CN115894926A - Epoxy phosphorus-containing polysiloxane, preparation method thereof and prepared epoxy composition - Google Patents
Epoxy phosphorus-containing polysiloxane, preparation method thereof and prepared epoxy composition Download PDFInfo
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- CN115894926A CN115894926A CN202211454972.9A CN202211454972A CN115894926A CN 115894926 A CN115894926 A CN 115894926A CN 202211454972 A CN202211454972 A CN 202211454972A CN 115894926 A CN115894926 A CN 115894926A
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- epoxy
- phosphorus
- containing polysiloxane
- polysiloxane
- epoxy resin
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- -1 polysiloxane Polymers 0.000 title claims abstract description 111
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 110
- 239000004593 Epoxy Substances 0.000 title claims abstract description 95
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 87
- 239000011574 phosphorus Substances 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 65
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 5
- 239000005022 packaging material Substances 0.000 claims abstract description 5
- 238000004100 electronic packaging Methods 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 26
- 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 22
- SLJFKNONPLNAPF-UHFFFAOYSA-N 3-Vinyl-7-oxabicyclo[4.1.0]heptane Chemical compound C1C(C=C)CCC2OC21 SLJFKNONPLNAPF-UHFFFAOYSA-N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 claims description 18
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003505 polymerization initiator Substances 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 5
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000012656 cationic ring opening polymerization Methods 0.000 claims description 4
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 claims description 4
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002841 Lewis acid Substances 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 3
- CZHYKKAKFWLGJO-UHFFFAOYSA-N dimethyl phosphite Chemical compound COP([O-])OC CZHYKKAKFWLGJO-UHFFFAOYSA-N 0.000 claims description 3
- 150000007517 lewis acids Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000000751 azo group Chemical class [*]N=N[*] 0.000 claims description 2
- 150000001768 cations Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 229910000510 noble metal Chemical class 0.000 claims description 2
- 229920003986 novolac Polymers 0.000 claims description 2
- 150000007524 organic acids Chemical group 0.000 claims description 2
- 150000001451 organic peroxides Chemical class 0.000 claims description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims 1
- 239000002648 laminated material Substances 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 abstract description 20
- 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 abstract description 5
- 239000003063 flame retardant Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 38
- 238000003756 stirring Methods 0.000 description 24
- 238000001291 vacuum drying Methods 0.000 description 24
- 238000004821 distillation Methods 0.000 description 23
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 12
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 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 3
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- HYZQBNDRDQEWAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;manganese(3+) Chemical compound [Mn+3].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O HYZQBNDRDQEWAN-LNTINUHCSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- JNJGROHZMWDCCM-UHFFFAOYSA-N C(C)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C(C)(=O)O Chemical compound C(C)C1=C(C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C(C)(=O)O JNJGROHZMWDCCM-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- PBWZKZYHONABLN-UHFFFAOYSA-N difluoroacetic acid Chemical compound OC(=O)C(F)F PBWZKZYHONABLN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
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Abstract
The invention discloses epoxy group phosphorus-containing polysiloxane, which has a structure shown in a general formula(1) Shown;
1-30 wt% of epoxy group phosphorus-containing polysiloxane, 30-80 wt% of epoxy resin, 5-60 wt% of curing agent and 0-2 wt% of curing accelerator are mixed to prepare the epoxy composition containing epoxy group phosphorus-containing polysiloxane. The epoxy phosphorus-containing polysiloxane prepared by the invention not only can effectively improve the toughness of the cured epoxy resin, but also can greatly improve the flame retardant property of the cured epoxy resin. Is expected to be applied to the fields of adhesive materials, composite materials, copper clad plate materials and electronic packaging materials.
Description
Technical Field
The invention relates to the technical field of functional epoxy resin compositions, in particular to epoxy phosphorus-containing polysiloxane, a preparation method thereof and a prepared epoxy composition.
Background
Epoxy resin is widely applied to the fields of adhesives, coatings, semiconductor packaging materials, composite materials, building traffic and the like because of good electrical insulation performance, excellent bonding strength, small curing shrinkage, good dimensional stability, high hardness and solvent resistance. However, epoxy resins are generally cured to have high crosslinking density and large internal stress, and the cured products obtained are insufficient in toughness, large in brittleness and poor in impact resistance. Therefore, how to improve the toughness and the flame retardance of the cured epoxy resin has important research significance and application value.
Polysiloxane is a polymer with a main chain consisting of silicon-oxygen bonds, has very excellent comprehensive properties such as high thermal stability, excellent flexibility, excellent flame retardance, strong hydrophobic property and the like, is an excellent modifier of epoxy resin, can participate in curing of an epoxy resin matrix, and can effectively avoid a phase separation phenomenon, but the existence of the flexible reactive groups can often cause the glass transition temperature (T) of an epoxy cured product g ) Is reduced. The modifier for toughening and reinforcing the epoxy resin and improving the flame retardant property of the epoxy resin has important significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides epoxy phosphorus-containing polysiloxane, a preparation method thereof and a prepared epoxy composition. The invention has high toughness and good flame retardant property.
The technical scheme of the invention is as follows:
the first purpose of the invention is to provide epoxy phosphorus-containing polysiloxane, wherein the structure of the epoxy phosphorus-containing polysiloxane is shown as a general formula (1);
in the general formula (1), a is an integer ranging from 4 to 20; b. c is an integer ranging from 1 to 20;
r represents
In one embodiment of the invention, the phosphorus element mass fraction of the epoxy phosphorus-containing polysiloxane is 1 to 10wt%.
