚合苯乙烯单体和丁二烯单体生产“冷”苯乙烯丁二烯橡胶(SBR)共聚物。低温法可用来制备高分子量聚合物而不会引入过度交联。与低温法不同,生产苯乙烯-丁二烯共聚物分散体的高温法包括在大于40°C的温度下,通常在50°C-95°C范围内,在表面活性剂和羧化酸单体存在下,聚合苯乙烯单体和丁二烯单体。
通常使用制备苯乙烯-丁二烯共聚物分散体的低温方法生产用于上述许多用途的苯乙烯-丁二烯共聚物分散体,因为所述分散体可聚集产生通常超过65%固体的高固体含量的分散体,且可交联(即,固化)以提高该SBR的拉伸强度而不会显著降低其伸长率。另一方面,热聚合方法通常被认为仅在生产具有窄粒径分布且固体含量低于55%的苯乙烯-丁二烯共聚物分散体是有用的,上述特性使得分散体在制备例如纸张涂料等产品时有用,这些产品不需要聚合物固体大于60%,并且羧化作用的存在提供了在生产这类产品遭遇到的高剪切环境下的胶乳颗粒稳定性。因此,热聚合方法通常仅在纸张涂料和一些低固体压敏粘合剂应用中合乎需要。
低温SBR水性分散体所存在的一个问题是它们通常不能被用于热混沥青制剂,例如用于道路铺设和沥青瓦的应用中的沥青制剂。用于道路铺设的热混沥青制剂必须符合战略性高速公路研究计划(StrategicHighwayResearchProgram,SHRP)中所提出的要求,包括具有合乎需要的动态剪切模量和劲度。高分子量非羧化SBR水性分散体导致热混沥青制剂粘度的不合需要的增加,使得难以将该制剂均匀施用在表面上。低分子量非羧化胶乳聚合物可制备较低粘度的热混沥青制剂;然而,它们不具有合乎需要的SHRP性能特性。
发明内容
本文公开了一种共聚物、制备共聚物的方法以及包含所述共聚物的方法和组合物。使用高温方法在40°C或更高的温度制备该共聚物。在一些实施例中,该共聚物包含苯乙烯和酸单体单元,即为羧化的,并可任选地包含丁二烯单体单元。在一些实施例中,该共聚物使用例如硫固化剂固化(硫化)。该共聚物可包含基于该共聚物中丁二烯单元总数计,多于20%的量的顺式-1,4丁二烯和少于60%的量的反式-1,4丁二烯。在一些实施方案中,苯乙烯与丁二烯单体单元的重量比为20:80至80:20。共聚物可仅来源于苯乙烯、丁二烯和酸单体或可包含其他单体(例如,丙烯腈或丙烯酰胺)或分子量调节剂。该共聚物可在水性分散体中提供并被改性以具有总的阳离子电荷。
还公开了制备共聚物的方法,包括在40°C或更高的温度下在水性介质中聚合苯乙烯和任选地丁二烯生产未固化的共聚物,其中聚合步骤在酸单体存在下进行。该方法可进一步包括用硫基固化剂固化共聚物生产固化的共聚物的步骤。在一些实施方案中,聚合步骤发生在50°C或更高的温度。聚合步骤可仅包括苯乙烯、丁二烯和酸单体或可包括其他单体(例如,丙烯腈或丙烯酰胺)或分子量调节剂。该方法还可包括改性该共聚物分散体使其具有总的阳离子电荷的步骤。在一些实施方案中,聚合反应以单步方法进行。
还公开了共聚物的混合物,其含有高温聚合的共聚物和第二种苯乙烯-丁二烯共聚物。在一些实施方案中,该第二种苯乙烯-丁二烯共聚物为在温度小于40°C下聚合而成的较高分子量的苯乙烯-丁二烯共聚物。该共聚物的混合物可作为水性分散体在水中提供。例如,该混合物可通过含有高温聚合的共聚物的水性分散体与含有第二种苯乙烯-丁二烯共聚物的水性分散体混合而制备。在一些实施方案中,在混合共聚物之后,固化该混合物。在一些实施方案中,第一种共聚物分散体含有至少一种第一表面活性剂而第二种共聚物分散体含有至少一种第二表面活性剂,其中该至少一种第一表面活性剂和至少一种第二表面活性剂可包括至少一种相同的表面活性剂。
还公开了聚合物改性的沥青组合物,包含沥青和高温共聚物。在一些实施方案中,沥青组合物基本上不含水并且具有例如在135°C小于2000cp的粘度。在一些实施方案中,该沥青组合物还含有水和沥青,并且共聚物用表面活性剂分散在水中形成沥青乳液。该沥青组合物可具有以基于共聚物和沥青总的固体含量计0.5%-30%的量存在的共聚物。该沥青组合物可含有第二种苯乙烯-丁二烯共聚物。在一些实施方案中,该第二种苯乙烯-丁二烯共聚物中苯乙烯与丁二烯单体单元的重量比为20:80至80:20,并且可在小于40°C的温度下聚合。
还公开了制备聚合物改性沥青的方法,包括在高于水的沸点的混合温度下将高温聚合的共聚物的水性分散体与沥青混合。例如,混合温度可以是150°C以上。该聚合物改性的沥青可含有第二种苯乙烯-丁二烯共聚物或聚苯乙烯聚合物。在一些实施方案中,该第二种苯乙烯-丁二烯共聚物中苯乙烯与丁二烯单体单元的重量比可为20:80至80:20,并且可在小于40°C的温度聚合。
还公开了制备聚合物改性的沥青乳液的方法,包含提供一种水性沥青乳液,并且将该沥青乳液与高温聚合的共聚物的水性分散剂混合。在一些实施方案中,该水性分散体可进一步含有第二种苯乙烯-丁二烯共聚物或聚苯乙烯聚合物,例如苯乙烯与丁二烯单体单元的重量比为20:80至80:20、且在小于40°C的温度聚合的共聚物。在一些实施方案中,共聚物的水性分散体(任选地包括第二种苯乙烯-丁二烯共聚物或聚苯乙烯聚合物)可聚集来增加固体含量。
本文描述的共聚物能提供用于热混合沥青体系所需要的性能和粘度。该共聚物可单独或与其他苯乙烯-丁二烯共聚物或聚苯乙烯聚合物混合用于固化或未固化体系中。此外,在热混合沥青体系中使用该共聚物时,固化该共聚物仅产生最小的粘度增加。当该共聚物用于沥青乳液时,该共聚物赋予从被共聚物改性的乳液中回收的沥青残渣以极好的弹性回复和清除性能。
具体实施方式
如此处描述的,该共聚物使用高温方法通过包括苯乙烯和任选丁二烯(即,1,3-丁二烯)的单体在40°C以上的温度聚合而制备。在一些实施方案中,所述单体包含丁二烯,得到含苯乙烯和丁二烯单体单元的苯乙烯-丁二烯共聚物。在共聚物聚合中使用的苯乙烯与丁二烯单体单元的重量比可为1:99-100:0、1:99-99:1或20:80-80:20。该重量比可为25:75或更大,30:70或更大,35:65或更大或者40:60或更大。该重量比可为70:30或更小,60:40或更小,50:50或更小,40:60或更小或者30:70或更小。在一些实施方案中,共聚物中苯乙烯与丁二烯单体单元的重量比为25:75。
