CN114230787A - Modified benzoxazine prepolymer, preparation method thereof, resin composition, cured product thereof and electronic product component - Google Patents
Modified benzoxazine prepolymer, preparation method thereof, resin composition, cured product thereof and electronic product component Download PDFInfo
- Publication number
- CN114230787A CN114230787A CN202111515699.1A CN202111515699A CN114230787A CN 114230787 A CN114230787 A CN 114230787A CN 202111515699 A CN202111515699 A CN 202111515699A CN 114230787 A CN114230787 A CN 114230787A
- Authority
- CN
- China
- Prior art keywords
- benzoxazine
- prepolymer
- parts
- resin composition
- modified
- 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
- 150000005130 benzoxazines Chemical class 0.000 title claims abstract description 83
- 239000011342 resin composition Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 229920000098 polyolefin Polymers 0.000 claims abstract description 31
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 26
- 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 abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 12
- 150000003254 radicals Chemical class 0.000 claims abstract description 12
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000003063 flame retardant Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000005062 Polybutadiene Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- 229920002857 polybutadiene Polymers 0.000 claims description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 10
- -1 2, 5-dihydroxyphenyl Chemical group 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 6
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 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 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- HGTUJZTUQFXBIH-UHFFFAOYSA-N (2,3-dimethyl-3-phenylbutan-2-yl)benzene Chemical compound C=1C=CC=CC=1C(C)(C)C(C)(C)C1=CC=CC=C1 HGTUJZTUQFXBIH-UHFFFAOYSA-N 0.000 claims description 3
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 claims description 3
- CMSBLKQHGOOWBO-UHFFFAOYSA-N 1,1,3-trimethyl-5-(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1CC(C)CC(C)(C)C1 CMSBLKQHGOOWBO-UHFFFAOYSA-N 0.000 claims description 3
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 claims description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 3
- KMRIWYPVRWEWRG-UHFFFAOYSA-N 2-(6-oxobenzo[c][2,1]benzoxaphosphinin-6-yl)benzene-1,4-diol Chemical compound OC1=CC=C(O)C(P2(=O)C3=CC=CC=C3C3=CC=CC=C3O2)=C1 KMRIWYPVRWEWRG-UHFFFAOYSA-N 0.000 claims description 3
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 claims description 3
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- DYIZJUDNMOIZQO-UHFFFAOYSA-N 4,5,6,7-tetrabromo-2-[2-(4,5,6,7-tetrabromo-1,3-dioxoisoindol-2-yl)ethyl]isoindole-1,3-dione Chemical compound O=C1C(C(=C(Br)C(Br)=C2Br)Br)=C2C(=O)N1CCN1C(=O)C2=C(Br)C(Br)=C(Br)C(Br)=C2C1=O DYIZJUDNMOIZQO-UHFFFAOYSA-N 0.000 claims description 3
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- XSAOTYCWGCRGCP-UHFFFAOYSA-K aluminum;diethylphosphinate Chemical compound [Al+3].CCP([O-])(=O)CC.CCP([O-])(=O)CC.CCP([O-])(=O)CC XSAOTYCWGCRGCP-UHFFFAOYSA-K 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 3
- 229910002113 barium titanate Inorganic materials 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- 229910001593 boehmite Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 3
- 235000011010 calcium phosphates Nutrition 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 3
- RECMXUUCYFGBEZ-UHFFFAOYSA-N cyclohexyl cyclohexyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC1CCCCC1 RECMXUUCYFGBEZ-UHFFFAOYSA-N 0.000 claims description 3
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 3
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 3
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 3
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 239000005350 fused silica glass Substances 0.000 claims description 3
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
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- 239000000454 talc Substances 0.000 claims description 3
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- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 3
- CMLWFCUAXGSMBB-UHFFFAOYSA-N tris(2,6-dimethoxyphenyl)phosphane Chemical compound COC1=CC=CC(OC)=C1P(C=1C(=CC=CC=1OC)OC)C1=C(OC)C=CC=C1OC CMLWFCUAXGSMBB-UHFFFAOYSA-N 0.000 claims description 3
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- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims description 3
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims 2
- 230000004048 modification Effects 0.000 abstract description 8
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
-
- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- 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
- 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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a modified benzoxazine prepolymer and a preparation method thereof, a resin composition and a cured product thereof, and an electronic product assembly, and relates to the technical field of resin compositions. The preparation method of the modified benzoxazine prepolymer comprises the steps of mixing benzoxazine, epoxidized polyolefin, an accelerator and a solvent to carry out prepolymerization to obtain the modified benzoxazine prepolymer; according to the preparation method, the epoxidized polyolefin is introduced to carry out prepolymerization modification on the benzoxazine, so that the dielectric property of the prepared modified benzoxazine prepolymer is greatly improved compared with that of the traditional benzoxazine (before modification); meanwhile, the prepolymerization reaction in the preparation process has strong controllability and long product storability, and is suitable for all types of benzoxazine. The invention also provides a resin composition which comprises the modified benzoxazine prepolymer, specific thermosetting resin, a free radical initiator, a flame retardant, a filler and the like.
