CN102585155B - PUA (polyurethane) reactive resin and preparation method thereof - Google Patents
PUA (polyurethane) reactive resin and preparation method thereof Download PDFInfo
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- CN102585155B CN102585155B CN201210019074.0A CN201210019074A CN102585155B CN 102585155 B CN102585155 B CN 102585155B CN 201210019074 A CN201210019074 A CN 201210019074A CN 102585155 B CN102585155 B CN 102585155B
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- pua
- diolefine
- oligopolymer
- resin
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- 239000011347 resin Substances 0.000 title claims abstract description 248
- 229920005989 resin Polymers 0.000 title claims abstract description 248
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000004814 polyurethane Substances 0.000 title abstract description 9
- 229920002635 polyurethane Polymers 0.000 title abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 163
- -1 diisocyanate compound Chemical class 0.000 claims abstract description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 195
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 106
- 238000003756 stirring Methods 0.000 claims description 52
- 125000005442 diisocyanate group Chemical group 0.000 claims description 32
- 230000006837 decompression Effects 0.000 claims description 22
- 230000018044 dehydration Effects 0.000 claims description 22
- 238000006297 dehydration reaction Methods 0.000 claims description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 14
- 125000000524 functional group Chemical group 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 125000004434 sulfur atom Chemical group 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 17
- 239000002994 raw material Substances 0.000 abstract description 16
- 229920003023 plastic Polymers 0.000 abstract description 10
- 239000004033 plastic Substances 0.000 abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 abstract 1
- 125000004423 acyloxy group Chemical group 0.000 abstract 1
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 80
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 20
- 238000007599 discharging Methods 0.000 description 17
- 238000005984 hydrogenation reaction Methods 0.000 description 13
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 12
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 11
- 239000003085 diluting agent Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 10
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 10
- 239000005058 Isophorone diisocyanate Substances 0.000 description 9
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920001195 polyisoprene Polymers 0.000 description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 6
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 5
- 150000001875 compounds Chemical group 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical class N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 229940051250 hexylene glycol Drugs 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 3
- 229950006389 thiodiglycol Drugs 0.000 description 3
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- RISQCUQJUHIVTO-UHFFFAOYSA-N C(C)OC(C(C1=CC=CC=C1)(O)O)(C)OCC Chemical compound C(C)OC(C(C1=CC=CC=C1)(O)O)(C)OCC RISQCUQJUHIVTO-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229960005082 etohexadiol Drugs 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000003541 multi-stage reaction Methods 0.000 description 2
- 238000000016 photochemical curing Methods 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Chemical group 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- BDRRUSWEXWLMQQ-UHFFFAOYSA-N 2-(hydroxymethyl)-2-(2,2,2-triethoxyethyl)propane-1,3-diol Chemical compound C(C)OC(CC(CO)(CO)CO)(OCC)OCC BDRRUSWEXWLMQQ-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N 2-butenoic acid Chemical compound CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 description 1
- OJCBGTZZEGHDHR-UHFFFAOYSA-N 3-methylbuta-1,3-dien-1-ol Chemical compound CC(=C)C=CO OJCBGTZZEGHDHR-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229920013701 VORANOL™ Polymers 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- MHIBEGOZTWERHF-UHFFFAOYSA-N heptane-1,1-diol Chemical compound CCCCCCC(O)O MHIBEGOZTWERHF-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-dimethylbenzene Natural products CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 238000003847 radiation curing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a PUA (polyurethane) reactive resin and a preparation method thereof. The PUA (polyurethane) reactive resin is prepared from a terminal hydroxyl dialkene oligomer, a diisocyanate compound, an optional polyhydric alcohol, and -OH containing (methyl) acrylate; and the obtained reactive resin comprises a dialkene oligomer soft segment and a diamino formate hard segment, and molecular chain terminal containing a (methyl) acyloxy group. The PUA reactive resin disclosed by the invention is based on the principle of stepwise polymerization of hydroxyl groups and isocyanate groups, has low water absorptivity and good water resistance, chemical resistance, storage capability and plastic adhesion by reasonably configuring the proportional relation among raw materials.
Description
Technical field
The present invention relates to reaction resin field, especially relate to a kind of PUA reaction resin and preparation method thereof.
Background technology
The resin that contains carbon carbon unsaturated double-bond (C=C) is a class reaction resin, the mode of this reaction resin available light or thermal initiation is reacted moulding, can be used as the coating resin of photocuring, thermofixation, also can be used as the resin dedicated, of many uses of binding agent and encapsulation or sealing.The conventional reaction resin that contains C=C group comprises unsaturated polyester, epoxy acrylic resin (PEA), polyurethane acrylic resin (PUA), polyester acrylic resin, polyoxyalkylene acrylate resin, acrylated polyacrylic resin etc.These resins are easy to prepare; performance variable range is wide; the basic performance requriements that can meet general and normal condition; for example; can be used for the photo-cured coating of civilian decoration and protectiveness, Photocurable adhesive, the printing-ink etc. of general applications, these reaction resins are bases of current radiation curing technology and product.But for there being more the purposes of being strict with, as bonding, the electronic product packaging for plastic basis material etc., these resins can not meet performance requriements at aspects such as sticking power, water tolerance, erosion resistance chemical reagent.
In the existing reaction resin that contains C=C group, Comparatively speaking to have wetting ability strong for PUA resin, soft, the advantage good to the sticking power of polar substrates, but existing PUA resin, for example PUA taking the polyester of terminal hydroxy group or polyethers as main raw material, also there is the poor adhesive force to non-polar plastic, water-intake rate is high, and resistance to strong chemical reagent and water tolerance are bad, and waiting that weathering resistance is poor is not enough.
PUA type resin is that the isocyanate groups (NCO) that utilizes diisocyanate cpd is bridge-jointing unit, and the acrylate of hydroxyl (OH) group is connected to prepare with the resin of contain-OH.In order to improve the performance of existing PUA type resin, make it more meet application requiring, need to improve PUA type reaction resin.
In the patent that is CN201010297425.5 in China Patent Publication No., " a kind of light-cured resin with low water absorption and preparation method thereof " disclosed, wherein this light-cured resin is silane-modified Hydroxyl-terminated Polybutadiene Polyurethane acrylate, by two hydroxy-terminated polybutadienes oligopolymer are reacted with diisocyanate cpd, the intermediate of generation-NCO end-blocking, then be secondary amine with one end, the silicone compounds chain extension that the other end is secondary hydroxyl, contain multiple alkoxyl groups, last again by stay-NCO prepared with the acrylate reactions containing-OH group.
Although the siloxane unit in the molecular resin chain that above-mentioned patent obtains has reduced the water-intake rate of resin, but the stability to hydrolysis of the siloxane unit that contains multiple alkoxyl groups is bad, particularly under acid or alkali condition, even a small amount of water, even moisture all easily makes the siloxane groups of multiple alkoxyl groups be hydrolyzed, deviate from alkoxyl group, generate Si-O-Si structure, make resin gel.This chemical property of the siloxane groups that contains multiple alkoxyl groups, is the chemical fundamentals of siloxane compound as coupling agent application, but for reaction resin, particularly can causes serious problem to the stability in storage of light-cured resin.Therefore the light-cured resin that, this class contains multiple oxyalkylsiloxane groups can not be used for the photocuring product of slant acidity or alkalescence.
In addition, the activity of reacting with isocyanate compound due to amido is high, is being secondary amine with one end, and when silicone compounds chain extension that the other end is secondary hydroxyl, the controllability of reaction is bad, and resin viscosity is large, unfavorable to the use of product.
For PUA type reaction resin, also need further to improve its poor adhesive force to non-polar plastic, water-intake rate is high, and resistance to strong chemical reagent and water tolerance are bad, and waiting that weathering resistance is poor is not enough.
Summary of the invention
The present invention aims to provide a kind of PUA type reaction resin and preparation method thereof, and to solve, in prior art, PUA type reaction resin water-intake rate is high, water-fast and acidproof, alkali resistance is bad, the problem of poor adhesive force to plastics.
