CN115948121B - Modified asphalt coating based on monoepoxy end-capped diblock copolymer, and preparation method and application thereof - Google Patents
Modified asphalt coating based on monoepoxy end-capped diblock copolymer, and preparation method and application thereof Download PDFInfo
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- CN115948121B CN115948121B CN202310013089.4A CN202310013089A CN115948121B CN 115948121 B CN115948121 B CN 115948121B CN 202310013089 A CN202310013089 A CN 202310013089A CN 115948121 B CN115948121 B CN 115948121B
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- Prior art keywords
- modified asphalt
- diblock copolymer
- parts
- coating
- terminated
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- 239000010426 asphalt Substances 0.000 title claims abstract description 121
- 229920000359 diblock copolymer Polymers 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000576 coating method Methods 0.000 title claims description 54
- 239000011248 coating agent Substances 0.000 title claims description 52
- 239000003973 paint Substances 0.000 claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 32
- 239000003607 modifier Substances 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000004658 ketimines Chemical class 0.000 claims abstract description 26
- 239000004014 plasticizer Substances 0.000 claims abstract description 24
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004593 Epoxy Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 150000005215 alkyl ethers Chemical class 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 29
- -1 alkenyl arene Chemical class 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 239000003085 diluting agent Substances 0.000 claims description 15
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 15
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 14
- 239000007822 coupling agent Substances 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 13
- 239000002174 Styrene-butadiene Substances 0.000 claims description 12
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011115 styrene butadiene Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001350 alkyl halides Chemical class 0.000 claims description 6
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000003921 oil Substances 0.000 claims description 6
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- 239000003505 polymerization initiator Substances 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 claims description 2
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 claims description 2
- WAEOXIOXMKNFLQ-UHFFFAOYSA-N 1-methyl-4-prop-2-enylbenzene Chemical group CC1=CC=C(CC=C)C=C1 WAEOXIOXMKNFLQ-UHFFFAOYSA-N 0.000 claims description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 2
- ITMIRWIISVVMAK-UHFFFAOYSA-N 2-chloro-3-ethyloxirane Chemical compound CCC1OC1Cl ITMIRWIISVVMAK-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 101150012763 endA gene Proteins 0.000 claims description 2
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002641 lithium Chemical group 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 239000010690 paraffinic oil Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 claims 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000002982 water resistant material Substances 0.000 claims 1
- 238000004078 waterproofing Methods 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 21
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 230000002411 adverse Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000779 smoke Substances 0.000 abstract description 4
- 238000004939 coking Methods 0.000 abstract description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 20
- 229920001971 elastomer Polymers 0.000 description 17
- 239000007795 chemical reaction product Substances 0.000 description 13
- 239000005060 rubber Substances 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 10
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000012943 hotmelt Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920002725 thermoplastic elastomer Polymers 0.000 description 5
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 239000010692 aromatic oil Substances 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 4
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- RMGHERXMTMUMMV-UHFFFAOYSA-N 2-methoxypropane Chemical compound COC(C)C RMGHERXMTMUMMV-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- QJMYXHKGEGNLED-UHFFFAOYSA-N 5-(2-hydroxyethylamino)-1h-pyrimidine-2,4-dione Chemical compound OCCNC1=CNC(=O)NC1=O QJMYXHKGEGNLED-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 2
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical group C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- RQUBQBFVDOLUKC-UHFFFAOYSA-N 1-ethoxy-2-methylpropane Chemical compound CCOCC(C)C RQUBQBFVDOLUKC-UHFFFAOYSA-N 0.000 description 1
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 1
- ZXHQLEQLZPJIFG-UHFFFAOYSA-N 1-ethoxyhexane Chemical compound CCCCCCOCC ZXHQLEQLZPJIFG-UHFFFAOYSA-N 0.000 description 1
- VDMXPMYSWFDBJB-UHFFFAOYSA-N 1-ethoxypentane Chemical compound CCCCCOCC VDMXPMYSWFDBJB-UHFFFAOYSA-N 0.000 description 1
- ZYVYEJXMYBUCMN-UHFFFAOYSA-N 1-methoxy-2-methylpropane Chemical compound COCC(C)C ZYVYEJXMYBUCMN-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical compound CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- DBUJFULDVAZULB-UHFFFAOYSA-N 1-methoxypentane Chemical compound CCCCCOC DBUJFULDVAZULB-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ICBJCVRQDSQPGI-UHFFFAOYSA-N Methyl hexyl ether Chemical compound CCCCCCOC ICBJCVRQDSQPGI-UHFFFAOYSA-N 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920006465 Styrenic thermoplastic elastomer Polymers 0.000 description 1
- NTYDXFVCCCPXRG-UHFFFAOYSA-N [Li]C(C)(C)CC(C)(C)C Chemical compound [Li]C(C)(C)CC(C)(C)C NTYDXFVCCCPXRG-UHFFFAOYSA-N 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002998 adhesive polymer Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/30—Adapting or protecting infrastructure or their operation in transportation, e.g. on roads, waterways or railways
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to a single epoxy end-capped diblock copolymer-based modified asphalt paint, a preparation method and application thereof, wherein the raw materials of the modified asphalt paint comprise asphalt, a plasticizer, a modifier and a ketimine latent curing agent, the modifier is a single epoxy end-capped diblock copolymer, and the single epoxy end-capped diblock copolymer has the following structural formula:wherein R is 1 Is C 1 ‑C 10 A is a monoalkenyl arene polymer segment, C is a butadiene and/or isoprene polymer segment, R 2 Is C 1 ‑C 12 Alkyl ethers of (a). The invention adopts the single epoxy end-capped diblock copolymer as the modifier, which can effectively reduce the preparation temperature of the modified asphalt paint, shorten the preparation time, reduce the energy consumption and effectively slow down the adverse consequences of degradation, coking, gel and the like of the polymer in the high temperature process. Meanwhile, the modified asphalt paint has smaller viscosity, can be applied in construction at lower temperature and even normal temperature, and solves the problems of complex construction and smoke pollution existing in high-temperature construction of the paint.