共聚物可仅来源于苯乙烯、丁二烯和酸单体或可来源于其他单体,即,包含其他单体单元。在一些实施方案中,该共聚物含有20重量%或更少、15重量%或更少或者10重量%或更少的其他单体单元。例如,该聚合物可包含至少一种其他的共轭二烯单体(例如,异戊二烯)或天然橡胶。该共聚物还可包含至少一种其他的乙烯基芳族单体,例如α-甲基苯乙烯或邻氯苯乙烯。其他合适的单体包括丙烯腈、甲基丙烯腈、丙烯酰胺和甲基丙烯酰胺。在一些实施方案中,所述一种或多种其他的单体可包括至少一种(甲基)丙烯酸酯。例如,可使用甲基、乙基、正丁基、异丁基和2-乙基己基丙烯酸酯及甲基丙烯酸酯。
该共聚物中还可包含交联单体,例如二乙烯基苯。当该交联单体用于共聚物时,交联单体以0.2-5%的量存在,并且被认作是用于聚合物的单体总量的一部分。
该共聚物可包含酸单体单元。在一些实施方案中,该共聚物可包含20%或更少、15%或更少、10%或更少、5%或更少、4%或更少、3%或更少、2%或更少、1.5%或更少、1%或更少或者0.5%或更少的一种或多种酸单体,例如衣康酸、富马酸、丙烯酸、甲基丙烯酸和其混合物。
在一些实施方案中,共聚物仅包含苯乙烯、丁二烯和酸单体,以及任选地二乙烯基苯单体单元。在一些实施方案中,共聚物仅包含苯乙烯、丁二烯、酸和丙烯腈单体单元,以及任选地二乙烯基苯单体单元。在一些实施方案中,该共聚物可具有大于-80°C且小于100°C,或者大于-80°C且小于0°C的Tg。
当该共聚物由高温聚合生产时,该共聚物包含比低温聚合苯乙烯-丁二烯共聚物更多的顺式-1,4丁二烯单元。在一些实施方案中,该共聚物可包含基于该共聚物中丁二烯单元总量计多于20%的量的顺式-1,4丁二烯单元和少于60%的量的反式-1,4丁二烯单元。在一些实施方案中,该共聚物可包含基于该共聚物中丁二烯单元总量计多于30%的量的顺式-1,4丁二烯和少于55%的量的反式-1,4丁二烯。
在一些实施方案中,如在本文更详细描述的,使用硫固化剂交联或固化(即,硫化)该共聚物。可使用额外的交联剂或固化剂和/或交联单体,例如为二乙烯基苯;1,4-丁二醇二丙烯酸酯;甲基丙烯酸酐;含有1,3-二酮基团的单体(例如,(甲基)丙烯酸乙酰乙酰氧基乙基酯或双丙酮丙烯酰胺);含脲基团的单体(例如,脲基乙基(甲基)丙烯酸酯或丙烯酰胺基乙二醇酸和甲基丙烯酰胺基甘醇酸酯甲基醚);以及硅烷交联剂(例如,乙烯基三乙氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷和3-巯基丙基三甲氧基硅烷)。交联剂的其他例子包括环氧官能化的(甲基)丙烯酸酯单体(例如,缩水甘油基甲基丙烯酸酯);具有3-10个碳原子的α,β-单烯键式不饱和羧酸的N-烷氧基酰胺和其与带有1-4个碳原子的醇的酯(例如,N-甲氧基丙烯酰胺和N-甲氧基甲基丙烯酰胺);乙二醛基交联剂;含有两个乙烯基基团的单体;含有两个亚乙烯基基团的单体;和含有两个链烯基基团的单体。示例性交联单体包括二元和三元醇与α,β-单烯键式不饱和单羧酸的二酯或三酯(例如,二(甲基)丙烯酸酯、三(甲基)丙烯酸酯),其中可使用丙烯酸和甲基丙烯酸。这种含有两个非共轭烯键式不饱和双键的单体的例子有亚烷基二醇二丙烯酸酯和亚烷基二醇二甲基丙烯酸酯,例如乙二醇二丙烯酸酯、1,3-丁二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯和丙二醇二丙烯酸酯;甲基丙烯酸乙烯酯、丙烯酸乙烯酯、甲基丙烯酸烯丙酯、丙烯酸烯丙酯、马来酸二烯丙酯、富马酸二烯丙酯和亚甲基二丙烯酰胺。在一些实施方案中,该共聚物可包含0-5重量%的一种或多种交联单体。
该共聚物可以水性分散体提供。该共聚物分散体可包含一种或多种天然或合成的阴离子表面活性剂。该共聚物分散体可具有30-75%的固体含量。该分散体可具有30%或更大、35%或更大、40%或更大、45%或更大、50%或更大、55%或更大、60%或更大或者65%或更大的固体含量。该聚合物分散体可具有200nm或更小或者100nm或更小的平均粒径(例如20-100nm)。该共聚物分散体可具有总的阴离子电荷。在一些实施方案中,该共聚物分散体可被“反转(flipped)”,以通过加入一种或多种阳离子表面活性剂而将该共聚物分散体的电荷改变为具有总的阳离子电荷。适合的阳离子表面活性剂包括,例如,E-5(AkzoNobel,Chicago,IL)、(AkzoNobel,Chicago,IL)、
E-53(AkzoNobel,Chicago,IL)、E-606(AkzoNobel,Chicago,IL)、E-5127(AkzoNobel,Chicago,IL)、477HG(ChemturaCorp.,Greenwich,CT)、W-1(MeadWestvaco,Charleston,SC)、W-5(MeadWestvaco,Charleston,SC)、SBT(MeadWestvaco,Charleston,SC)和MQK(MeadWestvaco,Charleston,SC)。非离子型表面活性剂也可与阳离子表面活性剂一起使用。适合的非离子型离子表面活性剂包括BASFCorporation销售的TETRONICTM和PLURONICTM系列的环氧乙烷-环氧丙烷嵌段共聚物表面活性剂、乙氧基化壬基酚、辛基酚乙氧基化物、十二烷基酚乙氧基化物、直链醇乙氧基化物、支链醇乙氧基化物(例如十三烷醇乙氧基化物)、乙醇乙氧基化物、嵌段共聚物、PEG酯和蓖麻油乙氧基化物。