For achieving the above object, according to an aspect of the present invention, a kind of PUA type reaction resin is provided, PUA type reaction resin is prepared from by terminal hydroxy group diolefine oligopolymer, diisocyanate cpd, optional polyvalent alcohol, contain-OH (methyl) acrylate, the reaction resin making comprises hard section of soft section of diolefine oligopolymer and double carbamate, and the molecule chain end that contains (methyl) acryloyl-oxy group.
Further, number sum >=8 o'clock of carbon atom in the saturated carbon chains of above-mentioned polyvalent alcohol (C), Sauerstoffatom (O) and/or sulphur atom (S), also comprise soft section that is formed by saturated carbon chains in soft section of prepared reaction resin.
Further, on the molecular chain of above-mentioned PUA type reaction resin, on average contain 1-5 soft section, 2-6 hard section and 2-4 (methyl) acryloyl-oxy group molecule chain end.
Further, the mol ratio of above-mentioned polyvalent alcohol and terminal hydroxy group diolefine oligopolymer is 0～2: 1; In diisocyanate cpd-NCO functional group and polyvalent alcohol and terminal hydroxy group diolefine oligopolymer in-mol ratio of OH functional group sum is 6/5～2/1.
Further, the number-average molecular weight of above-mentioned both-end hydroxyl diolefine oligopolymer is 800-6000g/mol, or hydroxyl value is 0.3～2.5mmol/g.
Further, above-mentioned terminal hydroxy group diolefine oligopolymer comprises the terminal hydroxy group diolefine oligopolymer that contains itrile group group, and wherein the content of itrile group group is M, 0 < M≤22%, preferably, 5 < M≤22%.
Further, above-mentioned terminal hydroxy group diolefine oligopolymer comprises the terminal hydroxy group diolefine oligopolymer that contains phenyl group, and wherein the content of phenyl group is X, 0 < X≤22%, preferably, 0 < X≤18%.
Further, above-mentioned polyvalent alcohol is dibasic alcohol and/or the trivalent alcohol that contains 2～20 carbon atoms, and the mol ratio of polyvalent alcohol and terminal hydroxy group diolefine oligopolymer is 1: 10～2: 1;
Further, when polyvalent alcohol is dibasic alcohol and trivalent alcohol, the ratio of the molar weight of trivalent alcohol and dibasic alcohol and terminal hydroxy group diolefine oligopolymer molar weight sum is R, 0 < R≤2.
Meanwhile, in another aspect of the present invention, also provide a kind of preparation method of PUA type reaction resin, comprised the following steps: reacted the preform of generation end group as-NCO with diisocyanate cpd taking terminal hydroxy group diolefine oligopolymer, optional polyvalent alcohol; React with preform and generate PUA type reaction resin with (methyl) acrylate of contain-OH.
Further, above-mentionedly prepare end group and be-step of the preform of NCO comprises, the terminal hydroxy group diolefine oligopolymer after decompression dehydration mixed to formation solution A with optional polyvalent alcohol and optional catalyzer heated and stirred; In solution A, add diisocyanate cpd, the temperature that raises is gradually to higher than 70 DEG C, and reaction 1～2.5h obtains end group and is-preform of NCO; Or diisocyanate cpd is mixed with optional polyvalent alcohol, temperature not higher than 70 DEG C at stirring reaction 0.5～2h, form solution B, add terminal hydroxy group diolefine oligopolymer and optional catalyzer after decompression dehydration, control temperature to not higher than 70 DEG C of stirring reaction 1～2.5h, obtain end group and be-preform of NCO;
Further, (methyl) acrylate of contain-OH of above-mentioned use reacts generation PUA type reaction resin and comprises with preform, at end group be-add (methyl) acrylate and optional thinner containing-OH in the preform of NCO, at 50～70 DEG C of stirring reaction 1～3h, obtain PUA type reaction resin.
Beneficial effect of the present invention: the PUA type reaction resin that the application provides, based on oh group and the progressively principle of polymerization of isocyanate groups, by reasonably configuring the proportionlity between raw material and raw material, formation has hard section of soft section of diolefine oligopolymer and double carbamate, and (methyl) acryloyl-oxy group PUA type reaction resin that is molecule chain end, this PUA type reaction resin has that water-intake rate is low, water-fast and acidproof, alkali resistance is good, stability in storage is good and the advantage good to the sticking power of plastics.
Embodiment
It should be noted that, in the situation that not conflicting, the feature in embodiment and embodiment in the application can combine mutually.Describe the present invention in detail below with reference to specific embodiment.
In the typical embodiment of one of the present invention, a kind of PUA type reaction resin, (methyl) acrylate by terminal hydroxy group diolefine oligopolymer, diisocyanate cpd, optional polyvalent alcohol and contain-OH is prepared from, the reaction resin making comprises hard section of soft section of diolefine oligopolymer and double carbamate, and (methyl) acryloyl-oxy group molecule chain end.
The polarity of above-mentioned double carbamate group is large, and Intermolecular Forces is strong, is the rigid chain segment on molecular chain, and the polarity of chain of terminal hydroxy group oligopolymer is little, second-order transition temperature is usually less than or near room temperature, segment is relatively soft, is the soft segment on molecular resin chain.In order to describe the convenience of molecular structure, double carbamate is called to hard section in the present invention, diolefine oligopolymer is called to soft section.
The PUA type reaction resin that the application provides is based on oh group and isocyanate groups step-reaction polymerization, generates the principle of urethane polymer (PU).By reasonably selecting and configure raw material, form and there is hard section of soft section of diolefine oligopolymer and specific double carbamate, and the PUA type reaction resin of (methyl) acryloyl-oxy group molecule chain end.
Below provide the chemical equation of the main chemical reactions occurring between each feed composition in a kind of preparation process of PUA type reaction resin.In order to simplify this chemical equation, in following chemical equation,
represent both-end hydroxyl diolefine oligopolymer, OCN-R-NCO represents diisocyanate cpd, and polyvalent alcohol is selected butyleneglycol,
represent soft section, R '=-CH
3,-H,
Chemical equation is as follows:
Can be found out by above-mentioned chemical equation, in the molecular chain of prepared PUA type reaction resin, average packet is containing two soft section, two (methyl) acryloyl-oxy group molecule chain ends (be wherein R " be (methyl) acryloyl-oxy group molecule chain end) and four double carbamate segments that formed by vulcabond.Because used butyleneglycol carbochain section is relatively short, so two middle double carbamates are connected to form a hard section by shorter butane segment, this just makes only to contain three hard sections in the molecular chain of obtained PUA type reaction resin.
In the example providing at above-mentioned chemical equation, if with C, S, the saturated dibasic alcohol of number sum >=8 of O atom replaces butyleneglycol, now, the molecular chain middle portion of the PUA type reaction resin product obtaining becomes by C, S, the segment that the saturated carbon chains of number sum >=8 of O atom forms, and the two ends of this segment are connected with respectively hard section an of double carbamate, due to by C, S, the segment that the saturated carbon chains of number sum >=8 of O atom forms is flexible unit, now, the molecular chain of prepared PUA type reaction resin will increase a flexible carbochain unit, in the middle of being positioned at, two double carbamates on both sides, soft segment unit are separated by flexible carbochain simultaneously, form two hard sections.
With C in saturated carbon chains, S, the dibasic alcohol of number sum >=8 of O atom replaces C in saturated carbon chains, S, when the dibasic alcohol of the number sum < 8 of O atom (above-mentioned reaction adopt be butyleneglycol) carries out above-mentioned reaction, the molecular chain of prepared PUA type reaction resin becomes and comprises 3 soft section (soft section and one soft section of being formed by saturated carbon chains of two diolefine oligopolymer), 2 (methyl) acryloyl-oxy group molecule chain ends, hard section of (two double carbamates that are connected with soft section of two ends that formed by saturated carbon chains with 4 carbamates, with two double carbamates that are connected with molecule chain end).
