CN117946297A - Modified diallyl phthalate resin, preparation method thereof and curing composition - Google Patents
Modified diallyl phthalate resin, preparation method thereof and curing composition Download PDFInfo
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- CN117946297A CN117946297A CN202211297369.4A CN202211297369A CN117946297A CN 117946297 A CN117946297 A CN 117946297A CN 202211297369 A CN202211297369 A CN 202211297369A CN 117946297 A CN117946297 A CN 117946297A
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- diallyl phthalate
- phthalate resin
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- 239000011347 resin Substances 0.000 title claims abstract description 99
- 229920005989 resin Polymers 0.000 title claims abstract description 99
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical class C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 title claims abstract description 98
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 47
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000010992 reflux Methods 0.000 claims description 32
- -1 acrylic ester compounds Chemical class 0.000 claims description 26
- 239000000976 ink Substances 0.000 claims description 22
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 14
- 239000003054 catalyst Substances 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
- 239000002994 raw material Substances 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 239000003973 paint Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 9
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 8
- 125000004364 3-pyrrolinyl group Chemical group [H]C1=C([H])C([H])([H])N(*)C1([H])[H] 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 5
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-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
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 3
- 238000010146 3D printing Methods 0.000 claims description 3
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 claims description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 3
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 3
- 125000004366 heterocycloalkenyl group Chemical group 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 3
- ODHYIQOBTIWVRZ-UHFFFAOYSA-N n-propan-2-ylhydroxylamine Chemical compound CC(C)NO ODHYIQOBTIWVRZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229940078552 o-xylene Drugs 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 claims description 3
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 18
- 238000000576 coating method Methods 0.000 abstract description 18
- 239000000126 substance Substances 0.000 abstract description 10
- 230000032683 aging Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000001723 curing Methods 0.000 description 27
- 230000009257 reactivity Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920000742 Cotton Polymers 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001029 thermal curing Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 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
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a modified diallyl phthalate resin, a preparation method thereof and a curing composition. The modified diallyl phthalate resin has the structural general formula I: wherein x and y are each independently integers of 1 to 500; r 1 has the following structural formula II: n is any integer from 0 to 10, R 4、R5 is each independently selected from any one or more of H, substituted or unsubstituted C 1～C10 straight-chain alkyl, substituted or unsubstituted C 3～C10 branched-chain alkyl, -CH 2OC(O)(R8)C＝CH2; the modified diallyl phthalate resin of the application has extremely high polymerization rate and excellent film forming performance, and the coating formed by the modified diallyl phthalate resin has the characteristics of excellent gloss, heat resistance, aging resistance, chemical corrosion resistance and adhesion.
Description
Technical Field
The invention relates to the technical field of modification of diallyl phthalate resin, in particular to a modified diallyl phthalate resin, a preparation method thereof and a curing composition.
Background
Acrylic acid esters are esters containing acrylic acid or methacrylic acid structures, and representative compounds are methyl acrylate, ethyl acrylate, 2-methyl methacrylate, 2-ethyl methacrylate, 2-hydroxyethyl acrylate and the like. The acrylic ester compound has the characteristics of high reaction activity and low viscosity, is widely used as a reactive diluent in free radical polymerization reaction, and the prepared polymer has the performances of heat resistance, water resistance, ultraviolet light resistance and the like, and can be used in a plurality of industries such as coating, adhesive, leather, chemical fiber, papermaking, printing and the like.
Diallyl phthalate resin has the characteristics of excellent thermal stability, aging resistance, chemical corrosion resistance, electrical performance and the like, and the product is widely applied to a plurality of different fields such as manufacturing of electrical or electronic equipment, decoration plates, adhesives, UV ink and the like. The water-oil balance can be adjusted by adding a proper amount of diallyl phthalate resin into the UV ink composition, the emulsification phenomenon of the ink during printing is improved, meanwhile, the influence of temperature on the viscosity of the ink can be reduced, and the storage stability of the ink is improved.
An active energy ray curing ink developed by Nippon Toyo ink Co., ltd. Is characterized in that diallyl phthalate resin and monomers with free radical polymerizable double bonds are added in a water-based ink formula, so that the emulsification phenomenon of the ink in the printing process is greatly improved, the fluidity and the coating property of the ink are improved, the generation of ink stains is avoided, and the printing process is reproducible.
However, since allyl groups on branches in the molecular structure of diallyl phthalate resin cannot react with active radicals in the curing process, diallyl phthalate resin is often used as an inert resin to be added to the formulation, and increasing the addition amount of diallyl phthalate resin reduces the reactivity of the photocurable composition, resulting in a reduction of the curing rate, which greatly limits the application range of diallyl phthalate resin.
