CN108250408A - A kind of synthesis for hydrogenating phenol aldehyde type epoxy resin preparation method and applications resin - Google Patents
A kind of synthesis for hydrogenating phenol aldehyde type epoxy resin preparation method and applications resin Download PDFInfo
- Publication number
- CN108250408A CN108250408A CN201710531523.2A CN201710531523A CN108250408A CN 108250408 A CN108250408 A CN 108250408A CN 201710531523 A CN201710531523 A CN 201710531523A CN 108250408 A CN108250408 A CN 108250408A
- Authority
- CN
- China
- Prior art keywords
- hydrogenated bisphenol
- resin
- epoxy resin
- formaldehyde
- reaction
- 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.)
- Pending
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- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 78
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 77
- 229920005989 resin Polymers 0.000 title claims abstract description 45
- 239000011347 resin Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 13
- -1 phenol aldehyde Chemical class 0.000 title claims description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 230000005764 inhibitory process Effects 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000679 solder Inorganic materials 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003444 phase transfer catalyst Substances 0.000 claims abstract description 7
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 7
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 150000002989 phenols Chemical class 0.000 claims abstract 3
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract 2
- UNKQPEQSAGXBEV-UHFFFAOYSA-N formaldehyde;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical class O=C.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 UNKQPEQSAGXBEV-UHFFFAOYSA-N 0.000 claims description 75
- 239000004593 Epoxy Substances 0.000 claims description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000004925 Acrylic resin Substances 0.000 claims description 14
- 229920000178 Acrylic resin Polymers 0.000 claims description 14
- 239000000976 ink Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- 150000008065 acid anhydrides Chemical class 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 239000003112 inhibitor Substances 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000007792 addition Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 3
- PHRVSCXCYBJMDA-UHFFFAOYSA-N 1,1'-biphenyl;formaldehyde Chemical class O=C.C1=CC=CC=C1C1=CC=CC=C1 PHRVSCXCYBJMDA-UHFFFAOYSA-N 0.000 claims description 3
- HOYRZHJJAHRMLL-UHFFFAOYSA-N 2,6-dinitro-p-cresol Chemical compound CC1=CC([N+]([O-])=O)=C(O)C([N+]([O-])=O)=C1 HOYRZHJJAHRMLL-UHFFFAOYSA-N 0.000 claims description 3
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 3
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 3
- 229920006243 acrylic copolymer Polymers 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 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 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical class CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- SMOYQFCXYFMLQL-UHFFFAOYSA-M [P].[Br-].C(C1=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [P].[Br-].C(C1=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 SMOYQFCXYFMLQL-UHFFFAOYSA-M 0.000 claims description 2
- VLGMDPBTHVHBPP-UHFFFAOYSA-N [P].[Br-].C1(=CC=CC=C1)C(C1=CC=CC=C1)(C1=CC=CC=C1)[PH3+] Chemical compound [P].[Br-].C1(=CC=CC=C1)C(C1=CC=CC=C1)(C1=CC=CC=C1)[PH3+] VLGMDPBTHVHBPP-UHFFFAOYSA-N 0.000 claims description 2
- RIWQWHDNZIGXOI-UHFFFAOYSA-M [P].[Br-].C1(=CC=CC=C1)[P+](CC)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [P].[Br-].C1(=CC=CC=C1)[P+](CC)(C1=CC=CC=C1)C1=CC=CC=C1 RIWQWHDNZIGXOI-UHFFFAOYSA-M 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 claims description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- QCCWVNLOJADEAV-UHFFFAOYSA-N n,n-dimethyl-1h-pyrrol-3-amine Chemical class CN(C)C=1C=CNC=1 QCCWVNLOJADEAV-UHFFFAOYSA-N 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 2
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 238000009874 alkali refining Methods 0.000 claims 2
- 238000010612 desalination reaction Methods 0.000 claims 2
- 238000012805 post-processing Methods 0.000 claims 2
- 238000010992 reflux Methods 0.000 claims 2
- 230000001502 supplementing effect Effects 0.000 claims 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 239000002841 Lewis acid Substances 0.000 claims 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims 1
- 229940092714 benzenesulfonic acid Drugs 0.000 claims 1
- USFRYJRPHFMVBZ-UHFFFAOYSA-M benzyl(triphenyl)phosphanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)CC1=CC=CC=C1 USFRYJRPHFMVBZ-UHFFFAOYSA-M 0.000 claims 1
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 claims 1
- 125000002619 bicyclic group Chemical group 0.000 claims 1
- 238000006735 epoxidation reaction Methods 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 150000007517 lewis acids Chemical class 0.000 claims 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims 1
- 229920006324 polyoxymethylene Polymers 0.000 claims 1
- 238000002203 pretreatment Methods 0.000 claims 1
- 238000007142 ring opening reaction Methods 0.000 claims 1
