CN102796243B - Polyurethane modified epoxy resin adhesive, and preparation method and application thereof - Google Patents
Polyurethane modified epoxy resin adhesive, and preparation method and application thereof Download PDFInfo
- Publication number
- CN102796243B CN102796243B CN201110135746.XA CN201110135746A CN102796243B CN 102796243 B CN102796243 B CN 102796243B CN 201110135746 A CN201110135746 A CN 201110135746A CN 102796243 B CN102796243 B CN 102796243B
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- CN
- China
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- component
- epoxy resin
- weight
- polyurethane prepolymer
- epoxy
- Prior art date
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 71
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 71
- 239000000853 adhesive Substances 0.000 title claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 21
- 239000004814 polyurethane Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims description 38
- 229920002635 polyurethane Polymers 0.000 title abstract description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 47
- 150000001412 amines Chemical class 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 24
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920000768 polyamine Polymers 0.000 claims abstract description 15
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000004848 polyfunctional curative Substances 0.000 claims abstract description 10
- 239000004593 Epoxy Substances 0.000 claims description 71
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- -1 E-51 Polymers 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000006096 absorbing agent Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- 239000004902 Softening Agent Substances 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000010276 construction Methods 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 5
- DQRVWGKCDJKPAQ-UHFFFAOYSA-N prop-2-enyl hydrogen carbonate Chemical compound OC(=O)OCC=C DQRVWGKCDJKPAQ-UHFFFAOYSA-N 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 150000004982 aromatic amines Chemical class 0.000 claims description 3
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 229930185605 Bisphenol Natural products 0.000 abstract 2
- 230000002745 absorbent Effects 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 239000004014 plasticizer Substances 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 28
- 239000002585 base Substances 0.000 description 26
- 238000012360 testing method Methods 0.000 description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- 150000004985 diamines Chemical group 0.000 description 5
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000007086 side reaction Methods 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000010426 asphalt Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- ORTUYCUWCKNIND-UHFFFAOYSA-N 3-[2-(2-aminoethylamino)ethylamino]propanenitrile Chemical compound NCCNCCNCCC#N ORTUYCUWCKNIND-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 206010039203 Road traffic accident Diseases 0.000 description 2
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- OYOFUEDXAMRQBB-UHFFFAOYSA-N cyclohexylmethanediamine Chemical compound NC(N)C1CCCCC1 OYOFUEDXAMRQBB-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZETYUTMSJWMKNQ-UHFFFAOYSA-N n,n',n'-trimethylhexane-1,6-diamine Chemical compound CNCCCCCCN(C)C ZETYUTMSJWMKNQ-UHFFFAOYSA-N 0.000 description 2
- 150000002924 oxiranes Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 1
- PCHXZXKMYCGVFA-UHFFFAOYSA-N 1,3-diazetidine-2,4-dione Chemical compound O=C1NC(=O)N1 PCHXZXKMYCGVFA-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- ZMBQZWCDYKGVLW-UHFFFAOYSA-N 1-methylcyclohexa-3,5-diene-1,2-diamine Chemical compound CC1(N)C=CC=CC1N ZMBQZWCDYKGVLW-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- HVOBSBRYQIYZNY-UHFFFAOYSA-N 2-[2-(2-aminoethylamino)ethylamino]ethanol Chemical compound NCCNCCNCCO HVOBSBRYQIYZNY-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical class CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 1
- CFEKOKRYQRODRZ-UHFFFAOYSA-N 2-cyclohexylethane-1,1-diamine Chemical compound NC(N)CC1CCCCC1 CFEKOKRYQRODRZ-UHFFFAOYSA-N 0.000 description 1
- DYNWNNKAUGBOOZ-UHFFFAOYSA-N 3-n-methylbenzene-1,3-diamine Chemical compound CNC1=CC=CC(N)=C1 DYNWNNKAUGBOOZ-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- LCROJXCHJQJPAN-UHFFFAOYSA-N CCN(O)CCN(O)CCN Chemical compound CCN(O)CCN(O)CCN LCROJXCHJQJPAN-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- QZVCTJOXCFMACW-UHFFFAOYSA-N Phenoxybenzamine Chemical compound C=1C=CC=CC=1CN(CCCl)C(C)COC1=CC=CC=C1 QZVCTJOXCFMACW-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229920002396 Polyurea Polymers 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- NIHJEJFQQFQLTK-UHFFFAOYSA-N butanedioic acid;hexanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCCCC(O)=O NIHJEJFQQFQLTK-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 229960003418 phenoxybenzamine Drugs 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000010850 salt effect Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000005491 wire drawing Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane modified epoxy resin adhesive for a colored antiskid road surface. The polyurethane modified epoxy resin adhesive comprises an epoxy resin mixture component A and a polyurethane modified amine hardener component B, wherein the component A comprises bisphenol A-type epoxy resin and polypropylene glycol diglycidyl ether; the component B consists of organic polyamine, bisphenol A-type epoxy resin, polyoxypropylene glycol, diphenylmethane diisocyanate, an ultraviolet absorbent, a plasticizer and a solvent; the component A and the component B are separately stored; and during use, the component A and the component B are mixed for use according to a weight ratio of 100:100. The polyurethane modified epoxy resin adhesive can be used for paving the colored antiskid road surface.
Description
Technical field
The present invention relates to a kind of epoxy resin adhesive modified by PU, its preparation method and the application in anti-skid surface thereof.
Technical background
Current, the road traffic in China city problem of blocking up is more and more serious, but the practice result of China and in the world many countries and empirical evidence, road traffic accident can prevent and control, and wherein adopting effective Pavement Skid Resistance system, especially colored road surface antiskid system is a preferably measure.
Colored road surface antiskid system is a kind of resin base Pavement Skid Resistance system, comprises that the resin-based adhesive of special formulation and the aggregate of various different sizes are equipped with the pigment of being convenient to identification, is coated on pitch or cement pavement and forms with accurate quantity.At motorway culvert, permeable road and, car lane, road cross, bend slope road and mark isolation strip etc. need the occasion of the permeable decoration of safe anti-slipping, color anti-skid road surface travels on the road surface of regulation by the difference prompting driver of road color, thereby avoided the mixed row of different vehicle, and by providing the surface layer of high frictional force to play fine skidproof effect.Officer sails above-mentioned section into can advance reduction speed, and in case of emergency, shorten braking distance, and generation avoids traffic accident.