Disclosure of Invention
The invention mainly aims to provide a modified diallyl phthalate resin, a preparation method thereof and a curing composition, so as to solve the problem of low reactivity of the allyl phthalate resin in the curing composition in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a modified diallyl phthalate resin having the structural formula I:
wherein x and y are each independently integers of 1 to 500; r 1 has the following structural formula II:
n is any integer from 0 to 10, R 4、R5 is each independently selected from any one or more of H, substituted or unsubstituted C 1～C10 straight-chain alkyl, substituted or unsubstituted C 3～C10 branched-chain alkyl, -CH 2OC(O)(R8)C＝CH2; r 6、R7 is selected from any one or more of H and CH 2OC(O)(R8)C＝CH2, R 8 is selected from any one or more of H, substituted or unsubstituted C 1～C10 straight-chain alkyl and substituted or unsubstituted C 3～C10 branched-chain alkyl; each R 2、R3 is independently selected from any one or more of hydrogen, a linear alkyl group of substituted or unsubstituted C 1～C20, a branched alkyl group of substituted or unsubstituted C 3～C20, an alkenyl group of substituted or unsubstituted C 2～C20, an aryl group of substituted or unsubstituted C 6～C20, a heteroaryl group of substituted or unsubstituted C 4～C20, or any one or more of a cycloalkenyl group of substituted or unsubstituted C 3～C7, a heterocycloalkenyl group of substituted or unsubstituted C 3～C7, wherein R 2 and R 3 are bonded to each other; ". Times" indicates a ligation site.
Further, each R 4、R5 is independently selected from any one or more of H, substituted or unsubstituted C 1～C4 straight chain alkyl, substituted or unsubstituted C 3～C6 branched alkyl, preferably R 4、R5 is independently selected from any one or more of H, methyl, ethyl, propyl, isopropyl, isobutyl, isopentyl, further preferably R 4、R5 is independently selected from any one or more of H, methyl, ethyl.
Further, the R 8 is selected from any one or more of H, substituted or unsubstituted C 1～C4 straight-chain alkyl, substituted or unsubstituted C 3～C6 branched-chain alkyl; preferably, R 8 is selected from any one or more of H, methyl, ethyl, propyl, further preferably R 8 is H or methyl.
Further, each of the above R 2、R3 is independently selected from any one or more of hydrogen, a substituted or unsubstituted C 1～C12 straight chain alkyl group, a substituted or unsubstituted C 3～C12 branched alkyl group, a substituted or unsubstituted C 2～C10 alkenyl group, a substituted or unsubstituted C 6～C12 aryl group, a substituted or unsubstituted C 6～C12 heteroaryl group, or preferably R 2 and R 3 are bonded to each other to form a substituted or unsubstituted C 5 or C 6 cycloalkyl group, a substituted or unsubstituted C 5 or C 6 heterocycloalkyl group, preferably a substituted or unsubstituted C 1～C4 straight chain alkyl group is phenyl, preferably a substituted or unsubstituted cyclohexenyl group is isopropenyl, preferably R 2、R3 is each independently selected from any one or more of hydrogen, substituted or unsubstituted C 1～C4 straight chain alkyl, substituted or unsubstituted C 3～C5 branched alkyl, substituted or unsubstituted C 2～C4 alkenyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridinyl, or preferably R 2 and R 3 are bonded to each other to form any one or more of substituted or unsubstituted cyclopentenyl, substituted or unsubstituted cyclohexenyl, 3-pyrrolinyl, further preferably R 2、R3 is each independently selected from any one or more of hydrogen, methyl, ethyl, propyl, benzyl, propenyl, butenyl, phenyl, 4-pyridinyl, or preferably R 2 and R 3 are bonded to each other to form any one or more of cyclopentenyl, cyclohexenyl, 3-pyrrolinyl, further preferably R 2、R3 is each independently selected from hydrogen, methyl, benzyl, 3-pyrrolinyl, any one or more of propenyl, phenyl and 4-pyridyl.
Further, n is an integer of 0 to 6, preferably one or more of the discontinuous methylene groups in R 1 are replaced by-O-; any one of S-, -O (CO) -is substituted, preferably one or more of the discontinuous methylene groups in R 1 are replaced by-O-or-O (CO) -and further preferably the modified diallyl phthalate resin is selected from
Any one or more of the following.
According to an aspect of the present invention, there is provided a method for producing the above modified diallyl phthalate resin comprising: carrying out transesterification on raw materials comprising diallyl phthalate resin, acrylic ester compounds, polymerization inhibitor and catalyst to obtain a product system comprising modified diallyl phthalate resin; wherein, the structural general formula of diallyl phthalate resin and acrylic ester compounds is as follows:
x, y, R 1、R2、R3 have the same definition as above.
