CN110746458A - 一种含磷马来酰亚胺树脂及其制备方法 - Google Patents
一种含磷马来酰亚胺树脂及其制备方法 Download PDFInfo
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- CN110746458A CN110746458A CN201911017651.0A CN201911017651A CN110746458A CN 110746458 A CN110746458 A CN 110746458A CN 201911017651 A CN201911017651 A CN 201911017651A CN 110746458 A CN110746458 A CN 110746458A
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- phosphoryl
- phosphorus
- dibromide
- maleimide
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 46
- 239000011574 phosphorus Substances 0.000 title claims abstract description 46
- 239000011347 resin Substances 0.000 title claims abstract description 40
- 229920005989 resin Polymers 0.000 title claims abstract description 40
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 239000011230 binding agent Substances 0.000 claims description 17
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- -1 aryl diphenol Chemical compound 0.000 claims description 6
- TXFOLHZMICYNRM-UHFFFAOYSA-N dichlorophosphoryloxybenzene Chemical compound ClP(Cl)(=O)OC1=CC=CC=C1 TXFOLHZMICYNRM-UHFFFAOYSA-N 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- AXTADRUCVAUCRS-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrole-2,5-dione Chemical compound OCCN1C(=O)C=CC1=O AXTADRUCVAUCRS-UHFFFAOYSA-N 0.000 claims description 4
- BUXKULRFRATXSI-UHFFFAOYSA-N 1-hydroxypyrrole-2,5-dione Chemical compound ON1C(=O)C=CC1=O BUXKULRFRATXSI-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- QRTJRFWYCOYUSG-UHFFFAOYSA-N 1-(4-hydroxy-3,5-dimethylphenyl)pyrrole-2,5-dione Chemical compound CC1=C(O)C(C)=CC(N2C(C=CC2=O)=O)=C1 QRTJRFWYCOYUSG-UHFFFAOYSA-N 0.000 claims description 2
- BLLFPKZTBLMEFG-UHFFFAOYSA-N 1-(4-hydroxyphenyl)pyrrole-2,5-dione Chemical compound C1=CC(O)=CC=C1N1C(=O)C=CC1=O BLLFPKZTBLMEFG-UHFFFAOYSA-N 0.000 claims description 2
- BHPDNFUVYQFFNK-UHFFFAOYSA-N 1-(hydroxymethyl)pyrrole-2,5-dione Chemical compound OCN1C(=O)C=CC1=O BHPDNFUVYQFFNK-UHFFFAOYSA-N 0.000 claims description 2