For the purpose of sake of clarity, in the time of design and preparation PUA molecular resin, if number sum >=8 o'clock that the saturated carbon chains of the polyvalent alcohol using contains C and O and/or S atom, this saturated chain carbon will be calculated as soft section in PUA resin.The saturated carbon chains that what is called contains C and O and/or S atom number sum >=8, refers to that C and O and/or S atom, with saturated covalent linkage the carbochain that is directly connected with linear mode, wherein can have ehter bond or thioether bond; In the time calculating the atom number of saturated carbon chains, each O of the ehter bond in carbochain or thioether bond or S atom are calculated as an atom, are not counted in the atomicity of carbochain at the group of carbochain side group.For example, 1,8-ethohexadiol is the saturated carbon chains that has 8 carbon atoms, and Triethylene glycol has six carbon atom and two O atoms, and tripropylene glycol also has the carbochain of six C atoms and two O atoms, all meets the definition of soft section.
Those skilled in the art are according to explanation of the present invention, have the ability by combination raw materials reasonably, adjust order of addition(of ingredients), the stepwise reaction of raw material and control the level of response in per stage, and use chemically reactive is identical or discrepant diisocyanate cpd, can design, synthesize the PUA resin of different soft, hard hop count orders and molecular conformation.
Preferably, on the molecular chain of PUA type reaction resin of the present invention, on average contain 1-5 soft section, 2-6 individual hard section and individual (methyl) acryloyl-oxy group molecule chain end of 2-4, wherein soft section and the quantity employing aforesaid way calculating of section firmly.
PUA type reaction resin in above-mentioned characteristic range, easily, production technique is simple in preparation, and have that water-intake rate is lower, water-tolerant, storage characteristics, sticking power to plastics and to acid, the excellent in stability of alkali, the good characteristic of over-all properties.
The molecular chain of PUA type reaction resin provided by the present invention, include but not limited to linearity that following structural formula (1), (2), (3), (4) and (5) are represented or the molecular conformation of branching, in order to reduce structure length, in following structural formula (1), (2), (3), (4) and (5)
the hard section of representative,
represent soft section, A representative (methyl) acryloyl-oxy group.
Soft for not requiring, hard section has the PUA resin (for example, shown in structural formula (5)) of particular sorted order, or do not use the PUA resin of polyvalent alcohol, or only have 2 hard sections, the simplest PUA molecular resin (for example, shown in structural formula (1)) of 2 (methyl) acryloyl-oxy groups and 1 soft section, the preform of synthetic can first make-NCO of the raw materials mode group end capping of resin, and can first (methyl) acrylate of contain-OH be reacted with excessive diisocyanate cpd, and then add the mode of both-end hydroxyl diolefine oligopolymer reaction to prepare.
Preferably, in above-mentioned PUA type reaction resin preparation process, the mol ratio of polyvalent alcohol and terminal hydroxy group diolefine oligopolymer is 0～2: 1; In diisocyanate cpd-NCO functional group and polyvalent alcohol and terminal hydroxy group diolefine oligopolymer in-mol ratio of OH functional group sum is 6/5～2/1.Under this conditions of mixture ratios, favourable formation has soft section, hard section and the PUA type reacting resin of (methyl) acryloyl-oxy group molecule chain end quantity of specific quantity, and then promotes the over-all properties of prepared resin.
Terminal hydroxy group diolefine oligopolymer is a class telechelic oligoner in the present invention, has two terminal hydroxy group.The preparation method of the terminal hydroxy group diolefine oligopolymer of the distant pawl type of this class has a lot, for example, the diolefine active anionic polymerization that can cause with bifunctional initiator, then use the method for oxyethane termination reaction, again for example, can cause diolefine radical polymerization with hydrogen peroxide, prepared by the method for reacting by the double-basis coupling termination of terminal hydroxy group diolefine macromolecular radical; The diolefine oligopolymer of hydrogenation can carry out hydrogenation by terminal hydroxy group diolefine oligopolymer with palladium catalyst and suitable reaction conditions and make.The micro chemical of the terminal hydroxy group diolefine oligopolymer of the terminal hydroxy group diolefine oligopolymer that different methods is prepared and hydrogenation is different, for example 1,2 with ratio, the hydrogenation of the ratio of Isosorbide-5-Nitrae structure, genial transconfiguration after chain structure and the end of the chain be that the hydroxyl etc. of one-level or secondary is different.PUA type reaction resin provided by the present invention, can be according to the requirement of preparation method and required chemical structure, select the terminal hydroxy group diolefine oligopolymer of terminal hydroxy group diolefine oligopolymer and/or hydrogenation, and, can be primary hydroxyl or secondary hydroxyl at the hydroxyl of these oligomer chain ends.
The terminal hydroxy group diolefine oligopolymer using in above-mentioned PUA type reaction resin preparation process, includes but not limited to the terminal hydroxy group diolefine oligopolymer of hydroxyl terminated polyisoprene, hydroxy-terminated polybutadienes hydrocarbon and hydrogenation.Diolefine oligopolymer has that viscosity is low, good fluidity, water-fast, hydrophobic, resistance to strong chemical reagent, molecular chain softness, to features such as the sticking power of non-polar plastic are good, simultaneously diolefine low-grade polymer molecule chain end-OH radical reaction activity is high, fast with isocyanate reaction, also easily control, the raw material using diolefine low-grade polymer as PUA can effectively improve the performance of prepared PUA type reaction resin.
Preferably, it is 800g/mol～6000g/mol that above-mentioned terminal hydroxy group diolefine oligopolymer adopts number-average molecular weight, or hydroxyl value is at the terminal hydroxy group diolefine oligopolymer of 0.3mmol/g～2.5mmol/g.If oligopolymer hydroxyl value is too large, the molecular weight of diolefine oligopolymer will be relatively low, in the PUA type resin of gained soft section shorter, and carbamate hard segment content is larger, and the water-intake rate of resin is higher, and water tolerance is outstanding; If hydroxyl value is too little, the molecular weight of diolefine oligopolymer is just larger, and the resin viscosity of gained is larger, and property is soft, and physical strength is poor.More preferably, the number-average molecular weight of above-mentioned terminal hydroxy group diolefine oligopolymer is preferably 1400g/mol～6000g/mol, or the hydroxyl value of above-mentioned terminal hydroxy group diolefine oligopolymer is preferably 0.3～1.3mmol/g, within the scope of this, viscosity and the chemically reactive of terminal hydroxy group diolefine oligopolymer are suitable, and the over-all properties of the PUA type resin obtaining is also best.
In terminal hydroxy group diolefine oligopolymer of the present invention, can also contain appropriate itrile group group (CN), adding of-CN group is conducive to increase the sticking power of resin to polar substrates, also helps the consistency that improves PUA type reaction resin of the present invention and other resin or compound.
The above-mentioned terminal hydroxy group diolefine oligopolymer that contains itrile group group can, by the method for the radical polymerization of similar terminal hydroxy group diolefine oligopolymer, obtain with diolefine and acrylonitrile compolymer.Contain in the present invention the terminal hydroxy group diolefine oligopolymer of itrile group group, include but not limited to the multipolymer of terminal hydroxy group butadiene hydrocarbon-vinyl cyanide, the multipolymer of terminal hydroxy group isoprene hydrocarbon-vinyl cyanide, or the copolymerization of the isoprene of terminal hydroxy group and the dienes mixture of divinyl and vinyl cyanide.In the above-mentioned terminal hydroxy group diolefine oligopolymer that contains itrile group group, the mass content of-CN group is M, 0 < M≤22%.Preferably, 5% < M≤22%.Within the scope of this, the viscosity of oligopolymer is suitable, can reach the mechanical property that improves final PUA resin, improve and the object of the consistency of other resin, if-too high levels of CN group, the water-absorbent of final PUA resin can increase, the viscosity of resin is large simultaneously, and color is dark, resin hardens.
Preferably, in above-mentioned terminal hydroxy group diolefine oligopolymer, comprise the terminal hydroxy group diolefine oligopolymer of the terminal hydroxy group diolefine oligopolymer that contains CN group and do not contain-CN group simultaneously.Both are used in conjunction with, and can control preferably-CN group content, makes its content not too high, and the too high meeting of content of-CN group increases polarity, water-intake rate and the viscosity of prepared PUA type resin, resin hardens.More preferably, in above-mentioned terminal hydroxy group diolefine oligopolymer, the mass ratio of the terminal hydroxy group diolefine oligopolymer of contain-CN group and the terminal hydroxy group diolefine oligopolymer of do not contain-CN group is 0～5: 1.
