CN102504073A - Urethanation modified hybrid phenolic resin and preparation method thereof - Google Patents
Urethanation modified hybrid phenolic resin and preparation method thereof Download PDFInfo
- Publication number
- CN102504073A CN102504073A CN2011103554301A CN201110355430A CN102504073A CN 102504073 A CN102504073 A CN 102504073A CN 2011103554301 A CN2011103554301 A CN 2011103554301A CN 201110355430 A CN201110355430 A CN 201110355430A CN 102504073 A CN102504073 A CN 102504073A
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- China
- Prior art keywords
- phenol
- ammonia
- formaldehyde resin
- phenolic resin
- linear
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 77
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims abstract description 44
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 18
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 110
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- 229910021529 ammonia Inorganic materials 0.000 claims description 58
- 238000005886 esterification reaction Methods 0.000 claims description 53
- 230000004048 modification Effects 0.000 claims description 52
- 238000012986 modification Methods 0.000 claims description 52
- 230000032050 esterification Effects 0.000 claims description 51
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 238000007334 copolymerization reaction Methods 0.000 claims description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 24
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 21
- 239000003518 caustics Substances 0.000 claims description 21
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 20
- 229920002554 vinyl polymer Polymers 0.000 claims description 20
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 12
- WARQUFORVQESFF-UHFFFAOYSA-N isocyanatoethene Chemical class C=CN=C=O WARQUFORVQESFF-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 7
- 239000007859 condensation product Substances 0.000 claims description 6
- 229940100630 metacresol Drugs 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 125000004185 ester group Chemical group 0.000 claims description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 32
- 239000011248 coating agent Substances 0.000 abstract description 19
- 238000000576 coating method Methods 0.000 abstract description 19
- 239000002904 solvent Substances 0.000 abstract description 18
- 238000007639 printing Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 4
- ZTNJGMFHJYGMDR-UHFFFAOYSA-N 1,2-diisocyanatoethane Chemical class O=C=NCCN=C=O ZTNJGMFHJYGMDR-UHFFFAOYSA-N 0.000 abstract 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000005977 Ethylene Substances 0.000 abstract 1
- 229920003987 resole Polymers 0.000 description 74
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 26
- 229920005989 resin Polymers 0.000 description 23
- 239000011347 resin Substances 0.000 description 23
- 239000007787 solid Substances 0.000 description 21
- 239000000126 substance Substances 0.000 description 19
- 238000001514 detection method Methods 0.000 description 17
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 15
- 238000001228 spectrum Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 14
- 238000009835 boiling Methods 0.000 description 14
- 239000013065 commercial product Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 14
- 238000010907 mechanical stirring Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 239000000376 reactant Substances 0.000 description 14
- 238000010992 reflux Methods 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- 150000002148 esters Chemical class 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- -1 ammonia ester Chemical class 0.000 description 11
- 239000000975 dye Substances 0.000 description 11
- 229960003742 phenol Drugs 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000012296 anti-solvent Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 5
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 5
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- AMPCGOAFZFKBGH-UHFFFAOYSA-O [4-[[4-(dimethylamino)phenyl]-[4-(methylamino)phenyl]methylidene]cyclohexa-2,5-dien-1-ylidene]-dimethylazanium Chemical compound C1=CC(NC)=CC=C1C(C=1C=CC(=CC=1)N(C)C)=C1C=CC(=[N+](C)C)C=C1 AMPCGOAFZFKBGH-UHFFFAOYSA-O 0.000 description 4
- 230000002053 acidogenic effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 2
- XQCZBXHVTFVIFE-UHFFFAOYSA-N 2-amino-4-hydroxypyrimidine Chemical compound NC1=NC=CC(O)=N1 XQCZBXHVTFVIFE-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 2
- NPFYZDNDJHZQKY-UHFFFAOYSA-N 4-Hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 NPFYZDNDJHZQKY-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical group O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MDSVGJAUFNXYRR-TUNPWDSISA-N (2s)-n-[(4-aminocyclohexyl)methyl]-1-[(2r)-2-(methylamino)-3-phenylpropanoyl]pyrrolidine-2-carboxamide Chemical compound C([C@@H](NC)C(=O)N1[C@@H](CCC1)C(=O)NCC1CCC(N)CC1)C1=CC=CC=C1 MDSVGJAUFNXYRR-TUNPWDSISA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RPUJTMFKJTXSHW-UHFFFAOYSA-N 1-(methoxymethoxy)ethanol Chemical compound COCOC(C)O RPUJTMFKJTXSHW-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- RZTDESRVPFKCBH-UHFFFAOYSA-N 1-methyl-4-(4-methylphenyl)benzene Chemical group C1=CC(C)=CC=C1C1=CC=C(C)C=C1 RZTDESRVPFKCBH-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical class CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 1
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 1
- MVRPPTGLVPEMPI-UHFFFAOYSA-N 2-cyclohexylphenol Chemical compound OC1=CC=CC=C1C1CCCCC1 MVRPPTGLVPEMPI-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- BVLVGYXYGXOSOG-UHFFFAOYSA-N 2-hexoxybenzoic acid Chemical compound CCCCCCOC1=CC=CC=C1C(O)=O BVLVGYXYGXOSOG-UHFFFAOYSA-N 0.000 description 1
- ABMULKFGWTYIIK-UHFFFAOYSA-N 2-hexylphenol Chemical compound CCCCCCC1=CC=CC=C1O ABMULKFGWTYIIK-UHFFFAOYSA-N 0.000 description 1