- QXCYJMFCRHJFER-UHFFFAOYSA-N 1-dibromophosphorylethane Chemical compound CCP(Br)(Br)=O QXCYJMFCRHJFER-UHFFFAOYSA-N 0.000 claims description 2
- MKYQVWPVVHMCOU-UHFFFAOYSA-N 1-dibromophosphoryloxyethane Chemical compound CCOP(Br)(Br)=O MKYQVWPVVHMCOU-UHFFFAOYSA-N 0.000 claims description 2
- OWGJXSYVHQEVHS-UHFFFAOYSA-N 1-dichlorophosphorylethane Chemical compound CCP(Cl)(Cl)=O OWGJXSYVHQEVHS-UHFFFAOYSA-N 0.000 claims description 2
- YZBOZNXACBQJHI-UHFFFAOYSA-N 1-dichlorophosphoryloxyethane Chemical compound CCOP(Cl)(Cl)=O YZBOZNXACBQJHI-UHFFFAOYSA-N 0.000 claims description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 2
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-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
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- HMNBVBXMMXQKGZ-UHFFFAOYSA-N dibromophosphorylbenzene Chemical compound BrP(Br)(=O)C1=CC=CC=C1 HMNBVBXMMXQKGZ-UHFFFAOYSA-N 0.000 claims description 2
- JGHMKVLRTDTAGC-UHFFFAOYSA-N dibromophosphorylmethane Chemical compound CP(Br)(Br)=O JGHMKVLRTDTAGC-UHFFFAOYSA-N 0.000 claims description 2
- ONYHPQJRXORCDD-UHFFFAOYSA-N dibromophosphoryloxybenzene Chemical compound BrP(Br)(=O)OC1=CC=CC=C1 ONYHPQJRXORCDD-UHFFFAOYSA-N 0.000 claims description 2
- VZUNXXUSMINMCM-UHFFFAOYSA-N dibromophosphoryloxymethane Chemical compound COP(Br)(Br)=O VZUNXXUSMINMCM-UHFFFAOYSA-N 0.000 claims description 2
- SNVCRNWSNUUGEA-UHFFFAOYSA-N dichlorophosphoryloxymethane Chemical compound COP(Cl)(Cl)=O SNVCRNWSNUUGEA-UHFFFAOYSA-N 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- SCLFRABIDYGTAZ-UHFFFAOYSA-N methylphosphonic acid dichloride Chemical compound CP(Cl)(Cl)=O SCLFRABIDYGTAZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 abstract description 31
- 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 group 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 28
- 239000000463 material Substances 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 abstract description 7
