CN112194779A - Single-component epoxy resin composition containing latent imidazole curing accelerator and preparation method and application thereof - Google Patents
Single-component epoxy resin composition containing latent imidazole curing accelerator and preparation method and application thereof Download PDFInfo
- Publication number
- CN112194779A CN112194779A CN202011072183.XA CN202011072183A CN112194779A CN 112194779 A CN112194779 A CN 112194779A CN 202011072183 A CN202011072183 A CN 202011072183A CN 112194779 A CN112194779 A CN 112194779A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- curing accelerator
- resin composition
- component epoxy
- imidazole
- 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
Links
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 114
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 114
- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- -1 coatings Substances 0.000 claims abstract description 14
- 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 abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 238000004100 electronic packaging Methods 0.000 claims abstract description 5
- 239000005022 packaging material Substances 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052802 copper Inorganic materials 0.000 claims abstract 2
- 239000010949 copper Substances 0.000 claims abstract 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 19
- 239000004593 Epoxy Substances 0.000 claims description 14
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical class OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 13
- 229920003986 novolac Polymers 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical group C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 4
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 3
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000003172 aldehyde group Chemical group 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims 1
- 125000003277 amino group Chemical group 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 claims 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical group CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims 1
- 229960000935 dehydrated alcohol Drugs 0.000 claims 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000009477 glass transition Effects 0.000 abstract description 8
- 238000003860 storage Methods 0.000 abstract description 8
- CHTMVVAUYBTXSZ-UHFFFAOYSA-N 2-benzofuran-1,3-dione;1h-imidazole Chemical group C1=CNC=N1.C1=CC=C2C(=O)OC(=O)C2=C1 CHTMVVAUYBTXSZ-UHFFFAOYSA-N 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 26
- 239000000047 product Substances 0.000 description 13
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 7
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WBODDOZXDKQEFS-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-phenylbenzene Chemical group CC1=C(C)C(C)=CC(C=2C=CC=CC=2)=C1C WBODDOZXDKQEFS-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 125000002883 imidazolyl group Chemical group 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- 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 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
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- TZLVUWBGUNVFES-UHFFFAOYSA-N 2-ethyl-5-methylpyrazol-3-amine Chemical compound CCN1N=C(C)C=C1N TZLVUWBGUNVFES-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- WCEYJKCPOSACMI-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 2-methylcyclohex-3-ene-1,2-dicarboxylate Chemical compound C1OC1COC(=O)C1(C)C=CCCC1C(=O)OCC1CO1 WCEYJKCPOSACMI-UHFFFAOYSA-N 0.000 description 1
- ITZGNPZZAICLKA-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylate Chemical compound C1C2OC2CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 ITZGNPZZAICLKA-UHFFFAOYSA-N 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- ZXOATMQSUNJNNG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 ZXOATMQSUNJNNG-UHFFFAOYSA-N 0.000 description 1
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 description 1
- KIKYOFDZBWIHTF-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-3-ene-1,2-dicarboxylate Chemical compound C1CC=CC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KIKYOFDZBWIHTF-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- KBWLNCUTNDKMPN-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) hexanedioate Chemical compound C1OC1COC(=O)CCCCC(=O)OCC1CO1 KBWLNCUTNDKMPN-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- HXLVCCRPDYIRRX-UHFFFAOYSA-N iodoamine Chemical group IN HXLVCCRPDYIRRX-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- IGALFTFNPPBUDN-UHFFFAOYSA-N phenyl-[2,3,4,5-tetrakis(oxiran-2-ylmethyl)phenyl]methanediamine Chemical compound C=1C(CC2OC2)=C(CC2OC2)C(CC2OC2)=C(CC2OC2)C=1C(N)(N)C1=CC=CC=C1 IGALFTFNPPBUDN-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
Images
Classifications
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
本发明公开了一种含有潜伏性咪唑类固化促进剂的单组份环氧树脂组合物及其制备方法和应用，属于环氧树脂的改性及应用技术领域。本发明的单组份环氧树脂组合物包括环氧基体树脂、固化剂及固化促进剂；所述固化促进剂是一种邻苯二甲酸酐咪唑衍生物，可以有效提高单组份环氧树脂组合物的室温存储稳定性，且在高温下可以使体系快速发生固化反应，此外，该固化促进剂使得本发明的单组份环氧树脂组合物的固化物具有较高的玻璃化转变温度，从而使得本发明的单组份环氧树脂组合物在环氧树脂胶粘剂、涂料、覆铜板、复合材料、电子封装材料等领域具有良好的应用前景；同时，本发明的制备方法简单安全，可广泛推广应用。