Description
Technical Field
The invention relates to the technical field of building waterproof materials, in particular to a modified asphalt coating based on a monoepoxy end-capped diblock copolymer, and a preparation method and application thereof.
Background
The hot melt rubber asphalt waterproof paint is prepared by mixing asphalt, styrene thermoplastic elastomer and mineral powder serving as main materials with additives such as plasticizer, stabilizer and the like at high temperature, and has the advantages of large elongation, good adhesion and strong self-healing property. In engineering application, the hot-melt rubber asphalt waterproof coating is often used in combination with waterproof coiled materials, so that the problems of infirm adhesion, hollowing on a plane, sliding on a vertical surface, difficult operation of complex parts and the like of a single waterproof coiled material lap joint are solved, the influence on the waterproof coiled materials caused by deformation of a base layer is eliminated, and the reliability and durability of a waterproof layer are improved.
In the hot melt rubber asphalt waterproof coating, the styrene thermoplastic elastomer is dispersed in asphalt to form an aggregation state structure and a physical crosslinking point of a styrene chain segment, so that the cohesive force of the coating is provided, and the high-low temperature performance, the ageing resistance and the fatigue resistance of the asphalt coating are improved. However, in the preparation process of the hot melt rubber asphalt waterproof coating, due to the existence of physical crosslinking points in the styrene structure, the elastomer needs to be swelled for a long time at high temperature to be dispersed in the matrix asphalt, and the swelling and dissolving process of the elastomer needs to consume a large amount of energy, and simultaneously can cause degradation and performance loss of the elastomer in the high temperature process. In addition, because of the existence of the physical crosslinking point of the styrene structure, the coating is sticky and gelatinous, has extremely strong cohesive force and is difficult to directly carry out the blade coating construction, so that a heating and melting method is adopted in most cases, namely, the rubber asphalt waterproof coating is heated to a certain temperature through matched heating equipment to have good fluidity, and then the blade coating or the spray coating construction is carried out, but the difficulty of the construction is high and the energy consumption is high by using the method.
In general, in the prior art, the styrene thermoplastic elastomer is applied to the preparation of hot melt rubber asphalt waterproof materials, so that the contradiction between the physical and mechanical properties and the construction performance of the materials can not be solved. The addition amount of the elastomer is reduced, so that the viscosity of the rubber asphalt paint can be reduced, the workability is improved, and the cohesive force and the high temperature resistance of the paint can be reduced; the increased amount of the elastomer can improve the cohesive force and high temperature resistance of the coating, but at the same time, can cause the increase of the viscosity of the coating and the deterioration of the workability. In addition, because of the physical crosslinking and reinforcing effects of the styrene segments, the styrenic thermoplastic elastomers also need to be swollen for a long period of time at high temperatures to be dispersible in asphalt, which is also an insurmountable problem in the prior art.
Disclosure of Invention
The invention aims to solve the technical problems that the existing hot-melt rubber asphalt waterproof paint needs high-temperature treatment in preparation and application to cause energy loss, and the polymer generates degradation, performance loss and other adverse effects, so as to provide an improved modified asphalt paint.
The second object of the invention is to provide a preparation method of the modified asphalt paint.
A third object of the present invention is to provide the use of the modified asphalt paint described above.
In order to achieve the purpose, the invention adopts the following technical scheme:
the raw materials of the modified asphalt coating comprise asphalt, a plasticizer and a modifier, wherein the modifier is a single epoxy-terminated diblock copolymer, and the single epoxy-terminated diblock copolymer has the structural formula:wherein R is 1 Is C 1 -C 10 A is a monoalkenyl arene polymer segment, C is a butadiene and/or isoprene polymer segment, R 2 Is C 1 -C 12 The modified asphalt coating also includes a ketimine latent curing agent.
According to some embodiments of the invention, the mono alkenyl arene constituting the a is selected from the group consisting of one or more of styrene, p-methylstyrene, p-tert-butylstyrene, 2, 4-dimethylstyrene, a-methylstyrene, vinylnaphthalene, vinyltoluene, vinylxylene, 1-diphenylethylene.
Preferably, the mono alkenyl arene is selected from the group consisting of one or more of styrene, p-methylstyrene, alpha-methylstyrene. More preferably, the mono alkenyl arene is styrene.
According to some embodiments of the invention, the R 1 Selected from C 1 -C 6 Is a hydrocarbon group. Preferably, said R 1 Selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, hexyl. Further preferably, the R 1 Selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl.
According to some embodiments of the invention, the R 2 Selected from C 2 -C 8 Alkyl ethers of (a). Preferably, said R 2 Selected from the group consisting of methyl ethyl ether, methyl isopropyl ether, methyl butyl ether, methyl isobutyl ether, methyl amyl ether, methyl hexyl ether, diethyl ether, ethyl isopropyl ether, ethyl butyl ether, ethyl isobutyl ether, ethyl amyl ether, and ethyl hexyl ether. Further preferably, the R 2 Selected from methyl ethyl ether, methyl isopropyl ether, diethyl ether, ethyl isopropyl ether.
According to some embodiments of the invention, the monoepoxy-terminated diblock copolymer is a monoepoxy-terminated styrene-butadiene/isoprene diblock copolymer.
According to some embodiments of the invention, the a is present in the monoepoxy-terminated diblock copolymer in an amount of from 10 to 50% by mass, preferably from 20 to 40% by mass. More preferably 25 to 35%.
