CN115044016A - Halogen-free epoxidized soybean oil modified resin and preparation method and application thereof - Google Patents
Halogen-free epoxidized soybean oil modified resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN115044016A CN115044016A CN202210811104.5A CN202210811104A CN115044016A CN 115044016 A CN115044016 A CN 115044016A CN 202210811104 A CN202210811104 A CN 202210811104A CN 115044016 A CN115044016 A CN 115044016A
- Authority
- CN
- China
- Prior art keywords
- soybean oil
- halogen
- epoxidized soybean
- free
- resin
- 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.)
- Granted
Links
- 235000012424 soybean oil Nutrition 0.000 title claims abstract description 163
- 239000003549 soybean oil Substances 0.000 title claims abstract description 163
- 229920005989 resin Polymers 0.000 title claims abstract description 110
- 239000011347 resin Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000004593 Epoxy Substances 0.000 claims abstract description 108
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 35
- 239000000194 fatty acid Substances 0.000 claims abstract description 35
- 229930195729 fatty acid Natural products 0.000 claims abstract description 35
- 229920000768 polyamine Polymers 0.000 claims abstract description 34
- 239000011342 resin composition Substances 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000003822 epoxy resin Substances 0.000 claims description 32
- 229920000647 polyepoxide Polymers 0.000 claims description 32
- 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 26
- 239000003054 catalyst Substances 0.000 claims description 17
- 235000021355 Stearic acid Nutrition 0.000 claims description 15
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 15
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 15
- 239000008117 stearic acid Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000003063 flame retardant Substances 0.000 claims description 11
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 9
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012779 reinforcing material Substances 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 7
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011889 copper foil Substances 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 125000006835 (C6-C20) arylene group Chemical group 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 claims description 3
- 235000010469 Glycine max Nutrition 0.000 claims description 3
- 244000068988 Glycine max Species 0.000 claims description 3
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 3
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 3
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 229960004488 linolenic acid Drugs 0.000 claims description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- 235000021313 oleic acid Nutrition 0.000 claims description 2
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 claims description 2
- 229960003656 ricinoleic acid Drugs 0.000 claims description 2
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 claims description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 description 36
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 20
- 239000003292 glue Substances 0.000 description 15
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 13
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000012745 toughening agent Substances 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 10
- 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 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000003365 glass fiber Substances 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- -1 C20 fatty acid Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
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- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 2
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- 125000003118 aryl group Chemical group 0.000 description 2
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- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 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 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000004843 novolac epoxy resin Substances 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XAEWLETZEZXLHR-UHFFFAOYSA-N zinc;dioxido(dioxo)molybdenum Chemical compound [Zn+2].[O-][Mo]([O-])(=O)=O XAEWLETZEZXLHR-UHFFFAOYSA-N 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1477—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- 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
-
- 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
- C08G59/1494—Polycondensates modified by chemical after-treatment followed by a further chemical treatment thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
- B32B2260/023—Two or more layers
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Abstract
The invention provides a halogen-free epoxidized soybean oil modified resin and a preparation method and application thereof, wherein the preparation raw materials of the halogen-free epoxidized soybean oil modified resin comprise epoxidized soybean oil, C12-C20 fatty acid and polyamine; the epoxidized soybean oil reacts with C12-C20 fatty acid to generate an intermediate, and the intermediate reacts with polyamine to obtain the halogen-free epoxidized soybean oil modified treeAnd (3) fat. The halogen-free epoxy soybean oil modified resin contains a flexible long carbon chain structure and a proper branching degree, can keep the heat resistance of a cured resin at a high level while improving the toughness of the cured resin, does not contain halogen, and is green and environment-friendly. The preparation process of the halogen-free epoxy soybean oil modified resin has mild conditions, easy operation, wide raw material source and low cost, and is suitable for large-scale industrial mass production. The resin composition containing the halogen-free epoxy soybean oil modified resin and the copper-clad plate have excellent toughness and impact resistance and high T g And excellent heat resistance.
Description
Technical Field
The invention belongs to the technical field of copper-clad plates, and particularly relates to a halogen-free epoxy soybean oil modified resin and a preparation method and application thereof.
Background
Printed Circuit Boards (PCBs) are members for electrical connection in electronic devices and electronic components, and are one of important electronic materials; the PCB is generally manufactured by processing a copper-clad plate through different processes. Therefore, the quality, service life, manufacturing level, etc. of the PCB depend to a great extent on the performance of the copper clad laminate.
The copper clad laminate generally comprises a substrate with a reinforcing function and a resin layer attached to the substrate, wherein the most common resin layer is an epoxy resin system at present. The epoxy resin has good mechanical property, good cohesiveness, small shrinkage, good corrosion resistance and good processing property. However, epoxy resins are brittle after curing, have poor impact resistance, and are prone to cracking, which limits their use. Therefore, in order to reduce the brittleness of the cured epoxy resin and improve the toughness of the cured epoxy resin to meet the requirements of processing and application, intensive and thorough research on the toughener has been carried out, and a series of epoxy resin tougheners have been developed. The ideal toughening agent not only needs to improve the shock resistance of the cured epoxy resin, but also needs to have the smallest possible influence on other properties, and simultaneously has the cost advantage.
Epoxidized soybean oil is an auxiliary agent widely used in plastic processing, mainly plays roles in plasticization and stabilization, has a certain toughening effect, and is expected to be used in an epoxy resin system. For example, CN104557795A discloses a preparation method of an epoxidized soybean oil oligomer for an electronic-grade copper-clad plate toughening agent, which comprises the following raw materials: 100 parts of epoxidized soybean oil and 1.5-5 parts of diethylenetriamine and/or N, N-dimethylbenzylamine; in the preparation process, epoxidized soybean oil, diethylenetriamine and N, N-dimethylbenzylamine are sequentially added into a reactor for reaction to obtain the epoxidized soybean oil oligomer. The epoxy soybean oil oligomer is used for preparing electronic-grade products, namely copper-clad plates, has a certain toughening effect, but has a limited toughening effect, and has poor compatibility with main epoxy resin, so that the heat resistance and reliability of epoxy resin cured products and the copper-clad plates are influenced.