Further, the preparation method comprises the following steps: under the atmosphere of nitrogen or inert gas, carrying out a first reflux reaction on reaction raw materials comprising diallyl phthalate resin, acrylic ester compounds and organic solvents to obtain a first reflux system; carrying out a second reflux reaction on reaction raw materials comprising a first reflux system, a polymerization inhibitor and a catalyst to obtain a product system; the diallyl phthalate resin preferably has a weight average molecular weight of 5000 to 200000, more preferably 10000 to 100000, still more preferably 30000 to 60000; the polymerization inhibitor is preferably used in an amount of 0.001 to 1.00wt%, preferably 0.001 to 0.50wt%, more preferably 0.001 to 0.10wt% based on the total mass of the diallyl phthalate resin and the acrylic compound; preferably, the polymerization inhibitor is selected from any one or more of hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, 2, 5-di-tert-butyl-hydroquinone, 2-tert-butyl-hydroquinone, p-benzoquinone, 2, 5-dihydroxytoluene, 1-diphenyl-2-trinitrophenyl hydrazine, N-diethylhydroxylamine, p-phenylenediamine, m-phenylenediamine, N-isopropylhydroxylamine, N-nitroso-N-phenylhydroxylamine aluminum, 4-hydroxy-2, 6-tetramethylpiperidine-1-oxyl; the preferable catalyst is used in an amount of 0.5 to 3.0wt% based on the total mass of diallyl phthalate resin and the acrylic acid ester compound; preferably, the catalyst is selected from any one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium carbonate, sodium carbonate, triethylamine, tripropylamine, trioctylamine, dodecylamine, hexadecylamine, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, isopropyl zirconate, n-propyl zirconate, triisopropyl aluminate, and tribenzyl aluminate; preferably, the organic solvent is selected from any one or more of benzene, toluene, chlorobenzene, ethyl acetate, tetrahydrofuran, o-xylene, m-xylene, dichloromethane, dichloroethane and chloroform; preferably, the temperature of the first reflux reaction is 40-200 ℃, and preferably, the time of the first reflux reaction is 0.5-4 h; preferably the temperature of the second reflux reaction is 20 to 200 ℃, preferably 60 to 160 ℃, further preferably 80 to 120 ℃, preferably the time of the second reflux reaction is 4 to 24 hours; the off-gas from the second reflux reaction is preferably absorbed with a solvent, preferably selected from any one or more of water, ethanol, diethyl ether, chloroform.
Further, the acrylic acid ester compound is selected from
Any one or more of the following.
According to another aspect of the present invention, there is provided a curable composition comprising a diallyl phthalate resin, characterized in that the diallyl phthalate resin is a modified diallyl phthalate resin as described above, or the diallyl phthalate resin is a modified diallyl phthalate resin obtained by the above preparation method.
Further, the cured composition is any one of 3D printing, ink, paint, and adhesive.
By applying the technical scheme of the application, the structure of the modified diallyl phthalate resin contains an acrylic ester structure, so that the reactivity of the diallyl phthalate resin is greatly improved, the modified diallyl phthalate resin can be cured under lower active energy (photo-curing and thermal-curing), and the modified diallyl phthalate resin is used in a curing composition, so that the modified diallyl phthalate resin in the curing composition has the characteristics of extremely high polymerization rate and excellent film forming property, and a coating formed by the modified diallyl phthalate resin has the characteristics of excellent gloss, heat resistance, ageing resistance, chemical corrosion resistance and adhesiveness.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The present application will be described in detail with reference to examples.
As analyzed in the background of the application, there is a problem in the prior art that the reactivity of the allyl phthalate resin in the cured composition is low, and in order to solve the problem, the application provides a modified diallyl phthalate resin, a preparation method thereof and a cured composition.
In one exemplary embodiment of the present application, a modified diallyl phthalate resin is provided having the general structural formula I:
wherein x and y are each independently integers of 1 to 500; r 1 has the following structural formula II:
n is any integer from 0 to 10, R 4、R5 is each independently selected from any one or more of H, substituted or unsubstituted C 1～C10 straight-chain alkyl, substituted or unsubstituted C 3～C10 branched-chain alkyl, -CH 2OC(O)(R8)C＝CH2; r 6、R7 is selected from any one or more of H and CH 2OC(O)(R8)C＝CH2, R 8 is selected from any one or more of H, substituted or unsubstituted C 1～C10 straight-chain alkyl and substituted or unsubstituted C 3～C10 branched-chain alkyl; each R 2、R3 is independently selected from any one or more of hydrogen, a linear alkyl group of substituted or unsubstituted C 1～C20, a branched alkyl group of substituted or unsubstituted C 3～C20, an alkenyl group of substituted or unsubstituted C 2～C20, an aryl group of substituted or unsubstituted C 6～C20, a heteroaryl group of substituted or unsubstituted C 4～C20, or any one or more of a cycloalkenyl group of substituted or unsubstituted C 3～C7, a heterocycloalkenyl group of substituted or unsubstituted C 3～C7, wherein R 2 and R 3 are bonded to each other; ". Times" indicates a ligation site.