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 abstract description 4
- 238000009396 hybridization Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 5
- 239000002861 polymer material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- HHVCCCZZVQMAMT-UHFFFAOYSA-N 1-hydroxy-3-phenylpyrrole-2,5-dione Chemical compound O=C1N(O)C(=O)C=C1C1=CC=CC=C1 HHVCCCZZVQMAMT-UHFFFAOYSA-N 0.000 description 2
- LLOXZCFOAUCDAE-UHFFFAOYSA-N 2-diphenylphosphorylbenzene-1,4-diol Chemical compound OC1=CC=C(O)C(P(=O)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 LLOXZCFOAUCDAE-UHFFFAOYSA-N 0.000 description 2
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种含磷马来酰亚胺树脂,所述的含磷马来酰亚胺树脂化学结构式如式1所示:所述式1中的X如下式2‑1、2‑2或式3‑1、3‑2、3‑3、3‑4结构所示:所述式1中的Y如下式4‑1、式4‑2或式5‑1、5‑2结构所示:所述式1中的R如下式6‑1、式6‑2、式6‑3、式6‑4结构所示。本发明还公开了其制备方法。本发明将磷杂化型阻燃结构与马来酰亚胺基团结合,制备出一类含磷阻燃马来酰亚胺树脂,既能解决树脂阻燃、耐热性等固有难题,同时作为阻燃剂末端含有功能性的马来酰亚胺活性基团,作为反应性阻燃剂可以与其他树脂进行反应,提高阻燃剂与材料的相容性,并提升材料的热性能、介电性能等。
Description
技术领域
本发明属于磷系阻燃剂制备领域,具体涉及一种含磷马来酰亚胺树脂及其制备方法。
背景技术
目前,高分子材料应用范围日益扩大,越来越广泛应用于生活和生产中,但大多数高分子材料由碳、氢、氧等元素构成,极限氧指数(LOI)一般低于21%,所以这些材料的固有的易燃性带来的火灾隐患已成为全球关注的问题。随着安全环保意识日益增加,人们对高分子材料制品的阻燃要求也越来越高,无卤、低烟、低毒和高耐热性的环保阻燃剂已成为国内外阻燃剂研究开发的目标。近十多年来,磷系阻燃剂由于具有低烟、无卤、与高分子材料相容性良好、阻燃效果佳、耐热、耐水解、耐迁移性等优点,成为企业和研发结构研究的热点,具有很好的开发前景。
有机磷系阻燃剂一般包括磷酸酯型、亚磷酸酯型、有机磷盐、磷杂化型等磷系阻燃剂,磷酸酯型阻燃剂由于价格低廉、品种众多用途较为广泛,但是磷酸酯基团、亚磷酸酯基团的存在会导致材料的玻璃化转变温度较低,耐热性不及磷杂化型阻燃剂。
专利CN106832259A公开了一种支链为双DOPO的聚磷酸酯阻燃剂,由于双DOPO 结构存在,其阻燃剂具有较好的热稳定性和化学稳定性,但在反应体系中无反应性,相容性较差,存在阻燃剂在材料中迁移的风险。专利CN1062433385A公开了另外一种DOPO基阻燃剂,阻燃剂的一端为DOPO结构,另一端为具有双键的丙烯酸羟乙酯结构。该阻燃剂只有一端具有反应性,且只能在具有双键的自由基反应体系中使用,限制其使用范围,最终材料的性能如玻璃化转变温度不高,耐热性不高。
发明内容
为了克服现有技术的上述缺陷,本发明的目的之一在于提供一种含磷马来酰亚胺树脂。
本发明的目的之二在于提供一种含磷马来酰亚胺树脂的制备方法。
为了实现本发明的目的之一,所采用的技术方案是:
一种含磷马来酰亚胺树脂,其中,所述的含磷马来酰亚胺树脂化学结构式如式 1所示:
所述式1中的X如下式2-1、2-2或式3-1、3-2、3-3、3-4结构所示:
所述式1中的Y如下式4-1、式4-2或式5-1、5-2结构所示:
所述式1中的R如下式6-1、式6-2、式6-3、式6-4结构所示:
-CH2-
式6-1
-CH2CH2-
式6-2
为了实现本发明的目的之二,所采用的技术方案是:
一种含磷马来酰亚胺树脂的制备方法,包括以下步骤:
步骤一:在干燥惰性气体保护下,端羟基马来酰亚胺与磷酰二氯或磷酰二溴按照1:0.92-1.05摩尔比加入到反应器中,并加入无水溶剂和缚酸剂,在0-50℃下搅拌反应2-8小时;