In the molecular chain of terminal hydroxy group diolefine oligopolymer of the present invention, can also contain appropriate phenyl ring group (Ph), add-Ph of PUA molecular resin chain group is conducive to increase the mechanical strength of PUA resin and the sticking power to plastic basis material, is also conducive to improve the thermotolerance of PUA and the consistency with other resin or compound.
The terminal hydroxy group diolefine oligopolymer of above-mentioned containing-Ph group, can be by the preparation method of similar above-mentioned terminal hydroxy group diolefine oligopolymer, obtains taking diolefine and vinylbenzene as material copolymerization.The terminal hydroxy group diolefine oligopolymer of contain in the present invention-Ph group, include but not limited to terminal hydroxy group butadiene hydrocarbon-cinnamic multipolymer, terminal hydroxy group isoprene hydrocarbon-cinnamic multipolymer, or the isoprene of terminal hydroxy group and the dienes mixture of divinyl and cinnamic copolymerization.In the terminal hydroxy group diolefine oligopolymer of above-mentioned containing-Ph group, the mass content X of-Ph group, can be in 0 < X≤25% scope, preferably, and 0 < X≤18%.Within the scope of this, the viscosity of oligopolymer is suitable, can reach the mechanical property that improves PUA resin, improve and the object of the consistency of other resin, if-too high levels of Ph group, will make PUA resin hardens, simultaneously the transparency and light fastness aging decline.
In a kind of concrete embodiment of the present invention, in above-mentioned terminal hydroxy group diolefine oligopolymer, comprise the terminal hydroxy group diolefine oligopolymer of the terminal hydroxy group diolefine oligopolymer of contain-Ph group and do not contain-Ph group simultaneously.Both are used in conjunction with, the content of can more easily regulate-Ph group, the content of-Ph group is too high, can make the viscosity of prepared PUA type resin increase, resin hardens, the transparency and light fastness aging decline.More preferably, in above-mentioned terminal hydroxy group diolefine oligopolymer, the mass ratio of the terminal hydroxy group diolefine oligopolymer of contain-Ph group and the terminal hydroxy group diolefine oligopolymer of do not contain-Ph group is 0～5: 1.
In a kind of concrete embodiment of the present invention, in above-mentioned PUA type reaction resin preparation, also add polyvalent alcohol, for example two～tetravalent alcohol, preferably, polyvalent alcohol is selected from the dibasic alcohol and/or the trivalent alcohol that contain 2～20 carbon atoms.This polyvalent alcohol, except containing 2～20 carbon atoms, can also contain S and/or not belong to the O atom of hydroxyl.
In PUA type reaction resin of the present invention, if add appropriate small molecules polyvalent alcohol, can regulate on prepared PUA type reaction resin molecular chain content and the ratio of soft, hard section by the combination of polyvalent alcohol and terminal hydroxy group diolefine oligopolymer, strengthen the reactive force between molecular resin, improve the mechanical property of prepared PUA type reaction resin, and improve the bonding force to polar substrates; With trivalent alcohol or the polyvalent alcohol of high functionality more, can obtain the PUA molecular resin chain of branching form, and then obtain the PUA resin of excellent combination property.
The mol ratio of the polyvalent alcohol that preferably, in the present invention used and terminal hydroxy group diolefine oligopolymer is 0～2: 1.In actual mechanical process, can adjust according to the performance requriements of the molecular weight of terminal hydroxy group diolefine oligopolymer and prepared PUA type reaction resin: if the molecular weight of the terminal hydroxy group diolefine oligopolymer using is little, or the viscosity of required PUA type reaction resin is little, the consumption of polyvalent alcohol can reduce in right amount, does not even use.If the molecular weight of the terminal hydroxy group diolefine oligopolymer using is large, or the viscosity of required PUA type reaction resin is large, and the consumption of polyvalent alcohol just needs appropriate increasing, and makes the mol ratio of polyvalent alcohol and terminal hydroxy group diolefine oligopolymer reach 2.If but the consumption of polyvalent alcohol is too much, such as the mol ratio of polyvalent alcohol and terminal hydroxy group diolefine oligopolymer is greater than 2, hard section of the PUA resin of gained too many, it is large that water-intake rate becomes, viscosity is excessive.Preferably, the mol ratio of polyvalent alcohol and terminal hydroxy group diolefine oligopolymer is 1: 10～2: 1.
Polyvalent alcohol can adopt separately dibasic alcohol or trivalent alcohol in the present invention, also dibasic alcohol and trivalent alcohol can be used in conjunction with.While using dibasic alcohol, diatomic alcohol compounds and di-isocyanate reaction, what obtain is the resin of linear structure, while using trivalent alcohol, trivalent alcohol and di-isocyanate reaction, can obtain the resin of one or many branching, the degree of branching of molecule and end number are relevant with the ratio of functional groups of polyreaction, also relevant with the level of response of functional group.In theory, if only contain a trivalent alcohol unit on a molecular resin, once, molecular resin has three end groups to a molecular resin branching; If molecular resin contains two trivalent alcohols, molecular resin branching twice, molecular resin has four end groups.The end group of reaction resin of the present invention is reactive group, and end group is more, and the activity of resin is higher, but end group is more, and in resin, the content of the hard section of double carbamate is also more, and the viscosity of resin is also larger.Although simpler in theory with the resin of synthetic four chain ends of tetravalent alcohol, the polarity of small molecules tetravalent alcohol is large, poor with the consistency of terminal hydroxy group diolefine oligopolymer, solvability is little.So preferably adopt in the present invention dibasic alcohol and trivalent alcohol.
Preferably, above-mentioned polyvalent alcohol can comprise dibasic alcohol and trivalent alcohol simultaneously, and wherein the mol ratio of dibasic alcohol and terminal hydroxy group diolefine oligopolymer is 0～2: 1, and the ratio of the integral molar quantity of the molar weight of trivalent alcohol and dibasic alcohol and terminal hydroxy group diolefine oligopolymer is 0～2: 1.The mol ratio of dibasic alcohol, trivalent alcohol and terminal hydroxy group diolefine oligopolymer is controlled in above-mentioned scope, be conducive to form the PUA type reaction resin that soft section of diolefine oligopolymer in each molecule is 1-5,2-6 of the hard section of double carbamate, (methyl) acryloyl-oxy group molecule chain end 2-4, and then obtain the good PUA resin type of over-all properties reaction resin.
Optional dibasic alcohol includes but not limited to one or more in ethylene glycol, propylene glycol, butyleneglycol, glycol ether, pentanediol, neopentyl glycol, hexylene glycol, cyclohexanediol, heptanediol, ethohexadiol, dihydroxymethyl hexalin, glycol ether, tripropylene glycol, Thiodiglycol, Hydrogenated Bisphenol A, diethoxy dihydroxyphenyl propane in the present invention.Preferably carbon atom is at 2～20 binary primary alconol.Optional trivalent alcohol in the present invention, includes but not limited to one or more in glycerol, TriMethylolPropane(TMP), ethoxylated trimethylolpropane and propenoxylated TriMethylolPropane(TMP).Dibasic alcohol and trivalent alcohol be preferred primary alconol all, and the chemical reactivity of primary alconol and isocyanic ester is higher, is conducive to resin building-up reactions.
In a kind of embodiment of the present invention, the diisocyanate cpd of preparing above-mentioned PUA type reaction resin is aliphatic diisocyanate chemical combination or aromatic diisocyanate cpd.Particularly, diisocyanate cpd includes but not limited to tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), dimethylbenzene alkane two isocyanic acids (MDI) and hydrogenation TDI, hydrogenation MD etc. in the present invention.
Can select the type of used diisocyanate cpd according to the performance of required PUA type reaction resin.For example, if need the reaction resin that intensity is high, can select aromatic TDI and MDI; If need yellowing resistance good, the reaction resin that viscosity is less, can select aliphatic IPDI, HDI and hydrogenation TDI, hydrogenation MD.