The modified diallyl phthalate resin of the application has an acrylate structure, greatly improves the reactivity of the diallyl phthalate resin, can realize curing under lower active energy (photo-curing and thermal curing), and is used in a curing composition, so that the modified diallyl phthalate resin in the curing composition has extremely high polymerization rate and excellent film forming performance, and the formed coating has the characteristics of excellent gloss, heat resistance, ageing resistance, chemical corrosion resistance and adhesiveness.
In one embodiment of the present application, R 4、R5 is independently selected from any one or more of H, substituted or unsubstituted C 1～C4 straight chain alkyl, substituted or unsubstituted C 3～C6 branched chain alkyl, preferably R 4、R5 is independently selected from any one or more of H, methyl, ethyl, propyl, isopropyl, isobutyl, isopentyl, further preferably R 4、R5 is independently selected from any one or more of H, methyl, ethyl.
The above preferred R 4、R5 can enhance the reactivity of the acrylate structure in the modified diallyl phthalate resin by an electronic effect.
Preferably, R 8 is selected from any one or more of H, substituted or unsubstituted C 1～C4 straight-chain alkyl, substituted or unsubstituted C 3～C6 branched-chain alkyl; preferably, R 8 is selected from any one or more of H, methyl, ethyl, propyl, further preferably R 8 is H or methyl, thereby helping to increase the reactivity of the acrylate structure in the R 1 group.
Preferably, each of the above R 2、R3 is independently selected from any one or more of hydrogen, a substituted or unsubstituted C 1～C12 straight chain alkyl group, a substituted or unsubstituted C 3～C12 branched alkyl group, a substituted or unsubstituted C 2～C10 alkenyl group, a substituted or unsubstituted C 6～C12 aryl group, a substituted or unsubstituted C 6～C12 heteroaryl group, or preferably, R 2 and R 3 are bonded to each other to form any one or more of a substituted or unsubstituted C 5 or C 6 cycloalkyl group, a substituted or unsubstituted C 5 or C 6 heterocycloalkyl group; preferably the substituent in the linear alkyl group of substituted or unsubstituted C 1～C4 is phenyl, preferably the substituent in the substituted or unsubstituted cyclohexenyl is isopropenyl; preferably R 2、R3 is each independently selected from any one or more of hydrogen, a substituted or unsubstituted C 1～C4 straight chain alkyl, a substituted or unsubstituted C 3～C5 branched alkyl, a substituted or unsubstituted C 2～C4 alkenyl, a substituted or unsubstituted phenyl, a substituted or unsubstituted pyridinyl, or preferably any one or more of R 2 and R 3 are bonded to each other to form a substituted or unsubstituted cyclopentenyl, a substituted or unsubstituted cyclohexenyl, a 3-pyrrolinyl; further, preferably, each R 2、R3 is independently selected from any one or more of hydrogen, methyl, ethyl, propyl, benzyl, propenyl, butenyl, phenyl, 4-pyridyl, or preferably, R 2 and R 3 are bonded to each other to form any one or more of cyclopentenyl, cyclohexenyl, 3-pyrrolinyl; still further, it is preferred that each R 2、R3 is independently selected from any one or more of hydrogen, methyl, benzyl, propenyl, phenyl, 4-pyridyl, thereby helping to increase the polymerization activity of the carbon-carbon double bond in the acrylate structure.
In one embodiment of the present application, n is an integer of 0 to 6, preferably one or more of the discontinuous methylene groups in R 1 are replaced by-O-; any one of S-, -O (CO) -is substituted, preferably one or more of the discontinuous methylene groups in R 1 are replaced by-O-or-O (CO) -and further preferably the modified diallyl phthalate resin is selected from
Any one or more of the following.
The modified diallyl phthalate resin is more favorable for exerting the reactivity, can realize the curing of the curing composition in lower fixed-line energy, and ensures that the cured polymer has excellent heat resistance, ageing resistance, chemical corrosion resistance, adhesiveness and the like.
In an exemplary embodiment of the present application, there is provided a method for preparing the aforementioned modified diallyl phthalate resin comprising: carrying out transesterification on raw materials comprising diallyl phthalate resin, acrylic ester compounds, polymerization inhibitor and catalyst to obtain a product system comprising modified diallyl phthalate resin; wherein, the structural general formula of diallyl phthalate resin and acrylic ester compounds is as follows:
x, y, R 1、R2、R3 have the same definition as above.
The emulsion has extremely high polymerization rate and excellent film forming performance, and the coating formed by the emulsion has the characteristics of luster, heat resistance and adhesiveness, and the prepared target product can participate in polymerization reaction in the active energy ray curing process.