According to some embodiments of the invention, the single epoxy-terminated diblock copolymer has a number average molecular weight of 5000 to 150000, preferably 30000 to 80000, and more preferably 30000 to 50000.
According to some embodiments of the invention, the mass ratio of the asphalt, the monohydroxy terminated diblock copolymer, the plasticizer and the ketimine latent curing agent is 10:0.5-3:1.5-15: 0.05 to 0.5.
Further, the raw materials of the modified asphalt paint also comprise a curing accelerator.
According to some embodiments of the present invention, the raw materials of the modified asphalt coating comprise, by weight, 100 parts of asphalt, 5-30 parts of a single epoxy-terminated diblock copolymer, 15-150 parts of a plasticizer, 0.5-5.0 parts of a ketimine latent curing agent, and 0.1-2 parts of a curing accelerator. Preferably, the raw materials of the modified asphalt coating comprise, by weight, 100 parts of asphalt, 8-20 parts of a single epoxy-terminated diblock copolymer, 50-100 parts of a plasticizer, 1.0-4.0 parts of a ketimine latent curing agent and 0.2-1.0 parts of a curing accelerator.
Further, the asphalt is matrix asphalt, such as 70# asphalt and 90# asphalt.
Further, the ketimine latent curing agent is prepared by reacting one or more of aliphatic amine, alicyclic amine, polyether amine and polyamide with ketone, such as ketimine DA315 and ketimine DA360A.
Further, the plasticizer is one or a combination of more of aromatic oil, naphthenic oil and paraffinic oil.
Further, the curing accelerator is one or a combination of a plurality of aniline accelerators and fatty amine accelerators, for example, the curing accelerator is one or a combination of a plurality of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine and fatty amine.
According to some embodiments of the invention, the raw materials of the modified asphalt paint further comprise one or a combination of more of reactive diluents, fillers and coupling agents.
According to some specific embodiments of the invention, the raw materials of the modified asphalt paint comprise, by weight, 100 parts of asphalt, 5-30 parts of single epoxy end-capped diblock copolymer, 15-150 parts of plasticizer, 0.5-5.0 parts of ketimine latent curing agent, 0.1-2 parts of curing accelerator, 0-10 parts of reactive diluent, 0-120 parts of filler and 0-5 parts of coupling agent. Preferably, the raw materials of the modified asphalt coating comprise, by weight, 100 parts of asphalt, 8-20 parts of a single epoxy end-capped diblock copolymer, 50-100 parts of a plasticizer, 1-2 parts of a ketimine latent curing agent, 0.1-2 parts of a curing accelerator, 0-10 parts of a reactive diluent, 0-120 parts of a filler and 0-5 parts of a coupling agent.
Further, the filler is one or a combination of more of talcum powder, heavy calcium carbonate, light calcium carbonate, kaolin, attapulgite, bentonite and silicon micropowder.
Further, the reactive diluent is one or a combination of a plurality of single epoxy reactive diluents, double epoxy reactive diluents and multiple epoxy reactive diluents.
Further, the coupling agent is a silane coupling agent, such as one or more of gamma-aminopropyl triethoxysilane (KH 550), gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane, gamma-methacryloxypropyl trimethoxysilane (KH 570).
The second technical scheme adopted by the invention is as follows: the preparation method of the modified asphalt paint comprises the following steps:
step S1, preparation of a Single epoxy terminated diblock copolymer
Subjecting the monoalkenyl arene monomer constituting the A to anionic polymerization to produce a monoalkenyl arene polymer having an activated end;
polymerizing the polymer of mono alkenyl arene having an activated end with butadiene and/or isoprene to produce a diblock copolymer having an activated end;
reacting said diblock copolymer having an activated end with an alkylene oxide and an haloalkylene oxide in sequence to give a polymer having said activated endA structural monoepoxy-terminated diblock copolymer;
s2, preparing modified asphalt paint
And mixing all the raw materials of the modified asphalt coating to obtain the modified asphalt coating.
Further, the implementation of step S1 includes:
step S11, in the presence of a saturated hydrocarbon solvent and an anionic polymerization initiator, enabling the mono-alkenyl arene monomer to react to generate the mono-alkenyl arene polymer with an activated end, so as to obtain a solution system containing the mono-alkenyl arene polymer with the activated end;
step S12, adding butadiene and/or isoprene to a solution system containing the mono alkenyl arene polymer with the activated end, and enabling the mono alkenyl arene polymer with the activated end to react with butadiene and/or isoprene to generate the diblock copolymer with the activated end, so as to obtain a solution system containing the diblock copolymer with the activated end;
step S13, alkylene oxide and alkyl halide are sequentially added into a solution system containing the diblock copolymer with the activated end, so that the diblock copolymer with the activated end sequentially reacts with the alkylene oxide and the alkyl halide to obtain the diblock copolymer with the monoepoxy end.
Further, the implementation of step S2 includes:
step S21, mixing asphalt, plasticizer and/or filler, stirring and heating to 110-120 ℃ under the condition that the relative vacuum degree is minus 0.08-minus 0.095MPa, and dehydrating to obtain a first mixture;
step S22, heating the first mixture to 140-160 ℃, adding the single epoxy-terminated diblock copolymer, and dissolving the single epoxy-terminated diblock copolymer to obtain a second mixture;
and S23, cooling the second mixture to 60-70 ℃, adding a ketimine latent curing agent, or/and adding one or a combination of a curing accelerator, a reactive diluent and a coupling agent, and mixing to obtain the modified asphalt coating.
In some embodiments, the saturated hydrocarbon solvent is at least one of pentane, octane, heptane, cyclohexane, n-hexane, benzene, toluene, ethylbenzene, xylene.