The second purpose of the invention is to provide a preparation method of the epoxy phosphorus-containing polysiloxane, which comprises the following steps:
(1) Mixing octamethylcyclotetrasiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane, 1, 3-tetramethyldisiloxane and a cation ring-opening polymerization initiator, and reacting at 25-80 ℃ for 12-48 h to prepare hydrogen-containing polysiloxane;
(2) Mixing the hydrogen-containing polysiloxane prepared in the step (1), 1, 2-epoxy-4-vinylcyclohexane and a solvent, adding a catalyst, and reacting at 40-120 ℃ for 4-24 h to prepare epoxy polysiloxane;
(3) Mixing the epoxy polysiloxane prepared in the step (2), a phosphorus-containing monomer, a catalyst and a solvent, and reacting for 8-24 h at 80-160 ℃ to obtain the epoxy phosphorus-containing polysiloxane.
In one embodiment of the present invention, in the step (1), the molar ratio of octamethylcyclotetrasiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane and 1, 3-tetramethyldisiloxane is 4 to 16.
In one embodiment of the present invention, in the step (1), the cationic ring-opening polymerization initiator is a protonic acid or a lewis acid; the dosage of the cationic ring-opening polymerization initiator is 0.1-1% of the total mass of the octamethylcyclotetrasiloxane, the 1,3,5, 7-tetramethylcyclotetrasiloxane and the 1, 3-tetramethyldisiloxane.
Preferably, the protic acid is concentrated sulfuric acid, phosphoric acid, perchloric acid, chlorosulfonic acid, fluorosulfonic acid, dichloroacetic acid, difluoroacetic acid, trichloroacetic acid, trifluoroacetic acid, or trifluoromethanesulfonic acid; the Lewis acid is boron trifluoride, aluminum trichloride, titanium tetrachloride, stannic chloride, zinc chloride or antimony pentachloride.
In one embodiment of the present invention, in the step (2), the mass ratio of the hydrogenpolysiloxane to the 1, 2-epoxy-4-vinylcyclohexane is 1; the catalyst is one or more of organic alkali compounds, organic peroxides, azo compounds and noble metal compounds; the dosage of the catalyst is 0.01 to 0.1 percent of the total mass of the hydrogen-containing polysiloxane and the 1, 2-epoxy-4-vinyl cyclohexane;
preferably, the catalyst is one or more of 1, 3-divinyl-1, 3-tetramethyldisiloxane platinum (0), chloroplatinic acid, platinum carbon catalyst.
The solvent is one or more of toluene, xylene, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, ethanol, propanol, acetone, 2-butanone and dichloromethane; the solvent is used in an amount to ensure that the concentration of the hydrogenpolysiloxane and the 1, 2-epoxy-4-vinylcyclohexane is between 0.2 and 1.0g/mL.
In one embodiment of the present invention, in the step (3), the phosphorus-containing monomer is one or more of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dimethyl phosphite, diethyl phosphite, and diphenyl phosphite; the mass ratio of the epoxy polysiloxane to the phosphorus-containing monomer is 1.1-0.85; the solvent is one or more of toluene, xylene, acetonitrile, methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane, tetrahydrofuran, acetone and dimethyl sulfoxide; the dosage of the solvent is to ensure that the concentration of the epoxy polysiloxane and the phosphorus-containing monomer is 0.2-1.0 g/mL; the catalyst is one or more of triphenylphosphine, N-dimethylbenzylamine and tetrabutylammonium bromide; the dosage of the catalyst is 0.5-2% of the total mass of the epoxy polysiloxane and the phosphorus-containing monomer.
The third object of the present invention is to provide an epoxy composition containing the epoxy-based phosphorus-containing polysiloxane, which comprises the following components:
in one embodiment of the present invention, the epoxy resin is one or more of bisphenol a type epoxy resin, hydrogenated bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac type epoxy resin, aliphatic glycidyl ether epoxy resin, alicyclic epoxy resin; the curing agent is an organic acid anhydride or organic amine curing agent; the curing accelerator is one or more of tertiary amine, imidazole, organophosphorus compounds and acetylacetone metal salt.
Preferably, the epoxy resin is a bisphenol a type epoxy resin having an epoxy value of 0.4 to 0.6.
Preferably, the curing agent is one or more of methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, trimellitic anhydride, methyl nadic anhydride, 4 '-diaminodiphenylmethane, 4' -diaminodiphenyl sulfone and m-phenylenediamine.
Preferably, the curing accelerator is one or more of triethylamine, N-dimethylbenzylamine, 2-ethyl-4-methylimidazole, 2-methylimidazole, ethyl triphenyl phosphine acetate, triphenylphosphine, iron acetylacetonate and manganese acetylacetonate.
The fourth purpose of the invention is to provide the application of the epoxy composition, which is used for adhesive materials, composite materials, copper-clad plate materials and electronic packaging materials.
The beneficial technical effects of the invention are as follows:
the epoxy phosphorus-containing polysiloxane prepared by the invention can effectively improve the toughness of the cured epoxy resin and can greatly improve the flame retardant property of the cured epoxy resin. Is expected to be applied to the fields of adhesive materials, composite materials, copper clad plate materials and electronic packaging materials.
Drawings
FIG. 1 is a schematic diagram of a synthetic route for preparing an epoxy phosphorus-containing polysiloxane according to example 1 of the present invention;
FIG. 2 is a NMR chart of an epoxy phosphorus-containing polysiloxane according to example 1 of the present invention;
FIG. 3 is a Fourier transform infrared spectrum of an epoxyphosphorus-containing polysiloxane of example 1 in accordance with the present invention;
FIG. 4 is a graph showing the results of comparison of the flexural strengths of cured resins provided in examples 13 to 18 of the present invention and comparative example 1;
FIG. 5 is a graph showing the results of comparison of impact strengths of cured resins provided in examples 13 to 18 of the present invention and comparative example 1;
FIG. 6 is a graph showing the results of comparison of fracture toughness of cured resins provided in examples 13 to 18 of the present invention and comparative example 1;
FIG. 7 is a graph showing comparative results of limiting oxygen indexes of cured resins provided in examples 13 to 18 of the present invention and comparative example 1.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples. The method is regarded as a conventional method unless otherwise specified. The materials are commercially available from the open literature unless otherwise specified.