According to the preparation method disclosed by the application, the diallyl phthalate resin is modified by utilizing the acrylic ester compound through transesterification, so that the reactivity of the modified diallyl phthalate resin is greatly improved, the modified diallyl phthalate resin can be cured under lower active energy (photo-curing and thermal-curing), and the modified diallyl phthalate resin is used in a curing composition, so that the modified diallyl phthalate resin in the curing composition has the characteristics of extremely high polymerization rate and excellent film forming performance, and the formed coating has excellent gloss, heat resistance, ageing resistance, chemical corrosion resistance and adhesiveness. The whole preparation process has the advantages of low cost, high yield, simple operation, safe and environment-friendly reaction process and extremely high commercial value.
In one embodiment of the present application, the preparation method includes: under the atmosphere of nitrogen or inert gas, carrying out a first reflux reaction on reaction raw materials comprising diallyl phthalate resin, acrylic ester compounds and organic solvents to obtain a first reflux system; carrying out a second reflux reaction on reaction raw materials comprising a first reflux system, a polymerization inhibitor and a catalyst to obtain a product system; the diallyl phthalate resin preferably has a weight average molecular weight of 5000 to 200000, more preferably 10000 to 100000, still more preferably 30000 to 60000; the polymerization inhibitor is preferably used in an amount of 0.001 to 1.00wt%, preferably 0.001 to 0.50wt%, more preferably 0.001 to 0.10wt% based on the total mass of the diallyl phthalate resin and the acrylic compound; preferably, the polymerization inhibitor is selected from any one or more of hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, 2, 5-di-tert-butyl-hydroquinone, 2-tert-butyl-hydroquinone, p-benzoquinone, 2, 5-dihydroxytoluene, 1-diphenyl-2-trinitrophenyl hydrazine, N-diethylhydroxylamine, p-phenylenediamine, m-phenylenediamine, N-isopropylhydroxylamine, N-nitroso-N-phenylhydroxylamine aluminum, 4-hydroxy-2, 6-tetramethylpiperidine-1-oxyl; the preferable catalyst is used in an amount of 0.5 to 3.0wt% based on the total mass of diallyl phthalate resin and the acrylic acid ester compound; preferably, the catalyst is selected from any one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium carbonate, sodium carbonate, triethylamine, tripropylamine, trioctylamine, dodecylamine, hexadecylamine, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, isopropyl zirconate, n-propyl zirconate, triisopropyl aluminate, and tribenzyl aluminate; preferably, the organic solvent is selected from any one or more of benzene, toluene, chlorobenzene, ethyl acetate, tetrahydrofuran, o-xylene, m-xylene, dichloromethane, dichloroethane and chloroform; preferably, the temperature of the first reflux reaction is 40-200 ℃, and preferably, the time of the first reflux reaction is 0.5-4 h; preferably the temperature of the second reflux reaction is 20 to 200 ℃, preferably 60 to 160 ℃, further preferably 80 to 120 ℃, preferably the time of the second reflux reaction is 4 to 24 hours; the off-gas from the second reflux reaction is preferably absorbed with a solvent, preferably selected from any one or more of water, ethanol, diethyl ether, chloroform.
The first reflux reaction and the control of the conditions thereof are favorable for removing the water vapor in the reaction raw materials as much as possible, thereby avoiding the interference of the water vapor on the esterification reaction. The control of the conditions of the second reflux reaction is advantageous in improving the yield and efficiency of the esterification reaction in the second reflux reaction. The control of the kind of the catalyst is beneficial to improving the efficiency of the esterification reaction, and the control of the polymerization inhibitor and the kind of the polymerization inhibitor is beneficial to improving the stability of the final modified diallyl phthalate resin so as to be stored. And the absorption treatment of the tail gas generated by the second reflux reaction is beneficial to improving the environmental protection of the preparation method.
Preferably, the acrylic acid ester compound is selected from
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Any one or more of the above, thereby being beneficial to improving the modification effect of the acrylic ester compound on diallyl phthalate resin.
In yet another exemplary embodiment of the present application, a cured composition is provided that includes a diallyl phthalate resin, the diallyl phthalate resin being a modified diallyl phthalate resin as described above, or the diallyl phthalate resin being a modified diallyl phthalate resin resulting from the foregoing production process.
The modified diallyl phthalate resin in the curing composition greatly improves the reactivity of the diallyl phthalate resin, can realize curing under lower active energy (photo-curing and thermal curing), and is used in the curing composition, so that the modified diallyl phthalate resin in the curing composition has extremely high polymerization rate and excellent film forming performance, and the formed coating has the characteristics of excellent gloss, heat resistance, aging resistance, chemical corrosion resistance and adhesiveness.
In one embodiment of the present application, the above-described curable composition is any one of 3D printing, ink, paint, adhesive.
The coating formed by the curing composition has the characteristics of excellent gloss, heat resistance, aging resistance, chemical corrosion resistance and adhesion.
The advantageous effects of the present application will be described below with reference to specific examples and comparative examples.