In some embodiments, the anionic polymerization initiator is an alkyl lithium initiator, the alkyl lithium initiator is one or a combination of several of RLi, R is an alkane group with 1-10 carbon atoms, and Li is a lithium atom. Preferably, the alkyl lithium initiator is selected from the group consisting of methyl lithium, ethyl lithium, propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, amyl lithium, hexyl lithium, tert-octyl lithium. Further preferably, the alkyllithium initiator is selected from the group consisting of methyllithium, ethyllithium, propyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium.
In some embodiments, in step S11, the reaction is performed at 40-60 ℃; in the step S12, the reaction is carried out at 40-60 ℃; in step S13, the reactions with alkylene oxide and haloalkylene oxide in this order are carried out at 40 to 60 ℃.
In some embodiments, the alkylene oxide is selected from the group consisting of one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, 1, 2-pentane oxide, hexane oxide, phenyl ethylene oxide.
In some embodiments, the epoxyhaloalkane is selected from the group consisting of one or more of epichlorohydrin, epoxybromopropane, 1, 2-epoxychlorobutane.
The third technical scheme adopted by the invention is as follows: the waterproof material comprises a coating, wherein the coating is prepared from the modified asphalt paint or the modified asphalt paint prepared by the preparation method of the modified asphalt paint.
Further, the waterproof material may further include a modified asphalt waterproof roll disposed on at least one surface of the coating layer.
Still further, the modified asphalt waterproof coiled material is an elastomer modified asphalt waterproof coiled material, a plastomer modified asphalt waterproof coiled material or a self-adhesive polymer modified asphalt waterproof coiled material.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the modified asphalt coating provided by the invention adopts the single epoxy end-capped diblock copolymer as the modifier, so that the preparation temperature of the modified asphalt coating can be effectively reduced, the preparation time is shortened, the energy consumption is reduced, and the adverse consequences of degradation, coking, gel and the like of the polymer in the high-temperature process are effectively alleviated. Meanwhile, the modified asphalt paint has smaller viscosity, can be applied in construction at lower temperature and even normal temperature, and solves the problems of complex construction and smoke pollution existing in high-temperature construction of the paint.
The modified asphalt coating adopts the diblock copolymer with a single epoxy end cap as a modifier, and the ketimine latent curing agent is introduced into the formula, and can be subjected to crosslinking reaction with epoxy groups in the modifier under the action of moisture in a base layer or air after construction, so that a triblock copolymer similar to SBS or SIS is formed in situ, and the modified asphalt coating is endowed with certain cohesive strength and mechanical property, meets the application requirements of waterproof materials, and does not influence the service performance of end products.
Detailed Description
As described in the background art, the existing styrene thermoplastic elastomer modified hot-melt rubber asphalt waterproof material cannot solve the contradiction between the physical and mechanical properties and the construction properties of the material, and the existing styrene thermoplastic elastomer has high dispersion temperature and long time.
According to the invention, the single epoxy end-capped diblock copolymer is introduced into the modified asphalt paint as a modifier, and an effective physical crosslinking point cannot be formed by utilizing the aggregated structure of the single epoxy end-capped diblock copolymer, so that the preparation temperature of the modified asphalt paint can be effectively reduced, the preparation time is shortened, the energy consumption is reduced, and adverse effects of degradation, coking, gel and the like of the polymer in a high-temperature process can be effectively alleviated. Meanwhile, as the aggregated structure of the single epoxy end-capped diblock copolymer cannot form an effective physical crosslinking point, the cohesive strength of the coating is lower, the viscosity is lower, the coating can be applied in construction at lower temperature even normal temperature, and the problems of complex construction and smoke pollution existing in high-temperature construction of the coating are solved.
The ketimine latent curing agent is introduced into the formula, and can be subjected to crosslinking reaction with epoxy groups in the modifier under the action of moisture in a base layer or air after construction, so that a triblock copolymer similar to SBS or SIS is formed in situ, and the service performance of a terminal product is not affected.
The following detailed description of the present invention is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present invention, but is not intended to limit the scope of the present invention.
Part of the raw material sources in the following examples:
asphalt: 70# asphalt, china petrochemical Co., ltd.
Reactive diluent: 1, 6-hexanediol diglycidyl ether, guangzhou by new materials limited; alternatively, epoxidized soybean oil, shenzhen Kong chemical Co., ltd.
Ketimine latent curing agent: DA315 or DA360A, wittish chemical Co., ltd.
Curing accelerator: DMP30, guangzhou chemical industry Co., ltd; alternatively, dodecylamine, shandong Hao chemical Co., ltd.
Silane coupling agent: KH550 or KH570, national pharmaceutical chemicals limited.
And (3) a plasticizer: naphthenic oil.
Example 1
The single epoxy-terminated styrene-butadiene diblock copolymer provided in this example,
the preparation method comprises the following steps:
injecting 125g of cyclohexane solution containing 25g of styrene into a polymerization bottle (under the protection of nitrogen), adding 0.27g of tetrahydrofuran as an activating agent, slowly adding the cyclohexane solution of n-butyllithium into the polymerization bottle by using a syringe to break impurities, rapidly adding 1.5ml of effective n-butyllithium solution after the system is unchanged from colorless to pale yellow at 50 ℃, initiating polymerization for 30min, and obtaining a solution system of the polymer of mono alkenyl arene with an activated end; then, 300g of a cyclohexane solution containing 75g of butadiene was added at a time and polymerized at 50℃for 30 minutes to obtain a solution system of a styrene-butadiene diblock copolymer having an activated end; finally, 1.0ml of ethylene oxide was added and reacted for 15 minutes, and 1.2ml of epichlorohydrin was added and reacted for 15 minutes, followed by termination with 1.8ml of ethanol. 264 anti-aging agent with the mass percentage of 1.5 percent is added according to the mass measurement of the polymerization end product. And after the polymerization is finished, the reaction product is distilled off to remove the solvent, and then the reaction product is dried in a vacuum box, so that the monoepoxy terminated styrene-butadiene segmented copolymer is obtained. GPC test number average molecular weight of monoepoxy terminated styrene-butadiene block copolymer was 56400 and molecular weight distribution was 1.08.