Lay colored road surface and conventionally adopt color asphalt method and colo(u)r coating method.Color asphalt method is that pitch decarburization is made to decolouring pitch, paves after then adding pigment to make color asphalt with aggregate mix again.Its advantage is to carry out mechanized construction according to the constructional method of plain asphalt, but have that non-skid property is bad, the bright-coloured not abundant and shortcoming such as persistence is poor and laying depth is thicker of color.Colo(u)r coating method normally adopts colored acrylic to be coated with and to be layered on road surface as tackiness agent, then sprinkles anti-skidding sand or antiskid aggregate in the above, is finally coated with last layer colored acrylic on surface again and carries out cover.The advantage of the method is that set time is fast and construction is simple, larger to the alternative of color; Shortcoming be due to the cohesive strength of acrylic resin own is limited and high temperature under easily deliquescing distortion, cause it to be only applicable to some to the less demanding underloading traffic of non-skid property.
Summary of the invention
For overcoming the above-mentioned defect of prior art, one of object of the present invention is to provide a kind of epoxy resin adhesive modified by PU that can be used for anti-skid surface of environmental protection.
Another object of the present invention is to provide a kind of preparation method of above-mentioned epoxy resin adhesive modified by PU.
A further object of the present invention is to provide the application of above-mentioned tackiness agent in antiskid road road surface, the especially colored road surface of carrying communications and transportation.
For achieving the above object, the present invention adopts following technical scheme:
A kind of epoxy resin adhesive modified by PU, it comprises component A and B component, wherein
Component A is epoxy resin composition, and it comprises:
(i) bisphenol A type epoxy resin that 100 weight part oxirane values are 0.41-0.58mol/100g;
(ii) polypropylene glycol diglycidyl ether that 1-20 parts by weight average molecular weight is 100-1000, for regulating the viscosity of component A;
B component is polyurethane-modified amine hardener, and it comprises:
(i) organic polyamine of 100 weight parts,
This organic polyamine is at least one being selected from lower group: fatty amine, cycloaliphatic amines, aromatic amine, modified amine epoxy curing agent and their mixture;
(ii) the epoxy polyurethane prepolymer of 40-70 weight part,
This epoxy polyurethane prepolymer adds the softening agent of 80-120 weight part to mix by the base polyurethane prepolymer for use as of 100 weight parts and the bisphenol A type epoxy resin of 40-70 weight part (oxirane value is 0.41-0.58mol/100g) after polyreaction again,
The polyvalent alcohol that wherein said base polyurethane prepolymer for use as is 1000-10000 by one or more diphenylmethanediisocyanates (MDI) and one or more number-average molecular weights is by 100: 200-2000 part by weight is through being polymerized, and its isocyano (NCO) content is 0.5-6wt%;
(iii) UV light absorber of 0.5-5 weight part;
(iv) solvent of the solubilized epoxy polyurethane prepolymer of 15-30 weight part, for regulating the viscosity of B component;
Component A and B component are deposited separately, when use by component A: the weight ratio that B component is 100: 100 is used in conjunction with.
A method of preparing above-mentioned epoxy resin adhesive modified by PU, comprises the steps:
(1) preparation of component A:
The bisphenol A type epoxy resin of 100 weight parts (oxirane value is 0.41-0.58mol/100g) and the polypropylene glycol diglycidyl ether (number-average molecular weight 100-1000) of 1-20 weight part are stirred at the temperature of 60-80 ℃, obtain epoxy resin composition, epoxy equivalent (weight) is 160-260, after being cooled to room temperature, pack, sealing is deposited;
(2) preparation of B component
1. prepare base polyurethane prepolymer for use as:
The polyvalent alcohol that took off water that is 1000-10000 with at least one number-average molecular weight of 200-2000 weight part by least one diphenylmethanediisocyanate (MDI) of 100 weight parts reacts 1-4 hour at 60-90 ℃, generate isocyanate-terminated performed polymer, isocyano (NCO) content is 0.5-6wt%;
2. prepare epoxy polyurethane prepolymer
The above-mentioned base polyurethane prepolymer for use as of 100 weight parts is reacted to 1-4 hour with the bisphenol A type epoxy resin (oxirane value is 0.41-0.58mol/100g) of 40-70 weight part at 60-90 ℃ of temperature, in the time that NCO content drops to 0%, add the softening agent of 80-120 weight part, form epoxy polyurethane prepolymer, epoxy equivalent (weight) is 800-1600;
3. prepare polyurethane-modified amine hardener
The organic polyamine of 100 weight parts is warming up to 80-100 ℃, slowly add the above-mentioned epoxy polyurethane prepolymer of 40-70 weight part, at this temperature, react after 1-2 hour, add again the UV light absorber of 0.5-5 weight part, stir 0.25-0.5 hour, after guaranteeing that UV light absorber is dissolved completely, temperature of reaction is dropped to 60-80 ℃, the solvent adjustment viscosity that finally adds 15-30 weight part solubilized epoxy polyurethane prepolymer, amine value is 180-280mgKOH/g;
Tackiness agent of the present invention is a kind of polyurethane modified epoxy resin multipolymer of uniqueness, can there is good cohesive force with concrete, pitch, abrasion resistant particles and stone material etc., weather-resistant, good toughness makes it have the performance of anti-crevice of roadbed, is applicable to easily the advantages such as construction technology and curing time be shorter.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.Should be understood that following examples are only not used in the scope of the present invention that limits for the present invention is described.
Herein, " MDI " is the abbreviation of " diphenylmethanediisocyanate ", and such as 2,4-MDI refers to 2,4-diphenylmethanediisocyanate, and 4,4 '-MDI refers to 4,4 '-diphenylmethanediisocyanate; " NCO " is the abbreviation of " isocyano ".
Described " part " herein, except special instruction, all refers to " weight part "; Described percentage composition, except special instruction, all refers to weight percentage;
The composition of component A and preparation
Component A of the present invention is composition epoxy resin, and its raw materials comprises: the polypropylene glycol diglycidyl ether that the bisphenol A epoxide resin that oxirane value is 0.41-0.58mol/100g and number-average molecular weight are 100-1000.