该共聚物可与至少一种其他的苯乙烯-丁二烯共聚物或聚苯乙烯聚合物一起以水性分散体提供,例如,通过将上文描述的含高温聚合的共聚物的第一种水性分散体与含其他的苯乙烯-丁二烯共聚物或聚苯乙烯聚合物的第二种水性分散体混合。在一些实施方案中,在第一种共聚物分散体中存在的至少一种表面活性剂与在第二种苯乙烯-丁二烯共聚物或聚苯乙烯分散体中的至少一种表面活性剂相同。在一些共聚物被固化的实施方案中,第一种共聚物分散体与第二种苯乙烯-丁二烯共聚物或聚苯乙烯分散体可在固化之前混合或者各共聚物分散体之一或二者在混合之前固化。在一些共聚物分散体被聚集的实施方案中,第一种共聚物分散体与第二种苯乙烯-丁二烯共聚物或聚苯乙烯分散体可在聚集之前混合或者各共聚物分散体之一或二者在混合之前聚集。此外,在一些共聚物分散体被反转的实施方案中,第一种共聚物分散体与第二种苯乙烯-丁二烯共聚物或聚苯乙烯分散体可在反转之前混合或者这两种共聚物分散体在混合之前反转。
所述另外的苯乙烯-丁二烯共聚物或聚苯乙烯可在高温下聚合或者在低于40°C的低温下被聚合,例如在5-25°C。在一些实施方案中,所述另外的聚合物可以是在低温下聚合的苯乙烯-丁二烯共聚物。所述另外的苯乙烯-丁二烯共聚物可具有例如如上文对于高温共聚物所描述的那些苯乙烯与丁二烯单体重量比。所述另外的苯乙烯-丁二烯共聚物也可包含例如如上文对于高温共聚物所描述的那些其他的单体,尽管低温SBR通常将不包含酸单体单元。在一些实施例中,可使用硫固化剂交联或固化所述另外的苯乙烯-丁二烯共聚物。所述另外的苯乙烯-丁二烯共聚物可包含基于共聚物中丁二烯单元总量计少于20%的量的顺式-1,4丁二烯和大于60%的量的反式-1,4丁二烯。
高温聚合的共聚物可通过在水性乳液聚合反应中聚合苯乙烯单体、任选的丁二烯单体,以及酸单体而制备,其聚合反应温度可为高于40°C、高于50°C、或高于60°C或者低于100°C、低于90°C或低于80°C。高温聚合的共聚物可通过连续式、半分批式(半连续式)或分批式方法生产。在一些实施例中,高温聚合的共聚物使用连续方法通过一种或多种单体物流、表面活性剂物流和引发剂物流连续进料到一个或多个反应器中而制备。所述一种或多种单体物流中的单体可以合乎需要的丁二烯与苯乙烯重量比进料。种子胶乳也可初始加入反应器。在一些实施方案中,使用高温聚合的共聚物的聚合方法可由单步聚合反应进行,例如通过使用单个反应器。此外,可生产均匀的共聚物颗粒(而非嵌段共聚物)。在一些实施方案中,聚合方法在不使用有机溶剂(例如N-甲基吡咯烷酮)条件下进行。
表面活性剂物流包括表面活性剂和水,并且在一些实施方案中,可与引发剂物流结合。在乳液物流中的表面活性剂可以是天然的或者合成的表面活性剂。例如,该表面活性剂可以是天然的表面活性剂,例如油酸钠或油酸钾或者松香酸的钠盐或钾盐。基于单体总重量计,该表面活性剂在反应器中以0.5-5重量%的量存在。
在70°C或更高的聚合温度下,在反应器中可用热引发剂,例如过硫酸铵、过硫酸钾或过硫酸钠。在低于70°C的聚合温度下,热引发剂可与含有自由基发生剂、还原剂和活化剂(例如,水溶性金属盐)的氧化还原引发剂结合使用或被其替代。
适合的自由基发生剂包括有机过氧化合物,例如苯甲酰基过氧化物、过氧化氢、二叔丁基过氧化物、二异丙苯基过氧化物、2,4-二氯苯甲酰基过氧化物、癸酰基过氧化物、月桂酰基过氧化物,二异丙基苯氢过氧化物、异丙基苯氢过氧化物、对甲烷氢过氧化物、α-蒎烯氢过氧化物、叔丁基氢过氧化物、乙酰丙酮过氧化物、甲基乙基酮过氧化物、琥珀酸过氧化物、二鲸蜡基过氧化二碳酸酯、叔丁基过氧化乙酸酯、叔丁基过氧化马来酸、叔丁基过氧化苯甲酸酯等;和烷基过缩酮,例如2,2-二-(叔丁基过氧化)丁烷、3,3-二(叔丁基过氧化)丁酸乙酯,或者1,1-二-(叔丁基过氧化)环己烷。在一些实施方案中,自由基发生剂包括二异丙基苯氢过氧化物或对甲烷氢过氧化物。基于单体总重量计,该自由基发生剂通常以0.01-2重量%或0.01-1重量%的量存在。
用于引发剂物流中的合适的还原剂包括二氧化硫;碱金属焦亚硫酸盐;碱金属亚硫酸盐和亚硫酸氢铵;硫代硫酸盐;连二亚硫酸盐和甲醛次硫酸盐;盐酸羟胺;硫酸肼;葡萄糖和抗坏血酸。例如,还原剂包括二水合甲醛化次硫酸钠(SFS)、偏亚硫酸氢钠或其混合物。基于单体总重量计,该还原剂以0.01-1重量%的量存在。此外,还原剂与自由基发生剂的重量比在0.2:1-1:1之间。
水溶性金属盐可以是铁、铜、钴、镍、锡、钛、钒、锰、铬或银盐且可选自各种水溶性金属盐。合适的水溶性金属盐包括硝酸铜(II)胺、偏硼酸铜(II)、溴酸铜(II)、溴化铜(II)、高氯酸铜、重铬酸铜(II)、六水合硝酸铜(II)、乙酸亚铁(II)、溴化铁(III)、六水合溴化铁(III)、高氯酸亚铁(II)、重铬酸铁(III)、甲酸铁(III)、乳酸铁(III)、苹果酸铁(III)、硝酸铁(III)、草酸铁(III)、五水合硫酸铁(II)、乙酸钴(II)、苯甲酸钴(II)、六水合溴化钴(II)、氯化钴(III)、四水合氟化钴(II)、次磷酸镍、辛酸镍、酒石酸锡、草酸钛、三溴化钒、硝酸银和氟硅酸银。金属还可与化合物(例如乙二胺四乙酸(EDTA))络合以增加其在水中的溶解性。例如,可使用铁/EDTA配合物或钴/EDTA配合物。基于单体总重量计,该水溶性金属盐以低于0.01重量%的量存在。
聚合反应可在分子量调节剂存在下进行以降低共聚物的分子量。合适的分子量调节剂包括C8-C12硫醇,例如辛基、壬基、癸基或十二烷基硫醇。在一些实施方案中,使用叔-十二烷基硫醇作为分子量调节剂。所用叔-十二烷基硫醇的量取决于共聚物所需的分子量。在一些实施方案中,基于单体总重量计,该分子量调节剂以0.01-4%重量(例如,0.1-1重量%)的量存在。
一种或多种单体物流、表面活性剂物流和引发剂物流可被分别加入一个反应器,在该反应器中发生苯乙烯与丁二烯单体的聚合。基于单体总重量计,反应器中水的总量为60-75重量%。乳液聚合反应将苯乙烯与丁二烯单体转化为共聚物颗粒的转化率通常为60-80%。