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical class OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- JDFDHBSESGTDAL-UHFFFAOYSA-N 3-methoxypropan-1-ol Chemical compound COCCCO JDFDHBSESGTDAL-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241001479434 Agfa Species 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 229930192627 Naphthoquinone Natural products 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 241000405217 Viola <butterfly> Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- JVICFMRAVNKDOE-UHFFFAOYSA-M ethyl violet Chemical compound [Cl-].C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C1C=CC(=[N+](CC)CC)C=C1 JVICFMRAVNKDOE-UHFFFAOYSA-M 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 210000004884 grey matter Anatomy 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002496 iodine Chemical group 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- DSSXKBBEJCDMBT-UHFFFAOYSA-M lead(2+);octanoate Chemical compound [Pb+2].CCCCCCCC([O-])=O DSSXKBBEJCDMBT-UHFFFAOYSA-M 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical group 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical group 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- RINCXYDBBGOEEQ-UHFFFAOYSA-N succinic anhydride Chemical compound O=C1CCC(=O)O1 RINCXYDBBGOEEQ-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003459 sulfonic acid esters Chemical group 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000001017 thiazole dye Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000005259 triarylamine group Chemical group 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- MECHNRXZTMCUDQ-RKHKHRCZSA-N vitamin D2 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)/C=C/[C@H](C)C(C)C)=C\C=C1\C[C@@H](O)CCC1=C MECHNRXZTMCUDQ-RKHKHRCZSA-N 0.000 description 1
- 235000001892 vitamin D2 Nutrition 0.000 description 1
- 239000011653 vitamin D2 Substances 0.000 description 1
- 238000000207 volumetry Methods 0.000 description 1
Landscapes
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Urethanation modified hybrid phenolic resin is prepared through the following steps: the grafting of linear phenolic resin and ethylene monoisocyanates is conducted through the phenol hydroxyl urethanation reaction, then the linear phenolic resin serves as a high-polymer monomer to conduct the second radical linear polymerization independently or jointly with other ethylene monomers to obtain the hybrid phenolic resin; the weight-average molecular weight of the urethanation modified hybrid phenolic resin is 7.500 to 150.000; and the temperature of the softening point is 80 to 220 DEG C. The urethanation modified hybrid phenolic resin is used for thermosensitive flat printing plates, and can obviously enhance the solvent resistance and the durability of the thermal plate due to the existence of strongly polar urethane links, and the flat printing plate has the advantages of strong coating adhesion and toughness.
Description
Technical field
The invention belongs to printing technology, be specifically related to a kind of thermal CTP plate material with ammonia esterification modification hybrid phenol-formaldehyde resin and preparation method thereof.
Background technology
Lithography technique moves towards CTP technology (being called for short the CTP technology) from traditional laser photo film copy PS platemaking technology comprehensively, and the CTP plate is also popularized gradually.CTP plate kind is a lot, and that relatively popularizes comprises diffusion of silver salt CTP plate, UV-CTP version, purple laser polymerization CTP plate, thermal CTP plate material etc.Wherein most popular is thermal CTP plate material.At present, further improve the performance of heat-sensitive CTP plate, the solvent resistance and the Nai Yin ability that particularly improve plate are the thermal CTP plate material hot of research and development.
The anti-solvent of plate is meant the corrosion of the organic solvent in the anti-various printing chemical of printing plate, like washing oil, fountain solution, gum-solution, forme preserving agent, forme sanitising agent, the particularly corrosion of using in the printing of UV printing ink washing oil of printing ink.
Plate wear resistance and solvent resistance have certain cognation, but not absolute.In general, solvent resistance plate preferably generally has higher wear resistance, but the good plate of wear resistance not necessarily solvent resistance is all right, the particularly erosion of the plate printing ink of anti-UV.
The solvent resistance of raising heat-sensitive CTP plate plate and the method for Nai Yin ability are a lot; Wherein one of most important method is exactly the particularly exploitation of functional film-forming resin of printing plate organism; For example Kodak's patent CN101321632A is disclosed introduces phosphoric acid or diamantane side group at polymkeric substance, improves the chemical-resistant of plate.
Resol is a kind of important temperature-sensitive version film-forming resin, can improve the solvent resistance and the pressrun of temperature-sensitive version through modification, the modification of resol.
Printing plate generally is to carry out modification through the distant pawl group of phenolic hydroxyl group with modification, the modification of caustic solubility resol, for example EP-A 0934822 disclosed resol phenolic hydroxyl group and sulfonic group or carboxy moiety esterification modification.
The EP of Agfa Corp. [31] 02102446.8, CN1688441A disclose and a kind ofly through the distant pawl group of phenolic hydroxyl group resol have been carried out diazonium salt grafted method of modifying, are used for improving the chemical resistance of temperature-sensitive version.The Ai Kefa disclosed method is that resol is carried out the diazonium salt graft modification, forms azo-aromatic yl group (N=N-Q group, Q are aromatic group), improves chemical resistance of coating.
Fujiphoto [32] 2004.3.11 [33] JP [31] 2004-069478 has proposed main chain to have phenol skeleton and urea key (temperature-sensitive version resin NHCONH-) has solvent resistance.
Kodak proposes at WO2004/033206, in the macromolecule resin side chain, introduces the barbituric acid group, can obviously improve the solvent resistance and the wear resistance of plate coating.Kodak discloses a kind of method of passing through the phenolic hydroxyl group grafting barbituric acid group of resol.
Kodak discloses a kind of QHB modified phenolic resins at WO2004/033206 among the CN200380104739.7.The QHB modified phenolic resins is with iso-cytosine (2-amino-4-hydroxy pyrimidine) and isocyanate-modified resol, forms strong polarity tetrahydrochysene bonding structure, is used in i.e. second polymeric layer in multilayer heat-sensitive version upper strata, to improve the wear resistance of plate.