Description
Technical Field
The invention relates to the technical field of resin compositions, in particular to a modified benzoxazine prepolymer and a preparation method thereof, a resin composition and a cured product thereof, and an electronic product component.
Background
The benzoxazine is a novel thermosetting resin developed on the basis of the traditional phenolic resin, can form a three-dimensional network structure through ring-opening polymerization, has no release of small molecules in the curing process, has low product porosity and approximately zero volume shrinkage, and has the characteristics of high glass transition temperature, excellent mechanical property, good water resistance, high carbon residue rate and the like. The advantages enable the benzoxazine to show obvious performance advantages in the lead-free halogen-free copper-clad plate. However, phenolic hydroxyl groups generated after the benzoxazine is cured cause the dielectric property of the cured product to be higher, and the application requirements of high-order electronic products cannot be met.
In order to improve the dielectric property deficiency, further improve the performance of the benzoxazine resin and expand the application range thereof, chinese patent document CN104845363A adopts allyl benzoxazine resin as matrix resin, and physically blends the allyl benzoxazine resin with allyl modified maleimide resin, allyl modified polyphenylene ether resin and hydrocarbon resin. The modification method is simple, but compatibility problems easily occur among resins, and the ratio of each component cannot be adjusted in a wide range.
Chinese patent document CN109053980A reports "polystyrene-terminated main chain benzoxazine copolymer oligomer and copolymer resin", and poly-p-vinylphenol is used as a capping agent to chemically modify the benzoxazine resin to obtain the polyethylene-terminated main chain benzoxazine copolymer resin. The introduction of polystyrene chains improves the dielectric constant and dielectric loss of benzoxazines, but lowers the glass transition temperature and rigidity of the material.
Chinese patent document CN111518241A adopts a double bond structure-containing benzoxazine monomer and a diene monomer or a third unit of styrene to perform radical copolymerization to synthesize an olefin-benzoxazine copolymerized oligomer. The olefin resin with low dielectric property and the benzoxazine with excellent comprehensive performance are combined together, the problem of compatibility of two resin systems is solved, and the composition proportion of the benzoxazine and polydiene in a molecular chain can be regulated and controlled in a large range, so that the novel high polymer material with low dielectric constant, low dielectric loss, high heat resistance and high bonding performance is obtained. However, the benzoxazine monomer containing double bonds is adopted, so that the structure of the benzoxazine is limited, and the benzoxazine has limitation in wide-range use.
Accordingly, the present invention is directed to solving at least one of the problems set forth above.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of a modified benzoxazine prepolymer.
The second purpose of the invention is to provide a modified benzoxazine prepolymer prepared by the preparation method.
The third object of the present invention is to provide a resin composition.
A fourth object of the present invention is to provide an electronic product assembly.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a preparation method of a modified benzoxazine prepolymer, which comprises the following steps:
mixing benzoxazine, epoxidized polyolefin, an accelerator and a solvent to carry out prepolymerization to obtain a modified benzoxazine prepolymer;
the weight ratio of the benzoxazine to the epoxidized polyolefin is (50-95): (5-50).
Further, on the basis of the above technical scheme of the present invention, the benzoxazine includes any one of or a combination of at least two of bisphenol a type benzoxazine, bisphenol F type benzoxazine, phenolphthalein type benzoxazine, diphenylmethane type benzoxazine, dicyclopentadiene type benzoxazine, diaminodiphenyl ether type benzoxazine, and benzoxazine containing an unsaturated double bond structure;
preferably, the epoxidized polyolefin is epoxidized polybutadiene and has the structural formula:
wherein m is 4-11, n is 16-43.
Further, on the basis of the above technical solution of the present invention, the accelerator includes any one or a combination of at least two of 2-methylimidazole, 2-phenyl-imidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 4-dimethylaminopyridine, zinc octoate, cobalt acetylacetonate, or zinc acetylacetonate;
preferably, the solvent includes any one of butanone, acetone, toluene, dimethylbenzene, trimethylbenzene, N-dimethylformamide, N-dimethylacetamide, cyclohexanone, or propylene glycol methyl ether, or a combination of at least two thereof.
Further, on the basis of the technical scheme of the invention, the addition amount of the accelerator accounts for 0.1-3% of the weight of the mixture formed by the benzoxazine and the epoxidized polyolefin.
Further, on the basis of the technical scheme of the invention, the prepolymerization temperature is 60-200 ℃, and the prepolymerization time is 10-300 min;
preferably, the prepolymerization process is carried out with stirring.
The invention also provides a modified benzoxazine prepolymer prepared by the preparation method of the modified benzoxazine prepolymer.
The invention also provides a resin composition which mainly comprises the following components in parts by weight:
50-100 parts of modified benzoxazine prepolymer, 5-60 parts of thermosetting resin, 0.2-3 parts of free radical initiator, 5-40 parts of flame retardant and 50-200 parts of filler;
wherein the modified benzoxazine prepolymer is the modified benzoxazine prepolymer.