Examples 1 to 12 are methods for preparing epoxyphosphorus-containing polysiloxanes; examples 13 to 18 are methods for producing cured products of bisphenol A epoxy resins modified with the epoxy phosphorus-containing polysiloxane prepared in examples 1 to 6; examples 19 and 20 are methods for producing cured products of hydrogenated bisphenol a epoxy resins modified with the epoxy group-containing phosphorus-containing polysiloxane prepared in examples 7 and 8; examples 21 and 22 are methods for producing cured products of bisphenol F epoxy resins modified with the epoxy phosphorus-containing polysiloxane prepared in examples 9 and 10; examples 23 and 24 are methods for producing cured products of epoxy phosphorus-containing polysiloxane-modified alicyclic epoxy resins produced in examples 11 and 12; comparative example 1 is a method for preparing an unmodified cured epoxy resin.
Example 1
An epoxy group phosphorus-containing polysiloxane is prepared by the following steps:
(1) 17.8g of octamethylcyclotetrasiloxane, 14.4g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 2.0g of tetramethyldisiloxane and 102.7mg of trifluoromethanesulfonic acid were added in this order to the flask and reacted at 25 ℃ for 24 hours. And after the reaction is finished, adding excessive anhydrous sodium bicarbonate, stirring for 1 hour, adding excessive anhydrous sodium sulfate, continuously stirring for 1 hour, standing overnight, filtering under reduced pressure, distilling under reduced pressure, and drying under vacuum to obtain the hydrogen-containing polysiloxane (PDMS-H).
(2) 20.0g of PDMS-H, 27.4g of 1, 2-epoxy-4-vinylcyclohexane, 9.2mg of 1, 3-divinyl-1, 3-tetramethyldisiloxane platinum (0) and 45.2mL of toluene were sequentially added to the flask and reacted at 100 ℃ for 12 hours. And after the reaction is finished, carrying out reduced pressure distillation and vacuum drying to obtain the epoxy polysiloxane (PDMS-CE).
(3) 15.0g of PDMS-CE, 5.2g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 0.2g of triphenylphosphine and 40.4mL of N, N-dimethylformamide are added into a flask in sequence and reacted for 8 hours at 150 ℃. After the reaction is finished, reduced pressure distillation and vacuum drying are carried out, and the epoxy phosphorus-containing polysiloxane (PDMS-DCE) can be obtained, wherein the content of the phosphorus element is 3.7wt%.
The nuclear magnetic resonance hydrogen spectrum and the Fourier infrared spectrum of the hydrogenpolysiloxane (PDMS-H), the epoxy polysiloxane (PDMS-CE) and the epoxy phosphorus polysiloxane (PDMS-DCE) prepared in the embodiment of the invention are respectively shown in the attached figures 2 and 3.
As can be seen from fig. 2, the Si-H signal of PDMS-CE at δ =4.70ppm was completely disappeared and the epoxy group proton signal peak appeared at δ =3.05-3.14ppm, compared to PDMS-H. Compared with PDMS-CE, PDMS-DCE shows a proton signal peak of a benzene ring on a DOPO group at delta =7.3-8.7ppm, and the successful synthesis of PDMS-DGE is proved.
As can be seen from FIG. 3, 919 and 2158cm -1 Characteristic of absorption peak being Si-HPeak, after hydrosilylation reaction, si-H characteristic peak disappears, and the PDMS-CE infrared spectrogram also shows alicyclic epoxy group (880 cm) -1 ) Si-O-Si symmetrical bond (1104 cm) -1 ) And asymmetric keys (1038 cm) -1 ) Waiting for new characteristic peaks to show that the PDMS-CE is successfully synthesized; in the infrared spectrum of PDMS-DCE, the spectrum is at 2435cm -1 The peak at P-H stretching vibration disappears, and is 3403cm -1 The characteristic peak of-OH appears and P = O (1203 cm) -1 ) And P-O-C (1152 cm) -1 ) Characteristic peaks, which prove the successful synthesis of PDMS-DGE.
Example 2
An epoxy group phosphorus-containing polysiloxane is prepared by the following steps:
(1) 17.8g of octamethylcyclotetrasiloxane, 14.4g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 2.0g of tetramethyldisiloxane and 102.7mg of trifluoromethanesulfonic acid were added in this order to the flask and reacted at 25 ℃ for 24 hours. And after the reaction is finished, adding excessive anhydrous sodium bicarbonate, stirring for 1H, adding excessive anhydrous sodium sulfate, continuously stirring for 1H, standing overnight, filtering under reduced pressure, distilling under reduced pressure, and drying under vacuum to obtain the hydrogen-containing polysiloxane (PDMS-H).
(2) 20.0g of PDMS-H, 27.4g of 1, 2-epoxy-4-vinylcyclohexane, 9.2mg of 1, 3-divinyl-1, 3-tetramethyldisiloxane platinum (0) and 45.2mL of toluene are sequentially added into a flask, reacted at 100 ℃ for 12 hours, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy polysiloxane (PDMS-CE).
(3) 15.0g of PDMS-CE, 7.8g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 0.3g of catalyst triphenylphosphine and 45.6mL of N, N-dimethylformamide are sequentially added into a flask to react for 10 hours at 150 ℃, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy phosphorus-containing polysiloxane (PDMS-DCE), wherein the phosphorus content is 4.9wt%.