Fujiphoto JP 2000-7-13 2000-213142, CN01120259 have introduced a kind of Lighographic printing plate precursor; Contain three-dimensional POLYMETHYLENE POLYPHENYLISOCYANATE precrosslink structure and comprise the polymkeric substance of hydrophilic grafted chain, three-dimensional POLYMETHYLENE POLYPHENYLISOCYANATE precrosslink structure has improved the pressrun of printing plate.
Above-mentioned STUDY ON THE MODIFICATION OF PENOLIC RESIN, because phenolic hydroxyl group is partially enclosed, the caustic solubility of resin and plate more or less will arrive influenced.
Summary of the invention
The objective of the invention is to solve the anti-solvent ability of temperature-sensitive version that exists in the existing temperature-sensitive platemaking technology and the shortcoming of Nai Yin ability; Particularly improve the partially enclosed of that the anti-solvent ability of plate and Nai Yin ability exist because phenolic hydroxyl group through phenolic resin modified method, the caustic solubility of resin and plate will arrive affected shortcoming.A kind of brand-new ammonia esterification modification hybrid phenol-formaldehyde resin and preparation method thereof is provided, and the resol after the modification is used for heat-sensitive CTP plate and has good film-forming property, anti-solvent, advantage that pressrun is high, and the caustic solubility of plate is unaffected.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
Ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention; It is through phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates by linear phenolic resin; Carry out the hybrid phenol-formaldehyde resin that the second time, the radical linear polymerization obtained separately or with other vinyl monomer as high polymer monomer then, ammonia esterification modification hybrid phenol-formaldehyde resin weight-average molecular weight is 7500-150000; Softening temperature is 80-220 ℃.
Described linear phenolic resin is the linear condensation product of phenol, p-cresol, meta-cresol and composition thereof and formaldehyde, and molecular weight is 2500-14000.
Described vinyl monoisocyanates has following general structure:
In the formula, R
1Be Wasserstoffatoms or methyl, R
2Be ester group, penylene base or carbon-carbon single bond, r is the integer of 1-3, and phenolic hydroxyl group ammonia graft esterification rate is 10-90%.
Described other vinyl monomer is to contain at least a in the vinyl monomer that sulfoamido or active maleimide and N-thereof replace the caustic solubility verivate in the structure, and its weight accounts for the 10-50% of copolymerization weight.
The preparation method of ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention; With linear phenolic resin in reaction solvent; Heated and stirred to linear phenolic resin dissolving back adds catalyzer under the nitrogen protection condition, drips the vinyl monoisocyanates then, under 40-120 ℃, reacts to ammonia esterification terminal point; Unsaturated monoisocyanates and phenolic hydroxyl group molar ratio are 0.05-0.95, and catalyst levels is the 0.005-10% of unsaturated monoisocyanates monomer weight; Carry out the hybrid phenol-formaldehyde resin that the second time, the radical linear polymerization obtained separately or with other vinyl monomer as high polymer monomer then.
Elaborate in the face of the present invention down:
1, through the ammonia esterification, in resol, introduce strong polarity ammonia ester bond, introduce two keys simultaneously;
2, then with containing of ammonia esterification two keys the independent homopolymerization of resol radical or and other contain the extraordinary monomer copolymerization of caustic solubility group, form ammonia esterification modification hybrid phenol-formaldehyde resin;
3, introduce during copolymerization and contain alkali and dissolve group and the special wear-resisting group of anti-the solvent.
Strengthen the molecular resin amount owing to introduced strong polarity ammonia ester bond, the special wear-resisting group of anti-solvent the and repolymerization hydridization in the resin, the anti-solvent of plate, pressrun got and significantly improved.Simultaneously, for the second time free-radical polymerizedly introduced in structure that alkali dissolves that group has improved after the resol graft modification in the past that phenolic hydroxyl group reduces or caused the affected shortcoming of plate caustic solubility greatly because of the molecule quantitative change.
Synthetic route is in two steps:
1, at first passes through phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates by linear phenolic resin;
2, with the resol behind the grafting vinyl monoisocyanates, as high polymer monomer separately or and other extraordinary monomer that contains the caustic solubility group carry out the radical linear polymerization second time.
It below is detailed description of the present invention.
The present invention discloses a kind of ammonia esterification modification hybrid phenol-formaldehyde resin and preparation method thereof; It is by linear phenolic resin through phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates, carry out as high polymer monomer then that the radical linear polymerization obtains the second time separately or with other vinyl monomer.
Linear phenolic resin of the present invention is that phenols and aldehydes carry out the linear product that condensation reaction obtains.
Specifiable phenols example have phenol, m-cresol, p-cresol ,/to mixed methyl phenol, pyrogallol, isopropyl-phenol, tert.-butyl phenol, tert.-amyl phenol, hexylphenol, cyclohexylphenol, 3-methyl-4-chloro-uncle's 6-butylphenol and phenolic group verivate such as hydroxy styrenes or the like.
Specifiable aldehydes example alkanoic has formaldehyde, acetaldehyde, propenal, crotonaldehyde and aromatic series, heterocycle family aldehyde or the like
Linear phenolic resin of the present invention is preferentially selected the condensation product by P-F, hydroxy styrenes-formaldehyde or mixed phenol (phenol ,/to mixed methyl phenol)-formaldehyde, more preferably the linear condensation product of phenol, p-cresol, meta-cresol and composition thereof and formaldehyde for use.