- CQRYARSYNCAZFO-UHFFFAOYSA-N salicyl alcohol Chemical compound OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 abstract description 3
- 239000004843 novolac epoxy resin Substances 0.000 abstract description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract 2
- 229920001568 phenolic resin Polymers 0.000 abstract 2
- 239000005011 phenolic resin Substances 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 238000012938 design process Methods 0.000 abstract 1
- 238000012643 polycondensation polymerization Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 8
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 150000002118 epoxides Chemical class 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000000016 photochemical curing Methods 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WBOHXLDSPBIPTP-UHFFFAOYSA-N N,N-dimethyl-1,8-naphthyridin-4-amine Chemical compound CN(C1=CC=NC2=NC=CC=C12)C WBOHXLDSPBIPTP-UHFFFAOYSA-N 0.000 description 1
- ODJZWVFLHZHURI-UHFFFAOYSA-M [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] Chemical compound [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] ODJZWVFLHZHURI-UHFFFAOYSA-M 0.000 description 1
- JWAVKNHAOXJBAX-UHFFFAOYSA-M [P].[Cl-].C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound [P].[Cl-].C1(=CC=CC=C1)[P+](C1=CC=CC=C1)(C1=CC=CC=C1)C1=CC=CC=C1 JWAVKNHAOXJBAX-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- VIRPUNZTLGQDDV-UHFFFAOYSA-N chloro propanoate Chemical compound CCC(=O)OCl VIRPUNZTLGQDDV-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
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- 230000008023 solidification Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
Abstract
The present invention discloses a kind of synthesis of color inhibition high temperature resistant hydrogenation novolac epoxy resin preparation method and applications resin, under the conditions of this method is by nitrogen no oxygen, by the phenols of hydrogenation and paraformaldehyde or other hydrogenation class heterocycles in acid condition the hydrogenation phenolic resin of condensation polymerization, hydrogenation phenolic resin, epoxychloropropane, reducing agent and phase transfer catalyst heating are subjected to the first step again react, obtain the first reaction mixture；Under the action of basic catalyst, the mixture that above-mentioned steps are obtained carries out the second reaction, obtains epoxy resin；Hydrogenation novolac epoxy resin in the design process just hydrogenates phenyl ring, the resin has the characteristics that good high temperature resistance, color inhibition, cured film resistance to acid and alkali, solvent resistance and mechanical performance are outstanding compared with hydrogenated bisphenol A epoxy resin, is widely used in solder mask, photoresist, UV ink and coating, high-end copper-clad plate, composite material etc..
Description
Technical field
The present invention relates to a kind of preparation method of color inhibition high temperature resistant hydrogenation phenol aldehyde type epoxy resin and its in color inhibition
It is applied in LED-PCB white inks and photoresist.
Background technology
General purpose epoxy resin means bisphenol A type epoxy resin, has excellent physical mechanical strength, chemical-resistant resistance
The characteristics such as property, low-shrinkage, are widely used in high-new electronic information, nuclear power source exploitation, wind-power electricity generation, aerospace, automobile, height
Fast train, pressure vessel, advanced mold, communications and transportation, water conservancy, building, military project, remote conveying power transformation, long-distance sand transport are natural
All industries and emerging field of the national economy such as gas, oil drilling industry, just towards " seriation becomes more meticulous, decolorizable, special
With change, High Purity, environmentally protectiveization, cost performance maximize " etc. directions develop.
Containing undersaturated phenyl ring in bisphenol A type epoxy resin molecule segment structure, rich in double bond, in air or ultraviolet light
Be easily broken off under adverse circumstances, accelerate product aging, thus there are weatherability it is poor the shortcomings that, constrain outdoor application field,
Open source information shows that Japan is developed hydrogenated bisphenol A epoxy resin industrialization by Japanese Toto Kasei KK
The product come, this epoxy resin are that a color inhibition type epoxy resin has low viscosity, high transparency and the color that remains unchanged for a long period of time
Feature can cure at ambient temperature when making curing agent with amine or modified amine；General epoxy curing agent is substantially all can
To use；Solidfied material has good UV resistant performance；Solidfied material resisting ageing for long time, it is non-discolouring；Solidfied material has very
The good transparency；Higher heat resistance again, glass transition temperature is up to 80 DEG C or so during anhydride-cured；Solidfied material has good soft
Soft, caking property and water resistance；Solidfied material is normal with good acid and alkali resistance, chemical resistance and electrical property, low dielectric
Number.