CN113061223A discloses a preparation method of epoxidized soybean oil modified resin, which comprises the steps of adding epoxidized soybean oil subjected to ring opening of epoxy groups, bisphenol A and cardanol into a reaction kettle for addition reaction, then adding melamine, formaldehyde and phenol for polycondensation, and gelling the generated product to obtain nitrogenous epoxidized soybean oil modified resin; the nitrogen-containing epoxy soybean oil modified resin is mixed with epoxy resin to form glue solution for preparing the paper-based copper-clad plate. The nitrogen-containing epoxy soybean oil modified resin is actually an epoxy soybean oil modified phenolic resin containing melamine, and due to the low modification reactivity of epoxy soybean oil on the phenolic resin, the conversion rate of an epoxy group is still low even if the epoxy soybean oil reacts for a long time under alkaline and high-temperature conditions, so that the system contains more suspension chains grafted by etherification and free blends, the heat resistance of the resin is poor, and the performance of an epoxy cured product and a copper-clad plate is further influenced.
CN106433018A discloses a glue solution for a flame-retardant paper-based copper-clad plate and the copper-clad plate, wherein the glue solution comprises raw materials of epoxy soybean oil modified phenolic resin, epoxy resin, a flame retardant and an organic solvent; the epoxidized soybean oil modified phenolic resin is prepared from epoxidized soybean oil, phenol, bisphenol A, 2-methylimidazole, formaldehyde, an alkaline catalyst, graphene oxide and the like. Due to the insufficient toughening effect of the epoxy soybean oil modified phenolic resin, the copper-clad plate prepared from the glue solution has poor toughness and certain heat resistance.
Therefore, the development of a toughening agent having both excellent toughening effect and good heat resistance is a problem to be solved in the field.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the halogen-free epoxidized soybean oil modified resin, and the preparation method and the application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a halogen-free epoxidized soybean oil modified resin, which is prepared from raw materials including epoxidized soybean oil, C12-C20 fatty acid and polyamine.
The epoxidized soybean oil reacts with C12-C20 fatty acid to generate an intermediate, and the intermediate reacts with polyamine to obtain the halogen-free epoxidized soybean oil modified resin.
In the halogen-free epoxy soybean oil modified resin provided by the invention, firstly, C12-C20 fatty acid is used for carrying out esterification grafting reaction on epoxy soybean oil, then polyamine is used for carrying out chain extension, and a long fatty chain structure is introduced for effective chain growth, so that the halogen-free epoxy soybean oil modified resin has excellent flexibility and a certain branching degree. The halogen-free epoxy soybean oil modified resin is used as a toughening agent, so that the toughness and impact resistance of a cured resin can be effectively improved, the heat resistance of the cured resin is kept unchanged, and the heat resistance level is higher; meanwhile, the halogen-free epoxy soybean oil modified resin does not contain halogen, and meets the requirement of environmental protection.
In the present invention, the expression "Ca-Cb" represents that the number of carbon atoms in the group is a to b.
The C12-C20 fatty acid comprises C12, C13, C14, C15, C16, C17, C18, C19 and C20 fatty acid. It should be noted that the molecular structure of the C12-C20 fatty acid may contain other optional substituents such as hydroxyl groups, etc. in addition to the straight or branched carbon chain and carboxyl group.
In the present invention, the polyamine is a compound containing at least 2 (e.g., 2, 3, or 4, etc.) amino groups.
Preferably, the epoxidized soybean oil is a commercially available epoxidized soybean oil having an epoxy value of 5.9 to 6.9%, and may be, for example, 6.0%, 6.1%, 6.2%, 6.3%, 6.4%, 6.5%, 6.6%, 6.7%, 6.8%, or the like.
Preferably, the C12-C20 fatty acid is a C12-C20 (e.g., C12, C13, C14, C15, C16, C17, C18, C19, etc.) saturated fatty acid and/or a C12-C20 (e.g., C12, C13, C14, C15, C16, C17, C18, C19, etc.) unsaturated fatty acid, and more preferably a C12-C20 saturated fatty acid.
Preferably, the unsaturated fatty acid C12-C20 contains at least one (e.g., 1,2, or 3, etc.) unsaturated bond(s) including C ═ C and/or C ≡ C, preferably C ≡ C.
Preferably, the C12-C20 fatty acid comprises any one or a combination of at least two of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid or arachidic acid, and further preferably comprises stearic acid.
The molar ratio of the epoxidized soybean oil to the C12-C20 fatty acid is preferably 1 (0.3-0.4), and may be, for example, 1:0.31, 1:0.32, 1:0.33, 1:0.34, 1:0.35, 1:0.36, 1:0.37, 1:0.38 or 1:0.39, and more preferably 1 (0.329-0.399).
Preferably, the polyamine comprises a diamine and/or a triamine, more preferably a diamine.
As a preferred technical scheme of the invention, the polyamine comprises diamine, and the diamine is reacted with an intermediate (obtained by reacting epoxidized soybean oil and C12-C20 fatty acid) to perform effective chain extension, so that the halogen-free epoxidized soybean oil modified resin has excellent flexibility and proper branching degree. If the functionality of the polyamine is too high (such as triamine), the reaction process tends to crosslink, which affects the chain growth of the system, and thus is not favorable for obtaining the halogen-free epoxidized soybean oil modified resin with high flexibility.