Example 2
The single epoxy-terminated styrene-butadiene diblock copolymer provided in this example,
the preparation method comprises the following steps:
adding 175g of cyclohexane solution containing 35g of styrene into a polymerization bottle (under the protection of nitrogen), adding 0.11g of tetrahydrofuran as an activating agent, slowly adding the cyclohexane solution of n-butyllithium into the polymerization bottle by using a syringe to break impurities, rapidly adding 0.6ml of effective n-butyllithium solution after the system is unchanged from colorless to pale yellow at 50 ℃, initiating polymerization for 30min, and obtaining a solution system of the polymer of mono alkenyl arene with an activated end; then, 260g of a cyclohexane solution containing 65g of butadiene was added at a time and polymerized at 50℃for 30 minutes to obtain a solution system of a styrene-butadiene diblock copolymer having an activated end; finally, 0.5ml of propylene oxide was added and reacted for 15 minutes, and then 0.6ml of epichlorohydrin was added and reacted for 15 minutes, and the reaction was terminated with 0.9ml of ethanol. 264 anti-aging agent with the mass percentage of 1.5 percent is added according to the mass measurement of the polymerization end product. And after the polymerization is finished, the reaction product is distilled off to remove the solvent, and then the reaction product is dried in a vacuum box, so that the monoepoxy terminated styrene-butadiene segmented copolymer is obtained. GPC measured that the number average molecular weight of the monoepoxy-terminated styrene-butadiene block copolymer was 142500 and the molecular weight distribution was 1.10.
Example 3
The single epoxy-terminated styrene-isoprene diblock copolymer provided in this example,
the preparation method comprises the following steps:
injecting 125g of cyclohexane solution containing 25g of styrene into a polymerization bottle (under the protection of nitrogen), adding 0.36g of tetrahydrofuran as an activating agent, slowly adding the cyclohexane solution of n-butyllithium into the polymerization bottle by using a syringe to break impurities, rapidly adding 2.0ml of effective n-butyllithium solution after the system is unchanged from colorless to pale yellow at 50 ℃, initiating polymerization for 30min, and obtaining a solution system of the polymer of mono alkenyl arene with an activated end; then, 300g of a cyclohexane solution containing 75g of isoprene was added at a time and polymerized at 50℃for 30 minutes to obtain a solution system of a styrene-isoprene diblock copolymer having an activated end; finally, 1.4ml of ethylene oxide was added and reacted for 15min, and then 1.6ml of epichlorohydrin was added and reacted for 15min, followed by termination with 2.4ml of ethanol. 264 anti-aging agent with the mass percentage of 1.5 percent is added according to the mass measurement of the polymerization end product. And after the polymerization is finished, the reaction product is distilled off to remove the solvent, and then the reaction product is dried in a vacuum box, so that the monoepoxy-terminated styrene-isoprene segmented copolymer is obtained. GPC measurement showed that the number average molecular weight of the monoepoxy-terminated styrene-isoprene block copolymer was 43500, and the molecular weight distribution was 1.06.
Example 4
The single epoxy-terminated styrene-isoprene diblock copolymer provided in this example,
the preparation method comprises the following steps:
adding 175g of cyclohexane solution containing 35g of styrene into a polymerization bottle (under the protection of nitrogen), adding 0.90g of tetrahydrofuran as an activating agent, slowly adding the cyclohexane solution of n-butyllithium into the polymerization bottle by using a syringe to break impurities, rapidly adding 5.0ml of effective n-butyllithium solution after the system is unchanged from colorless to pale yellow at 50 ℃, initiating polymerization for 30min, and obtaining a solution system of the polymer of mono alkenyl arene with an activated end; then, 240g of a cyclohexane solution containing 65g of isoprene was added at a time and polymerized at 50℃for 30 minutes to obtain a solution system of a styrene-isoprene diblock copolymer having an activated end; finally, 3.5ml of propylene oxide was added and reacted for 15min, and then 4.2ml of epichlorohydrin was added and reacted for 15min, followed by termination with 6.0ml of ethanol. 264 anti-aging agent with the mass percentage of 1.5 percent is added according to the mass measurement of the polymerization end product. And after the polymerization is finished, the reaction product is distilled off to remove the solvent, and then the reaction product is dried in a vacuum box, so that the monoepoxy-terminated styrene-isoprene segmented copolymer is obtained. GPC measured that the number average molecular weight of the monoepoxy-terminated styrene-butadiene block copolymer was 18250 and the molecular weight distribution was 1.08.
Example 5
The modified asphalt paint provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of No. 70 asphalt, 14 parts of modifier (styrene-butadiene diblock copolymer prepared in example 1), 80 parts of plasticizer aromatic oil, 2 parts of ketimine latent curing agent DA315, 30 parts of curing accelerator DMP, 1 part of reactive diluent 1, 6-hexanediol diglycidyl ether, 40 parts of filler heavy calcium and 550.0 parts of coupling agent KH.
The preparation method comprises the following steps:
(1) Heating asphalt, plasticizer and filler to 95 ℃, mixing, stirring and heating to 115 ℃ under the condition of the relative vacuum degree of-0.09 MPa, and dehydrating for 3 hours to obtain a first mixture;
(2) Heating the first mixture to 140 ℃, adding the modifier, and after 2.5 hours, completely dissolving the modifier to obtain a second mixture;
(3) And cooling the second mixture to 60-70 ℃, adding the ketimine latent curing agent, the curing accelerator, the reactive diluent, the coupling agent and the like, and uniformly mixing and stirring to obtain the modified asphalt coating.