Further, on the basis of the above technical solution of the present invention, the thermosetting resin includes any one of polyphenylene ether, maleimide resin, polybutadiene, butadiene-styrene copolymer, diallyl bisphenol a, triallyl isocyanurate, triallyl cyanurate, divinylbenzene, or epoxy resin or a combination of at least two thereof.
Further, on the basis of the above technical solution of the present invention, the radical initiator includes any one or a combination of at least two of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 3-dimethyl-2, 3-diphenylbutane, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t-butylperoxy dicumyl, t-butyl peroxybenzoate, t-butylperoxy pivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, and dicyclohexyl peroxycarbonate;
preferably, the flame retardant comprises any one or a combination of at least two of brominated styrene, decabromodiphenyl ether, decabromodiphenyl ethane, ethylenebistetrabromophthalimide, tris (2, 6-dimethoxyphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, aluminum diethylphosphinate or hexaphenoxycyclotriphosphazene;
preferably, the filler includes any one of crystalline silica, fused silica, spherical silica, alumina, aluminum hydroxide, carbon black, aniline black, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, aluminum nitride, boron nitride, silicon nitride, aluminum silicon carbide, sodium carbonate, magnesium carbonate, titanium dioxide, zinc oxide, zirconium oxide, potassium titanate, strontium titanate, barium titanate, ceramic fiber, zinc molybdate, ammonium molybdate, calcium phosphate, boehmite, or polytetrafluoroethylene powder, or a combination of at least two thereof.
The invention also provides an electronic product component which is prepared by adopting the resin composition;
preferably, the electronic product assembly comprises a prepreg, a copper clad laminate or a printed circuit board.
Compared with the prior art, the invention has the following technical effects:
(1) the invention provides a preparation method of a modified benzoxazine prepolymer, which comprises the steps of mixing benzoxazine, epoxidized polyolefin, an accelerator and a solvent to carry out prepolymerization to obtain the modified benzoxazine prepolymer; according to the preparation method, the epoxidized polyolefin is introduced to carry out prepolymerization modification on the benzoxazine, so that the dielectric property of the prepared modified benzoxazine prepolymer is greatly improved compared with that of the traditional benzoxazine (before modification); meanwhile, the prepolymerization reaction in the preparation process has strong controllability and long product storability, and is suitable for all types of benzoxazine.
(2) The invention provides a modified benzoxazine prepolymer prepared by the preparation method.
(3) The invention provides a resin composition, which is prepared from the modified benzoxazine prepolymer, specific thermosetting resin, a free radical initiator, a flame retardant, a filler and the like, wherein the modified benzoxazine prepolymer has good dielectric property, so that the modified benzoxazine prepolymer and the specific thermosetting resin are subjected to polymerization reaction under the action of the free radical initiator and the like, and the modified benzoxazine prepolymer and the thermosetting resin have good compatibility, so that a cured product of the prepared resin composition has the characteristics of high glass transition temperature, low dielectric property and low absorption rate.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. Those who do not specify the conditions are performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
According to a first aspect of the present invention, there is provided a method for preparing a modified benzoxazine prepolymer, comprising the steps of:
mixing benzoxazine, epoxidized polyolefin, an accelerator and a solvent to carry out prepolymerization to obtain a modified benzoxazine prepolymer;
the weight ratio of the benzoxazine to the epoxidized polyolefin is (50-95): (5-50).
Specifically, the specific type of benzoxazine in the present invention is not limited, and may be any type of benzoxazine in the art.
The epoxidized polyolefin mainly refers to a polyolefin resin containing epoxy groups, and the specific kind thereof is not limited. The inventor discovers through a large amount of experimental researches that under certain prepolymerization conditions such as an accelerant, benzoxazine can generate a ring-opening reaction to generate an intermediate phenolic hydroxyl group, the intermediate phenolic hydroxyl group can generate a ring-opening reaction with an epoxy group on epoxidized polyolefin to obtain benzoxazine-polyolefin prepolymerization, the problem of poor compatibility of benzoxazine and olefin is solved, the epoxidized polyolefin can improve the dielectric property of benzoxazine by improving the dielectric constant and dielectric loss of benzoxazine, and the main mechanism is as follows: the C-C bond and the C-H bond in the olefin structure have smaller dipole moment and lower polarizability; secondly, the olefin structure can improve the hydrophobicity of the benzoxazine and reduce the hygroscopicity of a cured product, and water has higher dielectric constant and dielectric loss, so that the introduction of the olefin structure can improve the dielectric property of the benzoxazine.
