CN105061417B - Monoamine bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine and preparation method thereof - Google Patents
Monoamine bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine and preparation method thereof Download PDFInfo
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- CN105061417B CN105061417B CN201510458886.9A CN201510458886A CN105061417B CN 105061417 B CN105061417 B CN 105061417B CN 201510458886 A CN201510458886 A CN 201510458886A CN 105061417 B CN105061417 B CN 105061417B
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- hydroxyphenyls
- quinoxaline
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- benzaldehyde
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- ZHTXFOFNOCKVRR-UHFFFAOYSA-N 3-quinoxalin-2-yl-2H-1,2-benzoxazine Chemical compound N1=C(C=NC2=CC=CC=C12)C=1NOC2=C(C=1)C=CC=C2 ZHTXFOFNOCKVRR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229930185605 Bisphenol Natural products 0.000 title abstract 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 title abstract 2
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 150000003141 primary amines Chemical class 0.000 claims abstract description 8
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 6
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzenecarboxaldehyde Natural products O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- RURYNVQCWRTPRI-UHFFFAOYSA-N C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.N1=CC=NC2=CC=CC=C12 Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.N1=CC=NC2=CC=CC=C12 RURYNVQCWRTPRI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical compound FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000001431 2-methylbenzaldehyde Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- SEPPVOUBHWNCAW-FNORWQNLSA-N (E)-4-oxonon-2-enal Chemical compound CCCCCC(=O)\C=C\C=O SEPPVOUBHWNCAW-FNORWQNLSA-N 0.000 claims description 2
- NDOPHXWIAZIXPR-UHFFFAOYSA-N 2-bromobenzaldehyde Chemical compound BrC1=CC=CC=C1C=O NDOPHXWIAZIXPR-UHFFFAOYSA-N 0.000 claims description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 2
- LLBZPESJRQGYMB-UHFFFAOYSA-N 4-one Natural products O1C(C(=O)CC)CC(C)C11C2(C)CCC(C3(C)C(C(C)(CO)C(OC4C(C(O)C(O)C(COC5C(C(O)C(O)CO5)OC5C(C(OC6C(C(O)C(O)C(CO)O6)O)C(O)C(CO)O5)OC5C(C(O)C(O)C(C)O5)O)O4)O)CC3)CC3)=C3C2(C)CC1 LLBZPESJRQGYMB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- IIDFEIDMIKSJSV-UHFFFAOYSA-N dipropoxyphosphinothioyloxy-dipropoxy-sulfanylidene-$l^{5}-phosphane Chemical compound CCCOP(=S)(OCCC)OP(=S)(OCCC)OCCC IIDFEIDMIKSJSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 150000002240 furans Chemical class 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- OVJGBTBVQPVQPO-UHFFFAOYSA-N 1-(4,4-dihydroxycyclohexa-1,5-dien-1-yl)-2-phenylethane-1,2-dione Chemical compound C1=CC(O)(O)CC=C1C(=O)C(=O)C1=CC=CC=C1 OVJGBTBVQPVQPO-UHFFFAOYSA-N 0.000 claims 1
- ILEIUTCVWLYZOM-UHFFFAOYSA-N 2-hydroxy-5-methylbenzaldehyde Chemical compound CC1=CC=C(O)C(C=O)=C1 ILEIUTCVWLYZOM-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- HUMNYLRZRPPJDN-KWCOIAHCSA-N benzaldehyde Chemical group O=[11CH]C1=CC=CC=C1 HUMNYLRZRPPJDN-KWCOIAHCSA-N 0.000 claims 1
- QPBQEXGQGCAOKS-UHFFFAOYSA-N cyclohexa-2,4-diene-1,1-diol Chemical class OC1(O)CC=CC=C1 QPBQEXGQGCAOKS-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical group N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 abstract description 17
- 239000011347 resin Substances 0.000 abstract description 12
- 229920005989 resin Polymers 0.000 abstract description 10
- -1 amino bis-phenol Chemical compound 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000012545 processing Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 150000002989 phenols Chemical class 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract description 2
- 240000000203 Salix gracilistyla Species 0.000 abstract 1
- 125000003277 amino group Chemical group 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- FYTRVVJHEWUARG-UHFFFAOYSA-N n-(2-aminophenyl)nitramide Chemical class NC1=CC=CC=C1N[N+]([O-])=O FYTRVVJHEWUARG-UHFFFAOYSA-N 0.000 abstract 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000002329 infrared spectrum Methods 0.000 description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical class C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 150000003252 quinoxalines Chemical class 0.000 description 6
- 125000001567 quinoxalinyl group Chemical group N1=C(C=NC2=CC=CC=C12)* 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 238000001723 curing Methods 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 229920001568 phenolic resin Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 description 2
- RQQDJYROSYLPPK-UHFFFAOYSA-N N1=CC=CC2=CC=CC=C21.N1=CC=CC2=CC=CC=C21 Chemical compound N1=CC=CC2=CC=CC=C21.N1=CC=CC2=CC=CC=C21 RQQDJYROSYLPPK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 150000004893 oxazines Chemical class 0.000 description 2