一旦达到所需的转化水平,通过往反应器中添加速止剂终止该聚合反应。速止剂可迅速地与自由基和氧化剂反应,因此破坏了任何存在的引发剂和聚合物自由基并阻止了新自由基的形成。典型的速止剂包括含有醌型结构的有机化合物(例如,醌)和可被氧化成醌型结构的有机化合物(例如,氢醌),任选地结合水溶性硫化物,例如,硫化氢、硫化铵、或碱金属或碱土金属的硫化物或硫氢化物;N-取代的二硫代氨基甲酸盐;亚烷基多胺与硫的反应产物,大致包含硫化物、二硫化物、多硫化物和/或其与其他化合物的混合物;二烷基羟胺;N,N'-二烷基-N,N'-亚甲基二羟胺;二硝基氯苯;二羟基二苯基硫醚,;二硝基苯基苯并噻唑基硫化物;和其混合物。在一些实施方案中,速止剂可以为氢醌或二甲基二硫代氨基甲酸钾。基于单体总重量计,该速止剂可以0.01-0.1重量%的量添加。然而,高温聚合可允许持续到单体完全转化,即,转化率大于99%,该情况下可不使用速止剂。
如上所提及的,高温聚合的共聚物还可以使用分批式方法生产。在分批式方法中,单体、表面活性剂、自由基发生剂和水全部被加入反应器且搅拌。在达到所需的聚合温度后,如果需要,加入包含还原剂和水溶性金属盐(如果需要)的活化剂溶液以引发聚合。
如果使用半分批式方法,单体、在水溶液中的表面活性剂及在水溶液中的自由基发生剂在一段时间内全部加入反应器,通常为3-9小时或3-6小时。如果需要,包括还原剂和/或水溶性金属盐的活化剂溶液可在开始其它进料之前加入反应器,或在一定时间间隔内加入到反应器中。优选使高温聚合的共聚物实现单体完全转化,即转化率大于99%,在这种情况下可不使用速止剂。然而,若需要,如果所需的转化率小于99%,可加入速止剂终止聚合反应。
一旦聚合反应终止(在连续式、半分批式或分批式方法中),可从胶乳分散体中除去未反应的单体。例如,在大气压力下闪蒸然后在减压下闪蒸除去丁二烯单体。苯乙烯单体可通过在塔中汽提除去。由此形成的聚合物分散体通常含有的固体含量小于60%。
共聚物分散体可被聚集,例如使用化学、冷冻或压力聚集,且移除水得到大于50%至75%的固体含量。在一些实施方案中,固体含量为55%或更大、60%或更大或者65%或更大。如上所述,高温共聚物分散体可在聚集之前与其他的苯乙烯-丁二烯共聚物混合。聚集的颗粒得到了具有更宽的粒径分布的更大颗粒的聚合物分散体。本文所描述的聚集的颗粒具有100nm-5μm的粒径。例如,粒径的范围可为100nm-2μm或200nm-1μm。
即使一旦所述的共聚集的分散体被浓缩,其也具有使其容易流动的粘度(即,其未胶凝)。例如,固体含量大于60%的水性分散体可具有在20°C下小于1000cp的粘度。当共聚物分散体为阴离子形式(在反转之前)可进行高温聚合共聚物分散体的聚集。
可向胶乳分散体中加入抗氧化剂来防止聚合物中双键的氧化,并且可在该胶乳硫化之前或之后加入。抗氧化剂可以是取代的苯酚或仲芳胺。示例性取代苯酚包括2,6-二-叔丁基-对甲酚(DBT);4,4'-硫代二(6-叔丁基-间甲酚);3-叔丁基-4-羟基苯甲醚(3-BHT);2-叔丁基-4-羟基苯甲醚(2-BHT);2,2-亚甲基二(4-甲基-6-叔丁基苯酚)(MBMBP);2,2-亚甲基二(4-乙基-6-叔丁基苯酚)(MBEBP);4,4'-亚丁基二(3-甲基-6-叔丁基苯酚)(SBMBP);2,2-亚乙基二(4,6-二-叔丁基苯酚);2,6-二-叔丁基-4-仲丁基苯酚;苯乙烯化苯酚;苯乙烯化-对甲酚;1,1,3-三(2-甲基-4-羟基-5-叔丁基苯酚)丁烷;四[亚甲基-3-(3,5-二-叔丁基-4-羟基苯酚)丙酸酯]甲烷;正十八烷基-3-(4-羟基-3,5-二-叔丁基苯酚)丙酸酯;二[3-(3-叔丁基-5-甲基-4-羟基苯基)丙酸]三甘醇酯;1,3,5-三甲基-2,4,6-三(3,5-二-叔丁基-4-羟基苄基)苯;2,2'-二羟基-3,3'-二(α-甲基环己基)-5,5'-二甲基二苯基甲烷;4,4-亚甲基二(2,6-二-叔丁基苯酚);三(3,5-二-叔丁基-4-羟基苯酚);三(3,5-二-叔丁基-4-羟基苯酚)异氰脲酸酯;1,3,5-三(3',5'-二-叔丁基-4-羟基苯甲酰)异氰脲酸酯;二[2-甲基-4-(3-正烷基硫代丙酰氧基)-5-叔丁基苯基]硫化物;1-氧代-3-甲基异丙基苯;2,5-二丁基氢醌;2,2'-亚甲基二(4-甲基-6-壬基苯酚);烷基化双酚;2,5-二-叔戊基氢醌;聚丁基化双酚-A、双酚-A;2,6-二-叔丁基-对乙基酚;2,6-二(2'-羟基-3-叔丁基-5'-甲基苄基)-4-甲基酚;1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯;对苯二甲酰基-二(2,6-二甲基-4-叔丁基-3-羟基苄基硫化物);2,6-叔丁基酚;2,6-二-叔丁基-2-二甲基氨基-对甲酚;2,2'-亚甲基二(4-甲基-6-环己基苯酚);二(3,5-叔丁基-4-羟基苯基)丙酸己二醇酯;(4-羟基-3,5-二-叔丁基苯胺基)-2,6-二(辛基硫代)-1,3,5-三嗪;2,2-硫代[二乙基-二-3-(3,5-二-叔丁基-4-羟基苯基)丙酸酯];N,N'-六亚甲基(3,5-二-叔丁基-4-羟基肉桂酰胺);3,5-二-叔丁基-4-羟基苄基磷酸二乙酯;2,4-二甲基-6-叔丁基苯酚;4,4'-亚甲基双(2,6-二-叔丁基苯酚);4,4'-硫代二(2-甲基-6-叔丁基苯酚);三[2-(3,5-二-叔丁基-4-羟基苯基)丙酰氧基乙基]异氰脲酸酯;2,4,6-三丁基苯酚;二[3,3-二(4'-羟基-3'-叔丁基苯基)丁酸]乙二醇酯;4-羟甲基-2,6-二-叔丁基苯酚;和二(3-甲基-4-羟基-5-叔丁基苄基)硫化物。示例性仲芳胺包括N-苯基-N'-异丙基-对苯二胺;N-苯基-N'-(1,3-二甲基丁基)-对苯二胺;N,N'-二苯基-对苯二胺;二辛基-二苯胺;二-β-萘基-对苯二胺;2,2,4-三甲基-1,2-二氢喹啉聚合物和二芳基-对苯二胺。此外,可使用含硫抗氧化剂,例如二月桂基硫代二丙酸酯、二硬脂基硫代二丙酸酯和2-巯基-苯并咪唑;含磷抗氧化剂,例如二硬脂基季戊四醇二亚磷酸酯;含镍抗氧化剂,如二异丁基二硫代氨基甲酸镍、二甲基二硫代氨基甲酸镍和二正丁基二硫代氨基甲酸镍;2-巯基甲代苯并咪唑;2-巯基甲代苯并咪唑锌;和1,11-(3,6,9-三氧杂十一烷基)二-3-(十二烷基硫代)丙酸酯。基于共聚物的重量计,该抗氧化剂可以0.1-5.0重量%或0.5-2.0重量%的量添加。