Hydrogenated bisphenol A formaldehyde epoxy resin is the resistance to Huang of a kind of high temperature resistant researched and developed on the basis of hydrogenated bisphenol A epoxy resin
Become the special epoxy resin of high softening-point, a kind of color inhibition for adapting to the high speed development of semi-conductor industry and electronics industry and developing
Polyfunctional group glycidyl ether resin.There is the hydrogenation phenolic structure of color inhibition heatproof in resinous molecular structure, and have epoxy group,
High performance reticulated crosslinked rigid structure is easily formed after resin solidification, there is excellent thermal stability, electrical insulating property, mechanics is strong
Degree is high, and adhesive property is good, and contraction is small, and moisture-proof, chemical resistance are good.Another distinguishing feature of this resin is that softening point becomes
During change, epoxide number is substantially unchanged, imparts resin excellent technology stability and processing technology.It is the resistance to Huang of current high temperature resistant
Become the main adhesives of epoxy molding plastic, dependable performance, packaging technology is easy, is mainly used in laminated product, bonding electronics member
The encapsulating of device, special arc protection, heat-resisting, insulation and civilian light current product etc., is widely used in high-new sophisticated electronic
The encapsulating material of industry, semiconductor integrated circuit（IC）, large scale integrated circuit（LIC）Deng capacitance, resistance, triode, two
The encapsulation of pole pipe, potentiometer etc., this epoxy resin due to outstanding high temperature resistant anti-yellowing property LED industry obtain extensively should
With particularly color inhibition high temperature resistant LED-PCB-UV solder masks have good craftsmanship.Since melt viscosity is not with epoxide number
Variation, and there is good high temperature resistant anti-yellowing property, this patent product fills up domestic high temperature resistant color inhibition high softening-point at present
The blank of epoxy resin, can extensively using with high-end LED whites photosensitive solder resist ink and high-end LED whites UV photocuring welding resistances
Ink.
The present invention discloses a kind of high temperature resistant color inhibition hydrogenation phenol aldehyde type epoxy resin, can be extensively using white with high-end LED
Color sensation light solder mask and high-end LED whites UV photocuring solder masks, patent is also disclosed to be hydrogenated by high temperature resistant color inhibition
Phenol aldehyde type oxygen resin it is acrylic acid modified, synthesize the LED whites UV photocurings solder mask with high temperature resistant color inhibition with third
Olefin(e) acid resin；Simultaneously by introducing phthalic anhydride to hydrogenation phenolic epoxy acrylic resin；Synthesizing can be with the water-soluble hydrogenation of alkali
Epoxy novolac acrylic resin, available for preparing the LED white photosensitive solder resist ink alkali solubility epoxies third of high temperature resistant color inhibition
Olefin(e) acid performed polymer.
Invention content
The present invention relates to a kind of preparation method of color inhibition high temperature resistant hydrogenation phenol aldehyde type epoxy resin and its in color inhibition
It is applied in LED-PCB white inks and photoresist.
The present invention discloses the preparation method and skill of the hydrogenated bisphenol A formaldehyde epoxy resin in color inhibition high-temperature-resistant epoxy resin
Art scheme.
The present invention relates to a kind of synthetic methods of linear hydrogenated bisphenol A formaldehyde resin.
The manufacturing method of the linear hydrogenated bisphenol A formaldehyde resin of the present invention is characterized in that, according to hydrogenated bisphenol A and formaldehyde
Molar ratio 1:1-1.4:1, with careless acid as catalyst, prepare the linear hydrogenated bisphenol A formaldehyde resin of different softening point.
The invention discloses a kind of preparation methods of linear hydrogenated bisphenol A formaldehyde resin to include the following steps：
Under nitrogen protective condition by hydrogenated bisphenol A, acidic catalyst, MIBK solvents, in reaction kettle stirring and dissolving, heat temperature raising
To 80-100 DEG C, equimolar than 30% paraformaldehyde aqueous solution is added drop-wise to reaction kettle by head tank, paraformaldehyde is water-soluble
Liquid is added dropwise to complete within 2 hours；And 6 hours are reacted at this temperature.MIBK solvents and generation are distilled out under normal pressure
Water after then solvent is sloughed in decompression, is washed with boiling water and repeatedly removes unreacted hydrogenated bisphenol A, last decompression dehydration obtains
The linear solids hydrogenated bisphenol A formaldehyde resin of light colour.
It is characterized in that preferred, linear hydrogenated bisphenol A formaldehyde resin raw material hydrogenated bisphenol A and paraformaldehyde feed intake
Than for（1.1-1.4）：1, oxalic acid rate of charge is the 1-2% of phenolic aldehyde batch mixing quality.
It is characterized in that preferred, the acidic catalyst is oxalic acid, p-methyl benzenesulfonic acid, hydrochloric acid, one kind in phosphoric acid or
Person is several.
The present invention relates to a kind of synthetic methods of linear hydrogenated bisphenol A formaldehyde epoxy resin.
The manufacturing method of the linear hydrogenated bisphenol A formaldehyde epoxy resin of the present invention is characterized in that, upper step is produced
Linear hydrogenated bisphenol A formaldehyde resin and the epoxychloropropane throwing more than linear hydrogenated 3-12 times of molal weight of bisphenol A formaldehyde resin
Enter reaction kettle.Color inhibition high temperature resistant hydrogenated bisphenol A formaldehyde epoxy resin is obtained by the reaction by open loop and alkaline ring closure.
A）In the absence of oxygen, turn the hydrogenated bisphenol A formaldehyde resin prepared, epoxychloropropane, reducing agent and mutually
Shifting catalyst heating carries out the first reaction, obtains the first reaction mixture.