The modified benzoxazine prepolymer is mainly prepared by pre-polymerizing benzoxazine and epoxidized polyolefin. Wherein the weight ratio of benzoxazine to epoxidized polyolefin in the modified benzoxazine prepolymer is 50-95: 5-50. Typical, but not limiting, specific gravities of benzoxazines and epoxidized polyolefins are 50: 5. 50: 10. 50: 15. 50: 20. 50: 25. 50: 30. 50: 35. 50: 40. 50: 45. 50: 50. 55: 15. 55: 25. 55: 35. 55: 40. 55: 45. 60: 5. 60: 10. 60: 15. 60: 20. 60: 25. 60: 30. 60: 35. 60: 40. 60: 45. 60: 50. 70: 5. 70: 10. 70: 15. 70: 20. 70: 25. 70: 30. 70: 35. 70: 40. 70: 45. 70: 50. 75: 5. 75: 15. 75: 25. 75: 35. 75: 45. 80: 5. 80: 10. 80: 15. 80: 20. 80: 25. 80: 30. 80: 35. 80: 40. 80: 45. 80: 50. 95: 5. 95: 10. 95: 15. 95: 20. 95: 25. 95: 30. 95: 35. 95: 40. 95: 45 or 95: 50.
the weight ratio between the above-mentioned benzoxazine and epoxidized polyolefin has an important influence on the properties of the finally obtained modified benzoxazine prepolymer. If the amount of benzoxazine is too small, the cured product of the resin composition prepared from the prepolymer tends to have a low glass transition temperature, a low peel strength and poor heat resistance, and if the amount of benzoxazine is too small, the cured product of the resin composition prepared from the prepolymer tends to have a poor dielectric constant, so that the blending ratio of benzoxazine to epoxidized polyolefin needs to be maintained within a proper blending ratio range.
The invention provides a preparation method of a modified benzoxazine prepolymer, which comprises the steps of mixing benzoxazine, epoxidized polyolefin, an accelerator and a solvent to carry out prepolymerization to obtain the modified benzoxazine prepolymer; according to the preparation method, the epoxidized polyolefin is introduced to carry out prepolymerization modification on the benzoxazine, so that the dielectric property of the prepared modified benzoxazine prepolymer is greatly improved compared with that of the traditional benzoxazine (before modification); meanwhile, the prepolymerization reaction in the preparation process has strong controllability and long product storability, and is suitable for all types of benzoxazine.
In addition, double bonds on the modified benzoxazine prepolymer can participate in subsequent curing reaction, so that the dielectric property of benzoxazine is improved, the crosslinking density of a cured product of the resin composition is not greatly reduced, and the influence on the heat resistance of the material is small.
The specific class of benzoxazines may be that which is common in the art. As an alternative embodiment of the present invention, the benzoxazine includes any one of bisphenol a type benzoxazine, bisphenol F type benzoxazine, phenolphthalein type benzoxazine, diphenylmethane type benzoxazine, dicyclopentadiene type benzoxazine, diaminodiphenyl ether type benzoxazine, benzoxazine containing an unsaturated double bond structure, or a combination of at least two thereof.
In order to further increase the number of reactive functional groups of the prepolymer, increase the crosslink density of the cured product of the resin composition, and decrease the thermal expansion coefficient of the cured product, there is a further optimization for the specific kind of epoxidized polyolefin. In a preferred embodiment of the present invention, the epoxidized polyolefin is epoxidized polybutadiene having a general structural formula:
wherein m is 4-11, n is 16-43.
In the present invention, m is typically, but not limited to, 4, 5, 6, 7, 8, 9,10 or 11, and n is typically, but not limited to, 16, 17, 18, 20, 22, 24, 25, 26, 28, 30, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42 or 43.
The inventors found that when m is too small, it results in a small number of epoxy functional groups and a low degree of pre-polymerization reaction with benzoxazine, and when m is too large, it results in poor dielectric properties of the prepolymer; when n is too small, it results in a low double bond content of the prepolymer, a low crosslinking density with a thermosetting resin when applied to a resin composition, and when n is too large, it results in a high viscosity of the epoxidized polybutadiene and difficulty in the operation of the prepolymerization reaction. Therefore, the comprehensive characteristics and the operation process of the prepolymer are optimally balanced by further defining m and n in the structural general formula of the epoxidized polybutadiene.
As an alternative embodiment of the invention, the accelerator comprises any one or a combination of at least two of 2-methylimidazole, 2-phenyl-imidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 4-dimethylaminopyridine, zinc octoate, cobalt acetylacetonate or zinc acetylacetonate.
As an alternative embodiment of the present invention, the solvent includes any one of butanone, acetone, toluene, dimethylbenzene, trimethylbenzene, N-dimethylformamide, N-dimethylacetamide, cyclohexanone, or propylene glycol methyl ether, or a combination of at least two thereof.
As an alternative embodiment of the invention, the promoter is added in an amount of 0.1% to 3% by weight of the mixture of benzoxazine and epoxidized polyolefin.
Typical but non-limiting mass fractions of accelerator(s) by weight of the mixture are 0.1%, 0.5%, 0.8%, 1.0%, 1.2%, 1.5%, 1.8%, 2.0%, 2.2%, 2.5%, 2.8% or 3.0%.
As an alternative embodiment of the present invention, the temperature of the prepolymerization is 60-200 ℃ and the prepolymerization time is 10-300 min.
The temperature of the prepolymerization is typically, but not limited to, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃ or 200 ℃.
As an alternative embodiment of the invention, the prepolymerization process is carried out with stirring.
As a preferred embodiment of the present invention, the preparation method of the modified benzoxazine prepolymer comprises the steps of:
mixing benzoxazine, epoxidized polyolefin, an accelerator and a solvent, heating to 60-200 ℃ under a stirring state, maintaining for 10-300min to perform prepolymerization reaction, and cooling to room temperature to obtain the modified benzoxazine prepolymer.
