CN104558600B - A kind of nitrogenous poly-functionality methyl acrylate, preparation method and applications - Google Patents
A kind of nitrogenous poly-functionality methyl acrylate, preparation method and applications Download PDFInfo
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- CN104558600B CN104558600B CN201310494717.1A CN201310494717A CN104558600B CN 104558600 B CN104558600 B CN 104558600B CN 201310494717 A CN201310494717 A CN 201310494717A CN 104558600 B CN104558600 B CN 104558600B
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- acid
- reaction
- temperature
- nitrogen
- acrylate resin
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 42
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000016 photochemical curing Methods 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 239000000853 adhesive Substances 0.000 claims abstract description 8
- 230000001070 adhesive effect Effects 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 162
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 239000004925 Acrylic resin Substances 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 32
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 26
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- 238000010992 reflux Methods 0.000 claims description 24
- 150000003512 tertiary amines Chemical class 0.000 claims description 24
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 24
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 20
- 239000013067 intermediate product Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 17
- -1 amine compound Chemical class 0.000 claims description 17
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 16
- 239000001361 adipic acid Substances 0.000 claims description 13
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 12
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 12
- 239000003112 inhibitor Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 11
- 239000012074 organic phase Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 10
- 150000007519 polyprotic acids Polymers 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 239000012965 benzophenone Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 6
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 6
- 244000028419 Styrax benzoin Species 0.000 claims description 6
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 6
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 6
- 150000004056 anthraquinones Chemical class 0.000 claims description 6
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical class C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 6
- 229960002130 benzoin Drugs 0.000 claims description 6
- 235000019382 gum benzoic Nutrition 0.000 claims description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 6
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 5
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 5
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 claims description 5
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 5
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 5
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 claims description 5
- 238000007639 printing Methods 0.000 claims description 5
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- OQBLGYCUQGDOOR-UHFFFAOYSA-L 1,3,2$l^{2}-dioxastannolane-4,5-dione Chemical compound O=C1O[Sn]OC1=O OQBLGYCUQGDOOR-UHFFFAOYSA-L 0.000 claims 1
- FQYHHEJETOLDHR-UHFFFAOYSA-K butyl(chloro)tin(2+);dihydroxide Chemical compound CCCC[Sn](O)(O)Cl FQYHHEJETOLDHR-UHFFFAOYSA-K 0.000 claims 1
- NPAIMXWXWPJRES-UHFFFAOYSA-N butyltin(3+) Chemical compound CCCC[Sn+3] NPAIMXWXWPJRES-UHFFFAOYSA-N 0.000 claims 1
- 239000011347 resin Substances 0.000 abstract description 13
- 229920005989 resin Polymers 0.000 abstract description 13
- 238000001723 curing Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000976 ink Substances 0.000 abstract description 5
- 238000007086 side reaction Methods 0.000 abstract description 4
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000000926 separation method Methods 0.000 description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 150000005676 cyclic carbonates Chemical class 0.000 description 8
- 238000005886 esterification reaction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000005070 sampling Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- YQPCHPBGAALCRT-UHFFFAOYSA-N 2-[1-(carboxymethyl)cyclohexyl]acetic acid Chemical compound OC(=O)CC1(CC(O)=O)CCCCC1 YQPCHPBGAALCRT-UHFFFAOYSA-N 0.000 description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 4
- DWOXXMGPEQVGNI-UHFFFAOYSA-N 2,5-dimethylhexanedioic acid Chemical compound OC(=O)C(C)CCC(C)C(O)=O DWOXXMGPEQVGNI-UHFFFAOYSA-N 0.000 description 4
- WXUAQHNMJWJLTG-UHFFFAOYSA-N 2-methylbutanedioic acid Chemical compound OC(=O)C(C)CC(O)=O WXUAQHNMJWJLTG-UHFFFAOYSA-N 0.000 description 4
- XJMMNTGIMDZPMU-UHFFFAOYSA-N 3-methylglutaric acid Chemical compound OC(=O)CC(C)CC(O)=O XJMMNTGIMDZPMU-UHFFFAOYSA-N 0.000 description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 4
- QCNWZROVPSVEJA-UHFFFAOYSA-N Heptadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCC(O)=O QCNWZROVPSVEJA-UHFFFAOYSA-N 0.000 description 4
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 4
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 4
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 4
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 4
- 229960001124 trientine Drugs 0.000 description 4
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 4
- GAYWCADKXYCKCG-UHFFFAOYSA-N 5-pyridin-3-yl-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound N1NC(=S)N=C1C1=CC=CN=C1 GAYWCADKXYCKCG-UHFFFAOYSA-N 0.000 description 3
- SYEOWUNSTUDKGM-UHFFFAOYSA-N beta-methyladipic acid Natural products OC(=O)CC(C)CCC(O)=O SYEOWUNSTUDKGM-UHFFFAOYSA-N 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 3
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 description 3
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WVUYYXUATWMVIT-UHFFFAOYSA-N 1-bromo-4-ethoxybenzene Chemical compound CCOC1=CC=C(Br)C=C1 WVUYYXUATWMVIT-UHFFFAOYSA-N 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 2
- FBHUSVAOESXOGM-UHFFFAOYSA-N 2,3-dimethylheptanedioic acid Chemical compound OC(=O)C(C)C(C)CCCC(O)=O FBHUSVAOESXOGM-UHFFFAOYSA-N 0.000 description 2
- LQNGULJVMSGMOE-UHFFFAOYSA-N 2,3-dimethylpentanedioic acid Chemical compound OC(=O)CC(C)C(C)C(O)=O LQNGULJVMSGMOE-UHFFFAOYSA-N 0.000 description 2
- KLZYRCVPDWTZLH-UHFFFAOYSA-N 2,3-dimethylsuccinic acid Chemical compound OC(=O)C(C)C(C)C(O)=O KLZYRCVPDWTZLH-UHFFFAOYSA-N 0.000 description 2
- RLEQVGMLDNITBW-UHFFFAOYSA-N 2,4,4-trimethylhexanedioic acid Chemical compound OC(=O)C(C)CC(C)(C)CC(O)=O RLEQVGMLDNITBW-UHFFFAOYSA-N 0.000 description 2
- VIWYMIDWAOZEAZ-UHFFFAOYSA-N 2,4-dimethylpentanedioic acid Chemical compound OC(=O)C(C)CC(C)C(O)=O VIWYMIDWAOZEAZ-UHFFFAOYSA-N 0.000 description 2
- JZUMVFMLJGSMRF-UHFFFAOYSA-N 2-Methyladipic acid Chemical compound OC(=O)C(C)CCCC(O)=O JZUMVFMLJGSMRF-UHFFFAOYSA-N 0.000 description 2