Example 1
Into a 500mL four-necked flask, nitrogen gas was introduced, and 100g of diallyl phthalate resin (mw=41000), 500g of acrylic acid ester compound raw material b1 and 174g of toluene were charged under nitrogen atmosphere, followed by stirring, heating to 120 ℃ and refluxing, and water in the system was removed by a water separator. 0.2g of p-hydroxyanisole and 7.7g of tetraethyl titanate are slowly added dropwise. After the dripping, the temperature is raised to 110 ℃ for reaction for 12 hours, and the tail gas is absorbed by 500mL of ethanol. After the reaction, the temperature was reduced to 60℃and the solvent was distilled off under reduced pressure of 80 mbar. Cooled to room temperature, and the obtained liquid was added to 1000mL of methanol and stirred for crystallization for 1 hour. The crude product is filtered off and washed once with 500ml of methanol. Filtration and drying gave a modified diallyl phthalate resin white solid I1 of 108g having a Mw of 45900 as measured by gel chromatography. The structure of the product I1 was confirmed by nuclear magnetic resonance hydrogen-spectroscopy 1H-NMR (CDCl 3, 400 MHz): peaks at 6.1ppm represent a hydrogen atom on a c=c double bond in the structural unit of methacrylic acid of the raw material b1, peaks at 3.7 and 4.2ppm represent a hydrogen atom on a-CH 2-CH2 -fragment in the structural unit of ethylene glycol of the raw material b1, and peaks at 7.4 to 7.8ppm represent a hydrogen atom on a benzene ring in the side chain structure of diallyl phthalate resin.
Examples 2 to 10 referring to the experimental procedure of example 1, the kinds b2 to b10 of the acrylic compounds were changed and the reaction conditions were appropriately adjusted to obtain diallyl phthalate resins as white solids I1 to I10, see in particular table 1.
TABLE 1
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UV light curable ink composition examples:
UV light curable inks refer to inks in which the sensitizer in the ink initiates polymerization of the monomers in the ink vehicle to a polymer upon exposure to UV light, which causes the ink to film and dry.
The photocurable inks of the examples and comparative examples were prepared according to the formulations shown in table 2. The units of each component in Table 2 are g. The UV curable ink substrates of the same composition and same composition ratio were used for each group of examples, except that the modified product added was different.
TABLE 2
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Cure speed test
The ink to be measured was roll-coated onto a PET film (common industrial film FP2 of Lekai groups) using a 10 μm bar, and a 385nm UVLED crawler-type exposure machine (Shenzhen Runwo electromechanical Co., ltd.) was used as a radiation source, and the irradiation intensity of the UVLED light source was 20w/cm 2. After the illumination, the method is carried out according to the method for measuring the drying time of paint film and putty film of GB1728-1979, and the method is carried out by adopting a finger touch method, namely, the coating is lightly touched by fingers, and the complete solidification is confirmed by smooth surface, no sticking to hands and no fingerprint pressing. The curing speed is expressed as the maximum exposure energy in mJ/cm 2 to achieve a complete curing effect.
Evaluation of Performance
The UV LED caterpillar type light source with the wavelength of 385nm has the exposure light intensity of 20W/cm 2. Except for the test of the surface drying speed of the coating, the solvent resistance and the abrasion resistance of the cured coating are evaluated by using 500mj energy exposure.
Solvent rub resistance test
The method is carried out according to the method A in GB/T23989-2009 paint solvent wiping resistance assay, and the specific implementation method is as follows:
Solvent-resistant wiper (tagda precision instruments, guangzhou), instrument parameters: wiping travel: 12 cm.+ -. 0.5cm; diameter of contact surface: 14mm + -0.5 mm; for test panel load: 1000 g.+ -. 10g; wiping frequency: the wiping is performed repeatedly every minute (60+/-5).
The test is carried out at room temperature of 18 to 27 ℃.
And after a proper amount of absorbent cotton is wetted by butanone solvent, squeezing the absorbent cotton until the absorbent cotton is dripped without solvent, wrapping the absorbent cotton on the contact surface of the wiping head, then placing the absorbent cotton into the inner cavity of the wiping head and the solvent guide hole, dripping a proper amount of solvent, and fixing the wiping head on a sliding arm of a solvent-resistant wiping instrument. The sample plate is fixed on the test bed, and the front and back positions are adjusted so that the wiping head can fall in the middle of the sample plate. The number of wipes (recorded as one reciprocation) was recorded after wiping to the bottom of the area 8cm in the middle of the length of the panel, and the test was stopped. The larger the number of wipes, the better the solvent resistance of the coating.
Coating abrasion resistance experiment
The measurement was carried out according to the method for measuring abrasion resistance of paint and varnish of GB/T1768-2006. The specific implementation method is as follows:
A500 g weight was applied to the rubber grinding wheel at 23.+ -. 2 ℃ and 50.+ -. 5% relative humidity, and the paint film was rubbed with the rubber grinding wheel fixed to the abrasion tester, and the abrasion resistance of the paint film was expressed by the mass loss of the paint film after 100 rubbing cycles. The mass loss of the paint film is expressed in percent (wt%) and the smaller the value, the better the abrasion resistance of the coating.