- 229920006389 polyphenyl polymer Polymers 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CQOZJDNCADWEKH-UHFFFAOYSA-N 2-[3,3-bis(2-hydroxyphenyl)propyl]phenol Chemical compound OC1=CC=CC=C1CCC(C=1C(=CC=CC=1)O)C1=CC=CC=C1O CQOZJDNCADWEKH-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001243 acetic acids Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- SMWDFEZZVXVKRB-UHFFFAOYSA-N anhydrous quinoline Natural products N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings
-
- 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
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The present invention relates to a kind of asymmetric three-functionality-degree quinoxalinyl benzoxazine and preparation method thereof.Using 4 dihydroxy benzils and 4 nitro-o-phenylenediamines as raw material, the quinoxaline intermediate containing a nitro and two phenolic hydroxyl groups is synthesized, mono amino bis-phenol base quinoxaline is obtained through being catalyzed reduction, again with bigcatkin willow aldehyde reaction, generate the phenolic compounds of quinoxaline three of the amine groups containing methylene, ring-closure reaction is carried out after sodium borohydride reduction, then with primary amine and paraformaldehyde, obtains a kind of monoamine bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine monomer.The present invention is by means of quinoxaline molecule possessed excellent heat resistance in itself, by introducing flexible alkyl chain and polymerizable groups, so that such monomer has relatively low fusing point and extra polymerization crosslinking position, so as to improve processing characteristics, plus the introducing of Geng Duo oxazine rings, its Polybenzoxazine resin shows excellent heat resistance and good mechanical property, available for manufacture high performance structures material etc..
Description
Technical field
The present invention relates to a kind of high-molecular organic material, and the present invention also relates to a kind of preparation of high-molecular organic material
Method.Specifically a kind of new monoamine-bisphenol type three-functionality-degree asymmetry quinoxalinyl benzoxazine monomer and its preparation
Method.
Background technology
Benzoxazine is a kind of compound obtained by phenolic compound, formaldehyde and primary amine through Mannich condensation reactions, can
So that ring-opening polymerisation occurs under heating or Louis acid catalysis effect, the cured product similar in construction to phenolic resin is formed,
It is a kind of new phenolic resin.This resin is in addition to the heat resistance and anti-flammability excellent with phenolic resin, also certain
The fragility and dimensional instability of phenolic resin are improved in degree.Its most significant advantage is formed by itself ring-opening polymerisation
Three-dimensional net structure, discharged without small molecule during solidification, product porosity is low, and its volume approximation zero is shunk, and has high geometry heat steady
Qualitative and good mechanical performance, electric property, fire resistance and high Residual carbon.These excellent performances cause benzo
Oxazine is in fields such as advanced composite matrix resin, Electronic Packaging, adhesive, fire proofing, ablation resistant material, insulating materials
It is widely used.In recent years, as what the species, synthetic method and catalytic polymerization of benzoxazine monomer were studied deepens continuously,
Polyfunctionality benzoxazine has caused the concern of many researchers.Such as woods celebrating, which is dazzled, has synthesized phosphorous triphenol and three amine type benzene and Evil
Piperazine monomer, the T of polymergRespectively 220 and 242 DEG C, initial pyrolyzation temperature (T5) it is 324 and 349 DEG C, 800 DEG C of carbon yields reach
48% and 58% (Lin CH, Cai1SX, Leu TS, Hwang TY, Lee HH.Synthesis and properties of
flame-retardant benzoxazines by three approaches.J Polym Sci A Polym Chem,
2006,44:3454-3468P；Chang CW,Lin CH,Lin HT,Huang HJ,Tu AP.Development of an
aromatic triamine-based flame-retardant benzoxazine and its high-performance
copolybenzoxazines.Eur Polym J,2009,49:680-689P).Liu Chengmei etc. is prepared for the official of tripolyphosphazene base four
Energy degree and six degree of functionality benzoxazine monomers, the T of its PolybenzoxazinegRespectively 254 DEG C and 152 DEG C, T5Respectively 442 DEG C and
403 DEG C, due to being crosslinked the increase of position, the hot property and fire resistance of polymer greatly improve (Wu X, Liu SZ, Tian DT,
Qiu JJ,Liu CM.Highly branched benzoxazine monomer based on
cyclotriphosphazene:Synthesis and properties of the monomer and
polybenzoxazines.Polym,2011,52:1004-1012P；Wu X,Liu SZ,Tian DT,Qiu JJ,Liu
CM.Well-defined organic–inorganic hybrid benzoxazine monomers based on
cyclotriphosphazene:Synthesis,properties of the monomers and
polybenzoxazines.Polym,2011,52:4235-4245P).In addition, also with triazine structure, POSS structures etc.