Example 6
The modified asphalt paint provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of 70# asphalt, 20 parts of modifier (styrene-butadiene diblock copolymer prepared in example 1), 100 parts of plasticizer aromatic oil, 4 parts of ketimine latent curing agent DA315, 30 parts of curing accelerator DMP, 2 parts of reactive diluent 1, 6-hexanediol diglycidyl ether, 50 parts of filler heavy calcium and 550 parts of coupling agent KH.
The preparation method is the same as in example 5.
Example 7
The modified asphalt paint provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of No. 70 asphalt, 8 parts of modifier (styrene-butadiene diblock copolymer prepared in example 1), 60 parts of plasticizer naphthenic oil, 1 part of ketimine latent curing agent DA315, 30 parts of curing accelerator DMP, 2 parts of reactive diluent 1, 6-hexanediol diglycidyl ether, 50 parts of filler heavy calcium and 550 parts of coupling agent KH.
The preparation method is the same as in example 5.
Example 8
The modified asphalt paint provided in this example is different from that in example 5 in that: the modifier is the styrene-butadiene diblock copolymer prepared in example 2, and in step (2), the time for complete dissolution of the modifier is 3.5 hours.
Example 9
The modified asphalt paint provided in this example is different from that in example 5 in that: the modifier was a styrene-isoprene diblock copolymer prepared in example 3, and in step (2), the time for complete dissolution of the modifier was 2.0h.
Example 10
The modified asphalt paint provided in this example is different from that in example 5 in that: the modifier was a styrene-isoprene diblock copolymer prepared in example 4, and in step (2), the time for complete dissolution of the modifier was 1.0h.
Example 11
The modified asphalt paint provided by the embodiment comprises the following raw materials in parts by weight: 100 parts of 70# asphalt, 20 parts of modifier (styrene-isoprene diblock copolymer prepared in example 4), 100 parts of plasticizer naphthenic oil, 2 parts of ketimine latent curing agent DA315 and 30 parts of curing accelerator DMP.
Comparative example 1
The modified asphalt paint provided by the comparative example comprises the following raw materials in parts by weight: 100 parts of 70# asphalt, 14 parts of modifier (Baling petrochemical 1301 SBS), 80 parts of plasticizer aromatic oil, 40 parts of filler heavy calcium and 550 parts of coupling agent KH.
The preparation method comprises the following steps:
heating 70# asphalt, plasticizer and filler to 160 ℃, stirring and melting, then adding modifier, stirring at a shear rate of 400r/min, completely dissolving the modifier after 3 hours, then adding coupling agent, stirring uniformly, cooling and discharging to obtain the modified asphalt coating.
Comparative example 2
The modified asphalt paint provided in this comparative example is different from comparative example 1 in that: the modifier is 1105SIS which is petrochemical by Baling, and the dissolution time of the modifier in the step (2) is 3.5h.
The modified asphalt coatings of examples 5 to 11 and comparative examples 1 to 2 were subjected to a test for viscosity at 25℃according to GB/T10247-2008 "viscosity test method", and a test for heat resistance, low-temperature flexibility, water impermeability and adhesive strength according to GB/T16777-2008 "building waterproof coating test method" and JC/T852-1999 "solvent type rubber asphalt waterproof coating", and the results are shown in Table 1.
Table 1 shows the results of performance tests of the modified asphalt coatings of examples 5 to 11 and comparative examples 1 to 2
Wherein, comparative example 1 and comparative example 2 are solid at normal temperature, viscosity can not be tested, and the application at normal temperature can not be realized, and the application and construction can be realized only by heating. While examples 5-11 are all viscous liquids, which can be used at ambient temperature. The result shows that the modified asphalt coating prepared by adopting the diblock copolymer with the single epoxy end-capped as the modifier can not form effective physical crosslinking points due to the aggregation state structure, has lower cohesive strength and lower viscosity, can be applied in construction at lower temperature even normal temperature, and can overcome the problems of complex construction and smoke pollution existing in high-temperature construction of the coating.
In addition, after the paint is formed into a film and cured according to GB/T16777-2008 'building waterproof paint experiment method', a coating with certain cohesive strength can be formed, because a ketimine latent curing agent is introduced into the formula, and after construction, the ketimine latent curing agent can be subjected to crosslinking reaction with epoxy groups in a modifier under the action of moisture in a base layer or air, so that the paint has certain mechanical strength, the standard requirement of JC/T852-1999 'solvent type rubber asphalt waterproof paint' is met, and the final service performance of the paint can reach or even exceed the performance of the commercial SBS or SIS modified asphalt paint.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
Claims (13)
1. The modified asphalt paint comprises asphalt, a plasticizer and a modifier, and is characterized in that: the modifier is a single epoxy-terminated diblock copolymer, wherein the single epoxy-terminated diblock copolymer has a structural formula:wherein R is 1 Is C 1 -C 10 Is an alkyl group of AA polymer segment of mono alkenyl arene, C is a polymer segment of butadiene and/or isoprene, R 2 Is C 1 -C 12 The modified asphalt coating further comprises a ketimine latent curing agent;
the mass ratio of the asphalt to the monohydroxy-terminated diblock copolymer to the plasticizer to the ketimine latent curing agent is 10:0.5-3:1.5-15: 0.05 to 0.5.
2. The modified asphalt coating of claim 1, wherein: the mono alkenyl arene composing the A is selected from one or a combination of more of styrene, p-methylstyrene, methyl styrene, p-tertiary butyl styrene, 2, 4-dimethyl styrene, alpha-methyl styrene, vinyl naphthalene, vinyl toluene, vinyl xylene and 1, 1-diphenyl ethylene; and/or, the R 1 Selected from C 1 -C 6 Alkyl of (a); and/or, the R 2 Selected from C 2 -C 8 Alkyl ethers of (a).