还可向共聚物分散体中加入抗臭氧剂来阻止大气中存在的臭氧通过裂解共聚物的双键而分解共聚物。典型的抗臭氧剂包括蜡(例如T.VanderbiltCo.,Inc.销售的VANWAXTMH)及对苯二胺的N,N'-烷基芳基、N-N'二烷基和N,N'-二芳基衍生物,例如N,N'-二(2-辛基)-对苯二胺、N,N'-二-3(5-甲基庚基)-对苯二胺、N-(1,3-二甲基丁基)-N'-苯基-对苯二胺(例如,R.T.VanderbiltCo.,Inc.销售的ANTOZITETM67P)、N-异丙基-N'-苯基-对苯二胺和N-环己烷基-N'-苯基-对苯二胺。基于共聚物的重量计,该抗臭氧剂以0.5-10重量%、1-5重量%或1.5-3重量%的量添加。
预硫化抑制剂也可加入到共聚物分散体中以防止聚合物的提前硫化或焦化。例如,N-环己基硫代邻苯二甲酰亚胺;邻苯二甲酸酐;N-环己基硫代邻苯二甲酰亚胺;N-苯基-N-(三氯甲基亚磺酰基)-苯磺酰胺;二-(磺酰氨基)-硫化物或多硫化物(例如,二-(N-甲基-对甲苯磺酰氨基)-二硫化物);取代的硫代膦酰胺(例如,N-环己基硫代-N-苯基二乙基膦酰胺);N-(亚磺酰基)甲基丙烯酰胺;硫取代的-1,3,5-三嗪、硫取代的二胺或硫取代的三胺;2-(硫代氨基)-4,6-二氨基-1,3,5-三嗪;N,N'-取代的二-(2,4-二氨基-s-三嗪-6-基)-低聚硫化物;和取代的硫代甲脒可用作预硫化抑制剂。在一些实施方案中,预硫化抑制剂为N-环己基硫代邻苯二甲酰亚胺(Flexsys销售的SANTOGARDTMPVI)或N-苯基-N-(三氯甲基亚磺酰基)苯磺酰胺(Bayer销售的VULKALENTTME)。基于聚合物的重量计,该预硫化抑制剂通常以1-5重量%或1.5-3重量%的量添加。
通常在硫化剂、硫化促进剂、抗返硫剂和任选地交联剂的存在下,通过加热共聚物,所述共聚物可被硫化以交联聚合物从而增加橡胶的拉伸强度和伸长率。示例性硫化剂包括各种硫,例如硫粉、沉淀硫、胶体硫、不溶硫和高分散的硫;卤化硫,例如一氯化硫和二氯化硫;硫供体,例如4,4'-二硫代二吗啉;硒;碲;有机过氧化物,如二异丙苯基过氧化物和二-叔丁基过氧化物;醌二肟,例如对醌二肟和p,p'-二苯甲酰基醌二肟;有机多胺化合物,如三亚乙基四胺、六亚甲基二胺氨基甲酸酯、4,4'-亚甲基二(环己基胺)氨基甲酸酯和4,4'-亚甲基二-邻氯苯胺;具有羟甲基的烷基苯酚树脂;以及它们的混合物。在一些实施例中,该硫化剂可包括硫分散体和硫供体。基于聚合物的重量计,该硫化剂可以0.1-15重量%、0.3-10重量%或0.5-5重量%的量添加。
示例性硫化促进剂包括亚磺酰胺类硫化促进剂,例如N-环己基-2-苯并噻唑亚磺酰胺、N-叔丁基-2-苯并噻唑亚磺酰胺、N-氧亚乙基-2-苯并噻唑亚磺酰胺、N-氧二亚乙基-2-苯并噻唑亚磺酰胺、N-氧二亚乙基-硫代氨基甲酰基-N-氧二亚乙基亚磺酰胺、N-氧亚乙基-2-苯并噻唑亚磺酰胺和N,N'-二异丙基-2-苯并噻唑亚磺酰胺;胍类硫化促进剂,例如二苯基胍、二-邻甲苯基胍和二-邻甲苯基双胍;硫脲型硫化促进剂,例如硫代羰基甲酰苯胺、二-磷甲苯基硫脲、亚乙基硫脲、二亚乙基硫脲、二丁基硫脲和三甲基硫脲;噻唑类硫化促进剂,例如2-巯基苯并噻唑、二苯并噻唑基二硫化物、2-巯基苯并噻唑锌盐、2-巯基苯并噻唑钠盐、2-巯基苯并噻唑环己胺盐、4-吗啉基-2-二苯并噻唑二硫化物和2-(2,4-二硝基苯基硫基)苯丙噻唑;噻二嗪类硫化促进剂,例如活化的噻二嗪;秋兰姆类硫化促进剂,如单硫化四甲基秋兰姆、二硫化四甲基秋兰姆、二硫化四乙基秋兰姆、二硫化四丁基秋兰姆和四硫化二-1,5-亚戊基秋兰姆;二硫代氨基甲酸类硫化促进剂,例如二甲基二硫代氨基甲酸钠、二乙基二硫代氨基甲酸钠、二-正丁基二硫代氨基甲酸钠、二甲基二硫代氨基甲酸铅、二戊基二硫代氨基甲酸铅、二戊基二硫代氨基甲酸锌、二甲基二硫代氨基甲酸锌、二乙基二硫代氨基甲酸锌、二-正丁基二硫代氨基甲酸锌、1,5-亚戊基二硫代氨基甲酸锌、乙基苯基二硫代氨基甲酸锌、二乙基二硫代氨基甲酸碲、二甲基二硫代氨基甲酸铋、二甲基二硫代氨基甲酸硒、二乙基二硫代氨基甲酸硒、二乙基二硫代氨基甲酸镉、二甲基二硫代氨基甲酸铜、二甲基二硫代氨基甲酸铁、二乙胺二乙基二硫代氨基甲酸酯、1,5-亚戊基二硫代氨基甲酸哌啶鎓和1,5-亚戊基二硫代氨基甲酸甲基哌啶鎓;黄原酸类硫化促进剂,例如异丙基黄原酸钠、异丙基黄原酸锌和丁基黄原酸锌;间苯二甲酸酯类硫化促进剂,例如氢间苯二甲酸二甲基铵;醛胺类硫化促进剂,例如丁醛-胺缩合产物和丁醛-单丁胺缩合产物;及其混合物。基于聚合物的重量计,该硫化促进剂以0.1-15重量%、0.3-10重量%或0.5-5重量%的量存在。
在硫化体系中还可包括抗返硫剂以防止返硫,即不合乎需要的交联密度的降低。合适的抗返硫剂包括脂肪族羧酸的锌盐、单环芳香酸的锌盐、双马来酰亚胺、双柠康酰亚胺、双衣康酰亚胺、芳基二-柠康酸、双琥珀酰亚胺和聚合的双琥珀酰亚胺多硫化物(例如,N,N'-二甲苯基二柠康酰胺)。基于聚合物的重量计,该抗返硫剂可以0-5重量%、0.1-3重量%或0.1-2重量%的量存在。
上述添加剂(抗氧化剂、抗臭氧剂、预硫化抑制剂、硫化剂、硫化促进剂和抗返硫剂)可与胶乳分散体混合。该硫化体系中也可以包含少量交联剂,以促进聚合物链的交联,并且交联剂通常为有机过氧化物。在升高的温度和压力下该胶乳分散体可被硫化,并且本领域技术人员熟知所述的硫化方法。