Preferably, the polyamine is
R is selected from the group consisting of C1-C10 linear or branched alkylene, C6-C20 arylene, C,
Any one of them.
Wherein, the C1-C10 linear or branched chain alkylene group includes C1, C2, C3, C4, C5, C6, C7, C8, C9, C10 linear or branched chain alkylene group, which exemplarily includes but is not limited to: methylene, 1, 2-ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, or the like.
The C6-C20 arylene group includes C6, C9, C10, C12, C14, C16 or C18 arylene groups, and the like, and exemplarily includes but is not limited to: phenylene radical
Naphthylene radical
Biphenylene radicals
Etc.; represents the attachment site of the group.
m 1 、m 2 Represents the number of methylene groups, each independently selected from integers of 0 to 5, for example 0, 1,2, 3, 4 or 5; and m is 1 +m 2 ＞0。
L is selected from any one of-O-, -S-, -SO-, C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9) straight chain or branched chain alkylene.
Represents the attachment site of the group.
Preferably, R is selected from C2-C8 linear or branched chain alkylene,
Any one of them.
Preferably, R is a group containing an aromatic functional group, for example, R is a C6-C20 arylene group,
Compared with aliphatic polyamine with alkylene R, the reaction process of polyamine containing aromatic functional groups and the intermediate is easy to control, and the halogen-free epoxidized soybean oil modified tree is more favorable to be promotedHeat resistance of the grease.
Preferably, the polyamine includes any one or a combination of at least two of ethylenediamine, hexamethylenediamine, m-phenylenediamine, m-xylylenediamine, or diaminodiphenylmethane, and further preferably includes any one or a combination of at least two of m-phenylenediamine, m-xylylenediamine, or diaminodiphenylmethane.
Preferably, the epoxy equivalent weight of the intermediate is 350g/eq, such as 315g/eq, 320g/eq, 325g/eq, 330g/eq, 335g/eq, 340g/eq or 345g/eq, and the specific values therebetween are not exhaustive for the purpose of brevity and brevity.
Preferably, the epoxy equivalent of the halogen-free epoxy soybean oil modified resin is 400-500g/eq, for example 410g/eq, 420g/eq, 430g/eq, 440g/eq, 450g/eq, 460g/eq, 470g/eq, 480g/eq or 490g/eq, and the specific values therebetween are limited in space and for the sake of brevity, and the invention is not exhaustive.
In a second aspect, the present invention provides a method for preparing the halogen-free epoxy soybean oil modified resin according to the first aspect, the method comprising: reacting epoxidized soybean oil with C12-C20 fatty acid to obtain an intermediate; and reacting the intermediate with polyamine to obtain the halogen-free epoxy soybean oil modified resin.
The preparation method of the halogen-free epoxidized soybean oil modified resin comprises two steps, wherein in the first step, the epoxidized soybean oil reacts with C12-C20 fatty acid to generate an intermediate, and the reaction formula can be represented as follows:
In a preferred embodiment of the present invention, the molar ratio of epoxidized soybean oil to C12-C20 fatty acid is 1 (0.3-0.4), more preferably 1 (0.329-0.399); the epoxy equivalent of the intermediate is preferably 300-350g/eq, and the intermediate is reacted with polyamine to obtain the halogen-free epoxidized soybean oil modified resin with excellent flexibility and a certain branching degree, so that the epoxy cured material has excellent toughness, impact resistance and good heat resistance. If the dosage of the C12-C20 fatty acid is too small, the epoxy equivalent of the intermediate is low, and the flexibility and toughening effect of the halogen-free epoxy soybean oil modified resin are influenced; if the use amount of the C12-C20 fatty acid is too much, the epoxy equivalent of the intermediate is higher, the reaction of the intermediate and the polyamine is influenced, the chain extension is insufficient, and the halogen-free epoxy soybean oil modified resin has small molecular weight and poor comprehensive performance.
The second step is a reaction of the intermediate with a polyamine, thereby obtaining a halogen-free epoxy soybean oil modified resin, illustratively, the halogen-free epoxy soybean oil modified resin comprises the following structural units:
wherein R is 1 Represents a fatty chain in a C12-C20 fatty acid, R represents a group for connecting 2 amino groups in a polyamine, and ESO represents a residue after epoxidized soybean oil (an epoxy group in epoxidized soybean oil) participates in the reaction.
As a preferred technical scheme of the invention, the intermediate with the epoxy equivalent of 300-350g/eq and the polyamine are subjected to chain extension reaction to obtain the halogen-free epoxy soybean oil modified resin (final product) with the epoxy equivalent of 400-500 g/eq. If the consumption of the polyamine is small, the chain extension reaction is insufficient, and the epoxy equivalent of the final product is relatively low (less than 400g/eq), the halogen-free epoxy soybean oil modified resin has small molecular weight and poor comprehensive performance; if the amount of the polyamine is too large and the epoxy equivalent of the halogen-free epoxy soybean oil modified resin is more than 500g/eq, the reactivity of the halogen-free epoxy soybean oil modified resin in the composition is poor, and the heat resistance of an epoxy cured product is affected.
Preferably, the reaction of the epoxidized soybean oil with the C12-C20 fatty acid is carried out in the presence of a catalyst.
Preferably, the catalyst comprises any one of triphenylphosphine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-phenyl-4-methylimidazole or a combination of at least two of them, and further preferably triphenylphosphine.
Preferably, the catalyst has a mass of 0.01 to 0.2%, for example, 0.03%, 0.05%, 0.08%, 0.1%, 0.11%, 0.13%, 0.15%, 0.17%, or 0.19%, based on 100% of the total mass of the epoxidized soybean oil and the C12 to C20 fatty acids, and specific values therebetween, not to be limited by space and for the sake of brevity, the invention is not exhaustive of the specific values included in the ranges.