B）Under the action of basic catalyst, by above-mentioned steps A）It is anti-that the first obtained reaction mixture carries out the second epoxy closed loop
Should, obtain hydrogenated bisphenol A formaldehyde epoxy resin.
It is characterized in that preferred, the reducing agent is Al, Zn, Fe, Na2SO3、FeSO4One or more of.
It is characterized in that preferred, the phase transfer catalyst is triphenylphosphine, etamon chloride, tetrabutyl phosphonium bromide
Ammonium, benzyltriethylammoinium chloride, benzyltrimethylammonium chloride, triphenylmethylphosphonium bromide phosphorus, triphenyl ethyl phosphonium bromide phosphorus, benzyl three
One or more of tetraphenylphosphonium chloride phosphorus, benzyltriphenylphosphonium bromide phosphorus, cetyl trimethylammonium bromide.
It is characterized in that preferred, the basic catalyst is NaOH solution, K2CO3Solution, KOH solution, Na2CO3Solution
In it is one or more.
It is characterized in that preferred, the mass ratio of the reducing agent and hydrogenated bisphenol A formaldehyde resin is（0.00015~
0.0025）：1.
It is characterized in that preferred, the mass ratio of the epoxychloropropane and hydrogenated bisphenol A formaldehyde resin is（3~12）：
1。
It is characterized in that preferred, the mass ratio of the phase transfer catalyst and hydrogenated bisphenol A formaldehyde resin is（0.0005
~0.005）：1.
It is characterized in that preferred, the mass concentration of the basic catalyst is 30~50%, molten in the basic catalyst
Matter and the mass ratio of hydrogenated bisphenol A formaldehyde resin are（0.025~0.5）：1.
It is characterized in that preferred, the time of first reaction is 4~8 hours；The time of second reaction for 3~
6 hours；The pressure of second reaction is 0.01~0.1MPa.
It is characterized in that preferred, the temperature of first reaction is 60~80 DEG C；The temperature of second reaction is 60
~90 DEG C.
The present invention provides a kind of high temperature resistant color inhibition hydrogenated bisphenol A first applied in LED white inks and photoresist
Aldehyde epoxy acrylic resin, which is characterized in that the hydrogenated bisphenol A formaldehyde epoxy resin including prepared by this patent carries out acrylic acid
Change, obtaining can be with the cured epoxy acrylate prepolymer of UV；It can be used to prepare the pure white high temperature resistant color inhibition UV solder masks of LED.
The present invention provides a kind of heatproof color inhibition alkali solubility A Hydrogenated Bisphenol As applied in LED white inks and photoresist
A formaldehyde epoxy acrylic resins, which is characterized in that the hydrogenated bisphenol A formaldehyde epoxy resin including prepared by this patent carries out third
Olefin(e) acid, obtaining can be with the cured epoxy acrylate prepolymer of UV；It is again that this UV epoxy acrylate prepolymer and tetrahydrophthalic anhydride is anti-
Should, it obtains to can be used to prepare the pure white high temperature resistant color inhibition photosensitive solder resist oil of LED with buck dissolubility epoxy acrylate prepolymer
Ink.
The present invention provides a kind of preparation method of hydrogenated bisphenol A formaldehyde epoxy acrylic resin, in the absence of oxygen,
In terms of mass fraction, 100 parts of the hydrogenated bisphenol A formaldehyde epoxy resin is taken, temperature is adjusted to 85~100 DEG C, is added in
0.05-2 parts of polymerization inhibitor, 0.3-3 parts of catalyst, are stirring evenly and then adding into 9-16 parts of acrylic acid；Then heat to 105
~125 DEG C, insulation reaction to acid value drops to below 5mgKOH/g and stops reaction, obtains acrylic acid modified epoxy acrylic
Copolymer UV resin solutions；The polymerization inhibitor is p methoxy phenol, 2,6- di-t-butyl -4- methylphenols, to benzene
Diphenol, p-tert-Butylcatechol or 2,6- dinitro-p-cresol；The catalyst is triphenylphosphine, 4- dimethylamino pyrroles
Pyridine, tetrabutylammonium bromide, tetraethylammonium bromide, benzyltriethylammoinium chloride or triethylamine.
The present invention provides a kind of preparation method of buck dissolubility hydrogenated bisphenol A formaldehyde epoxy acrylic resin, in anaerobic
Under conditions of, in terms of mass fraction, take the DBE solvents of the quality such as 100 parts of additions of product in step (0027), temperature adjustment
To 90~100 DEG C, 8-20 parts of acid anhydrides is added in, then heats to 105~125 DEG C, insulation reaction to acid value is substantially not
Until change, the buck dissolubility hydrogenated bisphenol A formaldehyde epoxy acrylic UV resins of high temperature resistant color inhibition are obtained；The acid anhydrides is four
Hydrogen phthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride or horse
Carry out acid anhydrides
Specific embodiment
For a further understanding of the present invention, the preferred A Hydrogenated Bisphenol A of phenol aldehyde type epoxy resin is hydrogenated to the present invention with reference to embodiment
A formaldehyde epoxy resin synthesis embodiment is described, but it is to be understood that these descriptions are intended merely to further illustrate this hair
Bright feature and advantage rather than the limitation to invention claim.