- STUWVUULGQLPGH-UHFFFAOYSA-N 2-methylundecanedioic acid Chemical compound OC(=O)C(C)CCCCCCCCC(O)=O STUWVUULGQLPGH-UHFFFAOYSA-N 0.000 description 2
- WGYUEZQGJJLCKF-UHFFFAOYSA-N 3-(5-methyl-1h-imidazol-2-yl)pyridine Chemical compound N1C(C)=CN=C1C1=CC=CN=C1 WGYUEZQGJJLCKF-UHFFFAOYSA-N 0.000 description 2
- BCERVBGVOSICNO-UHFFFAOYSA-N 3-[2-(2-carboxyethyl)phenyl]propanoic acid Chemical compound OC(=O)CCC1=CC=CC=C1CCC(O)=O BCERVBGVOSICNO-UHFFFAOYSA-N 0.000 description 2
- XAWFHZMTJUGGEE-UHFFFAOYSA-N 3-ethyl-3-methylpentanedioic acid Chemical compound OC(=O)CC(C)(CC)CC(O)=O XAWFHZMTJUGGEE-UHFFFAOYSA-N 0.000 description 2
- YDUOHBXBLZGANF-UHFFFAOYSA-N 4,4-dimethylheptanedioic acid Chemical compound OC(=O)CCC(C)(C)CCC(O)=O YDUOHBXBLZGANF-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- SUSAGCZZQKACKE-UHFFFAOYSA-N cyclobutane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC1C(O)=O SUSAGCZZQKACKE-UHFFFAOYSA-N 0.000 description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 2
- ASJCSAKCMTWGAH-UHFFFAOYSA-N cyclopentane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCC1C(O)=O ASJCSAKCMTWGAH-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 238000003847 radiation curing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000005028 tinplate Substances 0.000 description 2
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 2
- 239000002966 varnish Substances 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- FWPVKDFOUXHOKQ-UHFFFAOYSA-N 2-[1-(carboxymethyl)cyclopentyl]acetic acid Chemical compound OC(=O)CC1(CC(O)=O)CCCC1 FWPVKDFOUXHOKQ-UHFFFAOYSA-N 0.000 description 1
- FBKCIXGXXJOPJS-UHFFFAOYSA-N 3-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=C(C(C)C)C=C3SC2=C1 FBKCIXGXXJOPJS-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
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- ORBFAMHUKZLWSD-UHFFFAOYSA-N ethyl 2-(dimethylamino)benzoate Chemical compound CCOC(=O)C1=CC=CC=C1N(C)C ORBFAMHUKZLWSD-UHFFFAOYSA-N 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
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- IMENJLNZKOMSMC-UHFFFAOYSA-N n'-[2-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCNCCN IMENJLNZKOMSMC-UHFFFAOYSA-N 0.000 description 1
- RUSNFULRUJHOPI-UHFFFAOYSA-N n'-[2-[2-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCNCCNCCNCCN RUSNFULRUJHOPI-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The open a kind of nitrogenous poly-functionality methyl acrylate of the present invention, shown in its structure below formula (I):(I) wherein, (1) R1、R2And R3It is each independently hydrogen or methyl, but R1And R2It it is asynchronously methyl；(2) R4For having the k valency alkyl of the straight or branched of 2 18 carbon atoms, its segment can contain phenyl ring or naphthene group structure；(3) m=0 or 1, n are the integer of 0 16；K=2 or 3.This resin has resinamines and the advantage of polyfunctionality resin in photocuring is applied simultaneously, and application performance is excellent, and is substantially better than existing product；Further, the preparation method of the nitrogenous poly-functionality methyl acrylate that the present invention provides a kind of nonirritant and toxic and side effects, simple to operate and side reaction is few；This resin can be used in the various curing field such as photocureable coating, ink, adhesive.
Description
Technical Field
The invention belongs to the field of photosensitive high polymer materials, and particularly relates to a nitrogenous polyfunctional acrylate resin, a preparation method thereof and application thereof in a photocuring composition.
Background
Radiation curing refers to the process of cross-linking and polymerizing liquid oligomers (including monomers) to form solid products under the action of light (including ultraviolet, visible light) or high energy radiation (mainly electron beams). The radiation curing technology has the advantages of high curing speed (high production efficiency), less pollution, energy conservation, excellent performance of cured products and the like, and is an environment-friendly green technology. Any of the photocurable compositions includes three main components: photoinitiators, monomers and oligomers (resins).
The resins in the photocurable system generally contain polymerizable functional groups that can participate in the curing reaction. The resin containing 3 or more than 3 acrylate or methacrylate photoactive groups is a multifunctional resin. Due to the increased content of functional groups, these resins have the following characteristics compared to monofunctional resins: (1) the photocuring speed is high; (2) the hardness of a cured product is high; (3) the multifunctional monomer has high molecular weight, so that the volatility is low; (4) certain properties can be adjusted according to the use requirements, such as accelerating the curing speed, increasing the hardness of the dry film, improving the scratch resistance of the dry film and the like.
The nitrogen-containing acrylate compounds, such as urethane acrylate and the like, are relatively important photocuring components and have wide application in the fields of photocuring coatings, printing ink, adhesives and the like. The addition of the nitrogenous acrylate compound into the photocuring composition can increase the flexibility of a cured coating, reduce stress shrinkage and improve the adhesive force, and is particularly suitable for photocuring coating, pasting, printing and the like of soft substrates such as paper, soft plastics, leather, fabrics, ring-pull cans and the like. The traditional nitrogen-containing acrylate compounds are generally synthesized by the addition reaction of isocyanate and compounds with hydroxyl. This method has two drawbacks: firstly, isocyanate has pungent smell and has strong stimulation effect on skin, eyes and respiratory tract, and the toxic and side effect is large. Secondly, the synthesis method has more side reactions, and the alcohol compound and the isocyanate can be subjected to hydrolysis reaction. The trace amounts of moisture contained in the raw materials react with the isocyanate groups to form a biuret structure. Excessive carbamido structures in the polymer can cause excessive hydrogen bonds of the material, increase the brittleness of the film layer and reduce the waterproofness. In addition, the product contains N-H bonds and has strong hydrogen bonding effect, so that the viscosity of the product is generally high, and the application of the product is influenced.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides the nitrogenous multifunctional acrylate resin, the preparation method and the application thereof, and the resin has the advantages of both nitrogenous resin and multifunctional resin in photocuring application, has excellent application performance and is obviously superior to the existing products; in addition, the invention provides a preparation method of the nitrogenous multifunctional acrylate resin, which has no irritation and toxic or side effect, simple operation and less side reaction; the resin can be used in various photocuring fields such as photocuring paint, printing ink, adhesive and the like.