Wherein, the oxirane value of bisphenol A type epoxy resin is 0.41-0.58mol/100g.Under this oxirane value, be limited to 0.41mol/100g, more preferably 0.42,0.43,0.44,0.45,0.46,0.47,0.48,0.49 or 0.50mol/100g; On this oxirane value, be limited to 0.58mol/100g, more preferably 0.56,0.55,0.54,0.53,0.52,0.52 or 0.51mol/100g.
This epoxy resin can be synthetic by method well-known to those skilled in the art.For example, adopt two-step process, by dihydroxyphenyl propane and epoxy chloropropane catalyzer such as quaternary ammonium salt effect under, the first step generates diphenylol propane chloropharin ether intermediate by addition reaction, second step reacts generation epoxy resin under NaOH exists.
In a kind of embodiment, the bisphenol A epoxide resin that is used to form component A of the present invention is at least one being selected from lower group: E-42 epoxy resin, be called for short E-42, and oxirane value is 0.38-0.45mol/100g, epoxy equivalent (weight) is 222-263; E-44 epoxy resin, is called for short E-44, and oxirane value is 0.41-0.47mol/100g, and epoxy equivalent (weight) is 212-244; E-51 epoxy resin, is called for short E-51, and oxirane value is 0.48-0.54mol/100g, and epoxy equivalent (weight) is 185-208; E-55 epoxy resin, is called for short E-55, and oxirane value is 0.55-0.56mol/100g, and epoxy equivalent (weight) is 178-182.
The polypropylene glycol diglycidyl ether using in the present invention, as thinner, for regulating the viscosity of component A, number-average molecular weight is 100-1000.Under number-average molecular weight, be limited to 100, more preferably 120,150,180,200,220,250,280,300,320,350,380,400,420,450,480,500; In number-average molecular weight, be limited to 1000, more preferably 980,950,920,900,880,850,820,800,780,750,720,700,680,650,620,600.
In a kind of embodiment, being used to form polypropylene glycol diglycidyl ether of the present invention is at least one being selected from lower group: glycidyl ether, and number-average molecular weight is 130; Propylene glycol diglycidylether, number-average molecular weight is 246; Polypropylene glycol diglycidyl ether 6360, number-average molecular weight is 360; Polypropylene glycol diglycidyl ether PEGGE-400, number-average molecular weight is 600.
In the bisphenol A epoxide resin of 100 weight parts, the content of this thinner is 1-20 weight part.If the content of polypropylene glycol diglycidyl ether is less than 1 weight part, component A viscosity is excessive, is difficult for and aggregate mixing, easily causes the waste in construction simultaneously, and affects product use; If the content of polypropylene glycol diglycidyl ether, higher than 20 weight parts, can extend the products solidifying time etc.Preferably the content of polypropylene glycol diglycidyl ether is 1-15 weight part, preferably 1.2-10 weight part, more preferably 1.5-5 weight part, more preferably 1.8-4 weight part, more preferably 2-3 weight part.
The preparation of component A is that bisphenol A type epoxy resin and polypropylene glycol diglycidyl ether are uniformly mixed and are obtained at the temperature of 60-80 ℃, and preferably mixing temperature is 65-78 ℃, more preferably 68-75 ℃.
The epoxy equivalent (weight) of component A is 160-260, preferably 170-250, more preferably 180-240, more preferably 190-230, more preferably 200-220.
The composition of B component and preparation
In the present invention, the raw materials of polyurethane-modified amine hardener comprises: organic polyamine, bisphenol A type epoxy resin, the solvent of polyvalent alcohol that diphenylmethanediisocyanate (MDI), number-average molecular weight are 1000-10000, softening agent, UV light absorber, solubilized epoxy polyurethane prepolymer.
Refer to and contain two above-NH for organic polyamine of the present invention
2the fatty amine of group ,-NHR group, cycloaliphatic amines, aromatic amine, amine epoxy curing agent modified, preferred aliphat amine, cycloaliphatic amines, amine epoxy curing agent modified, more preferably commercial amine epoxy curing agent modified.
Such as organic polyamine is at least one being selected from lower group:
Quadrol, hexanediamine, 1,3-propylene diamine, new pentamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, two propylene triamines, dimethylaminopropylamine, diethyl amino propylamine, trimethylhexamethylenediamine, two base triamines, two amine adducts (trade(brand)name: L2505, amine value 160-210), trimethylammonium is diamines, polyethylene polyamine (trade(brand)name: E-100, amine value is 1257mgKOH/g), commercial modification cycloaliphatic amines epoxy solidifying agent (trade(brand)name: R-2253 amine value: 320mgKOH/g), commercial modified aliphatic amine epoxy curing agent (trade(brand)name: R-2011, amine value is 392mgKOH/g), polypropylene glycol diamine (trade(brand)name: DA-400, data molecular weight 400), polypropylene glycol diamine (trade(brand)name: DA-1000, number-average molecular weight 1000), polypropylene glycol diamine (trade(brand)name: DA-2000, data molecular weight 2000), N-methylol diethyl triamine, N-methylol quadrol, N-N-aminoethyl ethanolamine, N, N '-dihydroxy ethyl quadrol, N-hydroxyethyl diethylenetriamine, N, N '-dihydroxy ethyl diethylenetriamine, N-hydroxyethyl diamines, one cyanoethyl quadrol, one cyanoethyl diamines, dicyanoethyl quadrol, one cyanoethyl diethylenetriamine, two cyanoethyl diethylenetriamines, diaminomethyl cyclohexane, the Meng alkane diamines, aminoethyl croak piperazine, hexahydropyridine, isophorone diamine, diamino cyclohexane, diaminomethyl cyclohexyl methane, diamino cyclohexyl methane, mphenylenediamine, m-xylene diamine, diaminodiphenyl-methane, diamino diphenyl sulfone, m-aminophenyl methylamine, p-diaminodiphenyl, phenoxybenzamine base ether, mphenylenediamine and diaminodiphenyl-methane mixture (weight ratio 100: 30-70), mphenylenediamine and diaminodiphenyl-methane and tolylene diamine mixture (weight ratio is 30-70: 30-75: 15-50), ortho-toluene diamine, toluylenediamine and diaminodiphenyl-methane mixture (weight ratio 100: 50-60: 200-260), diaminodiphenyl-methane and isophorone diamine mixture (weight ratio 100: 150-250), P-F-diethylenetriamine condenses (trade(brand)name: T-31, amine value 360-450).