Example 3
An epoxy group phosphorus-containing polysiloxane, the preparation method comprises the following steps:
(1) 17.8g of octamethylcyclotetrasiloxane, 14.4g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 2.0g of tetramethyldisiloxane and 1.0mg of concentrated sulfuric acid were added in this order to a flask and reacted at 30 ℃ for 24 hours. And after the reaction is finished, adding excessive anhydrous sodium bicarbonate, stirring for 1H, adding excessive anhydrous sodium sulfate, continuously stirring for 1H, standing overnight, filtering under reduced pressure, distilling under reduced pressure, and drying under vacuum to obtain the hydrogen-containing polysiloxane (PDMS-H).
(2) 20.0g of PDMS-H, 27.4g of 1, 2-epoxy-4-vinylcyclohexane, 9.2mg of 1, 3-divinyl-1, 3-tetramethyldisiloxane platinum (0) and 45.2mL of xylene are sequentially added into a flask, reacted at 120 ℃ for 16 hours, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy polysiloxane (PDMS-CE).
(3) 15.0g of PDMS-CE, 10.4g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 0.3g of catalyst triphenylphosphine and 50.8mL of N, N-dimethylformamide are sequentially added into a flask to react for 12h at 150 ℃, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy phosphorus-containing polysiloxane (PDMS-DCE), wherein the content of phosphorus element is 5.8wt%.
Example 4
An epoxy group phosphorus-containing polysiloxane is prepared by the following steps:
(1) 17.8g of octamethylcyclotetrasiloxane, 14.4g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 1.0g of tetramethyldisiloxane and 99.6mg of trifluoromethanesulfonic acid were added in this order to the flask and reacted at 25 ℃ for 24 hours. And after the reaction is finished, adding excessive anhydrous sodium bicarbonate, stirring for 1 hour, adding excessive anhydrous sodium sulfate, continuously stirring for 1 hour, standing overnight, filtering under reduced pressure, distilling under reduced pressure, and drying under vacuum to obtain the hydrogen-containing polysiloxane (PDMS-H).
(2) 20.0g of PDMS-H, 27.4g of 1, 2-epoxy-4-vinyl cyclohexane, 13.3mg of 1, 3-divinyl-1, 3-tetramethyldisiloxane platinum (0) and 45.7mL of acetonitrile are sequentially added into a flask, and the mixture is reacted at 90 ℃ for 10 hours, then the reaction is carried out under reduced pressure, distillation and vacuum drying are carried out after the reaction is finished, thus obtaining the epoxy polysiloxane (PDMS-CE).
(3) 15.0g of PDMS-CE, 5.3g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 0.2g of catalyst triphenylphosphine and 40.6mL of dimethyl sulfoxide are sequentially added into a flask, and react for 8 hours at 150 ℃, after the reaction is finished, reduced pressure distillation and vacuum drying are carried out, so that epoxy phosphorus-containing polysiloxane (PDMS-DCE) is obtained, wherein the content of phosphorus is 3.7wt%.
Example 5
An epoxy group phosphorus-containing polysiloxane is prepared by the following steps:
(1) 17.8g of octamethylcyclotetrasiloxane, 14.4g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 1.0g of tetramethyldisiloxane and 332.0mg of perchloric acid were added in this order to the flask and reacted at 40 ℃ for 24 hours. And after the reaction is finished, adding excessive anhydrous sodium bicarbonate, stirring for 1H, adding excessive anhydrous sodium sulfate, continuously stirring for 1H, standing overnight, filtering under reduced pressure, distilling under reduced pressure, and drying under vacuum to obtain the hydrogen-containing polysiloxane (PDMS-H).
(2) 20.0g of PDMS-H, 27.4g of 1, 2-epoxy-4-vinyl cyclohexane, 13.3mg of 1, 3-divinyl-1, 3-tetramethyldisiloxane platinum (0) and 45.7mL of toluene are sequentially added into a flask, and reacted at 100 ℃ for 12 hours, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy polysiloxane (PDMS-CE).
(3) 15.0g of PDMS-CE, 8.0g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 0.1g of tetrabutylammonium bromide as a catalyst and 46.0mL of 1, 4-dioxane are sequentially added into a flask to react for 16h at 120 ℃, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy phosphorus-containing polysiloxane (PDMS-DCE), wherein the content of phosphorus element is 5.0wt%.
Example 6
An epoxy group phosphorus-containing polysiloxane, the preparation method comprises the following steps:
(1) 17.8g of octamethylcyclotetrasiloxane, 14.4g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 1.0g of tetramethyldisiloxane and 99.6mg of trifluoromethanesulfonic acid were added in this order to the flask and reacted at 25 ℃ for 24 hours. And after the reaction is finished, adding excessive anhydrous sodium bicarbonate, stirring for 1H, adding excessive anhydrous sodium sulfate, continuously stirring for 1H, standing overnight, filtering under reduced pressure, distilling under reduced pressure, and drying under vacuum to obtain the hydrogen-containing polysiloxane (PDMS-H).
(2) 20.0g of PDMS-H, 27.4g of 1, 2-epoxy-4-vinyl cyclohexane, 13.3mg of 1, 3-divinyl-1, 3-tetramethyldisiloxane platinum (0) and 45.7mL of toluene are sequentially added into a flask, and reacted at 100 ℃ for 12 hours, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy polysiloxane (PDMS-CE).
(3) 15.0g of PDMS-CE, 10.6g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 0.3g of catalyst triphenylphosphine and 51.2mL of N, N-dimethylformamide are sequentially added into a flask to react for 12 hours at 150 ℃, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy phosphorus-containing polysiloxane (PDMS-DCE), wherein the content of phosphorus is 5.9wt%.