For the report of the polyfunctionality benzoxazine monomer of basic skeleton structure.But the above-mentioned benzoxazine monomer overwhelming majority belongs to symmetrical
Oxazine ring structure.
Quinoxaline is a kind of heterocyclic compound, is formed by a phenyl ring and a pyrazine ring fusion, 2,3,6 can introduce
Various active group, there is very flexible MOLECULE DESIGN, it is sub- available for synthesis polyphenylene quinoxaline, quinoxalinyl polyamides
The polymer such as amine, polyethers, polyester.At the same time, this quinoxaline structure have higher bond energy, huge molal volume and
Weaker polarity, impart the excellent heat-resisting and thermo oxidative stability of such polymer, resistance to environmental stability, low-k with
Dielectric loss, in organic solvent good dissolubility and good mechanical property.
The content of the invention
It is an object of the invention to provide it is a kind of have excellent hot property, mechanical property and good processing characteristics and
The monoamine of toughness-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine.It is a kind of single the present invention also aims to provide
The preparation method of amine-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine.
The object of the present invention is achieved like this：
Monoamine-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine of the present invention has following structure：
In formula, R1For H, CH3、OCH3, one kind in F, Cl or Br, R2For C2~C12Alkyl, pi-allyl, propargyl or
One kind in fural.
The preparation method of monoamine-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine of the present invention includes：
(1) 4- dihydroxy benzil, NPD and glacial acetic acid are added into container, wherein, 4- dihydroxy benzenes
The mol ratio of even acyl and NPD is 1:1~1.2, mixture reacts 4~8h at a reflux temperature, is subsequently cooled to
Room temperature, filtering, filter cake drying, gained crude product are recrystallized 1~3 time with glacial acetic acid, obtain double (4- the hydroxyphenyls) -6- nitros of 2,3-
Quinoxaline；
(2) double (4- the hydroxyphenyls) -6- nitroquinoxalines of 2,3- and palladium carbon are added in ethanol, adding mass concentration ratio is
80% hydrazine hydrate, wherein, the mass ratio of 2,3- double (4- hydroxyphenyls) -6- nitroquinoxalines and palladium carbon is 1:0.02, hydrazine hydrate is same
The mol ratio of double (4- the hydroxyphenyls) -6- nitroquinoxalines of 2,3- is 3.2~4:1,5~10h is reacted at a reflux temperature, is then taken advantage of
Heat filtering, filtrate cooling room temperature, crystal, then filtered, vacuum drying are separated out, obtain double (4- the hydroxyphenyls) -6- amino quinolines of 2,3-
Quinoline；
(3) respectively by 2,3- double (4- hydroxyphenyls) -6- aminoquinoxalines, substituted or non-substituted salicylide, sulfuric acid and ethanol
It is added in reaction vessel, wherein, mole of 2,3- double (4- hydroxyphenyls) -6- aminoquinoxalines and substituted or non-substituted salicylide
Than for 1:The mol ratio of 1,2,3- double (4- hydroxyphenyls) -6- aminoquinoxalines and sulfuric acid is 5:1, heating reflux reaction under agitation
6~10h, room temperature is subsequently cooled to, adds sodium borohydride, continue 5~10min of stirring at room temperature, wherein, 2,3- double (4- hydroxyls
Phenyl) mol ratio of -6- aminoquinoxalines and sodium borohydride is 1:2, after reaction terminates, add water and dichloromethane, use distilled water
After washing organic phase for several times, rotated evaporation removes dichloromethane, and it is (substituted or non-substituted to obtain double (4- the hydroxyphenyls) -6- of 2,3-
Adjacent hydroxyl-benzamido group) quinoxaline abbreviation quinoxaline triphenol；
(4) quinoxaline triphenol, primary amine, paraformaldehyde and chloroform are added into reactor, wherein, quinoxaline triphenol,
The mol ratio of primary amine and paraformaldehyde is 1:2:5,16~24h of back flow reaction, room temperature is cooled to, then through 0.1~0.5mol/L's
Sodium hydroxide solution alkali cleaning, washing, the rotated evaporation of organic phase remove chloroform, vacuum drying, obtain monoamine-bisphenol type not
Symmetrical three-functionality-degree quinoxalinyl benzoxazine monomer.