In a kind of embodiment, the diphenylmethanediisocyanate (MDI) that is used to form base polyurethane prepolymer for use as is at least one being selected from lower group: 4,4 '-diphenylmethanediisocyanate (trade(brand)name: MDI-100,
1810), 2,4-diphenylmethanediisocyanate (trade(brand)name:
3051,
3056), carbodiimide diphenylmethanediisocyanate (trade(brand)name:
2020) and composition thereof.
The polyvalent alcohol that is used to form base polyurethane prepolymer for use as is polyether polyol or polyester polyol, and number-average molecular weight is 1000-10000.Under the number-average molecular weight of this polyvalent alcohol, be limited to 1000, be preferably 1100,1200,1300,1400,1500,1600,1700,1800,1900,2000,2100,2200,2300,2400,2500,2600,2700,2800,2900,3000; In number-average molecular weight, be limited to 10000, be preferably 9000,8500,8000,7500,7000,6500,6000,5500,5000,4500.
In a kind of embodiment, polyvalent alcohol is at least one being selected from lower group: polyoxytrimethylene ether glycol (number-average molecular weight 1000, trade(brand)name PPG-210; Number-average molecular weight 2000, trade(brand)name PPG-220; Number-average molecular weight 4000, trade(brand)name PPG-2028), polycaprolactone glycol (number-average molecular weight 1000, trade(brand)name PCL-210; Number-average molecular weight 2000, trade(brand)name PCL-220), poly adipate succinic acid ester (number-average molecular weight 1000, trade(brand)name P-144; Number-average molecular weight 2000, trade(brand)name P-244), PTMG (data molecular weight 1000, trade(brand)name PTMG-1000; Data molecular weight 2000, trade(brand)name PTMG-2000).
The preparation of base polyurethane prepolymer for use as can adopt the confessed polymerization process in this area, such as " plastics industry handbook (urethane): chapter 10 polyurethane elastomer " (Li Junxian chief editor, Chemical Industry Press, the 1st edition, 1999, P406) introduce relevant technology of preparing.
Specifically, its preparation mainly comprises: first polyvalent alcohol is carried out to processed, avoid the side reaction that causes polyureas because of the existence of water to occur, and then cause performed polymer quality to decline; Carry out before polyreaction first by MDI preheating, such as being heated to 60 ℃, avoid because of temperature variation unstable compared with causing greatly performed polymer molecular weight distribution ununiformity and quality.
In base polyurethane prepolymer for use as preparation, the weight ratio of diphenylmethanediisocyanate and polyvalent alcohol is 100: 200-2000; More preferably 100: 350-850; More preferably 100: 400-800.If the umber of polyvalent alcohol is too high, can cause NCO content to reduce, even cause gel; If the umber of polyvalent alcohol is too low, easily there is side reaction.
The base polyurethane prepolymer for use as that diphenylmethanediisocyanate and polyol reaction generate is isocyanate-terminated performed polymer, and isocyano (NCO) content is 0.5-6wt%.Preferably NCO content is 0.8-6wt%; More preferably 1-5wt%; More preferably 1.2-4.8wt%; More preferably 1.3-4.5wt%; More preferably more preferably 1.8-3.5wt% of 1.5-4wt%.If NCO content, higher than 6wt%, has reduced the content of soft segmer of final polymkeric substance, do not reach toughness reinforcing object; If NCO content, lower than 0.5wt%, reduces with the reactivity of bisphenol A epoxide resin, the modification degree of epoxy resin is reduced, package stability declines, and easily causes and is separated.
The polyreaction of diphenylmethanediisocyanate and polyvalent alcohol is controlled at 50-100 ℃, preferably 60-90 ℃, more preferably 60-85 ℃.If lower than 60 ℃, react not thorough, affect molecular weight and distribution thereof; If higher than 85 ℃, easily cause side reaction allophanate to produce.Reaction times is 1-4 hour, if it is not thorough to be less than reaction in 1 hour, affects molecular weight and distribution thereof; If exceed 4 hours, may cause the side reaction that generates uretdione to occur.
The end group of the molecular chain of epoxy polyurethane prepolymer of the present invention is epoxy group(ing), is formed through polyreaction by base polyurethane prepolymer for use as and bisphenol A type epoxy resin, after reaction finishes, adds softening agent to reduce the viscosity of this prepolymer.
In the preparation of this prepolymer, bisphenol A epoxide resin used can be used with component A bisphenol A epoxide resin identical, such as being at least one being selected from lower group: E-42 epoxy resin, be called for short E-42, oxirane value is 0.38-0.45mol/100g, and epoxy equivalent (weight) is 222-263; E-44 epoxy resin, is called for short E-44, and oxirane value is 0.41-0.47mol/100g, and epoxy equivalent (weight) is 212-244; E-51 epoxy resin, is called for short E-51, and oxirane value is 0.48-0.54mol/100g, and epoxy equivalent (weight) is 185-208; E-55 epoxy resin, is called for short E-55, and oxirane value is 0.55-0.56mol/100g, and epoxy equivalent (weight) is 178-182.
In the preparation of this prepolymer, the weight ratio of base polyurethane prepolymer for use as and bisphenol A type epoxy resin is 100: 40-70; Preferably 100: 45-65.More preferably 100: 50-60, if the umber of epoxy resin is too low, system degree of crosslinking is excessive, and gel easily occurs; If the umber of epoxy resin is too high, the relative content of urethane has just reduced, and finally affects product in the toughness of solidifying after fixing thing.
The polyreaction of base polyurethane prepolymer for use as and bisphenol A type epoxy resin is controlled at 60-90 ℃, preferably 60-85 ℃, more preferably 70-85 ℃.If lower than 60 ℃, react not thorough, the reaction times can extend, if higher than 90 ℃, easily causes side reaction to cause jello to form.Reaction end, using NCO=0% as criterion, 80 ℃ time, completes whole reaction process approximately 4 hours.
In the preparation of this prepolymer, selected softening agent is one or more in phthalic acid two (just) butyl ester, phthalic acid two (just) monooctyl ester, epoxy soybean oil, carbonic acid allyl ester, adipic acid di-isooctyl.