The structure of the nitrogenous multifunctional acrylate resin is shown in the following general formula (I):
(I)
wherein,
（1）R1、R2and R3Each independently is hydrogen or methyl, except that R1And R2Not being methyl at the same time;
（2）R4is a straight chain or branched chain k-valent alkyl with 2 to 18 carbon atoms, and the chain segment can contain a benzene ring or a naphthenic group structure;
(3) m =0 or 1, n is an integer from 0 to 16; k =2 or 3.
The preparation method of the nitrogenous multifunctional acrylate resin comprises the following steps:
(1) adding an amine compound shown as a formula (II) into a reaction kettle, and then adding a cyclic carbonate compound shown as a formula (III) into the reaction kettle under a nitrogen atmosphere, wherein the molar ratio of the cyclic carbonate compound to nitrogen atoms in the amine compound is 1: 1; after the charging is finished, the temperature is raised, and the reaction temperature is 60-120 DEGoAnd C, after the reaction is finished, cooling, and reacting to generate an intermediate product shown in the following formula (IV):
（II）
（III）
（IV）
(2) adding acrylic acid or methacrylic acid, a polymerization inhibitor, a catalyst and a water-carrying agent into the reaction kettle containing the intermediate product (IV), wherein the molar ratio of the intermediate product (IV) to the acrylic acid or the methacrylic acid is 1 (n + 1) to (n + 2); after the addition is finished, heating and reacting in a reflux state, and removing water generated in the reaction at the same time, wherein the reaction temperature is 70-130 DEGoC, the reaction time is 5-18h, and the temperature is reduced after the reaction is finished;
(3) adding polybasic acid R into a reaction kettle4(COOH)kCatalyst, and process for producing the sameWherein the molar ratio of the residual hydroxyl groups to the carboxyl groups of the polyacid is 1: 1; after the addition is finished, heating and reacting in a reflux state, wherein the reaction temperature is 70-130 DEGoC, when the acid value of the system is less than 10mgKOH/g, cooling;
(4) adding water into the reaction kettle, mixing, standing and separating liquid; and taking the organic phase, and removing the solvent and residual water to obtain the product, namely the nitrogenous polyfunctional acrylate resin.
The preparation method of the nitrogenous multifunctional acrylate resin is characterized by comprising the following steps: adding acrylic acid or methacrylic acid, a polymerization inhibitor, a catalyst and a water-carrying agent into the reaction kettle containing the intermediate product (IV) in the step (2), wherein the molar ratio of the intermediate product (IV) to the acrylic acid is 1 (n + 1) to (n + 2); after the addition is finished, heating and reacting in a reflux state, and removing water generated in the reaction at the same time, wherein the reaction temperature is 78-85 DEGoC。
The polymerization inhibitor in the step (2) is hydroquinone, p-hydroxyanisole, p-benzoquinone, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, nitrobenzene, 1-diphenyl-2-trinitrophenylhydrazine and the like, preferably p-hydroxyanisole, hydroquinone and 2-tert-butylhydroquinone, and the addition amount of the polymerization inhibitor is 1-5% of the total amount of the intermediate product (IV) and acrylic acid or methacrylic acid.
The catalyst in the above step is p-toluenesulfonic acid, concentrated sulfuric acid, strongly acidic ion exchange resin, etc., preferably p-toluenesulfonic acid, in an amount of 1 to 8% of the total amount of the Intermediate (IV) and acrylic acid or methacrylic acid.
The above polybasic acid R4(COOH)kAre commercially commonly used polybasic acids such as 1, 6-adipic acid, isophthalic acid, trimesic acid, 3-methyl-1, 6-adipic acid, and the like.
The water-carrying agent is common organic solvent, such as benzene, toluene, cyclohexane, etc. Toluene and cyclohexane are preferred, and the amount added is 10 to 200% of the total amount of the intermediate product (IV) and acrylic acid or methacrylic acid.
The nitrogenous multifunctional acrylate can be used in various photocuring technical fields such as photocuring coating, printing ink, adhesive and the like. Illustratively, the photo-curing composition containing the nitrogen-containing multifunctional acrylate comprises the following components (in percentage by mass):
0 to 80 percent of active diluent
15-90% of nitrogenous polyfunctional acrylate resin
5 to 10 percent of photoinitiator
The reactive diluent may be any one or more of monofunctional, difunctional and multifunctional (meth) acrylate monomers, depending on the application, including but not limited to: ethoxyethoxyethyl acrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate,
the above photoinitiator may be selected from any one or more of benzoin and derivatives thereof, benzil derivatives, dialkoxy acetophenones, alpha-hydroxyalkyl phenones, alpha-aminoalkylphenones, benzophenones/tertiary amines, anthraquinones/tertiary amines, thioxanthones/tertiary amines and camphorquinones/tertiary amines.
The components are uniformly mixed to obtain the photocuring mixture.
Compared with the prior art, the invention has the following beneficial effects:
the novel nitrogenous multifunctional acrylate resin disclosed by the invention is high in photopolymerization activity, can increase the flexibility of a cured coating, reduce stress shrinkage and improve adhesive force, is excellent in application performance, and is obviously superior to the existing similar products; meanwhile, the preparation method has the advantages of high conversion rate, mild reaction conditions, few side reactions, easy separation and purification of products and the like.