The preparation method of the asymmetric three-functionality-degree quinoxalinyl benzoxazine of the present invention can also include：
1st, described substituted or non-substituted salicylide be Benzaldehyde,2-hydroxy, 4- methyl-Benzaldehyde,2-hydroxy, 5- methyl-
Benzaldehyde,2-hydroxy, 4- methoxyl groups-Benzaldehyde,2-hydroxy, 5- methoxyl groups-Benzaldehyde,2-hydroxy, the fluoro- Benzaldehyde,2-hydroxies of 5-, 4-
One kind in fluoro- Benzaldehyde,2-hydroxy, 5- chlorine-2-hydroxyls benzaldehyde or the bromo- Benzaldehyde,2-hydroxies of 5-.
2nd, described primary amine is C2~C12One kind in fatty amine, allyl amine, propargyl amine or chaff amine.
3rd, monoamine-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine monomer is obtained using programmed temperature method to list
Body carries out heat cure, obtains Polybenzoxazine resin, curing cycle is：180 DEG C/2h, 200 DEG C/2h, 220 DEG C/3h, 240 DEG C/
2h。
The present invention has synthesized a kind of quinoxaline molecule containing an amino and two hydroxyls simultaneously by MOLECULE DESIGN,
Oxazine ring is incorporated into quinoxaline molecular structure by , on this basis, obtains a kind of monoamine-bisphenol type asymmetry three-functionality-degree quinoline
Quinoline base benzoxazine monomer (note：So-called asymmetric Shi oxazine rings are unsymmetric structure, and existing amine type has Fen Xing oxazines again
Ring), by regulating and controlling the quantity of aliphatic chain and aromatic rings, and assign such Polybenzoxazine there is excellent hot property, mechanical property
Energy and good processing characteristics and toughness.
After monoamine-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine monomer heat cure of the present invention, had
There is the asymmetric three-functionality-degree quinoxalinyl polyphenyl of excellent fire resistance, heat resistance, wet-hot aging performance and excellent toughness
Bing oxazine resins, by adjusting rigidity and flexible group in fatty amine and phenolic compound, to reduce benzoxazine monomer
Fusing point, the crosslink density and toughness of Polybenzoxazine are improved, solve the quinoxalinyl polyphenyl with larger space steric hindrance structure simultaneously
The problem of oxazine molecular weight is small, crosslink density is low, poor toughness and the introducing because of flexible group cause hot property to decline, improve poly-
The processing characteristics of compound, realize that the structure of Polybenzoxazine and performance are controllable, expand benzoxazine colophony application field.
The asymmetric three-functionality-degree quinoxalinyl benzoxazine monomer structural characterization of the present invention utilizes infrared spectrum
(Spotlight 100, PE companies of the U.S.) and nuclear magnetic resonance spectrometer (AVANCE-500, Switzerland Bruker), examination of infrared spectrum
Using pellet technique, Sample Scan 4 times, resolution ratio 4cm-1, scanning range to 4000~500cm-1；Proton nmr spectra
It is that internal standard is made with tetramethylsilane (TMS), deuterated dimethyl sulfoxide (DMSO) makees solvent；Polymer performance test is using thermogravimetric point
Analyzer (TGA, TA companies of the U.S.) and dynamic thermomechanical analysis apparatus (DMA, TA companies of the U.S.).Wherein TGA uses nitrogen atmosphere, rises
Warm speed is 20 DEG C/min；DMA uses air atmosphere, single-cantilever pattern, and heating rate is 3 DEG C/min.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that, the embodiment of the present invention is only
It is used to further illustrate the present invention, but it is not intended that limiting the scope of the invention, the technology in the field are ripe
Practice personnel and some nonessential modifications and adaptations are made according to the content of the invention described above.