In the process of preparation PUA type reaction resin of the present invention, in diisocyanate cpd-in NCO functional group and polyvalent alcohol and terminal hydroxy group diolefine oligopolymer total-mol ratio of OH functional group determines the molecular weight of resin, also affect the viscosity of resin, both proportionings more approach equal proportion, the molecular weight of resin is higher, and viscosity is larger.To the reaction resin of linear structure, diisocyanate cpd-NCO group number than diolefine and polyvalent alcohol total-many two of OH group number; To the resin of three chain ends, diisocyanate cpd-NCO group is than many three of-OH group, similarly, containing the resin of four chain ends, diisocyanate cpd-NCO group is than many four of-OH group, and additional-NCO group is for linking (methyl) acrylate of contain-OH group.Preferably, diisocyanate cpd-NCO functional group and polyvalent alcohol and terminal hydroxy group diolefine oligopolymer total-mol ratio of OH group is 6: 5～2: 1.
In a kind of embodiment of the present invention, be used for the end group-NCO radical reaction with preform, (methyl) acrylate of the contain-OH group of preparation PUA type reaction resin, includes but not limited to hydroxyethyl methylacrylate (HEMA), Rocryl 410 (HPMA), Hydroxyethyl acrylate (HEA) and Propylene glycol monoacrylate (HPA).Their consumption if can ensure by work in-process resin-NCO group total overall reaction is complete.
The preparation method that a kind of PUA type reaction resin is also provided in the present invention, comprises the following steps: react with diisocyanate cpd and generate the preform of end group as-NCO taking terminal hydroxy group diolefine oligopolymer, polyvalent alcohol; React with preform and generate sold resin with (methyl) acrylate of contain-OH.
Preferably, in the method for above-mentioned PUA type reaction resin, prepare end group and be-a kind of concrete steps of the preform of NCO comprise: the terminal hydroxy group diolefine oligopolymer after decompression dehydration is mixed to formation solution A with optional polyvalent alcohol and optional catalyzer heated and stirred; In solution A, add diisocyanate cpd, the temperature that raises is gradually to higher than 70 DEG C, and reaction 1～2.5h obtains end group and is-preform of NCO.
In the process of this PUA type reaction resin of preparation, because hydroxyl is almost irreversible with reacting of isocyanate groups, once reaction between functional group, just form the fixing order of connection, so, obtain specific soft, the hard section of molecular chain of mode in succession, the raw material reacting will add sequentially.The chemically reactive of the two-NCO reactive group of vulcabond is relevant with joined group, for example, in tolylene diisocyanate (TDI) and two different Buddhist diketone vulcabond (IPDI), the active difference of two-NCO reactive group is very large, can utilize the order of addition(of ingredients) of this chemically active difference and raw material, make soft, hard section to connect according to certain arrangement mode, to be prepared with the PUA molecule of specific soft, hard section sequence.
With reference to aforesaid PUA resin chemical equation, if first reacted with butyleneglycol and vulcabond, and then add the reaction of terminal hydroxy group diolefine oligopolymer to generate the preform of NCO end-blocking, finally add the feed way of (methyl) acrylate of contain-OH, because vulcabond in the reaction of butyleneglycol and vulcabond is excessive, the possibility that forms the polymer of butyleneglycol and vulcabond just significantly reduces, most product is that the two ends of butyleneglycol connect upper isocyanic ester, the terminal hydroxy group diolefine oligopolymer adding subsequently by with isocyanic ester on the two ends of butyleneglycol and reaction system in remaining di-isocyanate reaction, comprise two soft section as represented in front formula will be made, the molecule chain end of two methacryloxy groups and the product content of three hard segment structures maximize.
In the preparation process of aforementioned PUA type reaction resin, step-reaction polymerization is to carry out between hydroxyl and isocyanic ester, so can there is reacting of various ways between raw material and raw material, therefore, the molecular weight of reaction product and chemical constitution are not single, except the represented molecular structure of above formula, also may there is the molecule of part resin to be formed by soft section of diolefine oligopolymer and di-isocyanate reaction completely, also may there is a small amount of molecule to be formed by butyleneglycol and two di-isocyanate reactions completely, but the represented product structure of above-mentioned chemical equation is the component of content maximum in reaction product.Carry out molecular chain structure when design of PUA type reaction resin, taking the product structure of this maximum distribution as corresponding resin structure.About the detailed knowledge of step-reaction polymerization and reaction product, can be referring to the books of polymer chemistry.
In order to control branched structure and the viscosity of resin, in the time using optional polyvalent alcohol to adjust the performance of PUA, preferably, allow polyvalent alcohol first react with diisocyanate cpd, and then add terminal hydroxy group diolefine oligopolymer further to react, generate end group and be-preform of NCO.Such feed way, react time-NCO group with diisocyanate cpd because polyvalent alcohol is first excessive, can suppress the polymerization of polyvalent alcohol and diisocyanate cpd, and the structure of main generation-NCO group end capping, adding after terminal hydroxy group diolefine oligopolymer, polyvalent alcohol just can be distributed on molecular resin chain dispersedly, generates controlled branched structure.
Preferably, in the method for above-mentioned PUA type reaction resin, prepare end group and be-a kind of concrete steps of the preform of NCO comprise: diisocyanate cpd mixed with optional polyvalent alcohol, temperature is not higher than stirring reaction 0.5～2h at 70 DEG C, form solution B, in solution B, add terminal hydroxy group diolefine oligopolymer after decompression dehydration and optional catalyzer, control temperature to not higher than 70 DEG C of stirring reaction 1～2.5h, obtain end group and be-preform of NCO.
Preferably, in the above-mentioned method of preparing PUA type reaction resin, a kind of use react with preform and is generated PUA type reaction resin and comprise containing (methyl) acrylate of-OH: at end group be-add (methyl) acrylate of contain-OH and optional thinner in the preform of NCO, at 50～70 DEG C of stirring reaction 1～3h, obtain PUA type reaction resin.Thinner add the viscosity that is mainly used for reducing PUA type reaction resin.Thinner can be before (methyl) acrylate adding containing-OH, or adds forming after PUA type reaction resin.
Optional catalyzer is the compounds such as organometallic compound or organic amine in the present invention.For example: dibutyl tin dilaurate, dibutyltin diacetate, stannous octoate, naphthenate, triethylamine, Tributylamine, triethylenediamine etc.
Optional thinner comprises lipid, ketone, ethers organic compound, particularly carbonatoms this class organic solvent more than 4 in the present invention.Preferably (methyl) esters of acrylic acid, particularly to be not less than (methyl) acrylate ester of 4 alkyl alcohol be solvent to carbonatoms, for example: (methyl) butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid 12 alkyl esters; (methyl) isobornyl acrylate etc.Meanwhile, preferably carbonatoms is greater than 6 dibasic alcohol or two (methyl) acrylate or three (methyl) acrylate of trivalent alcohol, for example: hexylene glycol double methacrylate, trimethylolpropane tris (methyl) acrylate etc.These (methyl) acrylate, as reactive thinner, just can be removed and directly use.Preferably, the 0-25% that the consumption of thinner is resin quality.
Preferably, the number-average molecular weight of PUA type reaction resin provided by the present invention is 1600g/mol-20000g/mol, and the viscosity of resin is advisable at 6Pa.S-300Pa.S.The molecular weight of resin is too small, and the relative content of reactive group is high, although active large, the volumetric shrinkage of curing reaction is large, and the degree of crosslinking of product is excessive, and performance is not good.If the molecular weight of resin is excessive, such as being greater than 20000g/mol, the viscosity of resin is large, and the relative content of reactive functional groups is little, and curing degree of crosslinking is too small, and product feels like jelly, and performance is not good yet.The viscosity of resin is relevant with molecular size range on the one hand, and also relevant with the amount of diluent of adding, thinner strengthens, and the viscosity of resin is little, but the performance of resin can not give full play to, and curing volumetric shrinkage is large, and the smell of resin becomes greatly, and activity also may diminish; If without thinner, the viscosity of resin may be excessive, for example, be greater than 300Pa.S, is unfavorable for using.