According to the second aspect of the invention, the modified benzoxazine prepolymer is prepared by the preparation method of the modified benzoxazine prepolymer.
In view of the advantages of the preparation method, the prepared modified benzoxazine prepolymer has good dielectric properties.
According to a third aspect of the present invention, there is also provided a resin composition, which mainly comprises the following components in parts by weight:
50-100 parts of modified benzoxazine prepolymer, 5-60 parts of thermosetting resin, 0.2-3 parts of free radical initiator, 5-40 parts of flame retardant and 50-200 parts of filler;
wherein the modified benzoxazine prepolymer is the modified benzoxazine prepolymer;
the thermosetting resin comprises any one of polyphenylene oxide, maleimide resin, polybutadiene, butadiene-styrene copolymer, diallyl bisphenol A, triallyl isocyanurate, triallyl cyanurate, divinylbenzene or epoxy resin or a combination of at least two of the foregoing.
In the invention, the modified benzoxazine prepolymer has good dielectric property, so that the modified benzoxazine prepolymer and a specific thermosetting resin are subjected to polymerization reaction under the action of a free radical initiator and the like, and the modified benzoxazine prepolymer and the thermosetting resin have good compatibility, so that a cured product of the prepared resin composition has the characteristics of high glass transition temperature, low dielectric property and low absorption rate.
The filler has the main functions of reducing the expansion coefficient of the resin composition, improving the heat resistance of the resin composition, improving the flame retardant effect of the resin composition and reducing the water absorption rate of a material prepared by the resin composition at a later stage.
In the present invention, the amount of each raw material is limited. Specifically, the modified benzoxazine prepolymer is typically, but not limited to, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, or 100 parts by weight. Typical but non-limiting parts by weight of the thermosetting resin are 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, or 60 parts. Typical but non-limiting parts by weight of the free radical initiator are 0.2 parts, 0.5 parts, 0.8 parts, 1.0 parts, 1.2 parts, 1.5 parts, 1.8 parts, 2.0 parts, 2.2 parts, 2.5 parts, 2.8 parts, or 3.0 parts. Typical but non-limiting parts by weight of flame retardant are 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts. Typical, but non-limiting, parts by weight of the filler are 50 parts, 60 parts, 70 parts, 80 parts, 90 parts, 100 parts, 110 parts, 120 parts, 130 parts, 140 parts, 150 parts, 160 parts, 170 parts, 180 parts, 190 parts, or 200 parts.
When the weight part of the modified benzoxazine prepolymer is too low (less than 50 parts), the glass transition temperature of the cured product formed from the resin composition is liable to be low and the reliability is deteriorated, and when the weight part of the modified benzoxazine prepolymer is too high (more than 100 parts), the dielectric properties of the cured product formed from the resin composition are deteriorated. When the weight part of the thermosetting resin is too low (less than 5 parts), the dielectric properties of the cured product formed from the resin composition tend to be deteriorated, and when the weight part of the thermosetting resin is too high (more than 60 parts), the peel strength of the cured product formed from the resin composition tends to be deteriorated.
It is to be noted that "comprising", "mainly made of … …" in the present invention means that it may include other materials in addition to the materials, which give the liquid composition different characteristics. In addition, the terms "comprising," "made primarily of … …," and "made of … …," as used herein, are intended to be interchangeable.
As an alternative embodiment of the present invention, the radical initiator includes any one or a combination of at least two of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 3-dimethyl-2, 3-diphenylbutane, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t-butylperoxy-dicumyl, t-butyl peroxybenzoate, t-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, or dicyclohexyl peroxycarbonate.
As an alternative embodiment of the present invention, the flame retardant comprises any one or a combination of at least two of brominated styrene, decabromodiphenyl ether, decabromodiphenyl ethane, ethylenebistetrabromophthalimide, tris (2, 6-dimethoxyphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, aluminum diethylphosphinate or hexaphenoxycyclotriphosphazene.
As an alternative embodiment of the present invention, the filler includes any one or a combination of at least two of crystalline silica, fused silica, spherical silica, alumina, aluminum hydroxide, carbon black, aniline black, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, aluminum nitride, boron nitride, silicon nitride, aluminum silicon carbide, sodium carbonate, magnesium carbonate, titanium dioxide, zinc oxide, zirconium oxide, potassium titanate, strontium titanate, barium titanate, ceramic fiber, zinc molybdate, ammonium molybdate, calcium phosphate, boehmite, and polytetrafluoroethylene powder.
According to a fourth aspect of the present invention, there is also provided a cured product of a resin composition obtained using the above resin composition.
The cured product of the resin composition provided by the invention is mainly formed by curing the resin composition.
According to a fifth aspect of the present invention, there is also provided an electronic component made of the above resin composition or a cured product of the above resin composition.
The resin composition or the cured product thereof provided by the invention can be prepared into various electronic product components in different processing modes, such as a prepreg, a copper-clad laminate or a printed circuit board.