Linear phenolic resin of the present invention is preferentially selected the linear condensation product of phenol, p-cresol, meta-cresol and composition thereof and formaldehyde for use, and synthesis technique can be referring to " new test chemistry " the 300th of a polymer chemistry piece of writing (1993, Japanese ball is apt to press).
The synthetic preferred 1000-100000 of linear phenolic resin weight-average molecular weight of the present invention, 2000-50000 more preferably most preferably is and is 2500-14000.
Commercial linear phenolic resin can companies such as one-tenth, Switzerland DKSH, Bakelite, Clariant GmbH, B.P. chemistry be buied from sky, Weihai.
Synthetic used unsaturated monoisocyanates (code name M) structural formula of ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention grafting is:
R
1Be Wasserstoffatoms or methyl, R
2Be ester group, penylene base or carbon-carbon single bond etc., r is the integer of 1-3.
Detailed example is stated structural formula as follows, but the present invention is not limited to the structural formula of following M1-M3.
M1
M2
M3
Polymkeric substance ammonia graft esterification reaction synthetic of the present invention, unsaturated monoisocyanates and the preferred 0.05-0.95 of phenolic hydroxyl group molar ratio, optimum is 0.1-0.9, and perhaps phenolic hydroxyl group ammonia graft esterification rate is preferred 5-95%, and optimum does
10-90%。
The reaction solvent of the unsaturated monoisocyanates of grafting must be the solvent that does not contain active proton hydrogen, as 1, and 4-dioxane, N, dinethylformamide, N,N-DIMETHYLACETAMIDE, methylethylketone, pimelinketone, ETHYLE ACETATE, toluene etc., or their mixture.Preferably adopt ammonia ester level N, N,N-DIMETHYLACETAMIDE or pimelinketone.
The catalyzer of the unsaturated monoisocyanates of grafting such as lead octoate 36, stannous octoate, dibutyl tin laurate, triethylenediamine, cobalt octoate, iron octoate etc. all can; Dibutyl tin laurate preferably; Consumption is the 0.005-10% of unsaturated monoisocyanates monomer weight of feeding intake, and optimum quantity is 0.05-5%.40-120 ℃ of graft reaction temperature is preferably in 60-110 ℃.
The ammonia esterification is accomplished the judgement of terminal point: the ammonia esterification is accomplished the sign of terminal point: disappear through peak, ir spectra detection of active NCO 2275 place; Or liquid phase gel chromatography detection of active NCO disappears the disappearance of the reverse volumetry detection of active of also available Di-n-Butyl Amine NCO.
Resol after the ammonia esterification and since grafting activity double key, also can be directly as the photosensitive resin and the film-forming resin of polymerizability negativity plate.
The resol further hydridization of the present invention after with the ammonia esterification.
Linear phenolic resin is through behind the phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates; Can be used as the independent homopolymerization of high polymer monomer or carry out the radical linearity copolymerization second time with other vinyl monomer, polymerization obtains ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention.
Homopolymerization: the resol behind the ammonia graft esterification is as the independent homopolymerization of high polymer monomer, and the hybrid phenol-formaldehyde resin that obtains is as temperature-sensitive version film-forming resin, and it still is phenolic hydroxyl group that its alkali dissolves group.Because the reaction of ammonia graft esterification will consume the part phenolic hydroxyl group; Certainly will influence the alkali capacitive of the hybrid phenol-formaldehyde resin that after polymerization obtains; So ammonia graft esterification rate can not be too high, the resol before the grafting selects for use hydroxyl value bigger as far as possible; The resol that caustic solubility is good is in order to avoid influence the caustic solubility of hybrid resin.
Copolymerization: the resol behind the ammonia graft esterification can carry out the linear copolymerization of the radical second time by other vinyl monomer as high polymer monomer.
Other vinyl monomer can be selected the monomer of any free redical copolymerization for use in theory, as contains following monomer and verivate vinyl monomer: the known monomer of (methyl) acrylic acid or the like, (methyl) esters of acrylic acid, (methyl) acrylic amide, vinyl ester, styrenic, vinyl cyanide, maleic anhydride class, maleimide, lactone or the like.
The monomer of preferentially selecting for use as the present invention; Should possess alkali and dissolve group; Can in hybrid resin, form side group alkali after the copolymerization hydridization and dissolve group; The caustic solubility of ammonia graft esterification reaction consumes part phenolic hydroxyl group loss can remedy owing to can remedy after polymerization resol molecular weight simultaneously and increase the caustic solubility influence that brings.
The vinyl monomer that possesses the caustic solubility group, specifiable as contain the vinyl monomer that group such as carboxyl, phenolic hydroxyl group, sulfonic group, phosphate, sulfoamido, active imide base and alkali thereof dissolve verivate.
As the monomer that the present invention preferentially selects for use, the above-mentioned vinyl monomer that possesses the caustic solubility group also can be further preferred.For solvent resistance and the wear resistance that increases hybrid resin; Preferably the big perhaps chemicals-resistant of polarity corrodes or the good known special engineering plastics polymerization single polymerization monomer of wear resistance; Possess simultaneously in the above-mentioned monomer this specific character monomer we preferably contain the vinyl monomer that sulfoamido or active maleimide and N-thereof replace the caustic solubility verivate, wherein the N-substituting group of maleimide must have caustic solubility.