Detailed Description
A nitrogen-containing multifunctional acrylate resin having a structure represented by the following general formula (I):
(I)
wherein,
（1）R1、R2and R3Each independently is hydrogen or methyl, except that R1And R2Not being methyl at the same time;
（2）R4is a linear or branched k-valent alkyl radical having from 2 to 18 carbon atoms, R4 being derived from a polybasic acid R containing a group R44(COOH)kTransformed with R of4(COOH)kAre commercially customary polybasic acids, for example methylmalonic acid, 2-dimethylmalonic acid, succinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2-dimethylglutaric acid, 2, 3-dimethylglutaric acid, 3-dimethylglutaric acid, 2, 4-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, 2, 4-diethylglutaric acid, 1, 6-adipic acid, 2-methyladipic acid, 3-methyladipic acid, 2, 5-dimethyladipic acid, 2,4, 4-trimethyladipic acid, pimelic acid, 2, 3-dimethylpimelic acid, 4, 4-dimethylpimelic acid, Suberic acid, azelaic acid, sebacic acid, undecanedioic acid, 2-methylundecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, etc., preferably 1, 6-adipic acid, 3-methyladipic acid, which may contain a benzene ring or a cycloalkyl group structure in its chain segment, such as terephthalic acid, phthalic acid, isophthalic acid, trimesic acid, 1,2, 3-benzenetricarboxylic acid, 1,2, 4-benzenetricarboxylic acid, terephthallic acid, orthophthalic acid, isophthalic acid, benzenedipropionic acid, 1-cyclobutyldicarboxylic acid, 1-cyclopropyldicarboxylic acid, cyclobutane-1, 2-dicarboxylic acid, 1, 2-cyclopentanedicarboxylic acid, 1-cyclopentanediacetic acid, cyclohexanediacetic acid, 1, 4-cyclohexyldicarboxylic acid, cyclohexyl-1,3-dicarboxylic acid, 1-cyclohexanediacetic acid, 1, 2-cyclohexanedicarboxylic acid, 1-cyclohexanediacetic acid, preferably terephthalic acid, trimesic acid;
(3) m =0 or 1, n is an integer from 0 to 16, preferably n is from 1 to 10, most preferably from 1 to 5; k =2 or 3.
The preparation method of the nitrogenous multifunctional acrylate resin comprises the following steps: the method comprises the following steps:
(1) adding an amine compound shown as a formula (II) into a reaction kettle, and then adding a cyclic carbonate compound shown as a formula (III) into the reaction kettle under a nitrogen atmosphere, wherein the molar ratio of the cyclic carbonate compound to nitrogen atoms in the amine compound is 1: 1; after the charging is finished, the temperature is raised, and the reaction temperature is 60-120 DEGoAnd C, after the reaction is finished, cooling, and reacting to generate an intermediate product shown in the following formula (IV):
（II）
wherein n is an integer of 0 to 16, such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, heptaethyleneoctamine, octaethylenenonamine, nonaethylenedecamine, decaethyleneundecamide, undecenyldodecamine, dodecaethylenetridecylamine, tridecylenetetradecylamine, tetradecylenepentadecylamine, pentadecylenehexadecylamine, hexadecyleneheptadecylamine, heptadecyleneooctadecylamine, octadecylenenonadecyleneodecamine, nonadecyleneoicosanamine; preferably diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine;
（III）
wherein m =0 or 1, R1And R2Each independently is hydrogen or methyl, except that R1And R2Not being methyl at the same time; such as ethylene carbonate, propylene carbonate.
（IV）
m =0 or 1, n is an integer from 0 to 16, preferably n is from 1 to 10, most preferably n is from 1 to 5;
(2) adding acrylic acid or methacrylic acid, a polymerization inhibitor, a catalyst and a water-carrying agent into the reaction kettle containing the intermediate product (IV), wherein the molar ratio of the intermediate product (IV) to the acrylic acid or the methacrylic acid is 1 (n + 1) to (n + 2); after the addition is finished, heating and reacting in a reflux state, and removing water generated in the reaction at the same time, wherein the reaction temperature is 70-130 DEGoC, the preferred reaction temperature is 78-85oC. The reaction time is 5-18h, and after the reaction is finished, the temperature is reduced;
(3) adding polybasic acid R into a reaction kettle4(COOH)kA catalyst, wherein the molar ratio of the residual hydroxyl groups to the carboxyl groups of the polyacid is 1: 1; after the addition is finished, heating and reacting in a reflux state, wherein the reaction temperature is 70-130 DEGoC, the preferred reaction temperature is 78-85oC. When the acid value of the system is less than 10mgKOH/g, the temperature is reduced;
polybasic acid R4(COOH)kAre commercially customary polybasic acids, for example methylmalonic acid, 2-dimethylmalonic acid, succinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2-dimethylglutaric acid, 2, 3-dimethylglutaric acid, 3-dimethylglutaric acid, 2, 4-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, 2, 4-diethylglutaric acid, 1, 6-adipic acid, 2-methyladipic acid, 3-methyladipic acid, 2, 5-dimethyladipic acid, 2,4, 4-trimethyladipic acid, pimelic acid, 2, 3-dimethylpimelic acid, 4, 4-dimethylpimelic acid, Suberic acid, azelaic acid, sebacic acid, undecanedioic acid, 2-methylundecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acidAnd the like,preferably 1, 6-adipic acid, isophthalic acid, trimesic acid, 3-methyl-1, 6-adipic acid, etc.; the chain segment can contain benzene ring or naphthenic group structure,for exampleTerephthalic acid, phthalic acid, isophthalic acid, trimesic acid, 1,2, 3-benzenetricarboxylic acid, 1,2, 4-benzenetricarboxylic acid, terephthallic acid, orthophthalic acid, isophthalic acid, benzenedipropionic acid, 1-cyclobutyldicarboxylic acid, 1-cyclopropyldicarboxylic acid, cyclobutane-1, 2-dicarboxylic acid, 1, 2-cyclopentanedicarboxylic acid, 1-cyclopentanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, cyclohexyl-1, 3-dicarboxylic acid, 1-cyclohexanediacetic acid, 1, 2-cyclohexanedicarboxylic acid, 1-cyclohexanediacetic acidPreference is given toTerephthalic acid, trimesic acid;
(4) adding water into the reaction kettle, mixing, standing and separating liquid; and taking the organic phase, and removing the solvent and residual water to obtain the product, namely the nitrogenous polyfunctional acrylate resin.
Wherein the polymerization inhibitor in the step (2) is hydroquinone, p-hydroxyanisole, p-benzoquinone, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, nitrobenzene, 1-diphenyl-2-trinitrophenylhydrazine and the like, preferably p-hydroxyanisole, hydroquinone and 2-tert-butylhydroquinone, and the addition amount of the polymerization inhibitor is 1-5% of the total amount of the intermediate product (IV) and acrylic acid or methacrylic acid.
The catalyst in the above step is p-toluenesulfonic acid, concentrated sulfuric acid, strongly acidic ion exchange resin, etc., preferably p-toluenesulfonic acid, in an amount of 1 to 8% of the total amount of the Intermediate (IV) and acrylic acid or methacrylic acid.