The invention discloses a one-component epoxy resin composition containing a latent imidazole curing accelerator, a preparation method and application thereof, and belongs to the technical field of modification and application of epoxy resins. The one-component epoxy resin composition of the present invention includes an epoxy resin, a curing agent and a curing accelerator; the curing accelerator is a phthalic anhydride imidazole derivative, which can effectively improve the one-component epoxy resin. The storage stability of the composition at room temperature, and the curing reaction of the system can occur rapidly at high temperature, in addition, the curing accelerator enables the cured product of the one-component epoxy resin composition of the present invention to have a higher glass transition temperature, Therefore, the one-component epoxy resin composition of the present invention has good application prospects in the fields of epoxy resin adhesives, coatings, copper clad laminates, composite materials, electronic packaging materials and the like; at the same time, the preparation method of the present invention is simple and safe, and can be widely used. Promote the application.
Description
Technical Field
The invention relates to a single-component epoxy resin composition containing a latent imidazole curing accelerator and application thereof, belonging to the technical field of epoxy resin modification and application.
Background
The epoxy resin is an important polymer or semi-polymer material, the molecular structure of which contains two or more than two epoxy groups, and the epoxy resin is cured and crosslinked under the action of certain chemical reagents or physical conditions such as temperature, humidity, irradiation and the like to form a three-dimensional network-shaped cured product. The uncured epoxy resin is a thermoplastic oligomer, is a brittle solid or a viscous liquid, has no practical application value, and can improve the comprehensive performance only by reacting with a curing agent under certain conditions to form a thermosetting resin. The epoxy resin has the advantages of good mechanical property, thermal stability, easy processability, chemical corrosion resistance, low thermal expansion coefficient and the like, so that the epoxy resin is widely applied to the fields of aerospace, automobile parts, biological materials, composite materials, electronic packaging, adhesives, coatings and the like, and becomes an important material which cannot be replaced in the production and life of the current society.
Epoxy matrix resins can be classified into glycidyl ether epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, alicyclic epoxy resins, and the like according to their chemical structures. When the epoxy matrix resin and the curing agent are subjected to crosslinking reaction, the reaction is completed only at a very high temperature due to high activation energy, a large amount of energy is wasted, and the production process requirement and the production cost are increased, so that a curing accelerator is often added into an epoxy resin curing system to reduce the activation energy of the reaction, improve the reaction rate and shorten the reaction time. There are many commonly used curing accelerators including tertiary amines and salts thereof, acetylacetone metal salts, triphenylphosphine and salts thereof, organic carboxylates, aryl isocyanic acids, imidazole and salts thereof, and the like. Imidazole is a five-membered heterocyclic ring with two nitrogen atoms, one nitrogen atom forms secondary amine, and the other nitrogen atom forms tertiary amine, so that imidazole not only can open an epoxy group through the catalytic action of the tertiary amine but also can open a ring through the addition reaction of the secondary amine, and the structure of imidazole can be modified by various means to adjust the reactivity of the imidazole derivative; meanwhile, imidazole can be used together with a curing agent, and has the advantages of low toxicity, small using amount, quick curing, high thermal deformation temperature of a cured product, mild curing conditions and the like. However, for the common unmodified imidazole curing accelerator, because two nitrogen atoms of pyrrole nitrogen and pyridine nitrogen on an imidazole ring have high initiating activity, when the imidazole ring is directly added into epoxy matrix resin and a curing agent, a system can be quickly gelled, and a curing and crosslinking reaction occurs; if the epoxy resin and the imidazole are stored separately and prepared as they are, the storage cost and the time cost for mixing materials are increased, the production efficiency is reduced, and the practical application and the production requirement are influenced. Therefore, how to combine the epoxy resin, the curing agent and the imidazole curing accelerator into a one-component system and make the system have excellent storage stability at room temperature has been a problem of great research significance and application value.