3. The modified asphalt coating of claim 2, wherein: the mono alkenyl arene is selected from one or a combination of more of styrene, p-methyl styrene and alpha-methyl styrene; and/or the monoepoxy-terminated diblock copolymer is a monoepoxy-terminated styrene-butadiene/isoprene diblock copolymer.
4. The modified asphalt coating of claim 1, wherein: the mass content of the A in the single epoxy end capped diblock copolymer is 10-50%; and/or the single epoxy-terminated diblock copolymer has a number average molecular weight of from 5000 to 150000.
5. The modified asphalt paint of claim 4, wherein: the mass content of the A in the single epoxy-terminated diblock copolymer is 20-40%; and/or the single epoxy-terminated diblock copolymer has a number average molecular weight of 30000-80000.
6. The modified asphalt coating of claim 1, wherein: the raw materials of the modified asphalt paint also comprise a curing accelerator; and/or, the raw materials of the modified asphalt coating comprise, by weight, 100 parts of asphalt, 5-30 parts of single epoxy end-capped diblock copolymer, 15-150 parts of plasticizer, 0.5-5.0 parts of ketimine latent curing agent and 0.1-2 parts of curing accelerator.
7. The modified asphalt paint of claim 6, wherein: the raw materials of the modified asphalt coating comprise, by weight, 100 parts of asphalt, 8-20 parts of a single epoxy end-capped diblock copolymer, 50-100 parts of a plasticizer, 1.0-4.0 parts of a ketimine latent curing agent and 0.1-2 parts of a curing accelerator.
8. The modified asphalt paint of claim 6, wherein: the plasticizer is one or a combination of more of aromatic hydrocarbon oil, naphthenic oil and paraffinic oil; and/or the curing accelerator is one or a combination of more of 2,4, 6-tris (dimethylaminomethyl) phenol, triethanolamine and fatty amine; and/or, the asphalt is matrix asphalt; and/or the raw materials of the modified asphalt coating also comprise one or a combination of more of reactive diluents, fillers and coupling agents.
9. A method for preparing the modified asphalt paint as defined in any one of claims 1 to 8, comprising the steps of:
step S1, preparation of a Single epoxy terminated diblock copolymer
Subjecting the monoalkenyl arene monomer constituting the A to anionic polymerization to produce a monoalkenyl arene polymer having an activated end;
polymerizing the polymer of mono alkenyl arene having an activated end with butadiene and/or isoprene to produce a diblock copolymer having an activated end;
reacting said diblock copolymer having an activated end with an alkylene oxide and an haloalkylene oxide in sequence to give a polymer having said activated endA structural monoepoxy-terminated diblock copolymer;
s2, preparing modified asphalt paint
And mixing all the raw materials of the modified asphalt coating to obtain the modified asphalt coating.
10. The method for preparing a modified asphalt paint according to claim 9, wherein the specific implementation of step S1 includes:
step S11, in the presence of a saturated hydrocarbon solvent and an anionic polymerization initiator, enabling the mono-alkenyl arene monomer to react to generate the mono-alkenyl arene polymer with an activated end, so as to obtain a solution system containing the mono-alkenyl arene polymer with the activated end;
step S12, adding butadiene and/or isoprene to a solution system containing the mono alkenyl arene polymer with the activated end, and enabling the mono alkenyl arene polymer with the activated end to react with butadiene and/or isoprene to generate the diblock copolymer with the activated end, so as to obtain a solution system containing the diblock copolymer with the activated end;
step S13, sequentially adding alkylene oxide and haloalkane oxide into a solution system containing the diblock copolymer with the activated end, and enabling the diblock copolymer with the activated end to sequentially react with the alkylene oxide and haloalkane oxide to obtain the diblock copolymer with the monoepoxy end closure; and/or the number of the groups of groups,
the specific implementation of the step S2 comprises the following steps:
step S21, mixing asphalt, plasticizer and/or filler, stirring and heating to 110-120 ℃ under the condition that the relative vacuum degree is minus 0.08-minus 0.095MPa, and dehydrating to obtain a first mixture;
step S22, heating the first mixture to 140-160 ℃, and adding the single epoxy-terminated diblock copolymer to dissolve the single epoxy-terminated diblock copolymer to obtain a second mixture;
and S23, cooling the second mixture to 60-70 ℃, adding a ketimine latent curing agent, or/and adding one or a combination of a curing accelerator, a reactive diluent and a coupling agent, and mixing to obtain the modified asphalt coating.
11. The method for preparing a modified asphalt paint according to claim 10, wherein: the saturated hydrocarbon solvent is at least one of pentane, octane, heptane, cyclohexane, normal hexane, benzene, toluene, ethylbenzene and xylene, the anionic polymerization initiator is an alkyl lithium initiator, the alkyl lithium initiator is one or a combination of a plurality of RLi, R is an alkane group with 1-10 carbon atoms, and Li is a lithium atom; and/or the number of the groups of groups,
in the step S11, the reaction is carried out at 40-60 ℃; in the step S12, the reaction is carried out at 40-60 ℃; in the step S13, the reaction with alkylene oxide and haloalkane oxide in sequence is respectively carried out at 40-60 ℃; and/or the number of the groups of groups,
the alkylene oxide is selected from one or a combination of more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, 1, 2-pentane oxide, hexane oxide and phenyl ethylene oxide; and/or the number of the groups of groups,
the epoxy alkyl halide is selected from one or a combination of more of epoxy chloropropane, epoxy bromopropane and 1, 2-epoxy chlorobutane.