Preferably, the reaction temperature of the epoxidized soybean oil with the C12-C20 fatty acid is 100-180 ℃, and for example, may be 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃ or 175 ℃, and specific values therebetween, are limited to space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the reaction time of the epoxidized soybean oil with the C12-C20 fatty acid is 0.5-8h, for example, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h or 7.5h, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction temperature of the intermediate and the polyamine is 100-180 ℃, for example, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃ or 175 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the reaction time of the intermediate with the polyamine is 0.5 to 5h, for example 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h, and the specific values therebetween, limited to space and for the sake of brevity, are not exhaustive and the invention is not intended to include the specific values within the stated ranges.
Preferably, the preparation further comprises the step of adding a diluent.
Preferably, the diluent is added after the reaction of the intermediate with the polyamine is complete.
Preferably, the diluent comprises any one of toluene, xylene, acetone or butanone or a combination of at least two thereof.
Preferably, the preparation method specifically comprises the following steps:
(1) reacting epoxidized soybean oil with C12-C20 fatty acid in the presence of a catalyst to obtain an intermediate; the catalyst comprises any one or the combination of at least two of triphenylphosphine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-phenyl-4-methylimidazole; the reaction temperature is 100-180 ℃, and the reaction time is 0.5-8 h;
(2) and (2) reacting the intermediate obtained in the step (1) with polyamine at the temperature of 100-180 ℃ for 0.5-5h to obtain the halogen-free epoxy soybean oil modified resin.
In a third aspect, the present invention provides a resin composition comprising a host resin and the halogen-free epoxidized soybean oil-modified resin according to the first aspect.
Preferably, the host resin comprises an epoxy resin.
As a preferable technical scheme of the invention, the halogen-free epoxidized soybean oil modified resin is used in a resin composition taking an epoxy resin as a main body, has good compatibility with the main body resin, can remarkably improve the toughness and the impact resistance of an epoxy cured product, and can keep the heat resistance of the resin composition at a high level.
Preferably, the epoxy resin is an epoxy resin known in the art, exemplary including but not limited to: any one or a combination of at least two of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin or dicyclopentadiene type epoxy resin.
Preferably, the halogen-free epoxidized soybean oil modified resin is 10 to 45 parts by mass, for example, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, 32 parts, 35 parts, 38 parts, 40 parts, 42 parts or 44 parts by mass based on 100 parts by mass of the epoxy resin, and specific points between the above points are not enumerated in the present invention for brevity and conciseness.
In the resin composition provided by the invention, the mass of each component (including the epoxy resin, the curing agent and the halogen-free epoxidized soybean oil modified resin) is calculated by the solid part thereof, and the components do not include a solvent, a dispersant and the like.
Preferably, the resin composition further comprises any one or a combination of at least two of a curing agent, a curing accelerator, a flame retardant or a filler.
Preferably, the curing agent comprises any one or a combination of at least two of phenolic resin, amine curing agent, cyanate curing agent, active ester curing agent, carboxylic acid curing agent or anhydride curing agent, and further preferably phenolic resin.
Preferably, the mass of the curing agent is 20-30 parts, for example, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts or 29 parts, based on 100 parts of the mass of the epoxy resin, and specific points between the above points are not exhaustive, and for simplicity, the invention is not limited to the specific points included in the range.
Preferably, the curing accelerator includes any one of imidazole curing accelerator, organophosphine curing accelerator, organoamine curing accelerator, peroxide or organic metal salt or a combination of at least two thereof.
Preferably, the imidazole-based curing accelerator comprises any one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole or a combination of at least two of the same.
Preferably, the curing accelerator is 0.01 to 2 parts by mass, for example, 0.01 part, 0.03 part, 0.05 part, 0.07 part, 0.09 part, 0.1 part, 0.3 part, 0.5 part, 0.7 part, 0.9 part, 1 part, 1.2 part, 1.5 part or 1.8 part by mass based on 100 parts by mass of the epoxy resin, and specific point values between the above point values are limited to space and are not exhaustive, and the invention is not limited to specific point values included in the range for brevity.
Preferably, the kind of the flame retardant is not particularly limited, and flame retardants having a flame retardant effect may be used in the resin composition, and exemplary include, but are not limited to: any one or a combination of at least two of an inorganic flame retardant, a phosphorus-based organic flame retardant, a nitrogen-based organic flame retardant or a silicon-containing organic flame retardant.
Preferably, the filler is an organic filler and/or an inorganic filler, the kind is not particularly limited, and exemplary include but are not limited to: any one or a combination of at least two of silica, titanium dioxide, aluminum hydroxide, magnesium hydroxide, boehmite, talc, mica powder, molybdenum oxide, zinc molybdate, zinc oxide, boron nitride, aluminum nitride, silicon carbide, alumina, barium sulfate, barium titanate, calcium carbonate, glass powder, or short glass fibers.
Preferably, the filler is 20-60 parts by mass, for example, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts or 55 parts by mass based on 100 parts by mass of the epoxy resin, and specific points between the above points are not exhaustive, and the invention is not limited to specific points included in the range for brevity and conciseness.
The resin composition may further include a solvent, and the amount of the solvent is selected by a person skilled in the art according to experience and process requirements, so that the resin composition has a viscosity suitable for use, and the resin composition can be impregnated, coated, and the like. And in the subsequent drying, semi-curing or complete curing process, the solvent in the resin composition can be partially or completely volatilized.
The solvent of the present invention is not particularly limited, and generally, ketones such as acetone, methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene and xylene, esters such as ethyl acetate and butyl acetate, alcohols such as methanol, ethanol and butanol, alcohols such as ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, carbitol and butyl carbitol, nitrogen-containing compounds such as N, N-dimethylformamide, N-dimethylacetamide and N-methyl-2-pyrrolidone; the solvents may be used alone or in combination of two or more. Ketones such as methyl ethyl ketone, acetone and cyclohexanone, and aromatic hydrocarbons such as toluene and xylene are preferable.