The water-carrying agent is common organic solvent, such as benzene, toluene, cyclohexane, etc. Toluene and cyclohexane are preferred, and the amount added is 10 to 200% of the total amount of the intermediate product (IV) and acrylic acid or methacrylic acid.
Example 1:
100 parts of diethylenetriamine is added into 5L of double-layer glass for reactionIn the kettle, the reaction kettle is provided with a mechanical stirrer, a thermometer, a sampling port, a gas inlet, a constant pressure dropping funnel, a water separator, a vacuum joint and a vacuum jacket condensation column. After nitrogen was introduced for 10 minutes, 300 parts of ethylene carbonate was slowly added while keeping the reaction vessel under a nitrogen atmosphere and at a temperature of not more than 50 deg.CoC. After the addition was complete, the temperature of the reaction vessel was slowly raised to 80 deg.CoC. The reaction was monitored by infrared when 1805cm-1After the characteristic absorption peak of the cyclic carbonate completely disappears, the reaction is continued for 0.5 hour, and then the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the content is less than C, 5 parts of p-hydroxyanisole, 3 parts of p-toluenesulfonic acid, 500 parts of cyclohexane and 200 parts of acrylic acid are added into the reaction kettle. After the addition is finished, slowly raising the temperature of the reaction kettle to 78-85 DEGoC, refluxing, and removing water generated in the reaction through cyclohexane and a water separator. The reaction was continued until the amount of water formed reached a stoichiometric amount. The esterification reaction time is about 5 hours, and the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the reaction temperature is below C, 2 parts of dibutyltin dilaurate and 50 parts of 3-methyl-1, 6-adipic acid are added into the reaction kettle. After the charging is finished, the temperature is raised to 85 DEGoC, refluxing, measuring the acid value of the system after stirring for 1 hour, and cooling when the acid value is less than 10 mgKOH/g.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen C is less than C, 300 parts of water is added to the reaction vessel, and the mixture is stirred for half an hour and then allowed to stand for liquid separation. After the organic phase had separated off, the solvent and residual water were removed under vacuum to give a clear, slightly yellowish acrylate resin.
Example 2
100 parts of triethylene tetramine are added into a 5L double-layer glass reaction kettle which is provided with a mechanical stirrer, a thermometer, a sampling port, a gas inlet, a constant-pressure dropping funnel, a water separator, a vacuum connector and a vacuum jacket condensation column. After nitrogen was purged for 10 minutes, 400 parts of ethylene carbonate was slowly added while maintaining the reactionThe reaction kettle is in nitrogen atmosphere and the temperature is not more than 50 DEG CoC. After the addition was complete, the temperature of the reaction vessel was slowly raised to 80 deg.CoC. The reaction was monitored by infrared when 1805cm-1After the characteristic absorption peak of the cyclic carbonate completely disappears, the reaction is continued for 0.5 hour, and then the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the content is less than C, 2 parts of p-hydroxyanisole, 5 parts of p-toluenesulfonic acid, 500 parts of cyclohexane and 300 parts of acrylic acid are added into the reaction kettle. After the addition is finished, slowly raising the temperature of the reaction kettle to 78-85 DEGoC, refluxing, and removing water generated in the reaction through cyclohexane and a water separator. The reaction was continued until the amount of water formed reached a stoichiometric amount. The esterification reaction time is about 5 hours, and the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the temperature is lower than C, 4 parts of dibutyltin dilaurate and 50 parts of 1, 6-adipic acid are added into the reaction kettle. After the charging is finished, the temperature is raised to 85 DEGoC, refluxing, measuring the acid value of the system after stirring for 1 hour, and cooling when the acid value is less than 10 mgKOH/g.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen C is less than C, 300 parts of water is added to the reaction vessel, and the mixture is stirred for half an hour and then allowed to stand for liquid separation. After the organic phase had separated off, the solvent and residual water were removed under vacuum to give a clear, slightly yellowish acrylate resin.
Example 3
100 parts of tetraethylenepentamine were added to a 5L double-glass reaction vessel equipped with a mechanical stirrer, a thermometer, a sampling port, a gas inlet, a constant pressure dropping funnel, a water separator, a vacuum joint and a vacuum jacket condensation column. After nitrogen was introduced for 10 minutes, 500 parts of propylene carbonate was slowly added while keeping the reaction kettle under a nitrogen atmosphere at a temperature of not more than 50 deg.foC. After the addition was complete, the temperature of the reaction vessel was slowly raised to 80 deg.CoC. The reaction was monitored by infrared when 1805cm-1After the characteristic absorption peak of the cyclic carbonate completely disappears, the reaction is continuedAfter 0.5 hour, the reaction is completed and the temperature is reduced.
And when the temperature of the reaction kettle is reduced to be below 40 ℃, adding 5 parts of p-hydroxyanisole, 10 parts of p-toluenesulfonic acid, 500 parts of toluene and 400 parts of acrylic acid into the reaction kettle. After the addition is finished, the temperature of the reaction kettle is slowly raised to 100-120 ℃ for reflux, and the water generated in the reaction is removed through cyclohexane and a water separator. The reaction was continued until the amount of water formed reached a stoichiometric amount. The esterification reaction time is about 5 hours, and the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the temperature is lower than C, 5 parts of dibutyltin dilaurate and 50 parts of terephthalic acid are added into the reaction kettle. After the charging is finished, the temperature is raised to 110 DEGoC, refluxing, measuring the acid value of the system after stirring for 1 hour, and cooling when the acid value is less than 10 mgKOH/g.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen C is less than C, 300 parts of water is added to the reaction vessel, and the mixture is stirred for half an hour and then allowed to stand for liquid separation. After the organic phase had separated off, the solvent and residual water were removed under vacuum to give a clear, slightly yellowish acrylate resin.