The retrieval of the prior scientific and technological literature shows that the modification of imidazole is generally carried out by methods such as imidazole salification, microcapsule coating, metal complexing and the like, and then the modified product is directly added into a single-component epoxy resin system to improve the storage stability at room temperature, so that the related research and report are relatively extensive at present. However, the modified imidazole accelerator is often incompatible or poorly compatible with epoxy matrix resin and/or curing agent, and has problems of poor stability of a mixed system, reduction of thermal stability and glass transition temperature of the cured resin due to introduction of a flexible segment, increase of electric conductivity due to introduction of a metal element, and the like, and has direct consequences of uneven curing of a product, low glass transition temperature of a cured product, poor mechanical properties, reduction of dielectric properties, and the like. The invention patent of the publication No. CN107428914B discloses an epoxy resin composition, wherein a reaction product of a carbodiimide compound and an imidazole compound is used as a latent curing accelerator, so that the storage stability and the operability are improved while the characteristics of a cured resin are not reduced, but the preparation steps of the curing accelerator are still complicated, and the curing accelerator is not suitable for popularization and application in mass production.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides the single-component epoxy resin composition containing the latent imidazole curing accelerator, wherein the latent imidazole curing accelerator has good compatibility with epoxy resin, the room-temperature storage stability of the single-component epoxy resin composition can be effectively improved, the curing reaction of a system can be rapidly carried out at high temperature, and a cured substance of the single-component epoxy resin composition has higher glass transition temperature; in addition, the preparation method is simple and safe, and can be widely popularized and applied.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the invention discloses a one-component epoxy resin composition containing a latent imidazole curing accelerator, which comprises epoxy matrix resin, a curing agent and a curing accelerator; wherein the molar ratio of the reaction groups of the epoxy matrix resin and the curing agent is (0.5-1.5): 1; the addition amount of the curing accelerator is 0.5-15 wt% of the epoxy matrix resin, and the preferred amount of the curing accelerator is 1-10 wt%; the curing accelerator is phthalic anhydride imidazole derivative, and the chemical structure of the curing accelerator is shown as the following formula 1:
in the formula 1, R1Is hydrogen atom, methyl, ethyl, phenyl, amino, iodine atom, chlorine atom or bromine atom; r2And R3Each independently is a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a carboxyl group, a cyano group, an aldehyde group, a hydroxymethyl group, a chlorine atom or a bromine atom; r4And R5Each independently is a hydrogen atom, a methyl group or an ethyl group; r6Is a hydrogen atom or a methyl group;
the epoxy matrix resin is one or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin and alicyclic epoxy resin;
the curing agent is one or the combination of more than two of anhydride, polybasic aromatic amine, dicyandiamide and polyhydric phenol.
Further, the glycidyl ether type epoxy resin may be bisphenol a type epoxy resin, hydrogenated bisphenol a type epoxy resin, o-cresol novolac type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetramethylbiphenyl type epoxy resin, biphenol type epoxy resin, dicyclopentadienyl type epoxy resin; the glycidyl ester epoxy resin can be diglycidyl phthalate, diglycidyl hexahydrophthalate, diglycidyl terephthalate, diglycidyl isophthalate, diglycidyl tetrahydrophthalate, diglycidyl methyltetrahydrophthalate, diglycidyl endomethyltetrahydrophthalate and diglycidyl adipate; the glycidyl amine epoxy resin can be triglycidyl isocyanurate, triglycidyl para-aminophenol, tetraglycidyl diaminodiphenylmethane, diisopropylidenylidene tetraglycidyl amine, tetramethylisopropylidenylidene tetraglycidyl amine, N, N, N ', N ' -tetraepoxypropyl-4, 4-diaminodiphenylmethane, 4 ' -diaminodiphenyl ether tetraglycidyl amine; the alicyclic epoxy resin may be 3, 4-epoxycyclohexylmethyl 3, 4-epoxycyclohexyl formate, bis ((3, 4-epoxycyclohexyl) methyl) adipate, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, 4-vinyl-1-cyclohexene diepoxide, dicyclopentadiene diepoxide, 1, 4-cyclohexanedimethanol bis (3, 4-epoxycyclohexanecarboxylic acid) ester. The invention is not limited in scope by the examples described above. Preferred epoxy resins of the present invention are bisphenol a type epoxy resins, o-cresol novolac type epoxy resins, tetramethyl biphenyl type epoxy resins, dicyclopentadienyl diphenyl type epoxy resins and triglycidyl isocyanurate.