Embodiment 1
(1) 4- dihydroxy benzil (24.2g, 0.1mol) and NPD are separately added into three-necked flask
(16.8g, 0.11mol) and 50mL glacial acetic acids, mixture back flow reaction 5h, after being subsequently cooled to room temperature, are collected by filtration what is formed
Precipitation, drying, gained crude product are recrystallized 2 times with glacial acetic acid, obtain double (4- the hydroxyphenyls) -6- nitroquinoxalines of 2,3-
(30.4g), yield 84.6%；
(2) by double (4- the hydroxyphenyls) -6- nitroquinoxalines (18.1g, 0.05mol) of 2,3- and palladium-carbon catalyst (0.37g)
Add in 300mL ethanol, 80% hydrazine hydrate 8.8g is then added dropwise, reacts 8h at a reflux temperature, filters while hot, remove palladium
C catalyst, filtrate are cooled to room temperature, separate out crystal, filtering, then are washed 3~4 times with distilled water, last vacuum dried, obtain
To double (4- the hydroxyphenyls) -6- aminoquinoxalines (15.1g) of 2,3-, yield 91.2%；
(3) by double (4- the hydroxyphenyls) -6- aminoquinoxalines (16.5g, 0.05mol) of 2,3-, Benzaldehyde,2-hydroxy (6.1g,
0.05mol), the concentrated sulfuric acid (1.0g, 0.01mol) and 100mL ethanol be added to equipped with agitator, condenser pipe, three mouthfuls of thermometer
In flask, 8h is heated to reflux, reaction is cooled to room temperature after terminating, add sodium borohydride (3.8g, 0.10mol), continue at room temperature
7min is stirred, distilled water is then added, is extracted with dichloromethane, washes 5 times, is finally separating out organic phase, rotated evaporation removes
Dichloromethane is removed, obtains double (4- hydroxyphenyls) -6- (2- hydroxyls-benzamido group) quinoxalines (17.5g) of 2,3-, yield 80.4%；
(4) added into reactor double (4- hydroxyphenyls) -6- (2- hydroxyls-benzamido group) quinoxalines of 2,3- (8.7g,
0.02mol), n-butylamine (2.93g, 0.04mol), paraformaldehyde (3.0g, 0.10mol) and 50mL chloroforms, back flow reaction
Terminate after 20h, be cooled to room temperature, with 0.3mol NaOH solution alkali cleaning, then with distillation water washing 3~5 times, be then demultiplex out
Machine phase, rotary evaporation remove chloroform, vacuum drying, finally obtain butylamine-monoamine-bisphenol type asymmetry three-functionality-degree quinoline
Quinoline base benzoxazine monomer (10.6g), yield 82.6%, fusing point are 79 DEG C.
Proton nmr spectra test result (500M, DMSO, ppm)：8.33~6.63 (m, 13H, Ar-H), 5.20 (s, 2H,
O-CH2- N), 4.93 (s, 2H, O-CH2- N), 4.86 (s, 2H, O-CH2- N), 4.36 (s, 2H, Ar-CH2- N), 3.92 (s, 2H,
Ar-CH2- N), 3.87 (s, 2H, Ar-CH2- N), 2.77 (t, 4H, N-CH2-CH2), 1.32~1.55 (m, 8H, CH2-CH2-
CH2), 0.92 (t, 6H ,-CH3)；Examination of infrared spectrum result (KBr, cm-1)：1495 (phenyl ring three substitutes characteristic peak), 1375 Hes
1324 (be respectively the CH in oxazine rings that is connected with quinoxaline ring and phenyl ring2Rocking vibration), 1233~1242 and 1077 (are respectively
C-O-C is asymmetric and symmetrical stretching vibration), 1155 (C-N-C asymmetric stretching vibrations), 928~949 (be respectively with phenyl ring and
Quinoxaline ring is connected c h bond out-of-plane bending vibration in oxazine rings, and on phenyl ring Dai You oxazine rings characteristic absorption peak), 742
(the dibasic characteristic peak in phenyl ring ortho position), confirm to contain three oxazines in products therefrom with reference to proton nmr spectra and infrared spectrum
Ring, it is target product.