As an alternative embodiment of the present invention, the resin composition of the present invention may be prepared as a prepreg. The preparation method of the prepreg comprises the following steps: preparing the thermosetting resin composition into glue solution, then soaking the reinforcing material in the glue solution to form a layered object, heating the layered object at high temperature to form a prepreg, and baking the prepreg at the temperature of between 100 and 180 ℃. Examples of the reinforcing material are not particularly limited, and may be commercially available glass cloth that can be used for various printed circuit boards.
As an alternative embodiment of the present invention, the resin composition of the present invention may be used to produce a copper-clad laminate. The following methods may be mentioned: and taking at least one prepreg and the metal copper foil coated on one side or two sides of the prepreg, and heating and pressurizing to obtain the composite material. The metallic copper foil may be a standard electrolytic copper foil, a reverse copper foil, a low profile copper foil, or an ultra-low profile copper foil. The heating and pressing conditions may be appropriately adjusted depending on the kind of the composition or the thickness of the copper-clad laminate. For example, the pressing temperature may be set to 170 ℃ to 250 ℃ and the pressure may be set to 1.0 to 6.0 MPa. The copper clad laminate may be further processed according to various circuit board manufacturing processes known in the art.
The present invention will be further described with reference to specific examples and comparative examples.
The following examples and comparative examples were each prepared by using the raw materials in parts by mass, the manufacturers and types of the raw materials used were as shown in table 1, and the raw materials not shown in table 1 were obtained by commercially purchasing them.
TABLE 1
Example 1
The embodiment provides a preparation method of a modified benzoxazine prepolymer, which comprises the following steps:
dissolving 55g of benzoxazine (LZ 8290), 15g of epoxidized polybutadiene (JP-100) and 0.5g of accelerator (2E4Mz) in a mixed solution of butanone and trimethylbenzene (the volume ratio of butanone to trimethylbenzene is 1: 2), stirring uniformly, adding into a three-neck flask provided with a stirrer, a thermometer and a cooling reflux device, heating to 150 ℃, and stirring at the temperature for 150min in a heat preservation manner to obtain the modified benzoxazine prepolymer.
Example 2 to example 7
Examples 2 to 7 each provide a method for preparing a modified benzoxazine prepolymer, which was the same as in example 1 except that the kind and amount of each raw material used were different from those of example 1. The kinds and amounts of the raw materials of examples 1 to 7 are shown in Table 2.
TABLE 2
Comparative example 1
The comparative example provides a method of preparing a modified benzoxazine composition comprising the steps of:
55g of benzoxazine (LZ 8290), 15g of epoxidized polybutadiene (JP-100) and 0.5g of accelerator (2E4Mz) were directly physically mixed to obtain a modified benzoxazine composition.
Comparative example 2
The comparative example provides a method of preparing a modified benzoxazine composition comprising the steps of:
55g of benzoxazine (LZ 8290) and 0.5g of accelerator (2E4Mz) were physically mixed directly to give a modified benzoxazine composition.
Comparative example 3
This comparative example provides a preparation method of a modified benzoxazine prepolymer, except that the epoxidized polybutadiene (JP-100) was replaced with an equal amount of polybutadiene (Japanese Caoda, brand: B3000), and the other raw materials and steps were the same as in example 1.
Comparative example 4
This comparative example provides a method for preparing a modified benzoxazine prepolymer, which was the same as example 4 except that the mass of benzoxazine in example 4 was changed from 55g to 45g, and the mass of epoxidized polybutadiene was changed from 45g to 55 g.
Comparative example 5
This comparative example provides a method for preparing a modified benzoxazine prepolymer, which was the same as example 6 except that the mass of the epoxidized polybutadiene in example 6 was changed from 25g to 3 g.
Examples 8 to 14
Examples 8 to 14 each provide a resin composition using the modified benzoxazine prepolymers provided in examples 1 to 7, and examples 15 to 18 each use the modified benzoxazine prepolymer provided in example 3, and the kinds and amounts of the raw materials of the examples are shown in table 3.
TABLE 3
Comparative example 6
This comparative example provides a resin composition, except that the modified benzoxazine prepolymer in example 8 was replaced with the same amount of the modified benzoxazine composition provided in comparative example 1, and the kinds and amounts of the remaining raw materials were the same as those in example 8.
Comparative example 7
This comparative example provides a resin composition, except that the modified benzoxazine prepolymer in example 8 was replaced with the same amount of the modified benzoxazine composition provided in comparative example 1, while the amount of silica FB-3Y was replaced from 88g to 95g, and the kinds and amounts of the remaining raw materials were the same as those in example 8.
Comparative example 8
This comparative example provides a resin composition, except that the modified benzoxazine prepolymer in example 14 was replaced with the same amount of the modified benzoxazine composition provided in comparative example 2, and the kinds and amounts of the remaining raw materials were the same as those in example 14.
Comparative example 9
This comparative example provides a resin composition, except that the modified benzoxazine prepolymer in example 8 was replaced with the same amount of the modified benzoxazine prepolymer provided in comparative example 3, and the kinds and amounts of the remaining raw materials were the same as those in example 8.