The resin composition provided by the invention is prepared by adopting the following method, and the preparation method comprises the following steps: mixing the main resin (epoxy resin), the halogen-free epoxidized soybean oil modified resin, the curing agent and optionally a solvent, a curing accelerator, a filler and a flame retardant, and uniformly dispersing to obtain the resin composition.
In a fourth aspect, the present disclosure provides a prepreg comprising a reinforcing material and the resin composition of the third aspect attached to the reinforcing material.
Preferably, the resin composition is attached to the reinforcing material after being dried by impregnation.
Preferably, the reinforcing material comprises any one or a combination of at least two of natural fibers, organic synthetic fibers, organic fabrics, inorganic fibers or inorganic fabrics; such as glass fiber cloth, quartz glass fiber blended cloth, non-woven cloth, quartz cloth, paper, and the like.
Illustratively, the preparation method of the prepreg comprises the following steps: and infiltrating a reinforcing material by using the glue solution of the resin composition, and then drying to obtain the prepreg.
Preferably, the drying temperature is 120-.
In a fifth aspect, the invention provides a copper-clad plate, which comprises a copper foil and the prepreg according to the fourth aspect.
Preferably, the copper-clad plate comprises at least one prepreg and copper foils arranged on one side or two sides of the prepreg.
Preferably, the number of prepregs in the copper-clad plate is 1-12, for example, 2, 5, 8, 10 or 12 prepregs may be used.
Illustratively, the preparation method of the copper-clad plate comprises the following steps: pressing copper foils on one side or two sides of one prepreg, and curing to obtain the copper-clad plate; or laminating at least two prepregs into a laminated board, then pressing copper foils on one side or two sides of the laminated board, and curing to obtain the copper-clad plate.
Preferably, the curing is performed in a press.
Preferably, the curing temperature is 150-.
Preferably, the pressure for curing is 10-30kg/cm 2 E.g. 10kg/cm 2 、12kg/cm 2 、15kg/cm 2 、17kg/cm 2 、20kg/cm 2 、22kg/cm 2 、25kg/cm 2 、27kg/cm 2 Or 29kg/cm 2 And the like.
Preferably, the curing time is 60-150min, such as 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min or 145min, and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) the halogen-free epoxy soybean oil modified resin provided by the invention contains a flexible long carbon chain structure and a proper branching degree, has good compatibility with a main resin, can keep the heat resistance of a cured resin at a high level while obviously improving the toughness of the cured resin, does not contain halogen, and meets the requirements of environmental protection.
(2) The preparation process of the halogen-free epoxy soybean oil modified resin has mild conditions, is easy to operate, safe and environment-friendly, adopts renewable raw materials in the preparation process, has wide sources and low cost, is suitable for large-scale industrial mass production, and is easy to popularize and apply.
(3) Bag (bag)The cured product of the resin composition containing the halogen-free epoxidized soybean oil modified resin has excellent toughness and impact resistance and high T g And excellent heat resistance. The impact strength of a copper-clad plate containing the resin composition is more than 102kJ/m 2 The elastic modulus is 16511-19141MPa, the low modulus and the high impact strength are realized, the toughness is excellent, and the T is g The temperature is higher than 122 ℃, the thermal decomposition temperature is higher than 300 ℃, and the heat resistance is good, so that the resin composition and the copper-clad plate have excellent toughness, impact resistance and heat resistance.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
In the following embodiments of the invention, epoxidized soybean oil is commercially available, for example, from HM-01R of Nantong sea Fang science and technology GmbH.
In the following embodiments of the present invention, the epoxy equivalent (including intermediates and end products) is measured using an automated potentiometric titrator, and the specific method is perchloric acid titration.
Example 1
A halogen-free epoxidized soybean oil modified resin E-1 is prepared from epoxidized soybean oil (epoxy value of 6.6%), stearic acid and 4,4' -diaminodiphenylmethane; the preparation method comprises the following steps:
(1) mixing stearic acid and epoxidized soybean oil in a molar ratio of 0.364:1, adding triphenylphosphine which is 0.08 percent of the total mass of the mixture and serves as a catalyst, heating to 130 ℃ for reaction for 3 hours, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the actually measured epoxy equivalent is 318 g/eq;
(2) adding 0.313mol of 4,4' -diaminodiphenylmethane into the system obtained in the step (1), reacting for 2 hours under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxy soybean oil modified resin E-1, and actually measuring to obtain the epoxy equivalent of 450 g/eq; adding toluene with the mass accounting for 10% of the total mass of the product into the system to obtain the glue solution of the halogen-free epoxy soybean oil modified resin E-1.
Example 2
A halogen-free epoxidized soybean oil modified resin E-2 is prepared from epoxidized soybean oil (epoxy value of 6.6%), stearic acid and 4,4' -diaminodiphenylmethane; the preparation method comprises the following steps:
(1) mixing stearic acid and epoxidized soybean oil in a molar ratio of 0.329:1, adding triphenylphosphine which is 0.06 percent of the total mass of the mixture as a catalyst, heating to 160 ℃ for reaction for 1 hour, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the actually measured epoxy equivalent is 300 g/eq;
(2) adding 0.232mol of 4,4' -diaminodiphenylmethane into the system obtained in the step (1), reacting for 1 hour under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxy soybean oil modified resin E-2, and actually measuring to obtain the epoxy equivalent of 400 g/eq; adding toluene with the mass accounting for 10% of the total mass of the product into the system to obtain the glue solution of the halogen-free epoxy soybean oil modified resin E-2.