步骤二:按照1:0.95-1.05摩尔比加入含磷芳香基二苯酚,在1-80℃条件下反应2-10小时,反应后将产物过滤,然后用溶剂洗涤洗去缚酸剂,抽滤干燥即得含磷马来酰亚胺树脂产物。
在本发明的一个优选实施例中,所述的端羟基马来酰亚胺为N-羟基马来酰亚胺、N-羟甲基马来酰亚胺、N-羟乙基马来酰亚胺、N-(4-羟基苯基)马来酰亚胺、N-(4- 羟基-3,5-二甲基苯基)马来酰亚胺中的任意一种或多种。
在本发明的一个优选实施例中,所述的磷酰二氯或磷酰二溴分别选自于甲基磷酰二氯、甲氧基磷酰二氯、乙基磷酰二氯、乙氧基磷酰二氯、苯基磷酰二氯、苯氧基磷酰二氯或甲基磷酰二溴、甲氧基磷酰二溴、乙基磷酰二溴、乙氧基磷酰二溴、苯基磷酰二溴、苯氧基磷酰二溴中的任意一种或多种。
在本发明的一个优选实施例中,所述的含磷芳香基二苯酚为以下式7所示结构:
所述Y如下式4-1、式4-2或式5-1、5-2结构所示:
在本发明的一个优选实施例中,所述溶剂为丙酮、丁酮、环己酮、甲基异丁基酮、四氢呋喃、二氯甲烷、氯仿、乙酸乙酯、乙酸异丙酯、乙酸异丁酯、甲基异丁基甲醇、甲苯、二甲苯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的任意一种或多种。
在本发明的一个优选实施例中,所述惰性气体为氮气、氦气或氩气中的任意一种或多种。
在本发明的一个优选实施例中,所述缚酸剂为三乙胺、吡啶、N,N-二异丙基乙胺、4-二甲氨基吡啶、三乙醇胺、四丁基溴化铵、碳酸钾、碳酸铵和碳酸钠中的任意一种或多种。
本发明的有益效果在于:
本发明专利将磷杂化型阻燃结构与马来酰亚胺基团结合,制备出一类含磷阻燃马来酰亚胺树脂,既能解决树脂阻燃、耐热性等固有难题,同时作为阻燃剂末端含有功能性的马来酰亚胺活性基团,作为反应性阻燃剂可以与其他树脂进行反应,提高阻燃剂与材料的相容性,并提升添加材料的力学性能、热性能、介电性能等。
具体实施方式
本发明的工作原理在于:
本发明涉及到一种含磷马来酰亚胺树脂的合成,作为一种无卤且具有阻燃功效的功能性树脂,不仅具有良好的反应性,与热固性树脂组合物反应,可以将含磷分子链结合到热固性树脂体系之中,避免了添加型阻燃剂对材料性能不利的影响;而且封端的官能基团为马来酰亚胺基团,本身作为一种高性能树脂,提升了材料的玻璃化转变温度、剥离强度和耐热性能;同时改善了含磷化合物与其他树脂的相容性,将马来酰亚胺基团与具有较大侧基的含磷结构结合,具有较大自由体积的结构降低了含磷马来酰亚胺树脂的介电常数和介电损耗。与现有技术相比,采用本发明制备得到的低介电高Tg无卤覆铜板具有良好的流动性、超低的热膨胀系数和优异介电性能等。
实施例1
在干燥氮气气体保护下,在1000ml的三口烧瓶中加入200g无水甲苯和 50gN,N-二甲基甲酰胺,并加入195g(1mol)磷酰二氯和101g缚酸剂三乙胺,然后向烧瓶中缓慢滴加113g(1mol)N-羟基马来酰亚胺溶液,在冰水浴条件下搅拌反应8小时;然后再加入310g(1mol)2,5-二羟苯基(二苯基)氧化膦,加热至60℃反应5小时后,将产物过滤,然后用溶剂洗去缚酸剂,沉淀抽滤烘干后即制得含磷马来酰亚胺树脂A,反应过程如式8所示,树脂A磷含量为11.9%。
实施例2
在干燥氮气气体保护下,在1000ml的三口烧瓶中加入200g无水甲苯和 50gN,N-二甲基甲酰胺,并加入195g(1mol)磷酰二氯和101g缚酸剂三乙胺,然后向烧瓶中缓慢滴加173g(1mol)N-羟苯基马来酰亚胺溶液,在冰水浴条件下搅拌反应6小时;然后再加入324g(1mol)10-(2,5-二羟基苯基)-10-氢-9-氧杂-10- 磷杂菲-10-氧化物(DOPO-HQ),加热至70℃反应7小时后,将产物过滤,然后用溶剂洗去缚酸剂,沉淀抽滤烘干后即制得含磷马来酰亚胺树脂B,反应过程如式9所示,树脂B磷含量为9.5%。
实施例3
在干燥氩气气体保护下,在1000ml的三口烧瓶中加入200g无水甲苯和 50gN,N-二甲基甲酰胺,并加入144g(1mol)二氯化磷酸苯酯和101g缚酸剂三乙胺,然后向烧瓶中缓慢滴加141g(1mol)N-羟乙基马来酰亚胺溶液,在冰水浴下搅拌反应5小时;然后再加入324g(1mol)10-(2,5-二羟基苯基)-10-氢-9-氧杂 -10-苯氧磷-10-氧化物,加热至70℃反应8小时后,将产物过滤,然后用溶剂洗去缚酸剂,沉淀抽滤烘干后即制得含磷马来酰亚胺树脂C,反应过程如式10所示,树脂C磷含量为10.5%。
实施例4