The weight ratio of base polyurethane prepolymer for use as and softening agent is 100: 80-120; Preferably 100: 80-110, more preferably 100: 90-100; If the umber of softening agent is too high, tackiness agent bonding strength declines, and causes easily deliquescing distortion under the high temperature of road surface, and non-skid finish can come off from road surface; If the umber of softening agent is too low, viscosity increase is unfavorable for pavement construction and the combination with aggregate.
The epoxy polyurethane prepolymer epoxy equivalent (weight) of preparation is 800-1600, preferably 900-1500, more preferably 1000-1400, more preferably 1100-1300.In the preparation of B component, the weight ratio of organic polyamine and epoxy polyurethane prepolymer is 100: 40-70; Preferably 100: 50-70 more preferably 100: 50-65.If the umber of epoxy polyurethane prepolymer is too high, the unstable B component gel in producing and storing that causes of system; If the umber of epoxy polyurethane prepolymer is too low, do not have toughness reinforcing effect.
Can be a kind of in UV-328 and UV-320 or their mixture for the preparation of the UV light absorber of B component.
In the preparation of B component, the weight ratio of organic polyamine and UV light absorber is 100: 0.5-5; More preferably 100: 0.8-4; Further preferably 100: 1-3; More preferably 100: 2-3.
Solvent in B component is the solvent of solubilized epoxy polyurethane prepolymer, comprise ketone, ester class, ether alcohol class, amides and aromatic hydrocarbons etc., preferably be selected from one or more the mixture in lower group: such as acetone, butanone, pimelinketone,, METHYLPYRROLIDONE, ethyl acetate, butylacetate, Isoamyl Acetate FCC, tetrahydrofuran (THF), dioxane, ethylene glycol monomethyl ether, propylene glycol monobutyl ether, N, dinethylformamide, N,N-dimethylacetamide, toluene, dimethylbenzene.Consider for environmental protection, in conjunction with the surface properties of cement pavement, bituminous pavement, more preferably DMF or METHYLPYRROLIDONE or both mixtures.
In the preparation of B component, the weight ratio of organic polyamine and solvent is 100: 15-30.If the content of solvent is less than 15 weight parts, B component viscosity is excessive and can not make well aggregate obtain the fully wetting bonding strength that causes to decline, and affects product and use; If the content of solvent higher than 30 weight parts, can cause B component viscosity too small, cause extend set time.
B component prepares as follows: organic polyamine is warming up to after 80-100 ℃, slowly add epoxy polyurethane prepolymer, at this temperature, react, then add UV light absorber, being stirred to UV light absorber dissolves completely, again temperature of reaction is dropped to 60-80 ℃, finally add solvent adjustment viscosity.The epoxy polyurethane prepolymer amine value obtaining is 180-280mgKOH/g, preferably 190-270mgKOH/g, more preferably 200-260mgKOH/g, more preferably 210-250mgKOH/g.
Use of the present invention
Tackiness agent of the present invention uses conventionally together with aggregate, is coated on concrete road surface, bituminous pavement, ground mass road surface, porcelain base road surface, brick base road surface, and forms good cohesive force with these road surfaces.
Tackiness agent of the present invention can mix as required various colorants and use together, to form needed colored road surface.
Aggregate for making color anti-skid road surface answers entire body of the same colour, dry dustless, squarish, and median size is no more than 4mm, is advisable with 1-3mm, and Mohs' hardness is more than 6.Can select the colored ceramic particle through high-temperature calcination dyeing.By component A: the weight ratio mix that B component is 100: 100 is paved in road surface after evenly forming the fluid of homogeneous, sheds colored aggregate through artificial or machine, guarantees that the latter covers it on completely, form versicolor color anti-skid road surface after curing.
Antislip colour Lu Eryong epoxy resin adhesive modified by PU is a kind of two-component-type colored road surface material, and it is liquid.When construction, without main equipment, after only component A need being mixed in proportion with B component, being coated with and being laid on road surface, and add antislip colour aggregate with the mode of roller coating, pass through chemical crosslink reaction, fast setting becomes tough and tensile glued membrane, formation colored road surface.
Tackiness agent of the present invention is preferably in self-vulcanizing moulding.
Adopt technical scheme of the present invention, compared with prior art, adhesive compound of the present invention has apparent following advantage:
(1) modifier that B component is urethane, the water quality and the atmospheric pollution that while having avoided pungent migration and volatilization, have brought, have more environment friendly.
(2) said composition viscosity is low, can at relatively low temperature, process, and can room temperature fast-curing, glue-applying technique is easy, has greatly reduced energy consumption, has improved production efficiency.
(3) adhesive compound had both retained the higher feature of epoxy bond intensity, had increased again the toughness of cured article by introducing urethane, made it have higher mechanical property and good high and low temperature resistance.
Following embodiment will be used for illustrating the present invention, but not be that except as otherwise noted, the umber of addressing in following embodiment all refers to weight part for limiting claim scope of the present invention.
The color anti-skid road surface that following each embodiment is obtained sticks with glue agent carries out the testing evaluation of following technical indicator.
Test index comprises:
Epoxy equivalent (weight) is pressed GB/T 4612-2008 test;
Isocyano-content (NCO content) is pressed GB 12009.4-89 test;
Amine value is by the method test of " coating technology and digest " the 25th the 1st phase of volume 40-41 page description in 2004;
Ultimate tensile strength, elongation at break, hardness and ultimate compression strength are pressed ASTM D638 test;
Gel time is measured with reference to the manual method test in GB/T 7193.6-1987 testing standard, mix in the rear metal die that is evenly poured into 25 ℃ of constant temperature, volume 200mm × 200mm × 10mm the time of test wire drawing with 100g component A with 100g B component;
Setting time is with reference to the fingers-touch method test in GB 1728-1979 testing standard;
Shore hardness A is by the test method of Shao Shi A regulation in GB/T 2411 testing standards;
Sliding resistance, water tolerance, alkali resistance and low-temperature cracking-resistance are pressed JT/T712-2008 test.
Embodiment 1
1. the preparation of component A
The polypropylene glycol diglycidyl ether 6360 of the E-51 epoxy resin of 100 parts and 10 parts is stirred at the temperature of 60-80 ℃, obtain epoxy resin composition, test epoxy equivalent (weight) is 207.After being cooled to room temperature, pack, sealing is deposited.