Further, the acid anhydride can be tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, trimellitic anhydride, tung oil anhydride, nadic anhydride, maleic anhydride; the polyaromatic amine can be m-phenylenediamine, 4 '-diaminodiphenylmethane, 4' -diaminodiphenyl sulfone; the polyhydric phenol may be novolac resin, o-cresol novolac resin, dicyclopentadiene novolac resin, terpene novolac resin, phenol-aralkyl type resin having phenylene structure, phenol-aralkyl type resin having biphenylene structure, naphthol novolac resin. The invention is not limited in scope by the examples described above. Preferred curing agents of the present invention are methylhexahydrophthalic anhydride, 4 '-diaminodiphenylmethane, 4' -diaminodiphenylsulfone, dicyandiamide, and novolac resins.
The second aspect of the invention discloses a preparation method of a single-component epoxy resin composition containing a latent imidazole curing accelerator, which is characterized by comprising the steps of synthesizing the curing accelerator and preparing the single-component epoxy resin composition;
the curing accelerator is a latent curing accelerator, and is prepared by nucleophilic substitution reaction of chlorinated trimellitic anhydride or a derivative thereof and imidazole or a derivative thereof, but the invention is not limited to the above, for example, the latent curing accelerator is prepared by reaction of chlorinated trimellitic anhydride and imidazole, and the preparation method comprises the following steps:
s1, dissolving trimellitic anhydride chloride in an organic solvent under an ice bath condition, and fully mixing to completely dissolve the trimellitic anhydride chloride;
s2, dissolving imidazole and an acid binding agent in an organic solvent, and fully stirring to completely dissolve the imidazole and the acid binding agent;
s3, dropwise adding the solution prepared in the step S2 into the solution prepared in the step S1, and reacting at the temperature of 30-150 ℃ for 2-24 hours;
the single-component epoxy resin composition is prepared by melting and blending epoxy resin, a curing agent and a curing accelerator according to the proportion and then cooling to room temperature.
Further, the molar concentration ratio of the chlorinated trimellitic anhydride to the imidazole is 5: 1-1: 5;
the molar concentration ratio of the imidazole to the acid-binding agent is 10: 1-1: 10, and the optimal concentration ratio is 5: 1-1: 5; the acid-binding agent can be one or more of pyridine, 4-dimethylaminopyridine, triethylamine, N-diisopropylethylamine, triethanolamine and tetrabutylammonium bromide;
the organic solvent in steps S1 and S2 is one or a combination of two or more of methanol, toluene, acetonitrile, absolute ethanol, N-dimethylformamide, cyclohexane, tetrahydrofuran, and dichloromethane, but the present invention is not limited to the above-mentioned range, and tetrahydrofuran is preferred in the present invention.
The third aspect of the invention discloses a cured product of a one-component epoxy resin composition containing a latent imidazole curing accelerator, which is prepared by curing the one-component epoxy resin composition containing the latent imidazole curing accelerator.
The single-component epoxy resin composition containing the latent imidazole curing agent is suitable for the fields of epoxy resin adhesives, coatings, copper-clad plates, composite materials and electronic packaging materials.
Compared with the prior art, the invention has the advantages and beneficial effects that:
(1) the phthalic anhydride imidazole derivative has an anhydride group, can participate in epoxy resin curing, and improves the compatibility of the imidazole curing accelerator and epoxy matrix resin;
(2) the activity of pyrrole nitrogen on imidazole rings is effectively inhibited at room temperature, so that the single-component epoxy resin composition has good room-temperature storage stability, and the system can quickly generate a curing reaction at high temperature;
(3) the cured product has higher glass transition temperature, so that the epoxy resin composition has wide application prospect in the fields of epoxy resin adhesives, coatings, copper-clad plates, composite materials, electronic packaging materials and the like;
(4) the preparation method is simple and safe, has mild reaction conditions, and can be widely popularized and applied.