Further illustrate the beneficial effect of PUA type reaction resin provided by the present invention below with reference to specific embodiment 1-14 and comparative example 1-2.
Embodiment 1:
By hydroxyl terminated polyisoprene (the hydroxyl value 1.9mmol/g through 110 DEG C of decompression dehydration 1h, number-average molecular weight is 1000g/mol) 1000g, diethoxy dihydroxyphenyl propane 632g and 1g stannous octoate are in 40 DEG C of stirrings, mixing, add TDI 695g, temperature of reaction progressively rises, and controls temperature and is no more than 70 DEG C, after reaction 2h, adds hydroxyethyl methylacrylate 270g and 250g butyl methacrylate, in 50-65 DEG C of stirring reaction 2.5h discharging, make PUA type reaction resin 1.
The number-average molecular weight (diluent free, GPC, PS standard) of resin: 2000g/mol, resin viscosity (30 DEG C): 10Pa.S.
Embodiment 2:
By 134g TriMethylolPropane(TMP) and 845g HDI reaction 2h, control temperature and be no more than 70 DEG C, add hydroxyl terminated polyisoprene (the hydroxyl value 1.9mmol/g through 110 DEG C of decompression dehydration processing, number-average molecular weight 1000g/mol) 2500g and 2g stannous octoate, temperature progressively rises, control temperature and be no more than 70 DEG C, after reaction 2.5h, add hydroxyethyl methylacrylate 270g, after 50-65 DEG C of stirring reaction 3h, add 500g Isooctyl acrylate monomer, discharging after stirring, makes PUA type reaction resin 2.
Resin number-average molecular weight (diluent free, GPC, PS standard): 8000g/mol, resin viscosity (30 DEG C): 120Pa.S.
Embodiment 3:
28 Hydroxyethyl acrylates are mixed at normal temperature with 42g HDI, stirring reaction 2h, control temperature and be no more than 60 DEG C, then at 40 DEG C of 400g terminal hydroxy group butadiene hydrocarbon-acrylonitrile copolymer (hydroxyl value 0.49mmol/g that add through decompression dehydration drying treatment,-CN mass percent 1%, molecular weight 2000g/mol) and 80g hydroxy-terminated polybutadienes hydrocarbon (hydroxyl value 0.49mmol/g, number-average molecular weight～4000) and 0.1g dibutyl tin dilaurate, stirring reaction 3h, temperature progressively rises, control temperature and be no more than 75 DEG C, discharging after adding 70g butylacetate to stir, make PUA type reaction resin 3.
Resin number-average molecular weight (diluent free, GPC, PS standard): 4000g/mol, resin viscosity (30 DEG C): 70Pa.S.
Embodiment 4:
By 1000g hydroxyl terminated polyisoprene hydrocarbon (the hydroxyl value 0.95mmol/g through decompression dehydration drying treatment, number-average molecular weight 2000g/mol) and 60g ethylene glycol, 1g dibutyl tin dilaurate add IPDI 450g 40 DEG C of stirrings, after mixing, temperature of reaction progressively rises, control temperature and be no more than 70 DEG C, after reaction 1h, add Propylene glycol monoacrylate 130g, in 50-65 DEG C of stirring reaction 1.5h discharging, make PUA type reaction resin 4.
Resin number-average molecular weight (GPC, PS standard): 3500g/mol, resin viscosity (30 DEG C): 200Pa.S.
Embodiment 5:
By 13g TriMethylolPropane(TMP) and 88g HDI, be no more than stirring reaction 1h at 70 DEG C in temperature, then add 530g terminal hydroxy group butadiene hydrocarbon-acrylonitrile copolymer (the hydroxyl value 0.5mmol/g through decompression dehydration drying treatment,-CN mass percent 22%, molecular weight 2000g/mol) and 270g hydroxy-terminated polybutadienes hydrocarbon (hydroxyl value 0.49mmol/g, number-average molecular weight～4000), 6g Thiodiglycol, 1g triethylenediamine, temperature of reaction progressively rises, controlling temperature is no more than at 70 DEG C, stirring reaction 1h, add Rocryl 410 45g and 150g butyl methacrylate, in 50-65 DEG C of stirring reaction 2.5h discharging, make PUA type reaction resin 5.
Resin number-average molecular weight (diluent free, GPC, PS standard): 20000g/mol, resin viscosity (30 DEG C): 300Pa.S.
Embodiment 6:
Triethoxy TriMethylolPropane(TMP) 26g and 115g hydrogenation TDI, stirring reaction 1h, control temperature and be no more than 70 DEG C, add 165g hydroxy-terminated polybutadienes hydrocarbon (the hydroxyl value 2.46mmol/g through decompression dehydration drying treatment, number-average molecular weight 800g/mol), 166g terminal hydroxy group butadiene hydrocarbon-styrol copolymer (hydroxyl value 1.2mmol, phenyl ring mass percent 1%, molecular weight 1500g/mol) and 1g dibutyl tin dilaurate, temperature progressively rises, control temperature and be no more than 70 DEG C, after reaction 2.5h, add Hydroxyethyl acrylate 35g and 100g Viscoat 295, in 60-70 DEG C of stirring reaction 1h discharging, make PUA type reaction resin 6.
Resin number-average molecular weight (diluent free, GPC, PS standard): 4500g/mol, resin viscosity (30 DEG C): 90Pa.S.
Embodiment 7:
By hydroxy-terminated polybutadienes hydrocarbon (the hydroxyl value 0.3mmol/g through decompression dehydration drying treatment, number-average molecular weight 6000g/mol) 600g, 12 carbon glycol 10g and 1g triethylamine add 55g hydrogenation MDI 40 DEG C of stirrings, after mixing, temperature of reaction progressively rises, control temperature and be no more than 70 DEG C, after reaction 1.5h, add Hydroxyethyl acrylate 27g and 70g hexylene glycol double methacrylate, in 50-65 DEG C of stirring reaction 2h discharging, make PUA type reaction resin 3.
Resin number-average molecular weight (diluent free, GPC, PS standard): 4000g/mol, resin viscosity (30 DEG C): 200Pa.S.
Embodiment 8:
By 370g hydroxy-terminated polybutadienes hydrocarbon (the hydroxyl value 2.46mmol/g through 110 DEG C of decompression dehydration 1h, number-average molecular weight 800g/mol), 6g Thiodiglycol, 2g stannous octoate and 138g IPDI, stirring reaction, control temperature and be no more than 70 DEG C, after reaction 2.5h, add Rocryl 410 26g, after 50-65 DEG C of stirring reaction 3h, add 180g Isooctyl methacrylate, discharging after stirring, makes PUA type reaction resin 8.
Resin number-average molecular weight (diluent free, GPC, PS standard): 6000g/mol, resin viscosity (30 DEG C): 30Pa.S..
Embodiment 9:
By hydrogenation hydroxyl terminated polyisoprene (the hydroxyl value 1.9mmol/g through 110 DEG C of decompression dehydration 1h, number-average molecular weight 1000g/mol) 100g, tripropylene glycol 19g heats, stirs into homogeneous solution, after adding 2g stannous octoate, add IPDI70g, temperature of reaction progressively rises, control temperature and be no more than 70 DEG C, after reaction 2h, add Rocryl 410 26g, after 60-70 DEG C of stirring reaction 1h, add 50g Isooctyl acrylate monomer, discharging after stirring, makes PUA type reaction resin 9.
Resin number-average molecular weight (diluent free, GPC, PS standard): 8000g/mol, resin viscosity (30 DEG C): 6Pa.S..
Embodiment 10:
By 134g TriMethylolPropane(TMP) and 670g IPDI reaction 0.5h, control temperature and be no more than 70 DEG C, add hydroxyl terminated polyisoprene (the hydroxyl value 1.9mmol/g through 110 DEG C of decompression dehydration processing, number-average molecular weight 1000g/mol) 450g, 3g ethylene glycol and 2g stannous octoate, temperature progressively rises, control temperature and be no more than 70 DEG C, after reaction 2.5h, add hydroxyethyl methylacrylate 280g, after 50-65 DEG C of stirring reaction 2h, add 300g Isooctyl acrylate monomer, discharging after stirring, makes PUA type reaction resin 10.