Contain the vinyl monomer that sulfoamido or active maleimide and N-thereof replace the caustic solubility verivate, specifiable have N-(4-sulfoamido benzene) USAF RH-1, N-(4-ethyl sulfonamide base benzene) USAF RH-1, N-(4-benzenesulfonyl amine phenyl) USAF RH-1, N-(4-carboxyl benzene) USAF RH-1 maleimide, N-(4-hydroxybenzene) maleimide, N-(4-sulfoamido benzene) maleimide, N-(4-ethyl sulfonamide base benzene) maleimide, N-(4-benzenesulfonyl amine phenyl) maleimide, N-(4-carboxyl benzene) maleimide etc.
Optional random copolymerization of copolyreaction or block copolymerization, preferred random copolymerization.The initiator of radical polymerization comprises superoxide such as ditertiary butyl peroxide, benzoyl peroxide; Persulphate such as Potassium Persulphate, azo cpd such as Diisopropyl azodicarboxylate etc.; Reaction can be adopted letex polymerization, suspension polymerization or solution polymerization, preferably adopts solution polymerization.
Whole ammonia esterification hybrid modification reaction can adopt single stage method or two-step approach to accomplish; Preferably adopt single stage method synthetic, adopt single stage method, but reaction solvent must be the solvent that does not contain active proton hydrogen recited above; As 1; 4-dioxane, N, dinethylformamide, N,N-DIMETHYLACETAMIDE, methylethylketone, pimelinketone, ETHYLE ACETATE, toluene etc., or their mixture.Preferably adopt ammonia ester level N, N,N-DIMETHYLACETAMIDE or pimelinketone.40-110 ℃ of copolyreaction temperature is preferably in 50-100 ℃.
For the second time free-radical polymerized polymerization degree n ' control be the key that influences resin property; Can measure the molecular resin amount through gel permeation chromatography GPC; Estimation copolymerization for the second time polymerization degree n ' ≈ Mw (modified)/Mw (no-modified); Wherein Mw (modified) is resol weight-average molecular weight after the modification, and Mw (no-modified) so that control the Raolical polymerizable condition, adjusts resin property for resol weight-average molecular weight after the modification.
The weight-average molecular weight of ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention is 4000-300000, is preferably 6000-200000, most preferably is 7500-150000.Glass transition temperature is 30-300 ℃, is preferably 50-250 ℃, most preferably is 80-220 ℃.
Ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention, its purposes are to make positive thermosensitive CTP version.
Contain ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention and be used for temperature-sensitive flat stamping version; Can obviously strengthen the good solubility-resistence ability and the pressrun of temperature-sensitive version; This is that the flat stamping version has strong, the tough and tensile advantage of coating adhesion because strong polar ammonia ester bond exists in the ammonia esterification modification hybrid phenol-formaldehyde resin; Because of the linear polymerization hydridization second time, in resol, introduced the unique construction unit that contains the molten group of alkali again, improved the anti-dissolubility and the wear resistance of resin, the caustic solubility of resol is unaffected simultaneously.
Embodiment
Be synthetic instance of the present invention below, but the present invention is not limited to following instance.
12 sample P 01-P12 carry out ammonia esterification hybrid modification to resol, obtain corresponding modified product P01M-P12M respectively.
Resol P01-P12: all available from Switzerland DKSH.Comonomer is all competed available from the Shanghai thing.
Unsaturated monoisocyanates M1-M3 buys from Japanese Showa Denko K. K (SDK), M2 commercial disignation MOI.
Embodiment 1 (resol P01, modified phenolic resins P01M)
In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 565.7 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P01 (commercial product code: MV4020G; M/p=60/40; Mw ≈ 14000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 26.3gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 1.2gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain homopolymerization modified phenolic resins P01M.The performance table of seeing after.
Embodiment 2 (resol P02, modified phenolic resins P02M)
In the four-hole boiling flask of 1500 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 1091 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P02 (commercial product code: EPR6040A; M/p=40/60; Mw ≈ 2500), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 236.4gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 2.2gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain homopolymerization modified phenolic resins P02M.The performance table of seeing after.
Embodiment 3 (resol P03, modified phenolic resins P03M)
In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 598.5 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P03 (commercial product code: TR4020G; M/p=60/40; Mw ≈ 13000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 39.4gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 26.6g MI (maleimide), the dry DMAC that crosses of 66.5 g, 1.3gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P03M.The performance table of seeing after.
Embodiment 4 (resol P04, modified phenolic resins P04M)
In the four-hole boiling flask of 3000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 1058.3 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P04 (commercial product code: EPR5000B; MC/pC=50/50; Mw ≈ 3000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 223.3gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 423.3g MI (maleimide), the dry DMAC that crosses of 1058.3 g, 4.2gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P04M.The performance table of seeing after.
Embodiment 5 (resol P05, modified phenolic resins P05M)
In the four-hole boiling flask of 2000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 697g crosses through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P05 (commercial product code: PP3525G; P/phenol=35/65; Mw ≈ 11500), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 78.8gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 49.2g N-4ASAM [chemical name: N-4 (sulfoamido phenyl) acrylic amide], the dry DMAC that crosses of 123 g, 1.7gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P05M.The performance table of seeing after.
Embodiment 6 (resol P06, modified phenolic resins P06M)
In the four-hole boiling flask of 3000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 958.3g crosses through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P06 (commercial product code: MV6020G; M/p=40/60; Mw ≈ 3800), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 183.9gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 206.7g N-4ASAM [chemical name: N-4 (sulfoamido phenyl) acrylic amide], the dry DMAC that crosses of 516.8 g, 3gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P06M.The performance table of seeing after.
Embodiment 7 (resol P07, modified phenolic resins P07M)
In the four-hole boiling flask of 2000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 631.3 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P07 (commercial product code: EPR5010G; M/p=50/50; Mw ≈ 11000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 52.5gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 63.1g N-4HPAM [chemical name: N-4 (hydroxy phenyl) acrylic amide], the dry DMAC that crosses of 157.8g, 1.6gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P07M.The performance table of seeing after.