The invention discloses a kind of preparation methods of linear hydrogenated bisphenol A formaldehyde resin, include the following steps：
Under nitrogen protective condition by 100g hydrogenated bisphenol As, 4g acidic catalysts, 100g MIBK solvents, reaction kettle stir it is molten
Solution, is heated to 80-100 DEG C, 30% 18g paraformaldehydes aqueous solution is added drop-wise to reaction kettle by head tank, solution is 2
It is added dropwise to complete in a hour；And 6 hours are reacted at this temperature.MIBK solvents and the water generated are distilled out under normal pressure, so
After solvent is sloughed in decompression afterwards, the hydrogenated bisphenol A that repeatedly removal is reaction is washed with boiling water, last decompression dehydration obtains Transparent color
Linear solids hydrogenated bisphenol A formaldehyde resin.
The invention discloses a kind of preparation methods of linear hydrogenated bisphenol A formaldehyde epoxy resin, include the following steps：
A) in the absence of oxygen, linear hydrogenated bisphenol A formaldehyde resin 100g, 800g epoxy chloropropionate previous step produced
Alkane, reducing agent and phase transfer catalyst heating carry out the first reaction, obtain the first reaction mixture；
B）Under the action of basic catalyst, by above-mentioned steps A）It is anti-that the first obtained reaction mixture carries out second step closed loop
Should, obtain linear hydrogenated bisphenol A formaldehyde epoxy resin.
In the absence of oxygen, hydrogenated bisphenol A formaldehyde resin, epoxychloropropane, reducing agent and phase transfer are urged by the present invention
Agent heating reacts, i.e. addition open loop obtains the intermediary of chloropharin ether structure, obtains the first reaction mixture, then in alkalinity
Under the action of catalyst, the second epoxy ring-closure reaction occurs for above-mentioned first reaction mixture, obtains hydrogenated bisphenol A formaldehyde asphalt mixtures modified by epoxy resin
Fat.The present invention is segmented reaction and specific reaction condition by two steps, it is suppressed that the generation of side reaction.The hydrogen that the present invention obtains
Changing bisphenol A formaldehyde epoxy resin has a relatively low epoxide equivalent, and hydrolyzable chlorine content in 300ppm hereinafter, simultaneously, this hair
The hydrogenated bisphenol A formaldehyde epoxy resin color of bright preparation is shallower, and chromatic value 1 expands hydrogenated bisphenol A formaldehyde epoxy resin
Application range.
The present invention is after above-mentioned hydrogenated bisphenol A formaldehyde epoxy resin is obtained, to further improve hydrogenated bisphenol A formaldehyde epoxy
The purity of resin reduces the hydrolyzable chlorine content in hydrogenated bisphenol A formaldehyde epoxy resin, the hydrogenation preferably obtained to above-mentioned steps
Bisphenol A formaldehyde epoxy resin is refined.Refined method is not particularly limited in the present invention, with known to those skilled in the art
Bisphenol A formaldehyde epoxy resin process for purification, preferably follow the steps below, in the effect of the second basic catalyst
Under, the hydrogenated bisphenol A formaldehyde epoxy resin that above-mentioned steps obtain is dissolved in organic solvent and carries out third reaction, then passes through diatom
Further purification obtains refined hydrogenated bisphenol A formaldehyde epoxy resin for soil filtering.
The temperature of the third reaction is preferably 70~100 DEG C, more preferably 75~85 DEG C；The time of the third reaction
Preferably 1~3 hour, more preferably 2 hours；The organic solvent is preferably ethylene glycol, toluene, ethylbenzene, dimethylbenzene, isopropyl
Alcohol, methyl ethyl ketone or methyl iso-butyl ketone (MIBK), more preferably toluene, methyl iso-butyl ketone (MIBK) or isopropanol；The organic solvent with it is linear
The mass ratio of hydrogenated bisphenol A formaldehyde epoxy resin is preferably（2~8）：1, more preferably（3~7）：1.
Second basic catalyst is preferably KOH solution, K2CO3Solution, NaOH solution, Na2CO3One kind in solution
Or a variety of, more preferably KOH solution, K2CO3Solution, NaOH solution or Na2CO3, most preferably KOH solution or NaOH solution；Institute
It is preferably 40~50% to state the second basic catalyst mass concentration, and more preferably 45%；In second basic catalyst solute with
The mass ratio of hydrogenated bisphenol A formaldehyde epoxy resin is preferably（0.01~0.1）：1, more preferably（0.025~0.06）：1.