Example 3
A halogen-free epoxidized soybean oil modified resin E-3 is prepared from epoxidized soybean oil (epoxy value of 6.6%), stearic acid and 4,4' -diaminodiphenylmethane; the preparation method comprises the following steps:
(1) mixing stearic acid and epoxidized soybean oil in a molar ratio of 0.399:1, adding triphenylphosphine which is 0.10 percent of the total mass of the mixture as a catalyst, heating to 140 ℃ for reaction for 2 hours, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the actually measured epoxy equivalent is 350 g/eq;
(2) adding 0.398mol of 4,4' -diaminodiphenylmethane into the system obtained in the step (1), reacting for 3 hours under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxy soybean oil modified resin E-3, and actually measuring to obtain the epoxy equivalent of 500 g/eq; adding toluene with the mass accounting for 10 percent of the total mass of the product into the system to obtain the glue solution of the halogen-free epoxy soybean oil modified resin E-3.
Example 4
A halogen-free epoxidized soybean oil modified resin E-4 is prepared from epoxidized soybean oil (epoxy value of 6.6%), stearic acid and 4,4' -diaminodiphenylmethane; the preparation method comprises the following steps:
(1) mixing stearic acid and epoxidized soybean oil in a molar ratio of 0.347:1, adding triphenylphosphine which is 0.07 percent of the total mass of the mixture as a catalyst, heating to 120 ℃ to react for 5 hours, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the actually measured epoxy equivalent is 337 g/eq;
(2) adding 0.353mol of 4,4' -diaminodiphenylmethane into the system obtained in the step (1), reacting for 3 hours under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxy soybean oil modified resin E-4, and actually measuring to obtain the epoxy equivalent of 468 g/eq; adding toluene with the mass accounting for 10 percent of the total mass of the product into the system to obtain the glue solution of the halogen-free epoxy soybean oil modified resin E-4.
Example 5
A halogen-free epoxidized soybean oil modified resin E-5 is prepared from epoxidized soybean oil (epoxy value of 6.6%), stearic acid and 4,4' -diaminodiphenylmethane; the preparation method comprises the following steps:
(1) mixing stearic acid and epoxidized soybean oil in a molar ratio of 0.382:1, adding triphenylphosphine which is 0.09 percent of the total mass of the mixture and serves as a catalyst, heating to 150 ℃ to react for 4 hours, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the epoxy equivalent is measured to be 342 g/eq;
(2) adding 0.282mol of 4,4' -diaminodiphenylmethane into the system obtained in the step (1), reacting for 2 hours under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxy soybean oil modified resin E-5, and actually measuring to obtain the epoxy equivalent of 433 g/eq; adding toluene with the mass accounting for 10 percent of the total mass of the product into the system to obtain the glue solution of the halogen-free epoxy soybean oil modified resin E-5.
Example 6
A halogen-free epoxidized soybean oil modified resin E-6 is prepared from epoxidized soybean oil (epoxy value of 6.6%), oleic acid and 4,4' -diaminodiphenylmethane; the preparation method comprises the following steps:
(1) mixing oleic acid and epoxidized soybean oil in a molar ratio of 0.399:1, adding triphenylphosphine which is 0.10 percent of the total mass of the mixture as a catalyst, heating to 140 ℃ for reaction for 2 hours, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the epoxy equivalent is measured to be 342 g/eq;
(2) adding 0.398mol of 4,4' -diaminodiphenylmethane into the system obtained in the step (1), reacting for 3 hours under the temperature condition of the step (1), stopping the reaction to obtain the halogen-free epoxy soybean oil modified resin E-6, and actually measuring to obtain the epoxy equivalent of 495 g/eq; adding toluene with the mass accounting for 10 percent of the total mass of the product into the system to obtain the glue solution of the halogen-free epoxy soybean oil modified resin E-6.
Example 7
A halogen-free epoxidized soybean oil modified resin E-7 is prepared from epoxidized soybean oil (epoxy value of 6.6%), stearic acid and hexamethylenediamine; the preparation method comprises the following steps:
(1) mixing stearic acid and epoxidized soybean oil in a molar ratio of 0.364:1, adding triphenylphosphine which is 0.08 percent of the total mass of the mixture and serves as a catalyst, heating to 130 ℃ for reaction for 3 hours, and stopping the reaction to obtain an intermediate; testing the epoxy equivalent of the intermediate, wherein the actually measured epoxy equivalent is 318 g/eq;
(2) adding 0.213mol of hexamethylene diamine into the system in the step (1), reacting for 2 hours under the temperature condition in the step (1), stopping the reaction to obtain the halogen-free epoxy soybean oil modified resin E-7, and actually measuring to obtain the epoxy equivalent of 456 g/eq; adding toluene with the mass accounting for 10 percent of the total mass of the product into the system to obtain the glue solution of the halogen-free epoxy soybean oil modified resin E-7.
Comparative preparation example 1
A halogen-free epoxidized soybean oil modified resin E-D1 is prepared from epoxidized soybean oil (epoxy value of 6.6%), 4' -diaminodiphenylmethane and triphenylphosphine; the preparation method comprises the following steps:
(1) sequentially adding 100g of epoxidized soybean oil, 6.8g of 4,4' -diaminodiphenylmethane and 0.085g of triphenylphosphine into a reactor, heating to 120 ℃ while stirring, and reacting for 60min to obtain a reaction product;
(2) naturally cooling the reaction product obtained in the step (1) to 80 ℃, preserving heat at the temperature for reaction for 30min, naturally cooling to 60 ℃, preserving heat at the temperature for reaction for 30min, then cooling to room temperature to obtain halogen-free epoxy soybean oil modified resin E-D1, and actually measuring to obtain the epoxy equivalent of 448 g/eq; adding toluene with the mass being 10% of the total mass of the product into the system to obtain the glue solution of the halogen-free epoxy soybean oil modified resin E-D1.