Drawings
FIG. 1 is a schematic for the preparation of latent cure accelerator 2MI-T of the present invention;
FIG. 2 is a nuclear magnetic hydrogen spectrum of latent cure accelerator 2MI-T of the present invention;
FIG. 3 is a non-isothermal DSC curing profile of the one-component epoxy resin compositions prepared in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 4 is a graph showing curing conversion rate versus temperature for the one-component epoxy resin compositions prepared in example 1, comparative example 1 and comparative example 2 of the present invention;
FIG. 5 is a graph showing gel times of the one-pack epoxy resin compositions prepared in example 1, comparative example 1 and comparative example 2 of the present invention on a hot stage at 175 ℃;
FIG. 6 is a DSC chart of cured products of the one-component epoxy resin compositions prepared in example 1, comparative example 1 and comparative example 2 of the present invention.
Detailed Description
The following examples will further illustrate the invention in conjunction with the accompanying drawings. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a process are given, but the scope of the present invention is not limited to the following embodiments. The following examples are conducted under conditions not specified, usually in accordance with conventional conditions or conditions recommended by the manufacturer.
The raw materials used in the examples of the present invention are shown in table 1 below, but not limited thereto:
TABLE 1
| Name of raw materials | Molecular formula | CAS number/model number | Suppliers of goods |
| Chlorinated trimellitic anhydride | C18H10ClO11 | 1204-28-0 | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| 2-methylimidazole (2MI) | C4H6N2 | 693-98-1 | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Triethylamine | C6H15N | 121-44-8 | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Tetrahydrofuran (THF) | C4H8O | 109-99-9 | SINOPHARM CHEMICAL REAGENT Co.,Ltd. |
| Tetramethylbenzene type epoxy resin | / | YX-4000 | Yukka Shell Co Ltd |
| Phenol novolac resin (hydroxyl equivalent is 102g/eq) | / | PF-8011 | SHANDONG SHENGQUAN NEW MATERIAL Co.,Ltd. |
| Bisphenol A epoxy resin | / | E51 | China petrochemical Baslin division |
| Methyl hexahydrophthalic anhydride | C9H12O3 | 25550-51-0 | Polynt chemical Co Ltd |
Examples 1 to 6
The raw materials and the amounts used in the embodiments 1 to 6 of the present invention are shown in the following table 2:
TABLE 2
In Table 2, latent curing accelerator 2MI-T was prepared as follows: according to the preparation route of latent curing accelerator 2MI-T shown in FIG. 1, 4.64g (22mmol) of chlorinated trimellitic anhydride was added to a single-neck flask, and 40mL of tetrahydrofuran was added and dissolved in ice bath to obtain a chlorinated trimellitic anhydride solution; adding 1.64g (20mmol) of 2-methylimidazole and 2.23g (22mmol) of triethylamine into a beaker, and adding 40mL of tetrahydrofuran for complete dissolution to obtain a mixed solution of 2-methylimidazole and triethylamine; dropwise adding the mixed solution of 2-methylimidazole and triethylamine into a trimellitic anhydride chloride solution, and stirring and reacting for 12 hours at room temperature; filtering after the reaction is finished, carrying out rotary evaporation on the filtrate, washing with water, filtering and drying to obtain the latent curing accelerator 2 MI-T; as shown in fig. 2, the nuclear magnetic hydrogen spectrum of latent curing accelerator 2MI-T is shown, in which the chemical shifts δ of methyl group on imidazole group are 2.45(s, 3H), the chemical shifts δ of hydrogen atoms at three and four positions on imidazole ring are 7.54(dd, 2H), the chemical shifts δ of hydrogen atoms on benzene ring are 8.01(d, 1H), 8.23(d, 1H) and 8.74(s, 1H), respectively, and the chemical shift δ of deuterium reagent DMSO-d6 is 2.51 (m).