如上所述,高温聚合的苯乙烯-丁二烯共聚物分散体可与在温度低于40°C(例如5°C-25°C)下生产的低温聚合的苯乙烯-丁二烯共聚物分散体混合。应指出,除在较低温度下以外,可使用上述对于高温聚合的苯乙烯-丁二烯共聚物分散体描述的方法生产低温聚合的苯乙烯-丁二烯共聚物分散体。
高温苯乙烯-丁二烯共聚物及其分散体可在各种应用中使用。例如,高温共聚物可用于汽车轮胎、地毯背衬、粘合剂、泡沫和纸张涂料。在一些实施方案中,高温苯乙烯-丁二烯共聚物可用于沥青基体系,例如热混合沥青和沥青乳液。
在一些实施方案中,高温苯乙烯-丁二烯共聚物可用于热混合沥青制剂。例如,可通过在超过水的沸点的混合温度下将沥青与高温聚合共聚物的水分散体混合来制备聚合物改性的热混合沥青。例如混合温度可以是150°C或更高或者160°C或更高。高温聚合的共聚物可与本文所述的第二种苯乙烯-丁二烯共聚物混合。该聚合物改性的热混合沥青组合物基本上不含水,并且可具有例如在135°C为3000cp或更小、小于2000cp或者小于1500cp的粘度。在一些实施方案中,高温共聚物单独或作为混合物加入热混合沥青组合物可导致的粘度增加小于125%、小于100%、小于75%或小于50%。基于共聚物和沥青的总固体含量计,共聚物以0.5%-30重量%的量存在。例如,共聚物以1%或更多、1.5%或更多、2%或更多、2.5%或更多或者3%或更多的量存在,或者可以25%或更少、20%或更少、15%或更少、10%或更少、7.5%或更少或者5%或更少的量存在。在一些实施方案中,当该聚合物改性的热混合沥青组合物包含3%或更多的共聚物(例如,3.5%、4%、4.5%、5%、5.5%或6%)时,其粘度在135°C小于3000cp。此外,本文所描述的共聚物具有赋予热沥青(例如,135°C)以可调节粘度的能力,所述粘度可达20wt%胶乳聚合物的水平。如本文所指出的,高温聚合的共聚物可在与沥青混合之前被固化。在一些实施方案中,高温聚合的共聚物可与沥青混合,然后被固化。该聚合物改性的热混沥青制剂可用于道路铺设以形成路面或用于沥青瓦。
在一些实施方案中,高温共聚物可用于沥青乳液中。聚合物改性的沥青乳液包含沥青和用表面活性剂分散在水中的苯乙烯-丁二烯共聚物。通过提供水性沥青乳液并将该沥青乳液与高温共聚物的水性分散体混合,可以制备聚合物改性的沥青乳液。在一些实施方案中,水性分散体可进一步包含如本文所述的第二种苯乙烯-丁二烯共聚物。在一些实施方案中,共聚物(任选地包括第二种苯乙烯-丁二烯共聚物)的水性分散体可聚集以增加固体含量。基于共聚物和沥青的总固体含量计,共聚物可以0.5%-30%的量存在。例如,所述共聚物可以1%或更多、1.5%或更多、2%或更多、2.5%或更多的量存在,或者以25%或更少、20%或更少、15%或更少、10%或更少、7.5%或更少或者5%或更少的量存在。例如,所形成的沥青乳液可通过使用包括微表面处理的不同的表面处理而用于维护已铺设的沥青路面。
以下给出了非限制性的实施例。除非另有其他说明,百分比是基于重量比,溶液为水溶液。
实施例
实施例1-4和对比实施例1
采用热聚合制备胶乳
如上所列出的单体(以每100份单体的份数计(pphm))、叔-十二烷基硫醇(t-ddm),和过硫酸钠引发剂的水溶液在上述给出的时间段内加入到反应器中,该反应器被预热到聚合温度且初始包含水、聚苯乙烯种子胶乳和TRILONBX,为一种购自BASFCorporation(FlorhamPark,NJ)的乙二胺四乙酸。通过在聚合过程中加入表面活性剂的水溶液来实现聚合中胶乳颗粒的稳定。温度维持在所示的聚合温度下。聚合过程后,汽提除去胶乳分散体中的残余单体,得到残余苯乙烯含量小于400ppm的水性分散体。
胶乳聚合物改性的沥青样品的制备
沥青膏在160°C+/-3°C下预热至少两个小时,然后650克经加热的沥青膏倒入金属罐。该含有沥青的罐使用加热套加热到170°C+/-3°C。以大约20°的角度在该罐的中部插入一个叶片以提供最佳混合。根据上述方法制备的胶乳在300-325rpm的搅拌下缓慢加入到热沥青中。除非另有说明,该胶乳聚合物固体加入到沥青中的量基于胶乳聚合物和沥青总固体含量计为3wt%。在每次添加后,停留一段时间至大部分鼓泡停止,然后搅拌器的速度增加到大约400-700rpm以混合得到的混合物。在胶乳加入后,再继续搅拌两小时获得平衡的沥青聚合物混合物。对该聚合物改性的沥青样品取样用于粘度测定或倒入模具中用于任何所需的测试。
胶乳聚合物改性沥青的SHRP粘合剂测试
胶乳聚合物改性沥青的战略性公路研究计划(SHRP)评价是依据ASTMD7175或AASHTOT315程序,对原始的胶乳聚合物改性沥青(SHRP-新鲜)、暴露于滚动薄膜烘箱(RollingThin-FilmOven,RTFO)之后的胶乳聚合物改性沥青、以及在压力老化容器(PAV)中调节过的RTFO调节的胶乳聚合物改性沥青上实施。动态剪切流变仪(DSR)试验测量胶乳聚合物改性沥青的动态剪切模量和劲度。此外,弯曲梁流变仪(BBR)测试依据ASTMD6678或AASHTOT313进行,以测定胶乳聚合物改性的沥青粘合剂的低温劲度特征。原始的(未老化的或新鲜的)胶乳聚合物改性沥青的测试和RTFO暴露后的胶乳聚合物改性沥青的测试提供在性能等级(PG)尺度中高温的范围。RTFO和PAV暴露之后的胶乳聚合物改性沥青的测试提供涉及耐疲劳性的中间温度下的劲度,并且RTFO和PAV暴露之后的BBR测试提供了在PG尺度中低温的范围。
胶乳聚合物改性沥青的粘度
根据上述方法制备的胶乳聚合物改性沥青的粘度依据ASTMD4402或AASHTOT316(AmericanAssociationofStateHighwayandTransportationOfficials)测定。
沥青样品