2. B component is synthetic
(1) dehydration of polyvalent alcohol: first enough polyoxytrimethylene ether glycol PPG-2028 (data molecular weight 4000) are dropped into in the vacuum reaction still stirring, under stirring, be heated to 120 ℃, then be evacuated to-0.09mPa, dewater 120 minutes, be then cooled to room temperature stand-by.
(2) preparation of base polyurethane prepolymer for use as: by 100 parts 2,4-diphenylmethanediisocyanate
3056 put in another reactor; under nitrogen protection; stirring is warming up to 60 ℃; then slowly add 800 parts of PPG-2028 polyoxytrimethylene ether glycol that took off water by step (1); feed rate take temperature of reaction kettle at 80～85 ℃ as best; after adding polyoxytrimethylene ether glycol, continue reaction 4 hours, surveying NCO content is 1.86wt%.
(3) preparation of epoxy polyurethane prepolymer: by the E-51 epoxy resin of the base polyurethane prepolymer for use as of the above-mentioned steps of 100 parts (2) and 57 parts stirring reaction 4 hours at 80-85 ℃ of temperature, surveying NCO content is 0%, show that reaction completes, add again the carbonic acid allyl ester of 93 parts, form epoxy polyurethane resin prepolymer, epoxy equivalent (weight) is 910.
(4) preparation of polyurethane-modified amine hardener: by the commercial modified aliphatic amine epoxy curing agent (trade(brand)name: R-2011 of 100 parts, amine value is 392mg KOH/g) be warming up to 80-85 ℃, slowly add the above-mentioned epoxy polyurethane prepolymer of 54 parts, at this temperature, react after 1 hour, add again the UV light absorber UV-328 of 3 parts, stir 0.5 hour, after UV light absorber is dissolved completely, temperature of reaction is dropped to 60-80 ℃, finally add the N of 19 parts, dinethylformamide, surveying amine value is 203mgKOH/g.After being cooled to room temperature, pack, sealing is deposited.
3. the use of adhesive compound
By component A: the weight ratio mix that B component is 100: 100 is paved in road surface after evenly forming the fluid of homogeneous, sheds colored aggregate through artificial or machine, guarantees that the latter covers it on completely, form versicolor color anti-skid road surface after curing.
The performance of the tackiness agent of preparing by above-mentioned processing condition is in table 1.
Embodiment 2
1. the preparation of component A
The E-44 epoxy tree of 100 parts is stirred at the temperature of 60-80 ℃ to fat and the polypropylene glycol diglycidyl ether 6360 of 15 parts, obtain epoxy resin composition, testing epoxy equivalent (weight) is 223.After being cooled to room temperature, pack, sealing is deposited.
2. B component is synthetic
(1) dehydration of polyvalent alcohol: first enough polyoxytrimethylene ether glycol PPG-220 are dropped into in the vacuum reaction still stirring, be heated to 120 ℃ under stirring, be then evacuated to-0.09mPa, dewater 120 minutes, be then cooled to room temperature stand-by.
(2) preparation of base polyurethane prepolymer for use as: by 100 parts 2,4-diphenylmethanediisocyanate
3056 put in another reactor; under nitrogen protection; stirring is warming up to 60 ℃; then slowly add 400 parts of PPG-220 polyoxytrimethylene ether glycol that took off water by step (1); feed rate take temperature of reaction kettle at 80～85 ℃ as best; after adding polyoxytrimethylene ether glycol, continue reaction 4 hours, test NCO content is 3.36wt%.
(3) preparation of epoxy polyurethane prepolymer: by the E-51 epoxy resin of the base polyurethane prepolymer for use as of the above-mentioned steps of 100 parts (2) and 60 parts stirring reaction 4 hours at 80-85 ℃ of temperature, surveying NCO content is 0%, show that reaction completes, add again the carbonic acid allyl ester of 100 parts, form epoxy polyurethane resin prepolymer, epoxy equivalent (weight) is 907.
(4) preparation of polyurethane-modified amine hardener: by the two propylene triamines of 30 parts, polypropylene glycol diamine (the trade(brand)name: DA-2000 of the trimethylhexamethylenediamine of 20 parts and 50 parts, number-average molecular weight Mn=2000) mixture be warming up to 80-85 ℃, slowly add the above-mentioned epoxy polyurethane prepolymer of 60 parts, at this temperature, react after 1 hour, add again the UV light absorber UV-320 of 3 parts, stir 0.5 hour, after UV light absorber is dissolved completely, temperature of reaction is dropped to 60-80 ℃, finally add the N of 25 parts, N-N,N-DIMETHYLACETAMIDE, surveying amine value is 230mgKOH/g.After being cooled to room temperature, pack, sealing is deposited.
3. the use of adhesive compound
By component A: the weight ratio mix that B component is 100: 100 is paved in road surface after evenly forming the fluid of homogeneous, sheds colored aggregate through artificial or machine, guarantees that the latter covers it on completely, form versicolor color anti-skid road surface after curing.
The performance of the tackiness agent of preparing by above-mentioned processing condition is in table 1.
Embodiment 3
1. the preparation of component A
The polypropylene glycol diglycidyl ether PEGGE-400 of the E-51 epoxy resin of 100 parts and 20 parts is stirred at the temperature of 60-80 ℃, obtain epoxy resin composition, test epoxy equivalent (weight) is 196.After being cooled to room temperature, pack, sealing is deposited.
2. B component is synthetic
(1) dehydration of polyvalent alcohol: first enough polyoxytrimethylene ether glycol PPG-2028 are dropped into in the vacuum reaction still stirring, be heated to 120 ℃ under stirring, be then evacuated to-0.09mPa, dewater 120 minutes, be then cooled to room temperature stand-by.
(2) preparation of base polyurethane prepolymer for use as: by 100 parts 2,4-diphenylmethanediisocyanate
3056 put in another reactor; under nitrogen protection; stirring is warming up to 60 ℃; then slowly add 800 parts of PPG-2028 polyoxytrimethylene ether glycol that took off water by step (1); feed rate take temperature of reaction kettle at 80～85 ℃ as best; after adding polyoxytrimethylene ether glycol, continue reaction 4 hours, test NCO content is 1.86%.