In Table 2, the latent cure accelerator EMI-T was prepared by the following method: adding 4.64g (22mmol) of chlorinated trimellitic anhydride into a single-neck flask, adding 40mL of tetrahydrofuran, and dissolving under an ice bath condition to obtain a chlorinated trimellitic anhydride solution; adding 2.20g (20mmol) of 2-ethyl-4-methylimidazole and 2.23g (22mmol) of triethylamine into a beaker, and adding 40mL of tetrahydrofuran for complete dissolution to obtain a mixed solution of 2-ethyl-4-methylimidazole and triethylamine; dropwise adding the mixed solution of 2-ethyl-4-methylimidazole and triethylamine into a chlorinated trimellitic anhydride solution, and stirring and reacting for 12 hours at room temperature; and (3) filtering after the reaction is finished, carrying out rotary evaporation on the filtrate, washing with water, filtering and drying to obtain the latent curing accelerator EMI-T.
The preparation method of the one-component epoxy resin composition containing the latent imidazole curing accelerator in the embodiment 1 to 4 comprises the following specific steps: according to the mixture ratio shown in Table 2, the tetramethyl biphenyl type epoxy resin (YX-4000), the linear phenolic resin (PF-8011) and the latent curing accelerator 2MI-T are melted and blended for 2min at 120 ℃, and are uniformly mixed and cooled to room temperature, so that the single-component epoxy resin composition of the embodiment 1-4 is obtained.
The preparation method of the one-component epoxy resin composition containing the latent imidazole curing accelerator in the embodiment 5 comprises the following specific steps: according to the mixture ratio shown in table 2, bisphenol a type epoxy resin (E51), methylhexahydrophthalic anhydride and latent curing accelerator 2MI-T were mixed uniformly at room temperature using a high-speed homogenizer to obtain the one-component epoxy resin composition of example 5.
The preparation method of the one-component epoxy resin composition containing the latent imidazole curing accelerator in the embodiment 6 comprises the following specific steps: according to the mixture ratio shown in Table 2, the tetramethyl biphenyl type epoxy resin (YX-4000), the linear phenolic resin (PF-8011) and the latent curing accelerator EMI-T are melted and blended for 2min at 120 ℃, and after being uniformly mixed, the mixture is cooled to room temperature, so that the single-component epoxy resin composition of the embodiment 6 is obtained.
Comparative examples 1 to 2
The raw materials and the amounts used in comparative examples 1 to 2 are shown in table 3 below:
TABLE 3
The preparation method of the one-component epoxy resin composition of comparative example 1 specifically includes the steps of: according to the compounding ratio shown in Table 3, a tetramethylbiphenyl type epoxy resin (YX-4000), a phenol novolac resin (PF-8011) and an unmodified curing accelerator, 2-methylimidazole (2MI), were melt-mixed at 110 ℃ for 30 seconds and then cooled to room temperature, thereby obtaining a one-component epoxy resin composition of comparative example 1.
The preparation method of the one-component epoxy resin composition of comparative example 2 specifically includes the steps of: according to the compounding ratio shown in Table 3, a tetramethylbiphenyl type epoxy resin (YX-4000), a phenol novolac resin (PF-8011) and an unmodified curing accelerator, 2-ethyl-4-methylimidazole (EMI), were melt-mixed at 110 ℃ for 30 seconds and then cooled to room temperature, to obtain a one-component epoxy resin composition of comparative example 2.
Performance testing
The one-component epoxy resin compositions prepared in example 1 and comparative examples 1 and 2 and cured products thereof were subjected to curing behavior test using Differential Scanning Calorimetry (DSC).
The test conditions were: the sampling amount of each sample is about 5mg, and the heating rate is 10 ℃ for min-1In N at2And testing in the atmosphere, wherein the protective gas flow is 50mL/min, and the purge gas flow is 70 mL/min.
As shown in fig. 3, which is a non-isothermal DSC curing graph of the one-part epoxy resin compositions of example 1, comparative example 1, and comparative example 2, it can be seen that the curing behavior of the one-part epoxy resin composition of example 1 to which 2MI-T is added shows a significant latency, and curing hardly occurs at a temperature lower than 160 ℃, compared to unmodified curing accelerator 2MI and EMI added to comparative example 1 and comparative example 2, and thus has excellent room-temperature storage stability; whereas example 1 shows a narrower exothermic peak when the temperature is higher than 160 c, and it is shown that it has excellent high-temperature curing activity by the relationship of the conversion rate and the temperature of fig. 4.