在干燥氩气气体保护下,在1000ml的三口烧瓶中加入200g无水二甲苯和50g 丁酮,并加入195g(1mol)磷酰二氯和149g(1mol)三乙醇胺TEOA,然后向烧瓶中缓慢滴加113g(1mol)N-羟基马来酰亚胺溶液,在常温条件下25℃搅拌反应8 小时;然后再加入310g(1mol)2,5-二羟苯基(二苯基)氧化膦,加热至60℃反应 8小时后,将产物过滤,然后用溶剂洗去缚酸剂,沉淀抽滤烘干后即制得含磷马来酰亚胺树脂。
实施例5
在干燥氦气保护下,在1000ml的三口烧瓶中加入200g无水二甲苯和50g四氢呋喃,并加入195g(1mol)磷酰二氯和122g(1mol)缚酸剂4-二甲氨基吡啶,然后向烧瓶中缓慢滴加173g(1mol)N-羟苯基马来酰亚胺溶液,在常温条件下25℃搅拌反应6小时;然后再加入324g(1mol)10-(2,5-二羟基苯基)-10-氢-9-氧杂 -10-磷杂菲-10-氧化物(DOPO-HQ),加热至70℃反应5小时后,将产物过滤,然后用溶剂洗去缚酸剂,沉淀抽滤烘干后即制得含磷马来酰亚胺树脂。
实施例6
在干燥氩气气体保护下,在1000ml的三口烧瓶中加入200g无水甲苯和50g 甲基异丁基酮MIBK,并加入144g(1mol)二氯化磷酸苯酯和322g缚酸剂四丁基溴化铵,然后向烧瓶中缓慢滴加141g(1mol)N-羟乙基马来酰亚胺溶液,在常温下搅拌反应7小时;然后再加入324g(1mol)10-(2,5-二羟基苯基)-10-氢-9-氧杂 -10-苯氧磷-10-氧化物,加热至80℃反应5小时后,将产物过滤,然后用溶剂洗去缚酸剂,沉淀抽滤烘干后即制得含磷马来酰亚胺树脂。
实施例7
为了对比前例中所合成的具有反应性的含磷马来酰亚胺树脂的耐热性、电性能和阻燃性,本实施例将环氧丙烯酸酯作为基体,将实施例1-3所合成的含磷马来酰亚胺树脂A、B、C以及对比磷酸酯阻燃剂 PX-200(大八化学)、磷腈阻燃剂SPB-100(大冢化学)分别按下表所示配比均匀混合,并浇注到模具中固化制备样品。
本申请的实施例1-7与对比例1-4的对比参见表1:
表1
由上表1可知,在易燃的环氧丙烯酸酯树脂中,所合成的含磷马来酰亚胺树脂仅需15phr的添加量即可实现UL-V0级耐燃效果,显著提高材料的极限氧指数LOI 至30%左右,得到更好的阻燃效果,较其他阻燃剂如PX-200/SPB-100更少的添加量。而且使用含磷马来酰亚胺树脂A/B/C加入到基材中,可以较大地提高基体的玻璃化转变温度至140℃以上,也能提高材料的耐热性,材料的热分解温度TGA得到提升。
以上对本发明通过实施例做了较为详尽的描述,其目的在于让熟悉此领域技术的人士能够了解本发明内容并加以实施,但并不能以此限制本发明的保护范围,凡根据本发明的实质内容所做的修改或润饰,都应涵盖在本发明所要求保护的范围之内。
Claims (8)
2.如权利要求1所述的一种含磷马来酰亚胺树脂的制备方法,其特征在于,包括以下步骤:
步骤一:在干燥惰性气体保护下,端羟基马来酰亚胺与磷酰二氯或磷酰二溴按照1:0.92-1.05摩尔比加入到反应器中,并加入无水溶剂和缚酸剂,在0-50℃下搅拌反应2-8小时;
步骤二:按照1:0.95-1.05摩尔比加入含磷芳香基二苯酚,在1-80℃条件下反应2-10小时,反应后将产物过滤,然后用溶剂洗涤洗去缚酸剂,抽滤干燥即得所述的含磷马来酰亚胺树脂产物。
3.如权利要求2所述的一种含磷马来酰亚胺树脂的制备方法,其特征在于,所述的端羟基马来酰亚胺为N-羟基马来酰亚胺、N-羟甲基马来酰亚胺、N-羟乙基马来酰亚胺、N-(4-羟基苯基)马来酰亚胺、N-(4-羟基-3,5-二甲基苯基)马来酰亚胺中的任意一种或多种。
4.如权利要求2所述的一种含磷马来酰亚胺树脂的制备方法,其特征在于,所述的磷酰二氯或磷酰二溴分别选自于甲基磷酰二氯、甲氧基磷酰二氯、乙基磷酰二氯、乙氧基磷酰二氯、苯基磷酰二氯、苯氧基磷酰二氯或甲基磷酰二溴、甲氧基磷酰二溴、乙基磷酰二溴、乙氧基磷酰二溴、苯基磷酰二溴、苯氧基磷酰二溴中的任意一种或多种。
6.如权利要求2所述的一种含磷马来酰亚胺树脂的制备方法,其特征在于,所述溶剂为丙酮、丁酮、环己酮、甲基异丁基酮、四氢呋喃、二氯甲烷、氯仿、乙酸乙酯、乙酸异丙酯、乙酸异丁酯、甲基异丁基甲醇、甲苯、二甲苯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的任意一种或多种。
7.如权利要求2所述的一种含磷马来酰亚胺树脂的制备方法,其特征在于,所述惰性气体为氮气、氦气或氩气中的任意一种或多种。
8.如权利要求2所述的一种含磷马来酰亚胺树脂的制备方法,其特征在于,所述缚酸剂为三乙胺、吡啶、N,N-二异丙基乙胺、4-二甲氨基吡啶、三乙醇胺、四丁基溴化铵、碳酸钾、碳酸铵和碳酸钠中的任意一种或多种。
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