The pressure that the present invention reacts above-mentioned third is not particularly limited, with A Hydrogenated Bisphenol A well known to those skilled in the art
The pressure of A formaldehyde epoxy resin refining reactions；The other conditions of above-mentioned reaction are not particularly limited in the present invention, preferably exist
After refining reaction, add in deionized water and washed, filter, finally slough organic solvent and obtain refined hydrogenated bisphenol A
Formaldehyde epoxy resin.Deionized water is not particularly limited in the present invention, is gone with well known to those skilled in the art for washing
Ionized water；The method of filtering is not particularly limited in the present invention, with filter method well known to those skilled in the art；
The method for sloughing organic solvent is not particularly limited in the present invention, and the method with desolventizing well known to those skilled in the art is
Can, obtain refined hydrogenated bisphenol A formaldehyde epoxy resin.
The hydrogenated bisphenol A formaldehyde epoxy resin that the above method of the present invention is used to be prepared is detected, the results showed that,
Epoxide equivalent content be 201g/eq, hydrolyzable chlorine content 150ppm, content of inorganic chlorine 1ppm, chromatic value 1.
The present invention provides a kind of preparation method of hydrogenated bisphenol A formaldehyde epoxy acrylic resin, in the absence of oxygen,
In terms of mass fraction, 100 parts of the hydrogenated bisphenol A formaldehyde resin that patent system of the present invention is standby is taken, temperature is adjusted to 85~
100 DEG C, 0.05 part of polymerization inhibitor, 0.6 part of catalyst are added in, is stirring evenly and then adding into 36 parts of acrylic acid；Then heat to 105
~125 DEG C, insulation reaction to acid value drops to below 5mgKOH/g and stops reaction, obtains acrylic acid modified hydrogenated bisphenol A first
Aldehyde epoxy acrylic copolymers UV resin solutions；The polymerization inhibitor is p methoxy phenol, 2,6- di-t-butyl -4- first
Base phenol, hydroquinone, p-tert-Butylcatechol or 2,6- dinitro-p-cresol；The catalyst is triphenylphosphine, 4-
Dimethylamino naphthyridine, tetrabutylammonium bromide, tetraethylammonium bromide, benzyltriethylammoinium chloride or triethylamine.
The present invention provides a kind of preparation method of buck dissolubility hydrogenated bisphenol A formaldehyde epoxy acrylic resin, in anaerobic
Under conditions of, in terms of mass fraction, take the DBE solvents of the quality such as 100 parts of additions of product in step (0037), temperature adjustment
To 90~100 DEG C, 15 parts of acid anhydrides is added in, then heats to 105~125 DEG C, insulation reaction to acid value is basically unchanged
Until, obtain the alkali solubility hydrogenated bisphenol A formaldehyde epoxy acrylic photosensitive-ink resin of high temperature resistant color inhibition；The acid anhydrides is four
Hydrogen phthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride or horse
Carry out acid anhydrides.
Other hydrogenated biphenyl DCPD-containing epoxy resins, hydrogenated biphenyl formaldehyde epoxy resin, hydronaphthol bicyclic penta 2
Alkene epoxy resin, hydronaphthol formaldehyde epoxy resin, hydrogenated bisphenol A DCPD-containing epoxy resin, hydrogenation novolac epoxy resin,
It hydrogenates the hydrogenation phenolic high temperature resistant color inhibition special epoxy resin such as o-cresol formaldehyde epoxy resin or hydrogenation phenol and no phenyl ring is miscellaneous
Cyclics epoxy resin synthesis technology and this patent hydrogenated bisphenol A formaldehyde epoxy resin synthesis technology and acrylic acid modified tree
Aliphatic radical sheet is similar.
Fig. 1 is hydrogenated bisphenol A formaldehyde epoxy resin structural figure
Fig. 2 is hydrogenated bisphenol A DCPD-containing epoxy resin
Fig. 3 is hydrogenated biphenyl formaldehyde epoxy resin
Fig. 4 is hydrogenated biphenyl DCPD-containing epoxy resin
Fig. 5 is hydronaphthol formaldehyde epoxy resin
Fig. 6 is hydronaphthol DCPD-containing epoxy resin
Fig. 7 is hydrogenated bisphenol A formaldehyde resin synthesis route
Fig. 8 is hydrogenated bisphenol A formaldehyde epoxy resin synthesis route
Fig. 9 is hydrogenated bisphenol A formaldehyde epoxy acrylic resin synthesis route
Figure 10 is alkali solubility hydrogenated bisphenol A formaldehyde epoxy acrylic resin synthesis route.
Claims (10)
1. a kind of high temperature resistant color inhibition hydrogenates the preparation method of phenol aldehyde type epoxy resin and its in color inhibition LED-PCB white ink
With the application in photoresist, which is characterized in that the various hydrogenation phenols such as its structural formula such as formula (1) (2) (3) (4) (5) (6)
With aldehydes or hydrogenation phenols with heterocyclic without the weather-proof extraordinary hydrogenation phenolic epoxy of color inhibition high temperature resistant that benzene ring structure forms
Resin is exemplified below structural formula：
Structural formula（1）Hydrogenated bisphenol A formaldehyde epoxy resin
Structural formula（2）Hydrogenated bisphenol A DCPD-containing epoxy resin
Structural formula（3）Hydrogenated biphenyl formaldehyde epoxy resin
Structural formula（4）Hydrogenated biphenyl DCPD-containing epoxy resin
Structural formula（5）Hydronaphthol formaldehyde epoxy resin
Structural formula（6）Hydronaphthol DCPD-containing epoxy resin.