FIG. 5 shows the gel times of the one-pack epoxy resin compositions prepared in example 1, comparative example 1 and comparative example 2 on a hot stage at 175 ℃. It can be seen that the one-pack epoxy resin composition of example 1 has a longer gel time but less than 100s compared to comparative examples 1 and 2, indicating that the latent curing accelerator of the present invention enables a resin system to be rapidly cured at a high temperature.
As shown in fig. 6, which is a DSC graph of the cured products of the one-component epoxy resin compositions of example 1, comparative example 1, and comparative example 2, it can be seen that the cured product of the one-component epoxy resin composition of example 1 containing a latent imidazole derivative has a glass transition temperature similar to that of the 2MI (comparative example 1) and EMI (comparative example 2) systems, indicating that the phthalic anhydride imidazole derivative as a curing accelerator does not have a significant negative influence on the glass transition temperature of the epoxy cured product, and the cured product has a high glass transition temperature.
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto. All equivalent changes, simplifications and modifications which do not depart from the spirit and scope of the invention are intended to be covered by the scope of the invention.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011072183.XA CN112194779A (en) | 2020-10-09 | 2020-10-09 | Single-component epoxy resin composition containing latent imidazole curing accelerator and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011072183.XA CN112194779A (en) | 2020-10-09 | 2020-10-09 | Single-component epoxy resin composition containing latent imidazole curing accelerator and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112194779A true CN112194779A (en) | 2021-01-08 |
Family
ID=74014162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011072183.XA Pending CN112194779A (en) | 2020-10-09 | 2020-10-09 | Single-component epoxy resin composition containing latent imidazole curing accelerator and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112194779A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574534A (en) * | 2021-01-12 | 2021-03-30 | 陕西理工大学 | Medium-temperature curing latent epoxy resin curing agent |
| CN113563564A (en) * | 2021-06-22 | 2021-10-29 | 中国林业科学研究院林产化学工业研究所 | A kind of oil-based latent resin and its preparation method and application |
| CN114957619A (en) * | 2022-05-31 | 2022-08-30 | 安徽大学 | Epoxy flame-retardant composite material containing imidazole curing accelerator and preparation method thereof |
| CN115160229A (en) * | 2022-05-31 | 2022-10-11 | 上海大学 | Modified imidazole latent epoxy resin curing agent and preparation method thereof |
| CN117004172A (en) * | 2023-08-14 | 2023-11-07 | 江苏耀鸿电子有限公司 | Preparation method of high-toughness phenolic resin glue solution for copper-clad plate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009037862A1 (en) * | 2007-09-21 | 2009-03-26 | Nippon Soda Co., Ltd. | Inclusion complex containing epoxy resin composition for semiconductor encapsulation |
| CN107840942A (en) * | 2017-11-23 | 2018-03-27 | 武汉理工大学 | Imidazole Type Latent Curing Agent of the ring structure containing triazinetrione and preparation method thereof |
| CN108003326A (en) * | 2017-12-18 | 2018-05-08 | 武汉理工大学 | Imidazole Type Latent Curing Agent containing maleimide structure and preparation method thereof |
-
2020
- 2020-10-09 CN CN202011072183.XA patent/CN112194779A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009037862A1 (en) * | 2007-09-21 | 2009-03-26 | Nippon Soda Co., Ltd. | Inclusion complex containing epoxy resin composition for semiconductor encapsulation |
| CN107840942A (en) * | 2017-11-23 | 2018-03-27 | 武汉理工大学 | Imidazole Type Latent Curing Agent of the ring structure containing triazinetrione and preparation method thereof |
| CN108003326A (en) * | 2017-12-18 | 2018-05-08 | 武汉理工大学 | Imidazole Type Latent Curing Agent containing maleimide structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 狄宁宇等: ""环氧树脂潜伏性固化剂１，２，４，５－苯四甲酸／２－甲基咪唑盐的制备及表征"", 《材料导报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574534A (en) * | 2021-01-12 | 2021-03-30 | 陕西理工大学 | Medium-temperature curing latent epoxy resin curing agent |