Example 7
An epoxy group phosphorus-containing polysiloxane is prepared by the following steps:
(1) 11.9g of octamethylcyclotetrasiloxane, 4.8g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 1.3g of tetramethyldisiloxane and 0.5g of concentrated sulfuric acid were sequentially added to a flask, and reacted at 80 ℃ for 12 hours. And after the reaction is finished, adding excessive anhydrous sodium bicarbonate, stirring for 1H, adding excessive anhydrous sodium sulfate, continuously stirring for 1H, standing overnight, filtering under reduced pressure, distilling under reduced pressure, and drying under vacuum to obtain the hydrogen-containing polysiloxane (PDMS-H).
(2) 20.0g of PDMS-H, 26.1g of 1, 2-epoxy-4-vinylcyclohexane, 13.3mg of 1, 3-divinyl-1, 3-tetramethyldisiloxane platinum (0) and 45.7mL of dichloromethane are sequentially added into a flask, reacted at 40 ℃ for 24 hours, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy polysiloxane (PDMS-CE).
(3) 15.0g of PDMS-CE, 3.7g of dimethyl phosphite, 0.1g of catalyst triphenylphosphine and 37.4mL of xylene are sequentially added into a flask and reacted at 150 ℃ for 16h, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy phosphorus-containing polysiloxane (PDMS-DCE), wherein the content of phosphorus element is 5.6wt%.
Example 8
An epoxy group phosphorus-containing polysiloxane is prepared by the following steps:
(1) 11.9g of octamethylcyclotetrasiloxane, 4.8g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 1.3g of tetramethyldisiloxane and 0.5g of concentrated sulfuric acid were sequentially added to a flask and reacted at 40 ℃ for 12 hours. And after the reaction is finished, adding excessive anhydrous sodium bicarbonate, stirring for 1 hour, adding excessive anhydrous sodium sulfate, continuously stirring for 1 hour, standing overnight, filtering under reduced pressure, distilling under reduced pressure, and drying under vacuum to obtain the hydrogen-containing polysiloxane (PDMS-H).
(2) 20.0g of PDMS-H, 26.1g of 1, 2-epoxy-4-vinylcyclohexane, 23.1mg of 1, 3-dichloroplatinic acid and 45.7mL of acetonitrile are sequentially added into a flask, and reacted at 90 ℃ for 16 hours, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy polysiloxane (PDMS-CE).
(3) 15.0g of PDMS-CE, 7.8g of diphenyl phosphite, 0.1g of triphenylphosphine catalyst and 45.6mL of dimethyl sulfoxide are sequentially added into a flask and reacted at 160 ℃ for 10 hours, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy phosphorus-containing polysiloxane (PDMS-DCE), wherein the content of the phosphorus element is 4.5wt%.
Example 9
An epoxy group phosphorus-containing polysiloxane is prepared by the following steps:
(1) 47.5g of octamethylcyclotetrasiloxane, 9.6g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 2.6g of tetramethyldisiloxane and 0.3g of titanium tetrachloride were sequentially added to the flask, and reacted at 30 ℃ for 48 hours. And after the reaction is finished, adding excessive anhydrous sodium bicarbonate, stirring for 1H, adding excessive anhydrous sodium sulfate, continuously stirring for 1H, standing overnight, filtering under reduced pressure, distilling under reduced pressure, and drying under vacuum to obtain the hydrogen-containing polysiloxane (PDMS-H).
(2) 20.0g of PDMS-H, 23.3g of 1, 2-epoxy-4-vinylcyclohexane, 43.3mg of platinum carbon catalyst and 86.6mL of dichloromethane are sequentially added into a flask, and react at 40 ℃ for 24 hours, and after the reaction is finished, the epoxy polysiloxane (PDMS-CE) is obtained by reduced pressure distillation and vacuum drying.
(3) And (3) adding 15.0g of PDMS-CE, 3.9g of diethyl phosphite, 0.4g of catalyst tetrabutylammonium bromide and 37.8mL of tetrahydrofuran into a flask in sequence, reacting at 80 ℃ for 24 hours, and after the reaction is finished, carrying out reduced pressure distillation and vacuum drying to obtain the epoxy phosphorus-containing polysiloxane (PDMS-DCE), wherein the phosphorus content is 4.6wt%.
Example 10
An epoxy group phosphorus-containing polysiloxane is prepared by the following steps:
(1) 47.5g of octamethylcyclotetrasiloxane, 9.6g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 2.6g of tetramethyldisiloxane and 0.3g of titanium tetrachloride were sequentially added to the flask, and reacted at 30 ℃ for 48 hours. And after the reaction is finished, adding excessive anhydrous sodium bicarbonate, stirring for 1H, adding excessive anhydrous sodium sulfate, continuously stirring for 1H, standing overnight, filtering under reduced pressure, distilling under reduced pressure, and drying under vacuum to obtain the hydrogen-containing polysiloxane (PDMS-H).
(2) 20.0g of PDMS-H, 23.3g of 1, 2-epoxy-4-vinylcyclohexane, 34.6mg of chloroplatinic acid and 86.6mL of toluene are sequentially added into a flask, and reacted at 120 ℃ for 4 hours, and after the reaction is finished, the mixture is subjected to reduced pressure distillation and vacuum drying to obtain the epoxy polysiloxane (PDMS-CE).
(3) 15.0g of PDMS-CE, 6.0g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 0.2g of catalyst N, N' -dimethylbenzylamine and 37.8mL of dimethylbenzene are sequentially added into a flask to react for 16h at 120 ℃, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy phosphorus-containing polysiloxane (PDMS-DCE), wherein the content of phosphorus is 4.1wt%.
Example 11
An epoxy group phosphorus-containing polysiloxane, the preparation method comprises the following steps:
(1) 11.9g of octamethylcyclotetrasiloxane, 38.5g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 2.6g of tetramethyldisiloxane and 0.2g of trifluoromethanesulfonic acid were sequentially added to the flask, and reacted at 25 ℃ for 24 hours. And after the reaction is finished, adding excessive anhydrous sodium bicarbonate, stirring for 1H, adding excessive anhydrous sodium sulfate, continuously stirring for 1H, standing overnight, filtering under reduced pressure, distilling under reduced pressure, and drying under vacuum to obtain the hydrogen-containing polysiloxane (PDMS-H).