2. various high temperature resistant color inhibition hydrogenation phenol aldehyde type epoxy resins, patent of the present invention select hydrogenation according to claim 1
The preparation method of bisphenol A formaldehyde epoxy resin illustrates, and other structures synthesis technology is substantially similar, and following steps are included such as
Under：
（1）The synthesis of linear hydrogenated bisphenol A formaldehyde resin, it is characterised in that：Using hydrogenated bisphenol A and solid polyformaldehyde as original
Expect, nitrogen protection is led in reaction process, after pretreatment of raw material, in acidic catalyst, is reacted at 80-100 DEG C, formaldehyde
The ortho position of the higher phenolic hydroxyl group of cloud density in the carbonium ion attack hydrogenated bisphenol A of formation forms hydroxymethyl phenol, then into one
Step is condensed, reflux dewatering in reaction process, after reaction supplementing solvent, after washing desalination, adds alkali refining, then through water
It washes, neutralize, filtering, the post processings such as desolventizing, obtaining linear hydrogenated bisphenol A formaldehyde resin,
（2）The synthesis of high temperature resistant color inhibition hydrogenated bisphenol A formaldehyde epoxy resin, it is characterised in that：With in claim 2（1）System
Into linear hydrogenated bisphenol A formaldehyde resin and epoxychloropropane, reducing agent and phase transfer catalyst be raw material, lead in reaction process
Nitrogen is protected, and after pretreatment of raw material, using lewis acid as catalyst, etherificate ring-opening reaction is carried out at 85~105 DEG C, obtains chlorine
Alcohol ether is first step reaction, and alkali is then added in into reaction system, and it is that closed loop epoxidation reaction is carried out at 100~105 DEG C
Two steps are reacted, reflux dewatering in reaction process, after reaction supplementing solvent, after washing desalination, add alkali refining, then through water
It washes, neutralize, filtering, the post processings such as desolventizing, obtaining high temperature resistant color inhibition hydrogenated bisphenol A formaldehyde epoxy resin.
3. according in claim 2（1）The preparation method, which is characterized in that acidic catalyst described in A. is oxalic acid, to first
One or several kinds in benzene sulfonic acid, hydrochloric acid, phosphoric acid, B. pretreatments of raw material are that hydrogenated bisphenol A, acidic catalyst, MIBK is molten
Agent, in reaction kettle stirring and dissolving, the molar ratio of C. hydrogenated bisphenol As and paraformaldehyde is between 1.1-1.4.
4. according in claim 2（2）The preparation method, which is characterized in that reducing agent described in A. is Na2SO3、FeSO4In
One or more, phase transfer catalyst described in B. for triphenylphosphine, etamon chloride, tetrabutylammonium bromide, three second of benzyl
Ammonium chloride, benzyltrimethylammonium chloride, triphenylmethylphosphonium bromide phosphorus, triphenyl ethyl phosphonium bromide phosphorus, benzyltriphenylphosphonium chloride,
One or more of benzyltriphenylphosphonium bromide phosphorus, the mass ratio of reducing agent described in C. and linear hydrogenated bisphenol A formaldehyde resin are
（0.00015~0.0025）：The mass ratio of epoxychloropropane described in 1, D. and linear hydrogenated bisphenol A formaldehyde resin is（3~15）：
The mass ratio of phase transfer catalyst described in 1, E. and linear hydrogenated bisphenol A formaldehyde resin is（0.0005~0.005）：Described in 1, F.
Basic catalyst is sodium hydroxide solution, potassium hydroxide solution, and mass concentration is molten in basic catalyst described in 35~50%, G.
Matter and the mass ratio of linear hydrogenated bisphenol A formaldehyde resin are（0.025~0.5）：1.
5. according in claim 2（2）The preparation method, which is characterized in that the time of first reaction is small for 4~8
When；The time of second reaction is 3~6 hours；The pressure of second reaction is 0.01~0.1MPa, first reaction
Temperature be 60~95 DEG C；The temperature of second reaction is 60~120 DEG C.
6. according in claim 2（2）The preparation method, which is characterized in that the step（2）Specially：It is anti-first
It answers and the second reaction of basic catalyst progress is added dropwise in mixture, obtain hydrogenated bisphenol A formaldehyde epoxy resin.