Embodiment 8 (resol P08, modified phenolic resins P08M)
In the four-hole boiling flask of 3000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 1025.5 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P08 (commercial product code: EPR6050G; M/p=40/60; Mw ≈ 4000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 210.2gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 273.5g N-4HPAM [chemical name: N-4 (hydroxy phenyl) acrylic amide], the dry DMAC that crosses of 683.8 g, 3.4gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P08M.The performance table of seeing after.
Embodiment 9 (resol P09, modified phenolic resins P09M)
In the four-hole boiling flask of 2000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 894g crosses through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P09 (commercial product code: MV4080G; M/p=60/40; Mw ≈ 5000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 157.6gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 63.1g N-4ASMI [chemical name: N-4 (sulfoamido phenyl) maleimide], the dry DMAC that crosses of 157.8 g, 2.1gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P09M.The performance table of seeing after.
Embodiment 10 (resol P10, modified phenolic resins P10M)
In the four-hole boiling flask of 2000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 726.8g crosses through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P10 (commercial product code: EP30B20G; M/p/mx=60/30/10; Mw ≈ 9000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 105.1gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 164.3g N-4ASMI [chemical name: N-4 (sulfoamido phenyl) maleimide], the dry DMAC that crosses of 410.8g, 2.4gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P10M.The performance table of seeing after.
Embodiment 11 (resol P11, modified phenolic resins P11M)
In the four-hole boiling flask of 2000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 729.8 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P11 (commercial product code: MXP5560BF; MC/mC/phenol=30/20/50; Mw ≈ 8000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 91.9gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 73.0g N-4HPMI [chemical name: N-4 (hydroxy phenyl) maleimide], the dry DMAC that crosses of 182.5 g, 1.8gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P11M.The performance table of seeing after.
Embodiment 12 (resol P12, modified phenolic resins P12M)
In the four-hole boiling flask of 5000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 1055.8g crosses through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P12 (commercial product code: EPR3050G; M/p=50/50; Mw ≈ 6500), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 222.3gMOI (methylacryoyloxyethyl isocyanic ester) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add the dry DMAC that crosses of 430.4g N-4HPMI [chemical name: N-4 (hydroxy phenyl) maleimide] 1076 g, 4.3gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P12M.The performance table of seeing after.
Embodiment 13 (resol P13, modified phenolic resins P13M)
In the four-hole boiling flask of 1000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 587.4 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P03 (commercial product code: TR4020G; M/p=60/40; Mw ≈ 13000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 24.2g M1 (allyl group monoisocyanates) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 24.9g MI (maleimide), the dry DMAC that crosses of 66.5 g, 1.3gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P13M.The performance table of seeing after.
Embodiment 14 (resol P14, modified phenolic resins P14M)
In the four-hole boiling flask of 2000 ml band temperature control heating, mechanical stirring, condensing reflux and nitrogen protection device, add the DMAC (N that 738.6 g cross through anhydrous sodium sulfate drying; The N-N,N-DIMETHYLACETAMIDE) and 200.0g resol P11 (commercial product code: MXP5560BF; MC/mC/phenol=30/20/50; Mw ≈ 8000), nitrogen protects 60 ℃ of heated and stirred to solid dissolving backs and adds the 1.0g dibutyl tin laurate, slowly splashes into 104.9gM3 (4-methylpropenyl-penylene based isocyanate) then; Reacted 4 hours, up to disappearing through peak, ir spectra detection of active NCO 2275 place.
In above-mentioned reaction solution, add 76.2g N-4HPMI [chemical name: N-4 (hydroxy phenyl) maleimide], the dry DMAC that crosses of 182.5 g, 1.8gAIBN (Diisopropyl azodicarboxylate), 23 hours afterreactions of 70 ℃ of reactions finish.Reactant is separated out in deionized water, washed, and 40 ℃ of vacuum-dryings obtain modification by copolymerization resol P11M.The performance table of seeing after.
Use above-mentioned unmodified resol P01-P14 respectively, ammonia esterification modification hybrid phenol-formaldehyde resin P01M-P14M makes comparative example and embodiment positive heat-sensitive flat stamping version that the temperature-sensitive coating contains above-mentioned resin.
The version base is handled: the used version base of the present invention is through electrolyzing and coarsening and anodic oxidation and carries out sealing of hole and handle the back aluminium plate base that its medullary ray average boldness is at 0. 2-0., 6 u m.Preferred 0. 3-0., 5 u m.Version base like this can make through the method for various electrolyzing and coarsening.Aluminium plate base of the present invention is the high purity aluminium plate, and its aluminium content is preferably in more than 99%.Suitable aluminium plate base is (being limited to this but lose): iron accounts for 0. 1%-0. 5%, silicon accounts for 0.03%-0.3%, copper accounts for 0. 003 %-0. 03 %, and titanium accounts for 0.01%-0.l%.The used electrolytic solution of electrolyzing and coarsening can be the aqueous solution of acid, alkali or salt or the aqueous solution that contains organic solvent.Wherein, it is better to make electrolytic solution with the aqueous solution of hydrochloric acid, nitric acid or their salt.At first be placed on aluminium plate in the aqueous solution of sodium hydroxide, Pottasium Hydroxide, yellow soda ash, water glass etc. of 1 %-30%, under 20-80 ℃ temperature, carry out the 5-250 chemical corrosion of second.Then in the nitric acid of 10%-30% or sulfuric acid with 20-70 ℃ temperature neutralization, to remove grey matter.Like this through the aluminium plate of clean, under 10-6O ℃ temperature, with square wave, bench-type ripple or the sine wave etc. of positive and negative interaction variation, with the current density of 5-100A/d ㎡, electrolysis treatment 10-300 second in the electrolytic solution of nitric acid or hydrochloric acid.Then, carry out anodize through electrolytic aluminium plate.Sulfuric acid process is used in anodic oxidation usually.The vitriolic concentration of using is 5-30%, and current density is 1-15A/d ㎡, and oxidizing temperature is at 20-60 ℃, and oxidization time is 5-250 second, to form the sull of 1-10 g/ ㎡.The sull that forms like this has higher sull micropore usually, and adsorptive power is stronger, is easy to adhere to foul.So also need carry out sealing of hole usually handles.Sealing of hole is handled can use various methods, is good with the 50-80% volume that reaches sealing sull micropore, simultaneously hydrophilicity-imparting treatment.