在实施例1-4和对比实施例1中分别加入基于胶乳固体重量计2.1重量%的量的PARACURE850(含硫化促进剂的固化剂)。实施例以3重量%的量(基于干胶乳聚合物和干沥青计)与Nustar64-22热混合,Nustar64-22为具有64-22性能等级的NuStarAsphaltRefiningLLC(Savannah,GA)销售的沥青。提供Nustar64-22作为对照组。对比实施例2为通过冷聚合(即,在25°C或更低的温度)苯乙烯和丁二烯制备的苯乙烯-丁二烯共聚物。测定了沥青的PG等级和粘度并提供于表1中。
表1
如表1中所示,热聚合的非羧化苯乙烯-丁二烯(对比实施例1)和羧化苯乙烯-丁二烯(实施例1-4)共聚物分散体均具有用于聚合物改性沥青所需的性能。包含实施例4的用作新鲜(未老化)样品的沥青样品具有在70°C下小于76°的相角,该相角是合乎需要的,也具有良好的76-28的性能等级。羧化苯乙烯-丁二烯共聚物分散体具有1600cp或更小的粘度且比冷聚合苯乙烯-丁二烯分散体(对比实施例2)的粘度要小得多。
如上文所述制备实施例1和对比实施例1,但是使用如下表所示的不同量的PARACURE850。实施例用3重量%的量与Nustar64-22热混合。测定了沥青的PG等级和粘度并提供于表2中。
表2
如表2中所示,在不同的固化剂量下,热聚合的非羧化苯乙烯-丁二烯(对比实施例1)和羧化苯乙烯-丁二烯(实施例1)共聚物分散体均具有聚合物改性沥青中所需的性能。非羧化苯乙烯-丁二烯共聚物分散体在具有1.05wt%的固化剂时表现最佳,而羧化苯乙烯-丁二烯共聚物分散体在具有8.4wt%的固化剂时表现最佳。由于使用硫固化剂实际上要比共聚物分散体便宜,更高的固化剂用量是有利的。此外,羧化苯乙烯-丁二烯共聚物分散体通常具有很低的相角,这是合乎需要的。
所附权利要求的组合物和方法不限于本说明书所述的具体组合物和方法,本说明书所述的具体组合物和方法意在示例说明权利要求的一些方面,与其功能上等价的任何组合物和方法均落入权利要求的范围。除了本文所示和所描述的以外,组合物和方法的各种变形都将落入所附权利要求的范围。此外,虽然仅有本文公开的某些代表性的组合物材料和方法步骤进行了详细描述,组合物材料和方法步骤的其他组合即使没有具体提及,也将落入所附权利要求的范围。因此,一些步骤、元素、组分或成分的组合可在此处明确提及;然而,其他的一些步骤、元素、组分或成分的组合即使没有明确声明,也将包括在内。在此处使用的术语“包含”及其各种变化与术语“包括”及其各种变化是同义的,并且是开放式、非限制性的术语。尽管本文使用了“包含”和“包括”描述各种不同的实施方案,术语“基本上由……组成”和“由……组成”可用于代替“包含”和“包括”来提供更多的具体实施方案,并且也被公开。
Claims (41)
1.一种聚合物改性的沥青组合物,包括
沥青;和
一种共聚物分散体,包括:
在水性介质中在40℃或更高的温度下聚合苯乙烯、一种或多种酸单体和丁二烯产生未固化的共聚物;以及
将硫基固化剂与该共聚物混合,当共聚物暴露于高温下时所述固化剂使得共聚物固化,
其中基于共聚物中丁二烯单元总数计,顺式-1,4丁二烯单元的量大于20%并且反式-1,4丁二烯单元的量小于60%。
2.权利要求1的聚合物改性的沥青组合物,其中所述聚合步骤包含丁二烯。
3.权利要求1的聚合物改性的沥青组合物,其中所述聚合步骤包含10%或更少的所述一种或多种酸单体并且所述聚合步骤包括聚合苯乙烯和丁二烯。
4.权利要求1-3中任一项的聚合物改性的沥青组合物,其中所述聚合步骤包含5%或更少的所述一种或多种酸单体。
5.权利要求1-3中任一项的聚合物改性的沥青组合物,其中所述的聚合步骤包含3%或更少的所述的一种或多种酸单体。
6.权利要求1-3中任一项的聚合物改性的沥青组合物,其中所述聚合步骤中的所述一种或多种酸单体包括衣康酸、富马酸、丙烯酸和甲基丙烯酸中的一种或多种。
7.权利要求1-3中任一项的聚合物改性的沥青组合物,还包括在高温下用硫基固化剂固化共聚物的步骤以产生固化的共聚物。
8.权利要求7的聚合物改性的沥青组合物,其中所述固化步骤包括用硫基固化剂和硫化促进剂固化共聚物。
9.权利要求1-3中任一项的聚合物改性的沥青组合物,其中所述聚合步骤包括以苯乙烯和丁二烯重量比为20:80至80:20聚合苯乙烯和丁二烯。
10.权利要求1-3中任一项的聚合物改性的沥青组合物,其中所述聚合步骤包括在50℃或更高的温度下聚合苯乙烯和丁二烯。
11.权利要求1-3中任一项的聚合物改性的沥青组合物,其中所述聚合步骤包括仅聚合苯乙烯、丁二烯和酸单体。
12.权利要求1-3中任一项的聚合物改性的沥青组合物,其中所述聚合步骤包括聚合苯乙烯、丁二烯、酸单体,以及丙烯腈或丙烯酰胺中的一种或多种。
13.权利要求1-3中任一项的聚合物改性的沥青组合物,其中所述聚合步骤包括在分子量调节剂存在下聚合苯乙烯和丁二烯单体。
14.权利要求1-3中任一项的聚合物改性的沥青组合物,还包括通过在共聚物分散体中加入阳离子表面活性剂而将该共聚物分散体改变为具有总的阳离子电荷。
15.权利要求1-3中任一项的聚合物改性的沥青组合物,其中所述聚合以单步方法进行。
16.一种聚合物改性的沥青组合物,包括
沥青;和
一种共聚物,包含苯乙烯和酸单体单元,以及丁二烯,其中所述共聚物在40℃或更高的温度下聚合且被固化,
其中基于共聚物中丁二烯单元总数计,顺式-1,4丁二烯单元的量大于20%并且反式-1,4丁二烯单元的量小于60%。
17.权利要求16的聚合物改性的沥青组合物,还包含丁二烯单元。
18.权利要求17的聚合物改性的沥青组合物,其中所述共聚物包含10%或更少的所述酸单体单元。
19.权利要求16-18中任一项的聚合物改性的沥青组合物,其中苯乙烯和丁二烯单体单元的重量比为20:80至80:20。
20.权利要求16-18中任一项的聚合物改性的沥青组合物,其中所述共聚物仅得自苯乙烯、丁二烯和酸单体。
21.权利要求16-18中任一项的聚合物改性的沥青组合物,其中所述共聚物得自苯乙烯、丁二烯、酸单体以及丙烯腈或丙烯酰胺中的一种或多种。