(2) 20.0g of PDMS-H, 40.9g of 1, 2-epoxy-4-vinylcyclohexane, 48.7mg of chloroplatinic acid and 86.6mL of N, N-dimethylformamide are sequentially added into a flask, and react at 100 ℃ for 12 hours, and after the reaction is finished, the reaction is decompressed and distilled, and vacuum drying is carried out, so that the epoxy polysiloxane (PDMS-CE) is obtained.
(3) 15.0g of PDMS-CE, 9.1g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 0.5g of catalyst N, N' -dimethylbenzylamine and 48.2mL of dimethylbenzene are sequentially added into a flask to react for 12 hours at 150 ℃, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy phosphorus-containing polysiloxane (PDMS-DCE), wherein the content of phosphorus is 5.4wt%.
Example 12
An epoxy group phosphorus-containing polysiloxane, the preparation method comprises the following steps:
(1) 11.9g of octamethylcyclotetrasiloxane, 38.5g of 1,3,5, 7-tetramethylcyclotetrasiloxane, 2.6g of tetramethyldisiloxane and 0.2g of trifluoromethanesulfonic acid were sequentially added to the flask, and reacted at 25 ℃ for 24 hours. And after the reaction is finished, adding excessive anhydrous sodium bicarbonate, stirring for 1H, adding excessive anhydrous sodium sulfate, continuously stirring for 1H, standing overnight, filtering under reduced pressure, distilling under reduced pressure, and drying under vacuum to obtain the hydrogen-containing polysiloxane (PDMS-H).
(2) 20.0g of PDMS-H, 40.9g of 1, 2-epoxy-4-vinylcyclohexane, 11.8mg of 1, 3-divinyl-1, 3-tetramethyldisiloxane platinum (0) and 86.6mL of toluene are sequentially added into a flask, and reacted at 100 ℃ for 12 hours, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out, so that the epoxy polysiloxane (PDMS-CE) can be obtained.
(3) 15.0g of PDMS-CE, 9.9g of diphenyl phosphite, 0.2g of triphenylphosphine catalyst and 49.8mL of dimethyl sulfoxide are sequentially added into a flask and reacted at 150 ℃ for 16h, and after the reaction is finished, reduced pressure distillation and vacuum drying are carried out to obtain the epoxy phosphorus-containing polysiloxane (PDMS-DCE), wherein the content of the phosphorus element is 5.3wt%.
Example 13
100g of epoxy resin (E51, epoxy equivalent EEW =196g eq) -1 ) And 14.1g of the epoxy phosphorus-containing polysiloxane (PDMS-DCE) obtained in example 1 are melted and mixed uniformly at 90 ℃, 26.9g of the curing agent 4,4' -diaminodiphenylmethane are added, stirred and mixed uniformly, then placed in a vacuum oven at 90 ℃ for defoaming for 20min, poured into a preheated special mold for defoaming for 20min, and then placed in a high-temperature oven for staged curing. Curing according to the curing procedures of 120 ℃/2h +140 ℃/2h +160 ℃/2h + and 180 ℃/1h, and obtaining the cured product of the epoxy resin composition.
Example 14
100g of epoxy resinFat (E51, epoxy equivalent EEW =196g eq -1 ) And 14.0g of the epoxy group phosphorus-containing polysiloxane (PDMS-DCE) obtained in example 2 were melted and mixed uniformly at 90 ℃, 26.0g of the curing agent 4,4' -diaminodiphenylmethane was added, stirred and mixed uniformly, and then placed in a vacuum oven at 90 ℃ to be defoamed for 20min, poured into a preheated special mold, defoamed for 20min, and then placed in a high-temperature oven to be cured in stages. Curing according to the curing program of 120 ℃/2h 140 ℃/2h 160 ℃/2h + and 180 ℃/1h to obtain the cured product of the epoxy resin composition.
Example 15
100g of epoxy resin (E51, epoxy equivalent EEW =196g eq -1 ) And 13.9g of the epoxy group phosphorus-containing polysiloxane (PDMS-DCE) obtained in example 3 were melted and mixed uniformly at 90 ℃, 25.6g of the curing agent 4,4' -diaminodiphenylmethane was added, stirred and mixed uniformly, and then placed in a vacuum oven at 90 ℃ to be defoamed for 20min, poured into a preheated special mold, defoamed for 20min, and then placed in a high-temperature oven to be cured in stages. Curing according to the curing procedures of 120 ℃/2h +140 ℃/2h +160 ℃/2h + and 180 ℃/1h, and obtaining the cured product of the epoxy resin composition.
Example 16
100g of epoxy resin (E51, epoxy equivalent EEW =196g eq -1 ) And 14.1g of the epoxy phosphorus-containing polysiloxane (PDMS-DCE) obtained in example 4 were melted and mixed uniformly at 90 ℃, 26.9g of the curing agent 4,4' -diaminodiphenylmethane was added, stirred and mixed uniformly, and then placed in a vacuum oven at 90 ℃ to be defoamed for 20min, poured into a preheated special mold, defoamed for 20min, and then placed in a high-temperature oven to be cured in stages. Curing according to the curing procedures of 120 ℃/2h +140 ℃/2h +160 ℃/2h + and 180 ℃/1h, and obtaining the cured product of the epoxy resin composition.