Comparative example 10
This comparative example provides a resin composition, except that the modified benzoxazine prepolymer in example 11 was replaced with the same amount of the modified benzoxazine prepolymer provided in comparative example 4, and the kinds and amounts of the remaining raw materials were the same as those in example 11.
Comparative example 11
This comparative example provides a resin composition, except that the modified benzoxazine prepolymer in example 13 was replaced with the same amount of the modified benzoxazine prepolymer provided in comparative example 5, and the kinds and amounts of the remaining raw materials were the same as those in example 13.
Comparative example 12
This comparative example provides a resin composition, except that the thermosetting resin in example 8 was replaced with the same amount of cyanate ester, and the kinds and amounts of the raw materials were the same as those in example 8.
Comparative example 13
This comparative example provides a resin composition of the same kind and amount as those of example 17 except that the thermosetting resin in example 17 was replaced with the same amount of diallylbisphenol A.
Comparative example 14
This comparative example provides a resin composition, the kind and amount of the raw materials were the same as those in example 18 except that the thermosetting resin in example 18 was replaced with the same amount of trimethylolpropane triacrylate.
Comparative example 15
This comparative example provides a resin composition, except that the thermosetting resin in example 8 was replaced with BMI of 2.5g, TAIC of 5g and B-2000 of 25g in place of BMI of 5g, TAIC of 5g and B-2000 of 12.5g, and the kinds and amounts of the other raw materials were the same as those in example 8.
Comparative example 16
This comparative example provides a resin composition of the same kind and amount as those of example 17 except that the thermosetting resin in example 17 was replaced from 30 parts to 65 parts.
Comparative example 17
This comparative example provides a resin composition, and the kind and amount of the raw materials were the same as those in example 8 except that no filler was added in example 8.
In order to compare the effects of the respective examples and comparative examples, the following experimental examples were specifically set.
Experimental example 1
The resin compositions provided in examples 8 to 18 and comparative examples 6 to 17 were dissolved in a mixed solution of an appropriate amount of methyl ethyl ketone and toluene, respectively, and uniformly dispersed with stirring to obtain a glue solution, a 1080 glass fiber cloth was dipped in the glue solution, the solvent was dried in an oven at 170 ℃ to obtain prepregs, 8 sheets of 1080 prepregs were stacked, reverse copper foils with a thickness of 1oz were coated on both sides, and vacuum-cured for 2 hours in a press at a curing temperature of 240 ℃ to obtain a copper-clad laminate.
The properties of each copper-clad laminate obtained as described above, such as glass transition temperature, peel strength, copper-containing tin immersion, dielectric constant, dielectric loss tangent, and water absorption rate, were measured, and the specific results are shown in table 4. Wherein the glass transition temperature is tested by a Dynamic Mechanical Analysis (DMA) instrument with reference to IPC-TM-6502.4.24.4; the peel strength is tested by the method described in IPC-TM-6502.4.8; the copper-containing tin immersion detection method comprises the following steps: dipping the copper-clad plate with the size of 5cm by 5cm in a tin furnace at 288 ℃, and observing whether the phenomenon of layering and plate explosion occurs or not; the dielectric constant and dielectric loss tangent test method refers to IEC 61189-2-721-2015, frequency 10 GHz; the water absorption test method comprises the following steps: see IPC-TM-6502.6.2.1.
TABLE 4
As can be seen from the data in table 4, the copper clad substrate prepared from the modified benzoxazine prepolymer and the resin composition provided in the embodiments of the present invention has low water absorption rate, low dielectric constant, low dielectric loss, and excellent wet heat resistance. Different characteristic requirements of the copper-clad plate can be realized by adjusting the proportion of the components of the prepolymer and the type and proportion of the resin composition.
Specifically, comparative example 6 is a comparative experiment of example 8, and compared with comparative example 6, the glass transition temperature and the copper-containing tin immersion of example 8 are improved, and the Dk/Df value and the water absorption are reduced, which shows that compared with the physical mixing, the pre-polymerization modification can improve the compatibility between benzoxazine and epoxidized polyolefin, improve the cross-linking density, improve the reliability of the sheet material, and reduce the water absorption of the sheet material.
Comparative example 8 is a comparative experiment of example 14, and the Df of example 14 is reduced by 0.0028 compared to comparative example 8, which shows that the dielectric properties of the cured product can be reduced after the epoxidized polyolefin pre-polymerized modified benzoxazine.
Comparative example 12 is a comparative experiment of example 8, and the copper-containing wicking time of comparative example 12 is shortened, indicating that the heat resistance of the cured product is deteriorated after the thermosetting resin is replaced with cyanate ester.
Comparative example 13 is a comparative experiment of example 17, and the Df of comparative example 13 is increased by 0.0062 compared to example 17, which shows that the dielectric properties of the cured product become poor after the thermosetting resin is replaced with diallyl bisphenol A.
Comparative example 14 is a comparative experiment of example 18, and the glass transition temperature of comparative example 14 is lowered by 28 ℃ compared to example 18, indicating that the reliability of the cured product is lowered when the thermosetting resin is replaced with trimethylolpropane triacrylate.