Example 4
100 parts of pentaethylenehexamine were charged into a 5L double-glass reactor equipped with a mechanical stirrer, a thermometer, a sampling port, a gas inlet, a constant-pressure dropping funnel, a water separator, a vacuum joint and a vacuum jacket condensation column. After nitrogen was introduced for 10 minutes, 600 parts of ethylene carbonate was slowly added while keeping the reaction vessel under a nitrogen atmosphere and at a temperature of not more than 50 deg.CoC. After the addition was complete, the temperature of the reaction vessel was slowly raised to 80 deg.CoC. The reaction was monitored by infrared when 1805cm-1After the characteristic absorption peak of the cyclic carbonate completely disappears, the reaction is continued for 0.5 hour, and then the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the content is less than C, 6 parts of p-hydroxyanisole, 7 parts of p-toluenesulfonic acid, 500 parts of cyclohexane and 500 parts of methacrylic acid are added into a reaction kettle. After the addition is finished, slowly raising the temperature of the reaction kettle to 78-85 DEGoC, refluxing, and removing water generated in the reaction through cyclohexane and a water separator. The reaction was continued until the amount of water formed reached a stoichiometric amount. The esterification reaction time is about 7.5 hours, and the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the reaction temperature is below C, 6 parts of dibutyltin dilaurate and 33 parts of isophthalic acid are added into the reaction kettle. After the charging is finished, the temperature is raised to 85 DEGoC, refluxing, measuring the acid value of the system after stirring for 1 hour, and cooling when the acid value is less than 10 mgKOH/g.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen C is less than C, 300 parts of water is added to the reaction vessel, and the mixture is stirred for half an hour and then allowed to stand for liquid separation. After the organic phase had separated off, the solvent and residual water were removed under vacuum to give a clear, slightly yellowish acrylate resin.
Example 5
100 parts of hexaethyleneheptamine were charged into a 5L double-glass reaction vessel equipped with a mechanical stirrer, a thermometer, a sampling port, a gas inlet, a constant-pressure dropping funnel, a water separator, a vacuum joint, and a vacuum jacket condensation column. After nitrogen was introduced for 10 minutes, 700 parts of ethylene carbonate was slowly added while keeping the reaction vessel under a nitrogen atmosphere and at a temperature of not more than 50 deg.CoC. After the addition was complete, the temperature of the reaction vessel was slowly raised to 80 deg.CoC. The reaction was monitored by infrared when 1805cm-1After the characteristic absorption peak of the cyclic carbonate completely disappears, the reaction is continued for 0.5 hour, and then the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the content is less than C, 7.5 parts of p-hydroxyanisole, 8 parts of p-toluenesulfonic acid, 500 parts of cyclohexane and 650 parts of acrylic acid are added into the reaction kettle. After the addition is finished, slowly raising the temperature of the reaction kettle to 78-85 DEGoC, refluxing, and removing water generated in the reaction through cyclohexane and a water separator. The reaction was continued until the amount of water formed reached a stoichiometric amount. The esterification reaction time is about 5 hours, and the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the reaction temperature is below C, 15 parts of dibutyltin dilaurate and 25 parts of 3-methyl-1, 6-adipic acid are added into the reaction kettle. After the charging is finished, the temperature is raised to 85 DEGoC, refluxing, measuring the acid value of the system after stirring for 1 hour, and cooling when the acid value is less than 10 mgKOH/g.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen C is less than C, 300 parts of water is added to the reaction vessel, and the mixture is stirred for half an hour and then allowed to stand for liquid separation. After the organic phase had separated off, the solvent and residual water were removed under vacuum to give a clear, slightly yellowish acrylate resin.
Example 6
100 parts of diethylenetriamine are added into a 5L double-layer glass reaction kettle which is provided with a mechanical stirrer, a thermometer, a sampling port, a gas inlet, a constant-pressure dropping funnel, a water separator, a vacuum joint and a vacuum jacket condensation column. After nitrogen was introduced for 10 minutes, 300 parts of ethylene carbonate was slowly added while keeping the reaction vessel under a nitrogen atmosphere and at a temperature of not more than 50 deg.CoC. After the addition was complete, the temperature of the reaction vessel was slowly raised to 80 deg.CoC. The reaction was monitored by infrared when 1805cm-1After the characteristic absorption peak of the cyclic carbonate completely disappears, the reaction is continued for 0.5 hour, and then the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the temperature is lower than C, 3 parts of 2-tert-butylhydroquinone, 3 parts of p-toluenesulfonic acid, 500 parts of cyclohexane and 180 parts of acrylic acid are added into the reaction kettle. After the addition is finished, slowly raising the temperature of the reaction kettle to 78-85 DEGoC, refluxing, and removing water generated in the reaction through cyclohexane and a water separator. The reaction was continued until the amount of water formed reached a stoichiometric amount. The esterification reaction time is about 5 hours, and the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the reaction temperature is below C, 3 parts of dibutyltin dilaurate and 60 parts of 3-methyl-1, 6-adipic acid are added into the reaction kettle. After the charging is finished, the temperature is raised to 85 DEGoC, refluxing, measuring the acid value of the system after stirring for 1 hour, and cooling when the acid value is less than 10 mgKOH/g.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen C is less than C, 300 parts of water is added to the reaction vessel, and the mixture is stirred for half an hour and then allowed to stand for liquid separation. After the organic phase had separated off, the solvent and residual water were removed under vacuum to give a clear, slightly yellowish acrylate resin.
Example 7
100 parts of triethylene tetramine are added into a 5L double-layer glass reaction kettle which is provided with a mechanical stirrer, a thermometer, a sampling port, a gas inlet, a constant-pressure dropping funnel, a water separator, a vacuum connector and a vacuum jacket condensation column. After nitrogen was introduced for 10 minutes, 400 parts of ethylene carbonate was slowly added while keeping the reaction vessel under a nitrogen atmosphere and at a temperature of not more than 50 deg.CoC. After the addition was complete, the temperature of the reaction vessel was slowly raised to 80 deg.CoC. The reaction was monitored by infrared when 1805cm-1After the characteristic absorption peak of the cyclic carbonate completely disappears, the reaction is continued for 0.5 hour, and then the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the content is less than C, 3.5 parts of p-hydroxyanisole, 3 parts of concentrated sulfuric acid, 500 parts of cyclohexane and 250 parts of acrylic acid are added into the reaction kettle. After the addition is finished, slowly raising the temperature of the reaction kettle to 78-85 DEGoC, refluxing, and removing water generated in the reaction through cyclohexane and a water separator. The reaction was continued until the amount of water formed reached a stoichiometric amount. The esterification reaction time is about 5 hours, and the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the reaction temperature is below C, 3.5 parts of dibutyltin dilaurate and 50 parts of trimesic acid are added into the reaction kettle. After the charging is finished, the temperature is raised to 85 DEGoC, refluxing, measuring the acid value of the system after stirring for 1 hour, and cooling when the acid value is less than 10 mgKOH/g.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the content is less than C, 300 parts of water is added into the reaction kettle and stirredThe mixture was left to stand for half an hour for liquid separation. After the organic phase had separated off, the solvent and residual water were removed under vacuum to give a clear, slightly yellowish acrylate resin.