The results of the above cure speed test, solvent rub resistance test, and coating abrasion resistance test are shown in table 3.
TABLE 3 Table 3
From the performance evaluation results in table 3, it can be seen that the modified diallyl phthalate resin of the invention has higher reactivity, can significantly improve the solvent resistance and wear resistance of the cured coating, has relatively low process cost, and has a strong application prospect.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
The modified diallyl phthalate resin of the application has an acrylate structure, greatly improves the reactivity of the diallyl phthalate resin, can realize curing under lower active energy (photo-curing and thermal curing), and is used in a curing composition, so that the modified diallyl phthalate resin in the curing composition has extremely high polymerization rate and excellent film forming performance, and the formed coating has the characteristics of excellent gloss, heat resistance, ageing resistance, chemical corrosion resistance and adhesiveness.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A modified diallyl phthalate resin, characterized in that the modified diallyl phthalate resin has the general structural formula I:
Wherein x and y are each independently integers of 1 to 500;
R 1 has the following structural formula II:
n is any integer from 0 to 10, R 4、R5 is each independently selected from any one or more of H, substituted or unsubstituted C 1～C10 straight-chain alkyl, substituted or unsubstituted C 3～C10 branched-chain alkyl, -CH 2OC(O)(R8)C＝CH2;
R 6、R7 is selected from any one or more of H and CH 2OC(O)(R8)C＝CH2, R 8 is selected from any one or more of H, substituted or unsubstituted C 1～C10 straight-chain alkyl and substituted or unsubstituted C 3～C10 branched-chain alkyl; each R 2、R3 is independently selected from any one or more of hydrogen, a linear alkyl group of substituted or unsubstituted C 1～C20, a branched alkyl group of substituted or unsubstituted C 3～C20, an alkenyl group of substituted or unsubstituted C 2～C20, an aryl group of substituted or unsubstituted C 6～C20, a heteroaryl group of substituted or unsubstituted C 4～C20, or any one or more of a cycloalkenyl group of substituted or unsubstituted C 3～C7, a heterocycloalkenyl group of substituted or unsubstituted C 3～C7, wherein R 2 and R 3 are bonded to each other;
". Times" indicates a ligation site.
2. The modified diallyl phthalate resin according to claim 1, wherein said R 4, said R 5 are each independently selected from any one or more of H, substituted or unsubstituted C 1～C4 linear alkyl, substituted or unsubstituted C 3～C6 branched alkyl, preferably said R 4, said R 5 are each independently selected from any one or more of H, methyl, ethyl, propyl, isopropyl, isobutyl, isopentyl, further preferably said R 4, said R 5 are each independently selected from any one or more of H, methyl, ethyl.
3. The modified diallyl phthalate resin according to claim 1 or 2, wherein said R 8 is selected from any one or more of H, substituted or unsubstituted C 1～C4 linear alkyl, substituted or unsubstituted C 3～C6 branched alkyl; preferably, R 8 is selected from any one or more of H, methyl, ethyl, propyl, further preferably, R 8 is H or methyl.
4. The modified diallyl phthalate resin according to any of claims 1 to 3, wherein said R 2, said R 3 are each independently selected from any one or more of hydrogen, a linear alkyl group of substituted or unsubstituted C 1～C12, a branched alkyl group of substituted or unsubstituted C 3～C12, an alkenyl group of substituted or unsubstituted C 2～C10, an aryl group of substituted or unsubstituted C 6～C12, a heteroaryl group of substituted or unsubstituted C 6～C12, or preferably any one or more of a cycloalkyl group of substituted or unsubstituted C 5 or C 6, a heterocycloalkyl group of substituted or unsubstituted C 5 or C 6, wherein said R 2 and said R 3 are bonded to each other,
Preferably the substituent in the linear alkyl group of the substituted or unsubstituted C 1～C4 is phenyl, preferably the substituent in the substituted or unsubstituted cyclohexenyl is isopropenyl,
Preferably, each of said R 2, said R 3 is independently selected from any one or more of hydrogen, a linear alkyl group of substituted or unsubstituted C 1～C4, a branched alkyl group of substituted or unsubstituted C 3～C5, an alkenyl group of substituted or unsubstituted C 2～C4, a phenyl group of substituted or unsubstituted, a pyridinyl group of substituted or unsubstituted, or preferably, any one or more of a cyclopentenyl group of substituted or unsubstituted, a cyclohexenyl group of substituted or unsubstituted, a 3-pyrrolinyl group wherein said R 2 and said R 3 are bonded to each other,
Further, preferably, each of R 2 and R 3 is independently selected from any one or more of hydrogen, methyl, ethyl, propyl, benzyl, propenyl, butenyl, phenyl, 4-pyridyl, or preferably, R 2 and R 3 are bonded to each other to form any one or more of cyclopentenyl, cyclohexenyl, 3-pyrrolinyl,
Still further, it is preferred that each of said R 2, said R 3 is independently selected from any one or more of hydrogen, methyl, benzyl, propenyl, phenyl, 4-pyridyl.