12. A water resistant material comprising a coating, characterized in that: the coating is prepared from the modified asphalt paint according to any one of claims 1 to 8 or the modified asphalt paint prepared by the preparation method of the modified asphalt paint according to any one of claims 9 to 11.
13. The waterproofing material according to claim 12 wherein: the waterproof material also comprises a modified asphalt waterproof coiled material arranged on at least one surface of the coating.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5686535A (en) * | 1991-04-29 | 1997-11-11 | Shell Oil Company | Viscous conjugated diene block copolymers |
| CN1195361A (en) * | 1996-05-10 | 1998-10-07 | 埃尔弗安塔法国公司 | Process for preparing bitumen/polymer composition and its use |
| CN1635023A (en) * | 2003-12-25 | 2005-07-06 | 中国石油化工股份有限公司 | A kind of asphalt modified masterbatch and preparation method thereof |
| CN1646632A (en) * | 2002-02-07 | 2005-07-27 | 克拉通聚合物研究有限公司 | Polymer modified bitumen compositions |
| CN1820034A (en) * | 2002-10-15 | 2006-08-16 | 埃克森美孚化学专利公司 | Polyolefin adhesive compositions and articles made therefrom |
| CN1923870A (en) * | 2006-08-10 | 2007-03-07 | 大连海事大学 | Synthesis for copolymer of terminal amino and carboxyl styrene/butadiene and method of preparing storage stabilized modified asphalt |
| CN1923901A (en) * | 2006-08-10 | 2007-03-07 | 大连海事大学 | Synthesis for copolymer of terminal carboxyl styrene/butadiene and method of preparing storage stabilized modified asphalt |
| CN101696248A (en) * | 2002-04-10 | 2010-04-21 | 旭化成化学株式会社 | Modified polymers and compositions containing the same |
| CN106715595A (en) * | 2014-07-16 | 2017-05-24 | 霍尼韦尔国际公司 | Asphalt coatings for roofing waterproof membranes, waterproof membranes including the asphalt coatings and methods for making the asphalt coatings |
| US10323147B1 (en) * | 2016-05-26 | 2019-06-18 | Marathon Petroleum Company Lp | Asphalt composition containing ester bottoms |
| CN110577647A (en) * | 2018-06-07 | 2019-12-17 | 中国石油化工股份有限公司 | Epoxy-terminated polysulfide rubber modified SBS (styrene butadiene styrene), preparation method thereof and application thereof in modified asphalt |
| CN114133872A (en) * | 2021-10-27 | 2022-03-04 | 科顺防水科技股份有限公司 | Rubber asphalt waterproof paint and preparation method thereof |
| CN114456612A (en) * | 2022-01-21 | 2022-05-10 | 石家庄宏建防水材料有限公司 | Modified asphalt, preparation method thereof and modified asphalt waterproof coiled material |
-
2023
- 2023-01-05 CN CN202310013089.4A patent/CN115948121B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5686535A (en) * | 1991-04-29 | 1997-11-11 | Shell Oil Company | Viscous conjugated diene block copolymers |
| CN1195361A (en) * | 1996-05-10 | 1998-10-07 | 埃尔弗安塔法国公司 | Process for preparing bitumen/polymer composition and its use |
| CN1646632A (en) * | 2002-02-07 | 2005-07-27 | 克拉通聚合物研究有限公司 | Polymer modified bitumen compositions |
| CN101696248A (en) * | 2002-04-10 | 2010-04-21 | 旭化成化学株式会社 | Modified polymers and compositions containing the same |
| CN1820034A (en) * | 2002-10-15 | 2006-08-16 | 埃克森美孚化学专利公司 | Polyolefin adhesive compositions and articles made therefrom |
| CN1635023A (en) * | 2003-12-25 | 2005-07-06 | 中国石油化工股份有限公司 | A kind of asphalt modified masterbatch and preparation method thereof |
| CN1923901A (en) * | 2006-08-10 | 2007-03-07 | 大连海事大学 | Synthesis for copolymer of terminal carboxyl styrene/butadiene and method of preparing storage stabilized modified asphalt |
| CN1923870A (en) * | 2006-08-10 | 2007-03-07 | 大连海事大学 | Synthesis for copolymer of terminal amino and carboxyl styrene/butadiene and method of preparing storage stabilized modified asphalt |
| CN106715595A (en) * | 2014-07-16 | 2017-05-24 | 霍尼韦尔国际公司 | Asphalt coatings for roofing waterproof membranes, waterproof membranes including the asphalt coatings and methods for making the asphalt coatings |
| US10323147B1 (en) * | 2016-05-26 | 2019-06-18 | Marathon Petroleum Company Lp | Asphalt composition containing ester bottoms |
| CN110577647A (en) * | 2018-06-07 | 2019-12-17 | 中国石油化工股份有限公司 | Epoxy-terminated polysulfide rubber modified SBS (styrene butadiene styrene), preparation method thereof and application thereof in modified asphalt |
| CN114133872A (en) * | 2021-10-27 | 2022-03-04 | 科顺防水科技股份有限公司 | Rubber asphalt waterproof paint and preparation method thereof |
| CN114456612A (en) * | 2022-01-21 | 2022-05-10 | 石家庄宏建防水材料有限公司 | Modified asphalt, preparation method thereof and modified asphalt waterproof coiled material |
Non-Patent Citations (2)
| Title |
|---|
| 《The influence of styrene–butadiene diblock copolymer on styrene–butadiene–styrene triblock copolymer viscoelastic properties and product performance》;MCKAY, KW;《JOURNAL OF APPLIED POLYMER SCIENCE》;全文 * |
| 《基于苯乙烯-丁二烯-苯乙烯嵌段共聚物结构差异的改性沥青老化过程热重分析》;韩明哲;《合成橡胶工业》;全文 * |
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