Example 8
100 parts of tetraethylenepentamine were added to a 5L double-glass reaction vessel equipped with a mechanical stirrer, a thermometer, a sampling port, a gas inlet, a constant pressure dropping funnel, a water separator, a vacuum joint and a vacuum jacket condensation column. After nitrogen was introduced for 10 minutes, 500 parts of ethylene carbonate was slowly added while keeping the reaction vessel under a nitrogen atmosphere and at a temperature of not more than 50 deg.CoC. After the addition was complete, the temperature of the reaction vessel was slowly raised to 80 deg.CoC. The reaction was monitored by infrared when 1805cm-1After the characteristic absorption peak of the cyclic carbonate completely disappears, the reaction is continued for 0.5 hour, and then the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the content is less than C, 6 parts of p-hydroxyanisole, 3 parts of p-toluenesulfonic acid, 500 parts of cyclohexane and 440 parts of acrylic acid are added into the reaction kettle. After the addition is finished, slowly raising the temperature of the reaction kettle to 78-85 DEGoC, refluxing, and removing water generated in the reaction through cyclohexane and a water separator. The reaction was continued until the amount of water formed reached a stoichiometric amount. The esterification reaction time is about 5 hours, and the temperature is reduced.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen the reaction temperature is below C, 5.5 parts of dibutyltin dilaurate and 20 parts of trimesic acid are added into the reaction kettle. After the charging is finished, the temperature is raised to 85 DEGoC, refluxing, measuring the acid value of the system after stirring for 1 hour, and cooling when the acid value is less than 10 mgKOH/g.
When the temperature of the reaction kettle is reduced to 40 DEGoWhen C is less than C, 300 parts of water is added to the reaction vessel, and the mixture is stirred for half an hour and then allowed to stand for liquid separation. After the organic phase had separated off, the solvent and residual water were removed under vacuum to give a clear, slightly yellowish acrylate resin.
The nitrogenous multifunctional acrylate resin is used in various photocuring fields of photocuring paint, ink or adhesive.
The nitrogen-containing multifunctional acrylate used for the photocureable coating is specifically described as follows, and comprises the following components in percentage by mass: 0-80% of reactive diluent, 15-90% of nitrogenous polyfunctional acrylate resin and 5-10% of photoinitiator;
wherein the reactive diluent is any one or at least two of monofunctional, difunctional and polyfunctional (methyl) acrylate monomers, or any one or at least two of ethoxyethoxyethyl acrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate;
the photoinitiator can be selected from any one or at least two of benzoin and derivatives thereof, benzil derivatives, dialkoxy acetophenone, alpha-hydroxyalkyl phenone, alpha-amine alkyl phenone, benzophenone/tertiary amine, anthraquinone/tertiary amine, thioxanthone/tertiary amine and camphorquinone/tertiary amine;
the components are uniformly mixed to obtain the photocuring mixture.
Example 1: the nitrogen-containing multifunctional acrylate used for the photocureable coating is specifically described as follows, and comprises the following components in percentage by mass: 90% of nitrogenous polyfunctional acrylate resin and 10% of photoinitiator;
the photoinitiator can be selected from any one or at least two of benzoin and derivatives thereof, benzil derivatives, dialkoxy acetophenone, alpha-hydroxyalkyl phenone, alpha-amine alkyl phenone, benzophenone/tertiary amine, anthraquinone/tertiary amine, thioxanthone/tertiary amine and camphorquinone/tertiary amine;
the components are uniformly mixed to obtain the photocuring mixture.
Example 2: the nitrogen-containing multifunctional acrylate used for the photocureable coating is specifically described as follows, and comprises the following components in percentage by mass: 77% of reactive diluent, 15% of nitrogenous polyfunctional acrylate resin and 8% of photoinitiator;
wherein the reactive diluent is any one or at least two of monofunctional, difunctional and polyfunctional (methyl) acrylate monomers, or any one or at least two of ethoxyethoxyethyl acrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate;
the photoinitiator can be selected from any one or at least two of benzoin and derivatives thereof, benzil derivatives, dialkoxy acetophenone, alpha-hydroxyalkyl phenone, alpha-amine alkyl phenone, benzophenone/tertiary amine, anthraquinone/tertiary amine, thioxanthone/tertiary amine and camphorquinone/tertiary amine;
the components are uniformly mixed to obtain the photocuring mixture.
Example 3: the nitrogen-containing multifunctional acrylate used for the photocureable coating is specifically described as follows, and comprises the following components in percentage by mass: 35% of reactive diluent, 50% of nitrogenous polyfunctional acrylate resin and 5% of photoinitiator;
wherein the reactive diluent is any one or at least two of monofunctional, difunctional and polyfunctional (methyl) acrylate monomers, or any one or at least two of ethoxyethoxyethyl acrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate;
the photoinitiator can be selected from any one or at least two of benzoin and derivatives thereof, benzil derivatives, dialkoxy acetophenone, alpha-hydroxyalkyl phenone, alpha-amine alkyl phenone, benzophenone/tertiary amine, anthraquinone/tertiary amine, thioxanthone/tertiary amine and camphorquinone/tertiary amine;
the components are uniformly mixed to obtain the photocuring mixture.
Performance testing
The samples of preparation method examples 1-8 were formulated in the following formulation in mass percent according to the following method,
nitrogen-containing polyfunctional acrylates: 65 wt. -%)
Monomer (b): 30 wt. -%)
Photoinitiator 3-Isopropylthioxanthone (ITX): 2 wt. -%)
Photoinitiator Benzophenone (BP): 1.5 wt. -%)
Co-initiator ethyl N, N-dimethylaminobenzoate (EDAB): 1.5 wt. -%)
Wherein,
(1) the acid value was measured in accordance with GB/T2895-2008 "measurement of partial acid value and Total acid value of Plastic polyester resin".
(2) The coated substrate tinplate is prepared according to GB/T9271-2008 standard test board for color paint and varnish.
(3) The sample plate is prepared by coating a bar coater with 30um on tinplate
(4) Curing conditions of the coating film: light curing intensitya：300 mW/cm2Time: 60 s
a: the light curing intensity is tested by using an ultraviolet irradiator UV-A of Beijing university
(5) The coating adhesion is determined according to GB/T5210-
(6) The flexibility of the coating film was tested according to GB/T6742-2007 bending test for paints and varnishes (cylindrical shafts);
(7) the hardness of the coating is tested according to GB/T6739-;
(8) the comparative samples were: CN966 of Sadoma
The present invention is not limited to the above embodiments and application examples, and any schemes similar to the inventive concept fall into the protection scope of the present invention.