The maximum absorption wavelength scope of the contained infrared absorbing compounds of temperature-sensitive coating is 780-1100nm; Be selected from carbon black, triarylamine dyestuff, thiazole dye, indoline dye 、 oxazole dyestuff, cyanine dyes, polyaniline dye, polypyrole dye, polythiophene dye, methine dyes, naphthoquinone dyestuff, leuco dye and phthalocyanine pigment and dyestuff or the like, addition is the 0.5%-15% of total solid matters weight.
The temperature-sensitive coating contains dissolution inhibitor, and it contains polar group, can strengthen the hydrogen bonded intensity between the resin (like resol), reduces the solubleness of unexposed area figure layer, and it promotes the solubleness of ir radiation district figure layer under the protonic acid effect simultaneously.Dissolution inhibitor comprises low molecule quaternary ammonium salt, resol, sulphonate, SULPHOSUCCINIC ACID ESTER, aromatic carboxylic acid's ester, lactone ketone, aromatic hydrocarbons two sulfones, gathers particularly polyethylene glycols or the like of alkoxyl group ether.Addition is the 1%-20% of total solid matters weight.
The temperature-sensitive coating contains the thermic acidogenic agent, meets heat and can discharge strong protonic acid, can reduce the association intensity of dissolution inhibitor and resol.The thermic acidogenic agent comprises salt compounded of iodine class, sulfosalt class, pyridine salt, sulfonic acid esters, phosphoric acid ester, alicyclic ring ethers, triazines or the like.The addition of thermic acidogenic agent is the 1%-30% of total solid matters weight.
The temperature-sensitive coating contains dissolution accelerator, and it can improve dissolving sensitivity.Dissolution accelerator comprises organic acid, acid anhydrides, phenols or the like.Like sulfonic acid, phosphoric acid, alkyl benzene sulphonate(ABS), hexyloxy benzoic acid diacid, LAURIC ACID 99 MIN, xitix, diacetyl oxide, Tetra hydro Phthalic anhydride, maleic anhydride, chloromaleic acid acid anhydride, succinyl oxide, dihydroxyphenyl propane, p-NP, to oxyethyl group phenol, 2; 3; 4-trihydroxy-benzophenone, 4-hydroxy benzophenone or the like, the addition of dissolution accelerator are the 0.1%-10% of total solid matters weight.
The temperature-sensitive coating contains figure layer tinting material, and it comprises: purple in the pyoktanin blue, ethyl violet, Viola crystallina, crystallization, victoria blue, glossy dark green, oil blue, oil yellow, rhodamine B, pyoktanin blue rowland, malachite green, methylene blue, triazines or the like.Figure layer tinting material addition is the 0.1%-10% of total solid matters weight.
The temperature-sensitive coating contains tensio-active agent, can select nonionogenic tenside, amphoterics, silicon-containing surfactant, fluorochemical surfactant etc. for use.As betaines, stearin class, Sorbic Acid palm fibre grease class, polysiloxane-based, gather the fluoroalkyl ethers.The addition of tensio-active agent is the 0.01%-5% of total solid matters weight.
Preparation sensitization liquid solvent comprises: acetone; Methyl ethyl ketone; Hexanaphthene; ETHYLE ACETATE; Ethylene dichloride; THF; Toluene; EGME; Ethylene glycol ethyl ether; Glycol dimethyl ether; Propylene glycol monomethyl ether; Propylene-glycol ethyl ether; Methyl ethyl diketone; Pimelinketone; Diacetone alcohol; Ethylene glycol monomethyl ether acetate; Ethyl cellosolve acetate; Glycol isopropyl ether; The butyl glycol ether acetic ester; The 3-methoxypropanol; Methoxymethoxy ethanol; Diethylene glycol dimethyl ether; Diethylene glycol ether; Diethylene glycol dimethyl ether; Diethylene glycol diethyl ether; Propylene glycol methyl ether acetate; The propylene-glycol ethyl ether acetic ester; The N.N-N; Methyl-sulphoxide; Methyl lactate and ethyl lactate etc.Solvent can use with pure substance form or form of mixtures.The solid content of coating mixture is generally 2-50% (weight).
Photosensitive composition of the present invention usually with this field oneself know the technology coating (as cutter be coated with, blade coating, bar are coated with, roller coat, extrusion, coiling rod are coated with etc.) on the version base.Be dissolved in appropriate solvent to photosensitive composition of the present invention or/and in the water, be made into coating fluid.
Use above-mentioned unmodified resol P01-P14, ammonia esterification modification hybrid phenol-formaldehyde resin P01M-P14M makes the positive heat-sensitive flat stamping version 1-flat stamping version 24 that the temperature-sensitive coating contains above-mentioned resin.