The benzoxazine monomer of gained is put into electric drying oven with forced convection, thermosetting is carried out to monomer using programmed temperature method
Change, curing cycle is：180 DEG C/2h, 200 DEG C/2h, 220 DEG C/3h, 240 DEG C/2h, obtain Polybenzoxazine resin, through DMA and
TGA is tested, and the glass transition temperature for obtaining Polybenzoxazine resin (is abbreviated as Tg) for 335 DEG C, weightlessness it is 5% and 10% right
The heat decomposition temperature answered (is abbreviated as T5And T10) it is respectively that carbon yield at 360 and 392 DEG C, 800 DEG C (is abbreviated as Yc) up to
52.3%.
Embodiment 2
Except raw material Benzaldehyde,2-hydroxy is changed to 4- methyl-Benzaldehyde,2-hydroxy (6.8g, 0.05mol), step in step (3)
(4) double (4- hydroxyphenyls) -6- (2- hydroxyls-benzamido group) quinoxalines of 2,3- in are changed to double (4- hydroxyphenyls) -6- (the 2- hydroxyls of 2,3-
Base -5- methyl-benzyl amines base) quinoxaline (9.1g, 0.02mol) outside, other conditions finally obtain methylic fourth with embodiment 1
Amine-monoamine-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine monomer (10.8g), yield 82.3%, fusing point 91
℃。
Proton nmr spectra test result (500M, DMSO, ppm)：8.22~6.62 (m, 12H, Ar-H), 5.16 (s, 2H,
O-CH2- N), 4.95 (s, 2H, O-CH2- N), 4.87 (s, 2H, O-CH2- N), 4.33 (s, 2H, Ar-CH2- N), 3.90 (s, 2H,
Ar-CH2- N), 3.86 (s, 2H, Ar-CH2- N), 2.76 (t, 4H, N-CH2-CH2), 1.31~1.56 (m, 8H, CH2-CH2-
CH2), 0.91 (t, 9H ,-CH3)；Examination of infrared spectrum result (KBr, cm-1)：1496,1372,1322,1230~1244,
1072,1172,924~944, confirm to contain three oxazine rings in products therefrom with reference to proton nmr spectra and infrared spectrum, be
Target product.
Solidification and test condition are the same as embodiment 1, the T of Polybenzoxazine resing、T5、T10And YcRespectively 330 DEG C of value, 364
DEG C, 382 DEG C and 50.6%.
Embodiment 3
Except raw material Benzaldehyde,2-hydroxy is changed to the fluoro- Benzaldehyde,2-hydroxies of 5- (7.0g, 0.05mol), step in step (3)
(4) double (4- hydroxyphenyls) -6- (2- hydroxyls-benzamido group) quinoxalines of 2,3- in are changed to double (4- hydroxyphenyls) -6- (the 2- hydroxyls of 2,3-
The fluoro- benzamido groups of base -5-) quinoxaline (9.1g, 0.02mol), n-butylamine is changed to n-octyl amine (5.2g, 0.04mol) outside, other conditions
With embodiment 1, fluorine-containing octylame-monoamine-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine monomer is finally obtained
(12.1g), yield 78.3%, fusing point are 67 DEG C.
Proton nmr spectra test result (500M, DMSO, ppm)：8.34~6.65 (m, 12H, Ar-H), 5.24 (s, 2H,
O-CH2- N), 4.94 (s, 2H, O-CH2- N), 4.83 (s, 2H, O-CH2- N), 4.42 (s, 2H, Ar-CH2- N), 3.91 (s, 2H,
Ar-CH2- N), 3.83 (s, 2H, Ar-CH2- N), 2.73 (t, 4H, N-CH2-CH2), 1.30~1.55 (m, 24H, CH2-CH2-
CH2), 0.89 (t, 6H ,-CH3)；Examination of infrared spectrum result (KBr, cm-1)：1495,1370,1324,1232~1242,
1070,1167,925~946, confirm to contain three oxazine rings in products therefrom with reference to proton nmr spectra and infrared spectrum, be
Target product.
Solidification and test condition are the same as embodiment 1, the T of Polybenzoxazine resing、T5、T10And YcRespectively 323 DEG C of value, 358
DEG C, 377 DEG C and 43.1%.