22.权利要求16-18中任一项的聚合物改性的沥青组合物,其中所述共聚物得自苯乙烯、丁二烯、酸单体以及分子量调节剂。
23.一种聚合物改性的沥青组合物,包括一种权利要求16-22中任一项的共聚物和在小于40℃的温度下聚合的第二种苯乙烯-丁二烯共聚物的混合物。
24.权利要求23的聚合物改性的沥青组合物,其中所述共聚物与第二种苯乙烯-丁二烯共聚物混合然后固化。
25.一种聚合物改性的沥青组合物,包含水和权利要求16-22中任一项的共聚物或权利要求23或24的共聚物混合物。
26.权利要求25的聚合物改性的沥青组合物,还包含阳离子表面活性剂以制备具有总的阳离子电荷的分散体。
27.一种聚合物改性的沥青组合物,包括将具有至少一种第一表面活性剂的含有权利要求16-22中任一项的共聚物的水性分散体与在小于40℃的温度下聚合且含有至少一种第二表面活性剂的第二种苯乙烯-丁二烯共聚物的水性分散体混合,其中所述至少一种第一表面活性剂与所述至少一种第二表面活性剂包含至少一种相同的表面活性剂。
28.权利要求27的聚合物改性的沥青组合物,还包括固化所述混合步骤的混合物的步骤。
29.权利要求1、16和23中任一项的沥青组合物,其中所述组合物基本上不含水。
30.权利要求1、16和23中任一项的沥青组合物,具有在135℃下小于2000cp的粘度。
31.权利要求1、16和23中任一项的沥青组合物,还包含水,其中沥青和共聚物用表面活性剂分散在水中形成沥青乳液。
32.权利要求1、16和23中任一项的沥青组合物,其中基于共聚物和沥青的总固体含量计,共聚物以0.5%-30%的量存在。
33.权利要求1、16和23中任一项的沥青组合物,还包含苯乙烯和丁二烯单体单元的重量比为20:80至80:20且在小于40℃的温度下聚合的第二种苯乙烯-丁二烯共聚物。
34.制备聚合物改性的沥青的方法,包括:
在高于水的沸点的混合温度下,混合沥青和权利要求16-22中任一项的苯乙烯-丁二烯共聚物的水性分散体。
35.制备聚合物改性的沥青的方法,包括:
在高于水的沸点的混合温度下,混合沥青和根据权利要求1-15中任一项所制备的共聚物的水性分散体。
36.权利要求35的方法,还包括在共聚物与沥青混合时的混合温度下固化该共聚物的步骤。
37.权利要求34-36中任一项的方法,其中混合的温度为150℃或更高。
38.权利要求34-36中任一项的方法,其中所述水性分散体还包含苯乙烯和丁二烯单体单元的重量比为20:80至80:20且在小于40℃的温度下聚合的第二种苯乙烯-丁二烯共聚物。
39.制备聚合物改性的沥青乳液的方法,包括:
提供水性沥青乳液;和
将该沥青乳液与权利要求16-22中任一项的苯乙烯-丁二烯共聚物或根据权利要求1-15中任一项所制备的共聚物的水性分散体混合。
40.权利要求39的方法,其中所述水性分散体还包含苯乙烯和丁二烯单体单元的重量比为20:80至80:20且在小于40℃的温度下聚合的第二种苯乙烯-丁二烯共聚物。
41.权利要求39或40的方法,其中所述共聚物的水性分散体被聚集以增加固体含量。
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- 2011-10-13 EP EP11832217.1A patent/EP2627681B1/en active Active
- 2011-10-13 PL PL11832217T patent/PL2627681T3/pl unknown
- 2011-10-13 BR BR112013009015A patent/BR112013009015A2/pt not_active Application Discontinuation
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CN106905711A (zh) | 2017-06-30 |
EP2627704A1 (en) | 2013-08-21 |
PL2627681T3 (pl) | 2019-03-29 |
US20160289451A1 (en) | 2016-10-06 |
US9365707B2 (en) | 2016-06-14 |
CN103261310A (zh) | 2013-08-21 |
US8952092B2 (en) | 2015-02-10 |
BR112013009032A2 (pt) | 2016-07-12 |
CN103261245A (zh) | 2013-08-21 |
WO2012049650A1 (en) | 2012-04-19 |
EP2627681B1 (en) | 2018-09-19 |
EP2627681A4 (en) | 2014-04-16 |
EP2627681A1 (en) | 2013-08-21 |
US20130289172A1 (en) | 2013-10-31 |
EP2627704B1 (en) | 2018-08-22 |
US20130289173A1 (en) | 2013-10-31 |
WO2012049651A1 (en) | 2012-04-19 |
US9815984B2 (en) | 2017-11-14 |
US9139720B2 (en) | 2015-09-22 |
US20140378603A1 (en) | 2014-12-25 |
ES2698391T3 (es) | 2019-02-04 |
EP2627704A4 (en) | 2014-04-23 |
BR112013009015A2 (pt) | 2016-07-12 |
ES2701780T3 (es) | 2019-02-25 |
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