5. The modified diallyl phthalate resin according to any of claims 1 to 4, wherein said n is any integer from 0 to 6, preferably wherein one or more discontinuous methylene groups in said R 1 are replaced by any of-O-, -S-, -O (CO) -preferably wherein one or more discontinuous methylene groups in said R 1 are replaced by-O-or-O (CO) -and further wherein said modified diallyl phthalate resin is selected from the group consisting of
Any one or more of the following.
6. A process for preparing the modified diallyl phthalate resin of any of claims 1 to 5, comprising:
Carrying out transesterification on raw materials comprising diallyl phthalate resin, acrylic ester compounds, polymerization inhibitor and catalyst to obtain a product system comprising the modified diallyl phthalate resin;
wherein, the structural general formulas of the diallyl phthalate resin and the acrylic ester compound are as follows:
x, y, R 1、R2、R3 have the same definition as described in claim 1.
7. The method of manufacturing according to claim 6, characterized in that the method of manufacturing comprises:
under the atmosphere of nitrogen or inert gas, carrying out a first reflux reaction on the reaction raw materials comprising diallyl phthalate resin, the acrylic ester compound and the organic solvent to obtain a first reflux system;
Carrying out a second reflux reaction on the reaction raw materials comprising the first reflux system, the polymerization inhibitor and the catalyst to obtain the product system;
the diallyl phthalate resin preferably has a weight average molecular weight of 5000 to 200000, preferably 10000 to 100000, more preferably 30000 to 60000;
The polymerization inhibitor is preferably used in an amount of 0.001 to 1.00wt%, preferably 0.001 to 0.50wt%, and more preferably 0.001 to 0.10wt% based on the total mass of the diallyl phthalate resin and the acrylic compound;
Preferably, the polymerization inhibitor is selected from any one or more of hydroquinone, p-hydroxyanisole, 2, 6-di-tert-butyl-p-cresol, 2, 5-di-tert-butyl-hydroquinone, 2-tert-butyl-hydroquinone, p-benzoquinone, 2, 5-dihydroxytoluene, 1-diphenyl-2-trinitrophenyl hydrazine, N-diethylhydroxylamine, p-phenylenediamine, m-phenylenediamine, N-isopropylhydroxylamine, N-nitroso-N-phenylhydroxylamine aluminum, 4-hydroxy-2, 6-tetramethylpiperidine-1-oxygen radical;
Preferably, the catalyst is used in an amount of 0.5 to 3.0wt% based on the total mass of the diallyl phthalate resin and the acrylic compound;
Preferably, the catalyst is selected from any one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, potassium carbonate, sodium carbonate, triethylamine, tripropylamine, trioctylamine, dodecylamine, hexadecylamine, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, isopropyl zirconate, n-propyl zirconate, triisopropyl aluminate, and tribenzyl aluminate;
Preferably, the organic solvent is selected from any one or more of benzene, toluene, chlorobenzene, ethyl acetate, tetrahydrofuran, o-xylene, m-xylene, dichloromethane, dichloroethane and chloroform;
Preferably, the temperature of the first reflux reaction is 40-200 ℃, and preferably, the time of the first reflux reaction is 0.5-4 h;
Preferably, the temperature of the second reflux reaction is 20-200 ℃, preferably 60-160 ℃, further preferably 80-120 ℃, and preferably the time of the second reflux reaction is 4-24 h;
the off-gas generated by the second reflux reaction is preferably absorbed by a solvent, preferably any one or more of water, ethanol, diethyl ether, and chloroform.
8. The method according to claim 6 or 7, wherein the acrylic acid ester compound is selected from the group consisting of
Any one or more of the following.
9. A cured composition comprising a diallyl phthalate resin, wherein the diallyl phthalate resin is the modified diallyl phthalate resin of any of claims 1 to 5 or the diallyl phthalate resin is the modified diallyl phthalate resin obtainable by the method of any of claims 6 to 8.
10. The curing composition of claim 9, wherein the curing composition is any one of 3D printing, ink, paint, adhesive.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211297369.4A CN117946297A (en) | 2022-10-21 | 2022-10-21 | Modified diallyl phthalate resin, preparation method thereof and curing composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211297369.4A CN117946297A (en) | 2022-10-21 | 2022-10-21 | Modified diallyl phthalate resin, preparation method thereof and curing composition |
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| CN202211297369.4A Pending CN117946297A (en) | 2022-10-21 | 2022-10-21 | Modified diallyl phthalate resin, preparation method thereof and curing composition |
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