7. the present invention provides a kind of heatproof color inhibition hydrogenated bisphenol A formaldehyde rings applied in LED white inks and photoresist
Oxypropylene acid resin preparation method, which is characterized in that the hydrogenated bisphenol A formaldehyde epoxy resin including prepared by this patent carries out third
Olefin(e) acid, obtaining can be with the cured epoxy acrylate prepolymer of UV；It can be used to prepare the pure white high temperature resistant color inhibition UV welding resistances oil of LED
Ink reacts the cured hydrogenated bisphenol A formaldehyde epoxy acrylate prepolymers of UV prepared by this patent with tetrahydrophthalic anhydride, and obtaining can be with
Alkali solubility hydrogenated bisphenol A formaldehyde epoxy acrylate prepolymer can be used to prepare the pure white photosensitive solder resist ink of LED.
8. the present invention provides a kind of preparation method of hydrogenated bisphenol A formaldehyde epoxy acrylic resin, in the absence of oxygen, with
Mass fraction meter takes 100 parts of the hydrogenated bisphenol A formaldehyde epoxy resin, and temperature is adjusted to 85~100 DEG C, adds in resistance
Poly- agent 0.05-2 parts, 0.3-3 parts of catalyst, are stirring evenly and then adding into 9-16 parts of acrylic acid；Then heat to 105
~125 DEG C, insulation reaction to acid value drops to below 5mgKOH/g and stops reaction, obtains acrylic acid modified epoxy acrylic
Copolymer UV resin solutions；The polymerization inhibitor is p methoxy phenol, 2,6- di-t-butyl -4- methylphenols, to benzene
Diphenol, p-tert-Butylcatechol or 2,6- dinitro-p-cresol；The catalyst is triphenylphosphine, 4- dimethylamino pyrroles
Pyridine, tetrabutylammonium bromide, tetraethylammonium bromide, benzyltriethylammoinium chloride or triethylamine.
9. the present invention provides a kind of preparation method of alkali solubility hydrogenated bisphenol A formaldehyde epoxy acrylic resin, in the item of anaerobic
Under part, in terms of mass fraction, the quality such as 100 parts of additions of product hydrogenated bisphenol A formaldehyde epoxy acrylic resin in step are taken
DBE solvents, temperature adjusted to 90~100 DEG C, adds in 8-20 part of acid anhydrides, then heats to 105~125 DEG C, guarantor
Temperature reaction obtains the alkali solubility epoxy acrylic UV resins of high temperature resistant color inhibition until acid value is basically unchanged；The acid anhydrides
For tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride
Or maleic anhydride.
10. other high temperature resistant color inhibitions hydrogenation phenolic aldehyde based epoxy resin such as hydrogenated bisphenol A according to patent of the present invention is bicyclic
The preparation side of pentadiene epoxy resin etc. and its acrylic modified epoxy resin and alkali solubility hydrogenation epoxy novolac acrylic resin
Method is similar with more than claim 1-9.
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| CN112111187A (en) * | 2019-08-19 | 2020-12-22 | 信和新材料股份有限公司 | Ultraviolet-curing anticorrosive coating and preparation method and application thereof |
| CN113721422A (en) * | 2021-09-01 | 2021-11-30 | 大同共聚(西安)科技有限公司 | Preparation method of insulating protective layer on wiring board |
| CN114773786A (en) * | 2022-04-18 | 2022-07-22 | 天津珂赛思道路工程有限公司 | High-performance yellowing-resistant material |
| CN115386092A (en) * | 2022-08-11 | 2022-11-25 | 金发科技股份有限公司 | Epoxy resin modified polyformaldehyde, polyformaldehyde composition, and preparation method and application thereof |
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| JP2015165332A (en) * | 2015-05-29 | 2015-09-17 | 互応化学工業株式会社 | Photosensitive resin composition, composition for solder resist, and printed wiring board |
| CN105778618A (en) * | 2014-12-25 | 2016-07-20 | 上海飞凯光电材料股份有限公司 | Preparation method of liquid light-cured solder resist ink and photosensitive resin thereof |
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| CN102838727A (en) * | 2011-06-24 | 2012-12-26 | 中国石油化工集团公司 | Preparation method for high softening point o-cresol formaldehyde epoxy resin |
| CN105778618A (en) * | 2014-12-25 | 2016-07-20 | 上海飞凯光电材料股份有限公司 | Preparation method of liquid light-cured solder resist ink and photosensitive resin thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112111187A (en) * | 2019-08-19 | 2020-12-22 | 信和新材料股份有限公司 | Ultraviolet-curing anticorrosive coating and preparation method and application thereof |
| CN113721422A (en) * | 2021-09-01 | 2021-11-30 | 大同共聚(西安)科技有限公司 | Preparation method of insulating protective layer on wiring board |
| CN114773786A (en) * | 2022-04-18 | 2022-07-22 | 天津珂赛思道路工程有限公司 | High-performance yellowing-resistant material |
| CN115386092A (en) * | 2022-08-11 | 2022-11-25 | 金发科技股份有限公司 | Epoxy resin modified polyformaldehyde, polyformaldehyde composition, and preparation method and application thereof |
| CN115386092B (en) * | 2022-08-11 | 2023-12-15 | 金发科技股份有限公司 | Epoxy resin modified polyformaldehyde, polyformaldehyde composition, and preparation method and application thereof |
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