Comparative example 15 is a comparative experiment of example 8, and the dielectric properties are deteriorated due to the lowering of the glass transition temperature and the increase of Df of comparative example 15, as compared with example 8.
Comparative example 16 is a comparative experiment of example 17, and both the glass transition temperature reduction and the peel strength of comparative example 16 are greatly reduced compared to example 17.
Comparative example 17 is a comparative experiment of example 8, and comparative example 17 has a deteriorated copper-containing wicking and a greatly increased water absorption compared to example 8, indicating that the addition of the filler to the resin composition can improve the heat resistance and significantly reduce the water absorption.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a modified benzoxazine prepolymer is characterized by comprising the following steps:
mixing benzoxazine, epoxidized polyolefin, an accelerator and a solvent to carry out prepolymerization to obtain a modified benzoxazine prepolymer;
the weight ratio of the benzoxazine to the epoxidized polyolefin is (50-95): (5-50).
2. The production method according to claim 1, characterized in that the benzoxazine comprises any one of bisphenol a type benzoxazine, bisphenol F type benzoxazine, phenolphthalein type benzoxazine, diphenylmethane type benzoxazine, dicyclopentadiene type benzoxazine, diaminodiphenyl ether type benzoxazine, benzoxazine containing an unsaturated double bond structure, or a combination of at least two thereof;
preferably, the epoxidized polyolefin is epoxidized polybutadiene and has the structural formula:
wherein m is 4-11, n is 16-43.
3. The method according to claim 1, wherein the accelerator comprises any one or a combination of at least two of 2-methylimidazole, 2-phenyl-imidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, 4-dimethylaminopyridine, zinc octanoate, cobalt acetylacetonate, or zinc acetylacetonate;
preferably, the solvent includes any one of butanone, acetone, toluene, dimethylbenzene, trimethylbenzene, N-dimethylformamide, N-dimethylacetamide, cyclohexanone, or propylene glycol methyl ether, or a combination of at least two thereof.
4. A method of producing according to any one of claims 1 to 3, characterized in that the promoter is added in an amount of 0.1% to 3% by weight of the mixture of benzoxazine and epoxidized polyolefin.
5. The process according to any one of claims 1 to 3, wherein the prepolymerization temperature is 60 to 200 ℃ and the prepolymerization time is 10 to 300 min;
preferably, the prepolymerization process is carried out with stirring.
6. A modified benzoxazine prepolymer produced by the production method according to any one of claims 1 to 5.
7. The resin composition is characterized by mainly comprising the following components in parts by weight:
50-100 parts of modified benzoxazine prepolymer, 5-60 parts of thermosetting resin, 0.2-3 parts of free radical initiator, 5-40 parts of flame retardant and 50-200 parts of filler;
wherein the modified benzoxazine prepolymer is the modified benzoxazine prepolymer of claim 6;
the thermosetting resin comprises any one of polyphenyl ether, maleimide resin, polybutadiene, butadiene-styrene copolymer, diallyl bisphenol A, triallyl isocyanurate, triallyl cyanurate, divinyl benzene or epoxy resin or a combination of at least two of the polyphenyl ether, the maleimide resin, the polybutadiene, the butadiene-styrene copolymer, the diallyl bisphenol A, the triallyl isocyanurate and the triallyl cyanurate.
8. The resin composition of claim 7, wherein the radical initiator comprises any one or a combination of at least two of 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane, 2, 3-dimethyl-2, 3-diphenylbutane, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, dicumyl peroxide, di-t-butylperoxy dicumyl, t-butyl peroxybenzoate, t-butyl peroxypivalate, methyl ethyl ketone peroxide, cyclohexanone peroxide, diisopropyl peroxydicarbonate, or dicyclohexyl peroxycarbonate;
preferably, the flame retardant comprises any one or a combination of at least two of brominated styrene, decabromodiphenyl ether, decabromodiphenyl ethane, ethylenebistetrabromophthalimide, tris (2, 6-dimethoxyphenyl) phosphine, 10- (2, 5-dihydroxyphenyl) -9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2, 5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, aluminum diethylphosphinate or hexaphenoxycyclotriphosphazene;
preferably, the filler includes any one of crystalline silica, fused silica, spherical silica, alumina, aluminum hydroxide, carbon black, aniline black, magnesium oxide, magnesium hydroxide, calcium carbonate, talc, aluminum nitride, boron nitride, silicon nitride, aluminum silicon carbide, sodium carbonate, magnesium carbonate, titanium dioxide, zinc oxide, zirconium oxide, potassium titanate, strontium titanate, barium titanate, ceramic fiber, zinc molybdate, ammonium molybdate, calcium phosphate, boehmite, or polytetrafluoroethylene powder, or a combination of at least two thereof.
9. A cured product of a resin composition, characterized by being produced using the resin composition according to claim 7 or 8.
10. An electronic component produced using the resin composition according to claim 7 or 8 or a cured product of the resin composition according to claim 9;
preferably, the electronic product assembly comprises a prepreg, a copper clad laminate or a printed circuit board.
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