Comparative preparation example 2
The halogen-free epoxidized soybean oil modified resin E-D2 is prepared from epoxidized soybean oil, phenol, bisphenol A, 2-methylimidazole, formaldehyde, an alkaline catalyst, a solvent, graphene and graphene oxide; the preparation method comprises the following steps:
1400 parts of epoxidized soybean oil, 565 parts of phenol and 1100 parts of bisphenol A are added into a reaction kettle, stirred for 10min and mixed, 8 parts of 2-methylimidazole is added, reacting for 5 hours at 180 ℃, after the temperature in the reaction kettle is naturally cooled to 165 ℃, slowly feeding water and cooling to 85 ℃, 945 parts of formaldehyde is added and stirred for 10min, 80 parts of triethylamine and 27 parts of ammonia water are added and reacted for 60min at the temperature of 100 ℃, a sample is taken to measure the gelling time, when the gelation time reaches 240 +/-10 s (160 ℃), vacuumizing and dehydrating for 1h, stopping vacuumizing after a resin system in the reaction kettle is transparent, sampling again to measure the gelation time, and when the measured gel time reaches 130 +/-10 s (160 ℃), cooling the temperature in the reaction kettle to be not higher than 85 ℃, and adding a mixture of 30 parts of graphene, 28 parts of graphene oxide and methanol to prepare the epoxy soybean oil modified phenolic resin E-D2.
Materials of interest in the following embodiments of the invention include:
(1) epoxy resin: bisphenol a epoxy resin, DER331, available from DOW chemistry;
(2) curing agent: novolac, PF8063, available from santa junos, shandong;
(3) halogen-free epoxidized soybean oil modified resin
Halogen-free epoxidized soybean oil modified resin E-1, example 1;
halogen-free epoxidized soybean oil modified resin E-2, example 2;
halogen-free epoxidized soybean oil modified resin E-3, example 3;
halogen-free epoxidized soybean oil modified resin E-4, example 4;
halogen-free epoxidized soybean oil modified resin E-5, example 5;
halogen-free epoxidized soybean oil modified resin E-6, example 6;
halogen-free epoxidized soybean oil modified resin E-7, example 7;
halogen-free epoxidized soybean oil modified resin E-D1, comparative preparation example 1;
halogen-free epoxidized soybean oil modified phenolic resin E-D2, comparative preparation example 2;
(4) curing accelerator: 2-ethyl-4-methylimidazole;
(5) filling: aluminum hydroxide;
(6) other flexibilizers
Epoxidized soybean oil with an epoxy value of 6.6%, HM-01R, Nantong sea Fang technologies GmbH;
isopropylated triphenyl phosphate (IPPP).
Application example 1
A resin composition comprises the following components in parts by mass: 100 parts of bisphenol A epoxy resin, 22.4 parts of linear phenolic resin, 22 parts of halogen-free epoxidized soybean oil modified resin E-1, 0.1 part of 2-ethyl-4-methylimidazole and 30 parts of aluminum hydroxide.
A prepreg and a copper-clad plate containing the resin composition are prepared by the following steps:
(1) mixing the resin composition with butanone according to the formula amount, and uniformly dispersing by using a high-shear dispersing emulsifying machine to prepare a glue solution with the solid content of 70%; soaking the glass fiber cloth in the glue solution, and then drying the glass fiber cloth in an oven at 170 ℃ for 4min to obtain a prepreg;
(2) laminating 8 prepregs, covering 35 μm copper foil on the upper and lower sides, and vacuum pressing at 190 deg.C and 30kg/cm 2 And curing for 2h to obtain the copper-clad plate.
Application examples 2 to 5, comparative examples 1 to 9
A resin composition whose components and their masses are shown in tables 1 and 2; the mass units of the components in tables 1 and 2 are "parts".
TABLE 1
TABLE 2
The resin composition is prepared into a copper-clad plate according to the method in application example 1, and the following performance tests are carried out on the copper-clad plate:
(1) impact strength: the method is suitable for testing the impact strength of the laminated board material with the specified size and shape. The size of the sample is long: 120mm, 10mm wide; 10 samples are used for each batch, 5 pieces are used in the longitudinal direction, and 5 pieces are used in the transverse direction; and (3) testing by adopting a simply supported beam pendulum impact tester, calculating the impact strength of each sample according to the following formula A, and calculating the average impact strength according to the impact strength of each sample.
In the formula A, a k : impact strength, kJ/m 2 (ii) a A: work consumed to break the sample, J; b: the width of the sample or the width at the notch is mm; d: sample thickness or minimum thickness at the gap, mm.
(2) Modulus of elasticity: the measurement was carried out according to the IPC-TM-6502.4.4 method.
(3) Glass transition temperature T g : the measurement was carried out according to the IPC-TM-6502.4.25 method.
(4) Thermal decomposition temperature: the measurement was carried out according to the IPC-TM-6502.4.24.6 method.
The test results are shown in table 3:
TABLE 3
According to the test data in Table 3, it can be seen that, in the resin composition and the copper-clad plate provided in the application examples 1-7, the halogen-free epoxidized soybean oil modified resin provided by the invention is used as a toughening agent, the toughness and impact resistance of an epoxy cured product can be remarkably improved, and the impact strength of the copper-clad plate is 102.2-121.5kJ/m 2 The elastic modulus is 16511-19141MPa, the impact strength of the copper-clad plate is obviously improved, the modulus of the plate is effectively reduced, the toughness of the plate is finally improved, and the heat resistance of the plate is not greatly influenced, T g 122.6-129.4 deg.C, 300.4-305.6 deg.C, and high heat resistance.