Claims (9)
1. A nitrogen-containing multifunctional acrylate resin having a structure represented by the following general formula (I):
(I)
wherein,
（1）R1、R2and R3Each independently is hydrogen or methyl, except that R1And R2Not being methyl at the same time;
（2）R4is a straight chain or branched chain k-valent alkyl with 2 to 18 carbon atoms, and the chain segment can contain a benzene ring or a naphthenic group structure;
(3) m =0 or 1, n is an integer from 0 to 16; k =2 or 3.
2. The method for preparing a nitrogen-containing multifunctional acrylate resin according to claim 1, comprising the steps of:
(1) adding an amine compound shown as a formula (II) into a reaction kettle, and then adding a cyclic carbonate compound shown as a formula (III) into the reaction kettle under a nitrogen atmosphere, wherein the molar ratio of the cyclic carbonate compound to nitrogen atoms in the amine compound is 1: 1; after the charging is finished, the temperature is raised, and the reaction temperature is 60-120 DEGoAnd C, after the reaction is finished, cooling, and reacting to generate an intermediate product shown in the following formula (IV):
（II）
（III）
（IV）
(2) adding acrylic acid or methacrylic acid, a polymerization inhibitor, a catalyst and a water-carrying agent into the reaction kettle containing the intermediate product (IV), wherein the molar ratio of the intermediate product (IV) to the acrylic acid is 1 (n + 1) to (n + 2); after the addition is finished, heating and reacting in a reflux state, and removing water generated in the reaction at the same time, wherein the reaction temperature is 70-130 DEGoC, the reaction time is 5-8 h, and the temperature is reduced after the reaction is finished;
(3) adding polybasic acid R into a reaction kettle4(COOH)kA catalyst, wherein the molar ratio of the residual hydroxyl groups to the carboxyl groups of the polyacid is 1: 1; after the addition is finished, heating and reacting in a reflux state, wherein the reaction temperature is 70-130 DEGoC, when the acid value of the system is less than 1When the concentration is 0mgKOH/g, the temperature is reduced;
(4) adding water into the reaction kettle, mixing, standing and separating liquid; and taking the organic phase, and removing the solvent and residual water to obtain the product, namely the nitrogenous polyfunctional acrylate resin.
3. The method for preparing a nitrogen-containing polyfunctional acrylate resin according to claim 2, wherein: adding acrylic acid or methacrylic acid, a polymerization inhibitor, a catalyst and a water-carrying agent into the reaction kettle containing the intermediate product (IV) in the step (2), wherein the molar ratio of the intermediate product (IV) to the acrylic acid is 1 (n + 1) to (n + 2); after the addition is finished, heating and reacting in a reflux state, and removing water generated in the reaction at the same time, wherein the reaction temperature is 78-85 DEGoC。
4. The method for preparing a nitrogen-containing polyfunctional acrylate resin according to claim 2, wherein: in the step (2), the water-carrying agent is any one of common organic solvents of benzene, toluene or cyclohexane, and the adding amount of the water-carrying agent is 10-200% of the total amount of the intermediate product (IV) and acrylic acid or methacrylic acid.
5. The method for preparing a nitrogen-containing polyfunctional acrylate resin according to claim 2, wherein: the polymerization inhibitor in the above step is any one of hydroquinone, p-hydroxyanisole, p-benzoquinone, 2-tert-butylhydroquinone, 2, 5-di-tert-butylhydroquinone, nitrobenzene or 1, 1-diphenyl-2-trinitrophenylhydrazine, and the addition amount of the polymerization inhibitor is 1-5% of the total amount of the intermediate product (IV) and acrylic acid or methacrylic acid.
6. The method for preparing a nitrogen-containing polyfunctional acrylate resin according to claim 2, wherein: the catalyst in the above step is any one of p-toluenesulfonic acid, concentrated sulfuric acid, stannous oxalate, dibutyltin dilaurate, monobutyl tin, monobutyl dihydroxy tin chloride or strong acid ion exchange resin, and the addition amount of the catalyst is 1-8% of the total amount of the intermediate product (IV) and acrylic acid or methacrylic acid.
7. The method for preparing a nitrogen-containing polyfunctional acrylate resin according to claim 2, wherein: polybasic acid R4(COOH)kIs any one of 1, 6-adipic acid, isophthalic acid, terephthalic acid, trimesic acid or 3-methyl-1, 6-adipic acid.
8. Use of the nitrogen-containing polyfunctional acrylate resin according to claim 1, characterized in that: the nitrogenous multifunctional acrylate is used for photocureable coating, printing ink or adhesive.
9. Use of the nitrogen-containing multifunctional acrylate resin according to claim 8, wherein: the nitrogenous multifunctional acrylic ester is used for photocureable coating and comprises the following components in percentage by mass: 0-80% of reactive diluent, 15-90% of nitrogenous polyfunctional acrylate resin and 5-10% of photoinitiator;
wherein the reactive diluent is any one or at least two of monofunctional, difunctional and polyfunctional (methyl) acrylate monomers, or any one or at least two of ethoxyethoxyethyl acrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate or pentaerythritol tetraacrylate;
the photoinitiator can be selected from any one or at least two of benzoin and derivatives thereof, benzil derivatives, dialkoxy acetophenone, alpha-hydroxyalkyl phenone, alpha-amine alkyl phenone, benzophenone/tertiary amine, anthraquinone/tertiary amine, thioxanthone/tertiary amine and camphorquinone/tertiary amine;
the components are uniformly mixed to obtain the photocuring mixture.
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| CN101475502A (en) * | 2009-01-16 | 2009-07-08 | 北京化工大学 | Nitrogenous polyfunctional acrylic ester monomer, preparation and use thereof |
| CN101503378A (en) * | 2009-03-27 | 2009-08-12 | 北京化工大学 | Ultra-low viscosity simple function group carbamate monomer, and preparation and use thereof |
| CN102344533A (en) * | 2011-07-14 | 2012-02-08 | 青州市宝达化工有限公司 | Resin emulsion for water-borne wood paint and preparation method thereof |
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| CN101475502A (en) * | 2009-01-16 | 2009-07-08 | 北京化工大学 | Nitrogenous polyfunctional acrylic ester monomer, preparation and use thereof |
| CN101503378A (en) * | 2009-03-27 | 2009-08-12 | 北京化工大学 | Ultra-low viscosity simple function group carbamate monomer, and preparation and use thereof |
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