Example 17
100g of epoxy resin (E51, epoxy equivalent EEW =196g eq -1 ) And 14.0g of the epoxy phosphorus-containing polysiloxane (PDMS-DCE) obtained in example 5 were melted and mixed at 90 ℃ and then 26.0g of the curing agent 4,4' -diaminodiphenylmethane was added thereto, stirred and mixed uniformly, and then placed in a vacuum oven at 90 ℃ to be defoamed 20And (5) pouring the mixture into a preheated special mold, defoaming the mixture for 20min, and then putting the mixture into a high-temperature oven for stage curing. Curing according to the curing procedures of 120 ℃/2h +140 ℃/2h +160 ℃/2h + and 180 ℃/1h, and obtaining the cured product of the epoxy resin composition.
Example 18
100g of epoxy resin (E51, epoxy equivalent EEW =196g eq -1 ) And 13.9g of the epoxy phosphorus-containing polysiloxane (PDMS-DCE) obtained in example 6 were melted and mixed at 90 ℃ and then added with 25.6g of the curing agent 4,4' -diaminodiphenylmethane and stirred to be mixed uniformly, and then the mixture was placed in a vacuum oven at 90 ℃ to be defoamed for 20min, poured into a preheated special mold and then defoamed for 20min, and then the mixture was placed in a high-temperature oven to be cured in stages. Curing according to the curing procedures of 120 ℃/2h +140 ℃/2h +160 ℃/2h + and 180 ℃/1h, and obtaining the cured product of the epoxy resin composition.
Example 19
100g of epoxy resin (AL-3050, epoxy equivalent EEW =208g eq -1 ) And 13.8g of the epoxy phosphorus-containing polysiloxane (PDMS-DCE) obtained in example 7 were melted and mixed at 90 ℃ and then added with 24.2g of the curing agent 4,4' -diaminodiphenylmethane, stirred and mixed uniformly, and then placed in a vacuum oven at 90 ℃ to be defoamed for 20min, poured into a preheated special mold, and then defoamed for 20min, and then placed in a high-temperature oven to be cured in stages. Curing according to the curing procedures of 120 ℃/2h +140 ℃/2h +160 ℃/2h + and 180 ℃/1h, and obtaining the cured product of the epoxy resin composition.
Example 20
100g of epoxy resin (AL-3050, epoxy equivalent EEW =208g eq -1 ) And 13.8g of the epoxy phosphorus-containing polysiloxane (PDMS-DCE) obtained in example 8 were melted and mixed at 90 ℃ and then added with 24.2g of the curing agent 4,4' -diaminodiphenylmethane, stirred and mixed uniformly, and then placed in a vacuum oven at 90 ℃ to be defoamed for 20min, poured into a preheated special mold, and then defoamed for 20min, and then placed in a high-temperature oven to be cured in stages. Curing according to the curing program of 120 ℃/2h 140 ℃/2h 160 ℃/2h + and 180 ℃/1h to obtain the cured product of the epoxy resin composition.
Example 21
100g of epoxy resin (NPEF 170, epoxy equivalent EEW =165g eq -1 ) And 14.5g of the epoxy phosphorus-containing polysiloxane (PDMS-DCE) obtained in example 9 were melted and mixed at 90 ℃ and then added with 30.5g of the curing agent 4,4' -diaminodiphenylmethane, stirred and mixed uniformly, and then placed in a vacuum oven at 90 ℃ to be defoamed for 20min, poured into a preheated special mold and then defoamed for 20min, and then placed in a high-temperature oven to be cured in stages. Curing according to the curing program of 120 ℃/2h 140 ℃/2h 160 ℃/2h + and 180 ℃/1h to obtain the cured product of the epoxy resin composition.
Example 22
100g of epoxy resin (NPEF 170, epoxy equivalent EEW =165g eq -1 ) And 14.5g of the epoxy phosphorus-containing polysiloxane (PDMS-DCE) obtained in example 10 were melted and mixed at 90 ℃ and then added with 30.5g of the curing agent 4,4' -diaminodiphenylmethane and stirred to be mixed uniformly, and then the mixture was placed in a vacuum oven at 90 ℃ to be defoamed for 20min, poured into a preheated special mold and then defoamed for 20min, and then the mixture was placed in a high-temperature oven to be cured in stages. Curing according to the curing procedures of 120 ℃/2h +140 ℃/2h +160 ℃/2h + and 180 ℃/1h, and obtaining the cured product of the epoxy resin composition.
Example 23
25.9g of the epoxyphosphorus-containing polysiloxane obtained in example 11 (PDMS-DCE) and 100g of an epoxy resin (ERL-4221, epoxy equivalent EEW =131g eq -1 ) After being mixed evenly at 50 ℃, 133.1g of curing agent methyl hexahydrophthalic anhydride, 1.0g of curing accelerator ethyl triphenyl acetic phosphine and 1 drop of defoaming agent are added, and vacuum defoaming is carried out in a vacuum oven at 40 ℃ after the mixture is fully and evenly stirred. And then, injecting the fully defoamed epoxy resin composition into a mold, putting the mold into an oven for heating and curing, and curing at 90 ℃ for 3h, at 110 ℃ for 2h, at 130 ℃ for 2h and at 150 ℃ for 1h in sequence to obtain a cured product of the epoxy resin composition.
Example 24
25.8g of the epoxyphosphorosilicate obtained in example 11 (PDMS-DCE) and 100g of an epoxy resin (ERL-4221, epoxy)Equivalent EEW =131g eq -1 ) After being mixed evenly at 50 ℃, 132.2g of curing agent methyl hexahydrophthalic anhydride, 1.0g of curing accelerator ethyl triphenyl acetic phosphine and 1 drop of defoaming agent are added, and vacuum defoaming is carried out in a vacuum oven at 40 ℃ after the mixture is fully and evenly stirred. And then, injecting the fully defoamed epoxy resin composition into a mold, putting the mold into an oven for heating and curing, and curing at 90 ℃ for 3h, at 110 ℃ for 2h, at 130 ℃ for 2h and at 150 ℃ for 1h in sequence to obtain a cured product of the epoxy resin composition.