(3) preparation of epoxy polyurethane prepolymer: by the E-44 epoxy resin of the base polyurethane prepolymer for use as of the above-mentioned steps of 100 parts (2) and 60 parts stirring reaction 4 hours at 80-85 ℃ of temperature, survey NCO containing the most 0%, show that reaction completes, add again phthalic acid two (just) monooctyl ester of 100 parts, form epoxy polyurethane prepolymer, epoxy equivalent (weight) is 1032.
(4) preparation of polyurethane-modified amine hardener: by 100 parts of P-F-diethylenetriamine condenses (trade(brand)names: T-31, amine value 420) be warming up to 80-85 ℃, slowly add the above-mentioned epoxy polyurethane prepolymer of 65 parts, at this temperature, react after 1 hour, add again the UV light absorber UV-320 of 3 parts, stir 0.5 hour, after UV light absorber is dissolved completely, temperature of reaction is dropped to 60-80 ℃, finally add the METHYLPYRROLIDONE of 25 parts, surveying amine value is 215mgKOH/g.After being cooled to room temperature, pack, sealing is deposited.
3. the use of adhesive compound
By component A: the weight ratio mix that B component is 100: 100 is paved in road surface after evenly forming the fluid of homogeneous, sheds colored aggregate through artificial or machine, guarantees that the latter covers it on completely, form versicolor color anti-skid road surface after curing.
The performance of the tackiness agent of preparing by above-mentioned processing condition is in table 1.
Embodiment 4
1. the preparation of component A
The polypropylene glycol diglycidyl ether PEGGE-400 of the E-51 epoxy resin of 100 parts and 20 parts is stirred at the temperature of 60-80 ℃, obtain epoxy resin composition, test epoxy equivalent (weight) is 196.After being cooled to room temperature, pack, sealing is deposited.
2. B component is synthetic
(1) dehydration of polyvalent alcohol: first enough polyoxytrimethylene ether glycol PPG-220 are dropped into in the vacuum reaction still stirring, be heated to 120 ℃ under stirring, be then evacuated to-0.09mPa, dewater 120 minutes, be then cooled to room temperature stand-by.
(2) preparation of base polyurethane prepolymer for use as: by 100 parts 2,4-diphenylmethanediisocyanate
3056 put in another reactor; under nitrogen protection; stirring is warming up to 60 ℃; then slowly add 400 parts of PPG-220 polyoxytrimethylene ether glycol that took off water by step (1); feed rate take temperature of reaction kettle at 80～85 ℃ as best; after adding polyoxytrimethylene ether glycol, continue reaction 4 hours, test NCO content is 3.36wt%.
(3) preparation of epoxy polyurethane prepolymer: by the E-44 epoxy resin of the base polyurethane prepolymer for use as of the above-mentioned steps of 100 parts (2) and 60 parts stirring reaction 4 hours at 80-85 ℃ of temperature, surveying NCO content is 0%, show that reaction completes, add again the carbonic acid allyl ester of 100 parts, form epoxy polyurethane prepolymer, epoxy equivalent (weight) is 1032.
(4) preparation of polyurethane-modified amine hardener: the mixture of 30 parts of diamino diphenyl sulfones and 70 parts of commercial modification cycloaliphatic amines epoxy solidifying agent (trade(brand)name: R-2253 amine value: 320mgKOH/g) is warming up to 80-85 ℃, slowly add the above-mentioned epoxy polyurethane prepolymer of 55 parts, at this temperature, react after 1 hour, add again the UV light absorber UV-320 of 3 parts, stir 0.5 hour, after UV light absorber is dissolved completely, temperature of reaction is dropped to 60-80 ℃, finally add the METHYLPYRROLIDONE of 25 parts, recording amine value is 196mgKOH/g.After being cooled to room temperature, pack, sealing is deposited.
3. the use of adhesive compound
By component A: the weight ratio mix that B component is 100: 100 is paved in road surface after evenly forming the fluid of homogeneous, sheds colored aggregate through artificial or machine, guarantees that the latter covers it on completely, form versicolor color anti-skid road surface after curing.
The performance of the tackiness agent of preparing by above-mentioned processing condition is in table 1.
The performance index of epoxy resin adhesive modified by PU for table 1. color anti-skid road surface
As can be seen from Table 1, the ultimate tensile strength of various embodiments of the present invention all >=more than 18.6mPa; Elongation at break >=48.6%; Ultimate compression strength >=12.5mPa; Gel time >=22min; Setting time >=120min; Shore A hardness >=86; Sliding resistance >=73 (high anti-slip type).This shows, color anti-skid road surface of the present invention meets People's Republic of China's transportation industry standard of pavement antiskid paint completely with epoxy resin adhesive modified by PU, have broad application prospects.
Through the check of national building materials test center, the assay of color anti-skid road surface project that wear-resisting glue is examined of the present invention meets the technical requirement of anti-skidding cold painting type in JT/T712-2008 standard.
Although more than invention is intended to realize the bonding of highway pavement and antiskid aggregate, the present invention certainly can extend to other near field, and as the bonding of building leak stopping joint filling, Furniture panel etc., this is apparent for a person skilled in the art.Therefore, under thought of the present invention, those skilled in the art can make various changes or modification to the present invention on this basis, should belong to equally scope of the present invention.
Claims (10)
1. an epoxy resin adhesive modified by PU, it comprises component A and B component, wherein
Component A is epoxy resin composition, and it comprises:
(i) bisphenol A type epoxy resin that 100 weight part oxirane values are 0.41-0.58mol/100g;
(ii) polypropylene glycol diglycidyl ether that 1-20 parts by weight average molecular weight is 100-1000, for regulating the viscosity of component A;
B component is polyurethane-modified amine hardener, and it comprises:
(i) organic polyamine of 100 weight parts;
This organic polyamine is at least one being selected from lower group: fatty amine, cycloaliphatic amines, aromatic amine, modified amine epoxy curing agent or their mixture;
(ii) the epoxy polyurethane prepolymer of 40-70 weight part,
The bisphenol A type epoxy resin that this epoxy polyurethane prepolymer is 0.41-0.58mol/100g by base polyurethane prepolymer for use as and the 40-70 weight part oxirane value of 100 weight parts adds the softening agent of 80-120 weight part to mix after polyreaction again,
The polyvalent alcohol that wherein said base polyurethane prepolymer for use as is 1000-10000 by one or more diphenylmethanediisocyanates and one or more number-average molecular weights is by 100:200-2000 part by weight through being polymerized, and its isocyano NCO content is 0.5-6wt%:
(iii) UV light absorber of 0.5-5 weight part;
(iv) solvent of the solubilized epoxy polyurethane prepolymer of 15-30 weight part, for regulating the viscosity of B component,
Component A and B component are deposited separately, when use by component A: the weight ratio that B component is 100:100 is used in conjunction with.