Embodiment 4
Except raw material Benzaldehyde,2-hydroxy is changed to 5- methoxyl groups-Benzaldehyde,2-hydroxy (7.6g, 0.05mol) in step (3), step
Suddenly double (4- hydroxyphenyls) -6- (2- hydroxyls-benzamido group) quinoxalines of the 2,3- in (4) are changed to double (4- hydroxyphenyls) -6- (the 2- hydroxyls of 2,3-
Base -5- methoxy-benzylamines base) quinoxaline (9.3g, 0.02mol), n-butylamine is changed to chaff amine (3.9g, 0.04mol) outside, other
Part finally obtains the chaff amine-monoamine-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine containing methoxyl group with embodiment 1
Monomer (11.2g), yield 77.8%, fusing point are 83 DEG C.
Proton nmr spectra test result (500M, DMSO, ppm)：8.27~6.60 (m, 12H, Ar-H), 7.40 (s, 2H,
Furan nucleus-CH=CH-O-), 6.22~6.34 (s, 4H, furan nucleus=CH-CH=), 5.13 (s, 2H, O-CH2- N), 4.88 Hes
4.69 (s, 4H, furan nucleus O-CH2- N), 4.30 (s, 2H, Ar-CH2- N), 4.13 (s, 2H, the Ar-CH being connected with furan nucleus2-
N), 4.03 (s, 2H, the Ar-CH being connected with furan nucleus2- N), 3.93 (s, 3H ,-OCH3), 3.84 (s, 4H, N-CH2-)；Infrared light
Compose test result (KBr, cm-1)：1496,1375,1325,1231~1240,1068,1174 and 922~946,1570,974 and
763 (characteristic peaks of furan nucleus), confirm to contain three oxazine rings in products therefrom with reference to proton nmr spectra and infrared spectrum, be
Target product.
In addition to solidify afterwards temperature adds 260 DEG C/2h, early stage curing cycle and test condition with embodiment 1, finally give
Polybenzoxazine resin Tg、T5、T10And YcValue is respectively 377 DEG C, 412 DEG C, 444 DEG C and 65.3%.
Embodiment 5
Except the n-butylamine in step (4) is changed to allylamine (2.28g, 0.04mol) outside, other conditions are with embodiment 1, finally
Obtain allylamine-mono- phenol-two amine type three-functionality-degree quinoxalinyl benzoxazine monomer (10.1g), yield 82.7%, fusing point 82
℃。
Proton nmr spectra test result (500M, DMSO, ppm)：8.32~6.61 (m, 18H, Ar-H), 5.85 (m, 2H,
In pi-allyl=CH-), 5.18 (m, 4H, in pi-allyl=CH2), 5.24 (s, 2H, O-CH2- N), 4.83 and 4.79 (d, 4H, with
Pi-allyl Xiang Lian oxazine rings O-CH2- N), 4.33 (s, 2H, Ar-CH2- N), 3.97 and 3.91 (d, 4H, with pi-allyl Xiang Lian oxazines
Ring Ar-CH2- N), 3.33 (s, 4H, N-CH2-)；Examination of infrared spectrum result (KBr, cm-1)：1644 (C=C stretching vibrations),
1493,1372,1325,1234~1245,1066,1163,991 (=C-H is waved outside face), 923~950 and 744, with reference to nuclear-magnetism
Resonance and infrared spectrum confirm to contain San oxazine ring in products therefrom, are target product.
Curing cycle and test condition are with embodiment 4, the T of the Polybenzoxazine resin finally giveng、T5、T10And YcValue point
Wei not be 369 DEG C, 387 DEG C, 412 DEG C and 58.5%.
The present invention is by means of quinoxaline molecule possessed excellent heat resistance in itself, by drawing in quinoxaline molecular structure
Enter Bu same type oxazine rings, obtain a kind of new monoamine-bisphenol type three-functionality-degree quinoxalinyl benzoxazine monomer, pass through
Introducing flexible alkyl chain and polymerizable groups so that such monomer has relatively low fusing point and extra polymerization crosslinking position, from
And improve processing characteristics, plus the introducing of Geng Duo oxazine rings, the Polybenzoxazine resin that thus prepared by monomer shows excellent
Heat resistance and good mechanical property, available for manufacture high performance structures material, electronic package material, high-temperature Resistance Adhesives,
Ablation resistant material, resistant material etc., it is with a wide range of applications in fields such as electronics, Aero-Space, machine-building.