Positive heat-sensitive flat stamping version coating formula:
Sensitization liquid (each component by weight)
Resol (uses P01-P12, P01M-P12M) 71 respectively separately
Acidogenic agent (4,4'-dimethyl diphenyl salt compounded of iodine hexafluorophosphate, Shenyang sensitization research institute) 10
Resistance solvent NS-5000 (Lucky Huaguang Graphics Co., Ltd.) 8
Infrared absorbing agents ADS830AT 6
Dissolution accelerator (tosic acid) 2
Tensio-active agent (BYK306) 1
Pyoktanin blue (CI42535) 2
1-methoxyl group-2-propyl alcohol 900
The above-mentioned sensitization liquid of extrusion coated on above-mentioned version base descended dry 60 seconds at 120 ℃ then, obtained the coating dry weight of 1.8g/ ㎡.
Solvent resistance is investigated: above-mentioned plate sample is immersed in ethylene glycol butyl ether 80% aqueous solution 20 minutes and Virahol 50% aqueous solution 30 minutes respectively, cleans mensuration plate coating loss with the sponge wiping.
The plate imaging performance is investigated: Kodak's all-victorious 800 heat-sensitive plate-makings mechanism version, and Lekai China light produces the imaging of TPD-III developing liquid developing, and MASTER VIEW MV-CTP scouring machine is measured plate development flexibility and site performance.
Pressrun is investigated: machine on the above-mentioned plate sample is normally printed (Beiren's four looks four are driven high speed rotary press), investigate its pressrun.
The plate performance is seen attached list.
Application result by subordinate list shows; Contain ammonia esterification modification hybrid phenol-formaldehyde resin of the present invention and be used for temperature-sensitive flat stamping version; Can obviously strengthen the good solubility-resistence ability and the pressrun of temperature-sensitive version; This is that the flat stamping version has strong, the tough and tensile advantage of coating adhesion because strong polar ammonia ester bond exists in the ammonia esterification modification hybrid phenol-formaldehyde resin; Because of the linear polymerization hydridization second time, in resol, introduced the unique construction unit that contains the molten group of alkali again, improved the anti-dissolubility and the wear resistance of resin, the caustic solubility of resol is unaffected simultaneously.
Table 1: plate application performance table
Above-mentioned all embodiment plate development flexibility and site performance all satisfy print request.
Claims (8)
1. ammonia esterification modification hybrid phenol-formaldehyde resin; It is characterized in that: it is through phenolic hydroxyl group ammonia esterification grafting vinyl monoisocyanates by linear phenolic resin; Carry out the hybrid phenol-formaldehyde resin that the second time, the radical linear polymerization obtained separately or with other vinyl monomer as high polymer monomer then, ammonia esterification modification hybrid phenol-formaldehyde resin weight-average molecular weight is 7500-150000; Softening temperature is 80-220 ℃.
2. ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 1 is characterized in that: described linear phenolic resin is the linear condensation product of phenol, p-cresol, meta-cresol and composition thereof and formaldehyde, and molecular weight is 2500-14000.
3. ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 1, it is characterized in that: described vinyl monoisocyanates has following general structure:
In the formula, R
1Be Wasserstoffatoms or methyl, R
2Be ester group, penylene base or carbon-carbon single bond, r is the integer of 1-3, and phenolic hydroxyl group ammonia graft esterification rate is 10-90%.
4. ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 1; It is characterized in that: described other vinyl monomer is to contain at least a in the vinyl monomer that sulfoamido or active maleimide and N-thereof replace the caustic solubility verivate in the structure, and its weight accounts for the 10-50% of copolymerization weight.
5. the preparation method of the described ammonia esterification modification of claim 1 hybrid phenol-formaldehyde resin; It is characterized in that: with linear phenolic resin in reaction solvent; Heated and stirred to linear phenolic resin dissolving back adds catalyzer under the nitrogen protection condition, drips the vinyl monoisocyanates then, under 40-120 ℃, reacts to ammonia esterification terminal point; Unsaturated monoisocyanates and phenolic hydroxyl group molar ratio are 0.05-0.95, and catalyst levels is the 0.005-10% of unsaturated monoisocyanates monomer weight; Carry out the hybrid phenol-formaldehyde resin that the second time, the radical linear polymerization obtained separately or with other vinyl monomer as high polymer monomer then.
6. the preparation method of ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 5 is characterized in that: described linear phenolic resin is the linear condensation product of phenol, p-cresol, meta-cresol and composition thereof and formaldehyde, and molecular weight is 2500-14000.
7. the preparation method of ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 5 is characterized in that: described vinyl monoisocyanates has following general structure:
In the formula, R
1Be Wasserstoffatoms or methyl, R
2Be ester group, penylene base or carbon-carbon single bond, r is the integer of 1-3, and phenolic hydroxyl group ammonia graft esterification rate is 10-90%.
8. the preparation method of ammonia esterification modification hybrid phenol-formaldehyde resin according to claim 5; It is characterized in that: described other vinyl monomer is to contain at least a in the vinyl monomer that sulfoamido or active maleimide and N-thereof replace the caustic solubility verivate in the structure, and its weight accounts for the 10-50% of copolymerization weight.
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| CN114702634A (en) * | 2022-03-16 | 2022-07-05 | 陕西科技大学 | Modified phenolic resin for 3D printing and preparation method thereof |
| CN114702634B (en) * | 2022-03-16 | 2023-07-07 | 陕西科技大学 | Modified phenolic resin for 3D printing and preparation method thereof |
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