Comparative example 1
100g of epoxy resin (E51) and 25.3g of curing agent 4,4' -diaminodiphenylmethane are melted and mixed uniformly at the temperature of 90 ℃, then are placed in a vacuum oven at the temperature of 90 ℃ for deaeration for 20min, are poured into a preheated special mould for deaeration for 20min, and are then placed in a high-temperature oven for staged curing. Curing according to the curing procedures of 120 ℃/2h +140 ℃/2h +160 ℃/2h + and 180 ℃/1h, and obtaining the cured product of the epoxy resin composition.
TABLE 1 characterization data of properties of cured epoxy resins of examples and comparative examples
Note: flexural strength was measured according to GB/T-2567-2008, impact strength was measured according to GB/T-1843-2008, and Limiting Oxygen Index (LOI) was measured according to ASTM D2863-2017.
The bar graphs of the flexural strength, impact strength and fracture toughness of examples 13 to 18 and comparative example 1 are shown in fig. 4, 5 and 6, respectively. It can be seen that all epoxy phosphorus-containing polysiloxane modified epoxy resin cured products have higher bending strength, impact strength and fracture toughness than unmodified epoxy resin cured products, and the added polysiloxane modifier can improve the toughness of epoxy. The limiting oxygen index histograms of examples 13-18 and comparative example 1 are shown in FIG. 7. It can be seen that all epoxy phosphorus-containing polysiloxane modified epoxy resin cured products have a higher limiting oxygen index than unmodified epoxy resin cured products. This shows that the epoxy phosphorus-containing polysiloxane can improve the flame retardant property of the epoxy resin as a modifier.
Claims (10)
1. The epoxy phosphorus-containing polysiloxane is characterized in that the structure of the epoxy phosphorus-containing polysiloxane is shown as a general formula (1);
in the general formula (1), a is an integer ranging from 4 to 20; b. c is an integer ranging from 1 to 20;
r represents
One or more of (a).
2. The epoxyphosphorus-containing polysiloxane according to claim 1, wherein the phosphorus element mass fraction is 1-10 wt%.
3. A method for preparing an epoxyphosphorus-containing polysiloxane according to claim 1, which comprises the steps of:
(1) Mixing octamethylcyclotetrasiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane, 1, 3-tetramethyldisiloxane and cation ring-opening polymerization initiator, and reacting at 25-80 deg.C for 12-48 h to obtain hydrogen-containing polysiloxane;
(2) Mixing the hydrogen-containing polysiloxane prepared in the step (1), 1, 2-epoxy-4-vinylcyclohexane and a solvent, adding a catalyst, and reacting at 40-120 ℃ for 4-24 h to prepare epoxy polysiloxane;
(3) Mixing the epoxy polysiloxane prepared in the step (2), a phosphorus-containing monomer, a catalyst and a solvent, and reacting at 80-160 ℃ for 8-24 h to obtain the epoxy phosphorus-containing polysiloxane.
4. The method according to claim 3, wherein in the step (1), the molar ratio of octamethylcyclotetrasiloxane, 1,3,5, 7-tetramethylcyclotetrasiloxane and 1, 3-tetramethyldisiloxane is 4 to 16.
5. The production method according to claim 3, wherein in the step (1), the cationic ring-opening polymerization initiator is a protonic acid or a Lewis acid; the dosage of the cationic ring-opening polymerization initiator is 0.1-1% of the total mass of the octamethylcyclotetrasiloxane, the 1,3,5, 7-tetramethylcyclotetrasiloxane and the 1, 3-tetramethyldisiloxane.
6. The production method according to claim 3, wherein in the step (2), the mass ratio of the hydrogenpolysiloxane to 1, 2-epoxy-4-vinylcyclohexane is 1; the catalyst is one or more of organic alkali compounds, organic peroxides, azo compounds and noble metal compounds; the dosage of the catalyst is 0.01 to 0.1 percent of the total mass of the hydrogen-containing polysiloxane and the 1, 2-epoxy-4-vinyl cyclohexane; the solvent is one or more of toluene, xylene, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, ethanol, propanol, acetone, 2-butanone and dichloromethane; the solvent is used in an amount to ensure that the concentration of the hydrogenpolysiloxane and the 1, 2-epoxy-4-vinylcyclohexane is between 0.2 and 1.0g/mL.
7. The method according to claim 3, wherein in the step (3), the phosphorus-containing monomer is one or more of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, dimethyl phosphite, diethyl phosphite, and diphenyl phosphite; the mass ratio of the epoxy polysiloxane to the phosphorus-containing monomer is 1.1-0.85; the solvent is one or more of toluene, xylene, acetonitrile, methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, 1, 4-dioxane, tetrahydrofuran, acetone and dimethyl sulfoxide; the dosage of the solvent is to ensure that the concentration of the epoxy polysiloxane and the phosphorus-containing monomer is 0.2-1.0 g/mL; the catalyst is one or more of triphenylphosphine, N-dimethylbenzylamine and tetrabutylammonium bromide; the dosage of the catalyst is 0.5-2% of the total mass of the epoxy polysiloxane and the phosphorus-containing monomer.
8. An epoxy composition comprising the epoxy phosphorus-containing polysiloxane of claim 1, wherein the epoxy composition consists of:
9. the epoxy composition of claim 8, wherein the epoxy resin is one or more of a bisphenol a type epoxy resin, a hydrogenated bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a novolac type epoxy resin, an aliphatic glycidyl ether epoxy resin, and a cycloaliphatic epoxy resin; the curing agent is an organic acid anhydride or organic amine curing agent; the curing accelerator is one or more of tertiary amine, imidazole, organophosphorus compounds and acetylacetone metal salt.
10. Use of the epoxy composition according to claim 8 for adhesive materials, composite materials, copper clad laminate materials and electronic packaging materials.
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