2. tackiness agent according to claim 1, is characterized in that, the oxirane value of bisphenol A type epoxy resin described in described component A is 0.48-0.56mol/100g.
3. tackiness agent according to claim 1, is characterized in that, the number-average molecular weight of described polypropylene glycol diglycidyl ether is 120-600.
4. tackiness agent according to claim 1, it is characterized in that, in described B component, be at least one being selected from lower group for the synthesis of the described diphenylmethanediisocyanate of base polyurethane prepolymer for use as: 4,4 '-diphenylmethanediisocyanate, 2,4 '-diphenylmethanediisocyanate, their mixture.
5. tackiness agent according to claim 1, is characterized in that, described bisphenol A type epoxy resin is at least one being selected from lower group: epoxy resin E-44, E-51, epoxy resin E-55, their mixture.
6. tackiness agent according to claim 1, it is characterized in that, described softening agent is at least one being selected from lower group: be dibutyl phthalate, dioctyl phthalate (DOP), epoxy soybean oil, carbonic acid allyl ester, di-isooctyladinpate, two or more mixture in them.
7. tackiness agent according to claim 1, is characterized in that, described UV light absorber is at least one being selected from lower group: UV-328, UV-320, their mixture.
8. prepare according to a method for the tackiness agent described in any one in claim 1 to 7, comprise the steps:
(1) preparation of component A:
The polypropylene glycol diglycidyl ether of the bisphenol A type epoxy resin of 100 weight parts and 1-20 weight part is stirred at the temperature of 60-80 ℃, obtain epoxy resin composition, epoxy equivalent (weight) is 160-260, packs after being cooled to room temperature, and sealing is deposited;
(2) preparation of B component
1. prepare base polyurethane prepolymer for use as:
The polyvalent alcohol that took off water that is 1000-10000 with at least one number-average molecular weight of 200-2000 weight part by least one diphenylmethanediisocyanate of 100 weight parts reacts 1-4 hour at 60-90 ℃, generate isocyanate-terminated performed polymer, isocyano NCO content is 0.5-6wt%;
2. prepare epoxy polyurethane prepolymer
The above-mentioned base polyurethane prepolymer for use as of 100 weight parts is reacted to 1-4 hour with the bisphenol A type epoxy resin of 40-70 weight part at 60-90 ℃ of temperature, in the time that NCO content drops to 0%, add the softening agent of 80-120 weight part, form epoxy polyurethane prepolymer, epoxy equivalent (weight) is 800-1600;
3. prepare polyurethane-modified amine hardener
The organic polyamine of 100 weight parts is warming up to 80-100 ℃, slowly add the above-mentioned epoxy polyurethane prepolymer of 40-70 weight part, at this temperature, react after 1-2 hour, add again the UV light absorber of 0.5-5 weight part, stir 0.25-0.5 hour, after guaranteeing that UV light absorber is dissolved completely, temperature of reaction is dropped to 60-80 ℃, the solvent adjustment viscosity that finally adds 15-30 weight part solubilized epoxy polyurethane prepolymer, amine value is 180-280mgKOH/g.
9. the application in anti-skid surface according to the tackiness agent described in any one in claim 1 to 7.
10. application according to claim 9, is characterized in that, described anti-skid surface is color anti-skid road surface, when construction, will be used in conjunction with according to the tackiness agent described in any one in claim 1 to 7 and colored aggregate.
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| CN103964748B (en) * | 2014-04-10 | 2016-01-20 | 广东省建筑科学研究院集团股份有限公司 | A kind of expansion joint fast repairing material and preparation method thereof |
| CN106365508A (en) * | 2016-08-29 | 2017-02-01 | 福州皇家地坪有限公司 | Epoxy color sand coating |
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| CN112123499B (en) * | 2020-10-09 | 2023-05-09 | 北华大学 | Corrosion-resistant shaving board and preparation method thereof |
| CN112831301B (en) * | 2020-12-31 | 2023-04-07 | 山西省交通科技研发有限公司 | High-light-reflection environment-friendly colorful anti-skid pavement and preparation method thereof |
| CN113896861A (en) * | 2021-11-26 | 2022-01-07 | 中航复合材料有限责任公司 | Dicyandiamide cured epoxy resin suitable for out-of-tank molding and preparation method thereof |
| CN114163901A (en) * | 2021-12-15 | 2022-03-11 | 上铁芜湖高新材料技术有限公司 | Epoxy polyurethane composite waterproof material for high-speed rail bridge and construction method thereof |
| CN117125922B (en) * | 2022-05-18 | 2025-12-30 | 万华化学（宁波）有限公司 | A triple-curing, fast-drying polyurethane-modified epoxy permeable pavement adhesive, its preparation method, and its application. |
| CN116769277A (en) * | 2023-05-30 | 2023-09-19 | 江苏恒隆通新材料科技有限公司 | A medium temperature rapid curing high hardness laminated resin |
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| CN101348701A (en) * | 2008-09-12 | 2009-01-21 | 云南光电辅料有限公司 | Optical light color low stress modified epoxy adhesive and preparation of |
| CN101475788A (en) * | 2009-01-15 | 2009-07-08 | 湖南神力实业有限公司 | High strength polyurethane modified epoxy construction structure glue and manufacturing method thereof |
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| CN101348701A (en) * | 2008-09-12 | 2009-01-21 | 云南光电辅料有限公司 | Optical light color low stress modified epoxy adhesive and preparation of |
| CN101475788A (en) * | 2009-01-15 | 2009-07-08 | 湖南神力实业有限公司 | High strength polyurethane modified epoxy construction structure glue and manufacturing method thereof |
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