Claims (4)
- A kind of 1. monoamine-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine, it is characterized in that having following structure：In formula, R1For H, CH3、OCH3, one kind in F, Cl or Br, R2For C2~C12Alkyl, pi-allyl, propargyl or furans it is sub- One kind in methyl.
- 2. a kind of preparation method of monoamine-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine described in claim 1, It is characterized in that：(1) 4,4- dihydroxy benzil, NPD and glacial acetic acid are added into container, wherein, 4,4- dihydroxy benzenes The mol ratio of even acyl and NPD is 1:1~1.2, mixture reacts 4~8h at a reflux temperature, is subsequently cooled to Room temperature, filtering, filter cake drying, gained crude product are recrystallized 1~3 time with glacial acetic acid, obtain double (4- the hydroxyphenyls) -6- nitros of 2,3- Quinoxaline；(2) double (4- the hydroxyphenyls) -6- nitroquinoxalines of 2,3- and palladium carbon are added in ethanol, adds mass concentration ratio as 80% Hydrazine hydrate, wherein, the mass ratio of 2,3- double (4- hydroxyphenyls) -6- nitroquinoxalines and palladium carbon is 1:0.02, hydrazine hydrate is the same as 2,3- The mol ratio of double (4- hydroxyphenyls) -6- nitroquinoxalines is 3.2~4:1,5~10h is reacted at a reflux temperature, then mistake while hot Filter, filtrate cooling room temperature, crystal, then filtered, vacuum drying are separated out, obtain double (4- the hydroxyphenyls) -6- aminoquinoxalines of 2,3-；(3) 2,3- double (4- hydroxyphenyls) -6- aminoquinoxalines, substituted or non-substituted salicylide, sulfuric acid and ethanol are added respectively Into reaction vessel, wherein, the mol ratio of 2,3- double (4- hydroxyphenyls) -6- aminoquinoxalines and substituted or non-substituted salicylide is 1:The mol ratio of 1,2,3- double (4- hydroxyphenyls) -6- aminoquinoxalines and sulfuric acid is 5:1, under agitation heating reflux reaction 6~ 10h, room temperature is subsequently cooled to, adds sodium borohydride, continue 5~10min of stirring at room temperature, wherein, 2,3- double (4- oxybenzenes Base) mol ratio of -6- aminoquinoxalines and sodium borohydride is 1:2, after reaction terminates, add water and dichloromethane, washed with distillation After washing organic phase for several times, rotated evaporation removes dichloromethane, obtains double (4- hydroxyphenyls) -6- (the substituted or non-substituted neighbours of 2,3- Hydroxyl-benzamido group) quinoxaline, abbreviation quinoxaline triphenol；(4) quinoxaline triphenol, primary amine, paraformaldehyde and chloroform are added into reactor, wherein, quinoxaline triphenol, primary amine Mol ratio with paraformaldehyde is 1:2:5,16~24h of back flow reaction, it is cooled to room temperature, then the hydrogen-oxygen through 0.1~0.5mol/L Change sodium solution alkali cleaning, washing, the rotated evaporation of organic phase removes chloroform, vacuum drying, it is asymmetric to obtain monoamine-bisphenol type Three-functionality-degree quinoxalinyl benzoxazine monomer.
- 3. the preparation method of monoamine according to claim 2-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine, It is characterized in that：Described substituted or non-substituted salicylide is Benzaldehyde,2-hydroxy, 4- methyl-Benzaldehyde,2-hydroxy, 5- methyl -2- Hydroxy benzaldehyde, 4- methoxyl groups-Benzaldehyde,2-hydroxy, 5- methoxyl groups-Benzaldehyde,2-hydroxy, the fluoro- Benzaldehyde,2-hydroxies of 5-, 4- One kind in fluoro- Benzaldehyde,2-hydroxy, 5- chlorine-2-hydroxyls benzaldehyde or the bromo- Benzaldehyde,2-hydroxies of 5-.
- 4. the preparation side of monoamine-bisphenol type asymmetry three-functionality-degree quinoxalinyl benzoxazine according to Claims 2 or 3 Method, it is characterized in that：Described primary amine is C2~C12One kind in fatty amine or chaff amine.
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| "Synthesis of Quinoxaline Derivatives Using TiO2 Nanoparticles as an Efficient and Recyclable Catalyst";Heshmatollah Alinezhad，et al.;《Bull. Korean Chem. Soc.》;20111231;第32卷(第10期);3720-3725 * |
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