The resin compositions of comparative examples 1-5 have no toughening agent, so that the copper-clad plate has obviously lower impact strength, high elastic modulus and poor toughness. In the comparative example 6, the isopropylated triphenyl phosphate is used as the toughening agent, although the toughness of the copper-clad plate is improved, the glass transition temperature of a cured product is sharply reduced due to the plasticity of the material, the thermal decomposition temperature is synchronously reduced, and the heat resistance of the cured product is greatly influenced. The resin composition of comparative example 7 uses unmodified epoxidized soybean oil as a toughening agent, and since the material itself is a short flexible molecular chain segment, the toughening effect is limited, the impact toughness and heat resistance of the copper clad laminate prepared by the resin composition are difficult to meet the requirements of further processing, and the unmodified epoxidized soybean oil has poor compatibility with matrix epoxy resin and is easy to phase separate out in practical application, so that the heat resistance is obviously insufficient. In the comparative example 8, epoxy soybean oil modified resin prepared from polyamine and epoxy soybean oil is used as a toughening agent, and a molecular structure lacks a flexible chain segment, so that the toughening effect is limited, and the impact strength of the copper-clad plate is insufficient. The resin composition in comparative example 9 uses the epoxy soybean oil modified phenolic resin as a toughening agent, and because the epoxy soybean oil has low modification reactivity to the phenolic resin, the conversion rate of epoxy groups is still low even if the epoxy soybean oil reacts for a long time under alkaline and high-temperature conditions, so that the system contains more suspension chains grafted by etherification and blends in a free state, the heat resistance of the resin is deteriorated, and the performance of an epoxy cured product and a copper-clad plate is further influenced.
The applicant states that the invention is illustrated by the above examples to the halogen-free epoxy soybean oil modified resin, the preparation method and the application thereof, but the invention is not limited by the above examples, that is, the invention is not limited by the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The halogen-free epoxidized soybean oil modified resin is characterized in that the halogen-free epoxidized soybean oil modified resin is prepared from raw materials including epoxidized soybean oil, C12-C20 fatty acid and polyamine;
the epoxidized soybean oil reacts with C12-C20 fatty acid to generate an intermediate, and the intermediate reacts with polyamine to obtain the halogen-free epoxidized soybean oil modified resin.
2. The halogen-free epoxidized soybean oil modified resin according to claim 1, wherein the C12-C20 fatty acid is a C12-C20 saturated fatty acid and/or a C12-C20 unsaturated fatty acid;
preferably, the C12-C20 fatty acids include any one or a combination of at least two of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, or arachidic acid;
preferably, the molar ratio of the epoxidized soybean oil to the C12-C20 fatty acid is 1 (0.3-0.4), and more preferably 1 (0.329-0.399).
3. The halogen-free epoxy soybean oil modified resin according to claim 1 or 2, wherein the polyamine comprises a diamine and/or a triamine, preferably a diamine;
preferably, the polyamine is H 2 N-R-NH 2 R is selected from C1-C10 linear or branched alkylene, C6-C20 arylene, C,
Any one of the above;
m 1 、m 2 each independently selected from an integer of 0 to 5, and m 1 +m 2 ＞0；
L is selected from any one of-O-, -S-, -SO-, C1-C10 straight chain or branched chain alkylene;
represents the attachment site of the group;
preferably, R is selected from C2-C8 linear or branched chain alkylene,
Any one of the above;
preferably, the polyamine comprises any one of ethylenediamine, hexamethylenediamine, m-phenylenediamine, m-xylylenediamine, or diaminodiphenylmethane or a combination of at least two thereof.
4. The halogen-free epoxidized soybean oil modified resin as claimed in any one of claims 1 to 3, wherein the epoxy equivalent of the intermediate is 300-350 g/eq;
preferably, the epoxy equivalent of the halogen-free epoxy soybean oil modified resin is 400-500 g/eq.
5. The preparation method of the halogen-free epoxy soybean oil modified resin according to any one of claims 1 to 4, which comprises the following steps: reacting epoxidized soybean oil with C12-C20 fatty acid to obtain an intermediate; and reacting the intermediate with polyamine to obtain the halogen-free epoxy soybean oil modified resin.
6. The method of claim 5, wherein the reaction of epoxidized soybean oil with C12-C20 fatty acid is carried out in the presence of a catalyst;
preferably, the catalyst comprises any one of triphenylphosphine, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-phenyl-4-methylimidazole or a combination of at least two thereof;
preferably, the mass of the catalyst is 0.01-0.2% based on 100% of the total mass of the epoxidized soybean oil and the C12-C20 fatty acid;
preferably, the reaction temperature of the epoxidized soybean oil and the C12-C20 fatty acid is 100-180 ℃;
preferably, the reaction time of the epoxidized soybean oil and the C12-C20 fatty acid is 0.5-8 h;
preferably, the reaction temperature of the intermediate and the polyamine is 100-180 ℃;
preferably, the reaction time of the intermediate and the polyamine is 0.5 to 5 h.
7. A resin composition comprising a host resin and the halogen-free epoxidized soybean oil-modified resin of any one of claims 1 to 4.
8. The resin composition of claim 7, wherein the host resin comprises an epoxy resin;
preferably, the mass of the halogen-free epoxidized soybean oil modified resin is 10-45 parts based on 100 parts of the mass of the epoxy resin;
preferably, the resin composition further comprises any one or a combination of at least two of a curing agent, a curing accelerator, a flame retardant or a filler.
9. A prepreg comprising a reinforcing material and the resin composition of claim 7 or 8 attached to the reinforcing material;
preferably, the resin composition is attached to the reinforcing material after being dried by impregnation.
10. A copper-clad plate, characterized in that it comprises a copper foil and the prepreg according to claim 9.
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