Resin number-average molecular weight (diluent free, GPC, PS standard): 3500g/mol, resin viscosity (30 DEG C): 150Pa.S..
Embodiment 11:
By 500g terminal hydroxy group butadiene hydrocarbon-acrylonitrile copolymer (the hydroxyl value 0.4mmol/g adding through decompression dehydration drying treatment,-CN mass percent 5%, molecular weight 8000g/mol) and 12g HDI be no more than stirring reaction 2.5h at 70 DEG C in temperature, add hydroxyethyl methylacrylate 12g, after 50-65 DEG C of stirring reaction 3h, add 100g Isooctyl methacrylate, discharging after stirring, makes PUA type reaction resin 11.
Resin number-average molecular weight (diluent free GPC, PS standard): 9000g/mol, resin viscosity (30 DEG C): 180Pa.S..
Embodiment 12:
By 300g terminal hydroxy group butadiene hydrocarbon-styrol copolymer (the hydroxyl value 0.6mmol/g adding through decompression dehydration drying treatment, phenyl mass percent 18%, molecular weight 2000g/mol), 4g TriMethylolPropane(TMP), 0.2g triethylenediamine and 32g TDI be no more than stirring reaction 2.5h at 70 DEG C in temperature, add hydroxyethyl methylacrylate 40g, after 50-65 DEG C of stirring reaction 3h, add 70g Isooctyl acrylate monomer, discharging discharging after stirring, makes PUA type reaction resin 12.
Resin number-average molecular weight (GPC, PS standard): 8000g/mol, resin viscosity (30 DEG C): 90Pa.S..
Embodiment 13:
By 500g terminal hydroxy group isoprene hydrocarbon-styrol copolymer (the hydroxyl value 0.8mmol/g adding through decompression dehydration drying treatment, phenyl mass percent 10%, molecular weight 2500g/mol) and 100g hydroxyl terminated polyisoprene hydrocarbon (hydroxyl value 0.49mmol/g, number-average molecular weight～4000), 0.5g triethylenediamine, progressively rise with 80g TDI temperature of reaction, controlling temperature is no more than at 70 DEG C, stirring reaction 1h, be no more than stirring reaction 2.5h at 70 DEG C in temperature, add hydroxyethyl methylacrylate 13g
Resin number-average molecular weight (GPC, PS standard): 3800g/mol, resin viscosity (30 DEG C): 200Pa.S..
Embodiment 14:
By 32g polyethers pentavalent alcohol (the Dow chemical formula adding through decompression dehydration drying treatment, trade mark Voranol 520, hydroxyl value 9.3mmol/g, molecular weight 550g/mol), 110g TDI is no more than stirring reaction 2h at 70 DEG C in temperature, add 1200g terminal hydroxy group butadiene hydrocarbon-acrylonitrile copolymer (hydroxyl value 0.5mmol/g,-CN mass percent 22%, molecular weight 2500), 0.8g triethylenediamine, temperature of reaction progressively rises, controlling temperature is no more than at 70 DEG C, stirring reaction 2h, add hydroxyethyl methylacrylate 48g, after 50-60 DEG C of stirring reaction 1.5h, add 300g N-BUTYL ACETATE, discharging discharging after stirring, make PUA type reaction resin 14.
Resin number-average molecular weight (GPC, PS standard): 22000g/mol, resin viscosity (50 DEG C): 300Pa.S.
Comparative example 1:
Raw material: polycaprolactone dibasic alcohol (hydroxyl value 2mmol/g, number-average molecular weight～1000) 100g; Dibutyl tin dilaurate 0.12g; IPDI 45g; Hydroxyethyl acrylate 23g.
By the polycaprolactone dibasic alcohol through 110 DEG C of decompression dehydration 1h, dibutyl tin dilaurate is in 50 DEG C of stirrings, mixing, add IPDI, temperature of reaction progressively rises, control temperature and be no more than 70 DEG C, after reaction 1h, add Hydroxyethyl acrylate, in 50-65 DEG C of stirring reaction 2h discharging, make contrast PUA type reaction resin 1.
The number-average molecular weight (GPC, PS standard) of contrast PUA type reaction resin 1: 1800g/mo4, resin viscosity (50 DEG C): 100Pa.S..
Comparative example 2:
Raw material: polytetrahydrofuran dibasic alcohol (hydroxyl value 2mmol/g, number-average molecular weight～1000) 100g; Dibutyl tin dilaurate 0.12g; IPDI 45g; Hydroxyethyl methylacrylate 26g
By the polytetrahydrofuran dibasic alcohol through 110 DEG C of decompression dehydration 1h, dibutyl tin dilaurate is in 50 DEG C of stirrings, mixing, add IPDI, temperature of reaction progressively rises, control temperature and be no more than 70 DEG C, after reaction 1h, add hydroxyethyl methylacrylate, in 50-65 DEG C of stirring reaction 2h discharging, make contrast PUA type reaction resin 2.
The number-average molecular weight (GPC, PS standard) of contrast PUA type reaction resin 2: 1800g/mol, resin viscosity (30 DEG C): 120Pa.S..
For the ease of data and protection scope of the present invention in embodiment 1-14 and comparative example 1-2 are linked together, now the individual features of embodiment 1-14 and comparative example 1-2 is summarized in following table 1.
In table 1, corresponding constitutional features comprises:
A hurdle PB, PI, PB-CN, PI-CN, PB-St and PI-St represent respectively hydroxy-terminated polybutadienes, hydroxyl terminated polyisoprene, containing the hydroxy-terminated polybutadienes of CN group, containing the terminal hydroxy group isoprene of CN group, contain the hydroxy-terminated polybutadienes of Ph group and the both-end hydroxyl isoprene containing Ph group, the hydroxyl value (mmol/g) that the numerical value in bracket is resin;
B hurdle 2 and 3 represents respectively binary and trivalent alcohol, C
no
ms
lmiddle n represents carbonatoms, the m represention oxygen atom number of polyvalent alcohol, and 1 represents sulphur atom number;
C hurdle is the molar ratio between polyvalent alcohol, terminal hydroxy group diolefine oligopolymer and vulcabond, when wherein polyvalent alcohol comprises dibasic alcohol and trivalent alcohol simultaneously, adopt the mode of (trivalent alcohol mole number+dibasic alcohol mole number)/diolefine oligopolymer/vulcabond to represent;
The content of itrile group or phenyl group in the terminal hydroxy group diolefine oligopolymer that D hurdle represents to contain itrile group group or phenyl group, and the terminal hydroxy group diolefine oligopolymer that contains itrile group or phenyl group and the quality ratio of terminal hydroxy group diolefine oligopolymer that does not contain itrile group or phenyl group;
E hurdle represents in prepared PUA type reaction resin soft section, hard section, the number of (methyl) acryloyl-oxy group molecule chain end.
Table 1
Resin property test:
Sample preparation: the reaction resin 100g that gets synthesized in embodiment 1-14 and comparative example 1-2, add 20g butyl acrylate and 2g light trigger 1173 to stir, obtain mixture, mixture is placed between two-layer PET film, the spacing of two-layer PET film is 0.03mm, with the high voltage mercury lamp radiation 50s of 1000w, lamp is apart from 30cm, the sample 1-16 after must solidifying.
Evaluation method
The viscosity measurement of resin; Adopt rotary viscometer to test embodiment 1-14 and the prepared reaction resin of comparative example 1-2, measuring result is as shown in table 2.
The water-intake rate of resin is measured: above-mentioned sample 1-16 is put into the velocity of variation of weigh after the water 1h of 100 DEG C, measuring result is as table 2.
The stability to hydrolysis resistance of resin is measured: will in embodiment 1-14 and the prepared reaction resin of comparative example 1-2, add the water of mass ratio 5% and 1% phosphoric acid (mass concentration 85%), after stirring, in the baking oven of 60 DEG C, place 60h, inspection viscosity changes, and measuring result is as table 2.Viscosity changes and is less than 3% for excellent, be less than 8% for good, and being less than 15% is to be greater than 30% for poor.