| CN113563564A (en) * | 2021-06-22 | 2021-10-29 | 中国林业科学研究院林产化学工业研究所 | A kind of oil-based latent resin and its preparation method and application |
| CN113563564B (en) * | 2021-06-22 | 2022-07-22 | 中国林业科学研究院林产化学工业研究所 | Grease-based latent resin, and preparation method and application thereof |
| CN114957619A (en) * | 2022-05-31 | 2022-08-30 | 安徽大学 | Epoxy flame-retardant composite material containing imidazole curing accelerator and preparation method thereof |
| CN115160229A (en) * | 2022-05-31 | 2022-10-11 | 上海大学 | Modified imidazole latent epoxy resin curing agent and preparation method thereof |
| CN117004172A (en) * | 2023-08-14 | 2023-11-07 | 江苏耀鸿电子有限公司 | Preparation method of high-toughness phenolic resin glue solution for copper-clad plate |
| CN117004172B (en) * | 2023-08-14 | 2024-01-23 | 江苏耀鸿电子有限公司 | Preparation method of high-toughness phenolic resin glue solution for copper-clad plate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112194779A (en) | Single-component epoxy resin composition containing latent imidazole curing accelerator and preparation method and application thereof | |
| CN102220102B (en) | High-temperature resisting adhesive and preparation method thereof | |
| EP0009645B1 (en) | 5-(2,5-diketotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylicanhydride, its use as curing agent for epoxy resins and as raw material for the production of polyimides, epoxy resins containing it, and their use in the preparation of various articles, and powder coating compositions | |
| CN101629062A (en) | Polyimide-epoxy resin adhesive and preparation method and application thereof | |
| JP3497560B2 (en) | Method for producing modified epoxy resin, modified epoxy resin produced, and composition of this epoxy resin | |
| CN109053576B (en) | A kind of ionic liquid curing agent suitable for epoxy resin and preparation method thereof | |
| CN113667099B (en) | A one-component epoxy resin based on amino acid type curing agent | |
| CN112851911B (en) | Bio-based A2+ B3 type hyperbranched epoxy resin precursor, modified composition, preparation method and application thereof | |
| US5872196A (en) | Liquid epoxy resin composition | |
| CN101962436B (en) | High-temperature-resistant modified polyfunctional epoxy matrix resin for advanced composite material and preparation thereof | |
| CN108976391A (en) | A kind of epoxy resin curing accelerator and its methods for making and using same based on three phosphonitrile of ring and imidazolium compounds | |
| TW202313771A (en) | Carbonate-containing epoxy resin, preparation method thereof, epoxy curable product prepared thereby and a method for degrading epoxy curable product | |
| JPS60142973A (en) | Triglycidyl compound of aminophenol | |
| Wei et al. | Imidazole derivative with an intramolecular hydrogen bond as thermal latent curing accelerator for epoxy/phenolic resins | |
| CN118460160A (en) | Preparation method of novel high temperature resistant polyimide modified epoxy adhesive | |
| CN116355284B (en) | A DOPO-based reactive flame retardant for flame-retardant epoxy resin and preparation method thereof | |
| CN110872281A (en) | Tertiary phenol-furfuryl amine type benzoxazine monomer, cured resin and preparation method of copolymer resin of cured resin | |
| CN115466372A (en) | A kind of aldehyde group-containing epoxy resin prepolymer and its preparation method and application | |
| WO2016117298A1 (en) | Crystalline polymorphism of inclusion compound, curable composition containing same, and cured product | |
| CN110790903A (en) | One-component epoxy resin composition containing intramolecular hydrogen bond type imidazole curing accelerator and preparation method thereof | |
| JPS5817214B2 (en) | Acid anhydride-based heat-resistant curing agent composition | |
| CN115850916B (en) | Wide-temperature-range low-heat-conduction high-temperature-resistant neutron shielding composite material and preparation method thereof | |
| TWI609382B (en) | Dielectric material composition, insulated film and circuit board containing the same | |
| JP7330865B2 (en) | Phosphorus-containing epoxy resin and method for its preparation | |
| TWI854568B (en) | A single-ester epoxy resin, preparation method thereof, epoxy curable product prepared thereby and epoxy thermoset and degradation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210108 |