The stability in storage of resin is measured: embodiment 1-14 and the prepared reaction resin of comparative example 1-2 are placed on respectively to the variation that checks viscosity in the baking oven of 50 DEG C, measuring result is as table 2.Viscosity variation is less than 5% for excellent, is less than 15% for good, is greater than 30% for poor;
The buck stability measurement of resin: will add the NaOH aqueous solution (mass concentration 5%) of mass ratio 5% in embodiment 1-14 and the prepared reaction resin of comparative example 1-2, after stirring, in the baking oven of 60 DEG C, place 60h, inspection viscosity changes, and measuring result is as table 2.Viscosity changes and is less than 3% for excellent, be less than 8% for good, and being less than 15% is to be greater than 30% for poor.
The sticking power of resin is measured: the reaction resin 100g that gets embodiment and comparative example synthesized, add 20g butyl acrylate and 2g light trigger 1173 to stir, obtain mixture, mixture is applied on white ABS plastic plate, or on stainless steel plate, cover PET film in the above, coat-thickness 0.02mm, with the high voltage mercury lamp radiation 50s of 1000w again, lamp is apart from 30cm, obtain curing coating, evaluate sticking power with cross-hatching, measuring result is as table 2.Optimum is 0 grade, and the poorest is 5 grades.
Table 2 evaluation result table
From data in table 2, by the viscosity of the prepared PUA type reaction resin of embodiment of the present invention 1-14, water-absorbent, water-fast and acidproof, alkali resistance, the aspect such as stability and sticking power is all obviously better than the prepared PUA type reaction resin of comparative example 1-2, those skilled in the art are according to explanation of the present invention, have the ability by reasonably selecting and combine diolefine oligopolymer, polyvalent alcohol, the raw materials such as (methyl) acrylate of vulcabond and hydroxyl, select rational reinforced and stepwise reaction order and control the level of response in per stage, can design, synthesize the soft of PUA resin, hard hop count order and molecular conformation, adjust the performance of resin, the viscosity of for example resin, molecular weight, to the sticking power of metal or plastics, and the mechanical property of resin etc., make it to meet specific application requiring.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment of doing, be equal to replacement, improvement etc., within being all included in protection scope of the present invention.
Claims (5)
1. a PUA type reaction resin, it is characterized in that, described PUA type reaction resin by terminal hydroxy group diolefine oligopolymer, diisocyanate cpd, polyvalent alcohol and Han ?(methyl) acrylate of OH be prepared from, the preparation method of described PUA type reaction resin comprises the following steps:
Taking terminal hydroxy group diolefine oligopolymer, polyvalent alcohol react with diisocyanate cpd generate end group as ?the preform of NCO;
Yong Han ?(methyl) acrylate of OH react with preform and generate described PUA type reaction resin;
Wherein, prepare described end group Wei ?the step of preform of NCO comprise:
Described terminal hydroxy group diolefine oligopolymer after decompression dehydration is mixed with polyvalent alcohol and optional catalyzer heated and stirred, form solution A; In solution A, add diisocyanate cpd, the temperature that raises is gradually to higher than 70 DEG C, reaction 1～2.5h, obtain end group Wei ?the preform of NCO;
Described end group Wei ?add in the preform of NCO Han ?(methyl) acrylate and the optional thinner of OH, at 50～70 DEG C of stirring reaction 1～3h, obtain described PUA type reaction resin;
The number-average molecular weight of described terminal hydroxy group diolefine oligopolymer is 800g/mol～6000g/mol, or hydroxyl value is 0.3mmol/g～2.5mmol/g; The mol ratio of described polyvalent alcohol and described terminal hydroxy group diolefine oligopolymer is 1:10～2:1; Described diisocyanate cpd Zhong ?NCO functional group and described polyvalent alcohol and described terminal hydroxy group diolefine oligopolymer Zhong ?the mol ratio of OH functional group sum be 6/5～2/1;
Number sum >=8 of C, S, O atom in the saturated carbon chains of described polyvalent alcohol, described saturated carbon chains is C with O and/or S atom with saturated covalent linkage the carbochain that is directly connected with linear mode, when containing ehter bond or thioether bond in described saturated carbon chains, in the time calculating the atom number of saturated carbon chains, each O of ehter bond in carbochain or thioether bond or S atom are calculated as an atom, are not counted in the atomicity of carbochain at the group of carbochain side group;
The described reaction resin making comprises soft section of diolefine oligopolymer, formed by described saturated carbon chains soft section, hard section of double carbamate, and the molecule chain end that contains (methyl) acryloyl-oxy group, the number-average molecular weight of described PUA type reaction resin be 1600g/mol ?20000g/mol, the viscosity of resin, at 6Pa.S ?300Pa.S, on average contains 5 soft section of 2 ?, 6 hard sections of 2 ?and 4 (methyl) acryloyl-oxy group molecule chain ends of 2 ?on molecular chain.
2. PUA type reaction resin according to claim 1, it is characterized in that, described terminal hydroxy group diolefine oligopolymer comprises the terminal hydroxy group diolefine oligopolymer that contains itrile group group, in the described terminal hydroxy group diolefine oligopolymer that contains itrile group group, the weight content of itrile group group is M, 0 < M≤22%.
3. PUA type reaction resin according to claim 1, it is characterized in that, described terminal hydroxy group diolefine oligopolymer comprises the terminal hydroxy group diolefine oligopolymer that contains phenyl ring group, in the described terminal hydroxy group diolefine oligopolymer that contains phenyl ring group, the weight content of phenyl ring group is X, 0 < X≤18%.
4. PUA type reaction resin according to claim 1, it is characterized in that, described polyvalent alcohol is dibasic alcohol and trivalent alcohol, and the ratio of the molar weight of described trivalent alcohol and described dibasic alcohol and described terminal hydroxy group diolefine oligopolymer molar weight sum is R, 0 < R≤2.
5. a preparation method for PUA type reaction resin as claimed in claim 1, is characterized in that, comprises the following steps:
Taking terminal hydroxy group diolefine oligopolymer, polyvalent alcohol react with diisocyanate cpd generate end group as ?the preform of NCO;
Yong Han ?(methyl) acrylate of OH react with preform and generate described PUA type reaction resin;
Prepare described end group Wei ?the step of preform of NCO comprise:
Described terminal hydroxy group diolefine oligopolymer after decompression dehydration is mixed with polyvalent alcohol and optional catalyzer heated and stirred, form solution A; In solution A, add diisocyanate cpd, the temperature that raises is gradually to higher than 70 DEG C, reaction 1～2.5h, obtain end group Wei ?the preform of NCO;
Described end group Wei ?add in the preform of NCO Han ?(methyl) acrylate and the optional thinner of OH, at 50～70 DEG C of stirring reaction 1～3h, obtain described PUA type reaction resin.
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| CN106674476A (en) * | 2017-01-22 | 2017-05-17 | 江苏旭泽技术有限公司 | Low-shrinkage UV curing PUA resin, as well as preparation method and application thereof to preparation of hot bending membrane |
| KR102588034B1 (en) * | 2017-06-30 | 2023-10-11 | 다이이치 고교 세이야쿠 가부시키가이샤 | Polymerizable resin composition and cured product thereof |
| CN112048051B (en) * | 2019-06-05 | 2022-04-22 | 万华化学（北京）有限公司 | Polyurethane acrylate resin and preparation method thereof |
| CN113278125A (en) * | 2021-05-28 | 2021-08-20 | 南京玖泰新材料科技有限公司 | Photo-curing polyurethane and application thereof |
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Effective date of registration: 20180625 Address after: 528451 nun Lang Industrial Zone, Nan Lang Town, Zhongshan, Guangdong Patentee after: Zhongshan JEME Fine Chemical Co., Ltd. Address before: 610065 Sichuan University, Sichuan, 24 ring 1 South, Sichuan University Patentee before: Wang Yuechuan |