TW201811809A - 一種含有酯基的磷腈化合物、製備方法及用途 - Google Patents
一種含有酯基的磷腈化合物、製備方法及用途 Download PDFInfo
- Publication number
- TW201811809A TW201811809A TW106119355A TW106119355A TW201811809A TW 201811809 A TW201811809 A TW 201811809A TW 106119355 A TW106119355 A TW 106119355A TW 106119355 A TW106119355 A TW 106119355A TW 201811809 A TW201811809 A TW 201811809A
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- Prior art keywords
- substituted
- unsubstituted
- group
- phosphazene compound
- ester group
- Prior art date
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- -1 Phosphazene compound Chemical class 0.000 title claims abstract description 79
- 125000004185 ester group Chemical group 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title description 7
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical class CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 19
- 125000004437 phosphorous atom Chemical group 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims description 28
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical group N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 230000000269 nucleophilic effect Effects 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 7
- 239000011889 copper foil Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000011188 CEM-1 Substances 0.000 claims description 4
- 239000011190 CEM-3 Substances 0.000 claims description 4
- 101100257127 Caenorhabditis elegans sma-2 gene Proteins 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 238000007344 nucleophilic reaction Methods 0.000 claims description 4
- 125000000962 organic group Chemical group 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000011342 resin composition Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- WJYZUJWXUHDLJI-UHFFFAOYSA-N 1,3,5,7,2,4,6,8-tetrazatetraphosphocine Chemical group N1=PN=PN=PN=P1 WJYZUJWXUHDLJI-UHFFFAOYSA-N 0.000 claims description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 125000002015 acyclic group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000005248 alkyl aryloxy group Chemical group 0.000 claims description 2
- 125000004414 alkyl thio group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 claims description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical group OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 12
- 239000003063 flame retardant Substances 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 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 11
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000005886 esterification reaction Methods 0.000 description 10
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 239000003822 epoxy resin Substances 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000004843 novolac epoxy resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 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 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 150000003017 phosphorus Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- LTNCYKRVIPCLLU-UHFFFAOYSA-N 1,2,3,4,5,6-hexahydro-1,3,5,7,2,4,6,8-tetrazatetraphosphocine Chemical compound N1=PNPNPNP1 LTNCYKRVIPCLLU-UHFFFAOYSA-N 0.000 description 1
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940024545 aluminum hydroxide Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- GPRDLRZMTVQCHM-UHFFFAOYSA-L magnesium;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Mg+2] GPRDLRZMTVQCHM-UHFFFAOYSA-L 0.000 description 1
- IJFXRHURBJZNAO-UHFFFAOYSA-N meta--hydroxybenzoic acid Natural products OC(=O)C1=CC=CC(O)=C1 IJFXRHURBJZNAO-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical class [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
Classifications
-
- 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 System
- 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
- C07F9/6581—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
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- B32B15/00—Layered products comprising a layer of metal
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/246—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
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Abstract
本發明關於一種含有酯基的磷腈化合物,前述含有酯基的磷腈化合物具有式(I)所示的結構。在磷腈化合物中接入酯基基團,通過末端接枝的羥基和羧基與聚合物基體發生反應,使磷腈化合物在引入基材提高阻燃性能的同時,產生降低介電常數的效果。由於N原子和P原子是通過反應直接鍵合在前述的基材聚合物中,而非現有技術的添加組合,不存在由於阻燃劑添加,對母體造成的機械性能的降低。
Description
本發明屬於磷腈化合物的技術領域,尤其關於一種含有酯基的磷腈化合物、製備方法及在複合金屬基板上的用途。
以手機、電腦、攝影機、電子遊戲機為代表的電子產品、以空調、冰箱、電視影像、音響用品等為代表的家用、辦公電器產品以及其他領域使用的各種產品,為了安全,很大部分的產品都要求其具備不同程度的阻燃性能。
為了使產品達到所要求的阻燃性能或等級,傳統的技術常常使用向材料體系中添加如氫氧化鋁水合物、氫氧化鎂水合物等含有結晶水的金屬氫氧化物等類的無機阻燃物質、和向體系材料中添加如溴化雙酚A、溴化雙酚A型環氧樹脂等含溴量比較高的或含鹵素量比較高的有機化學物質。為了提高這些含有鹵素的有機化學物質的阻燃性,還常常在體系中再加入如三氧化二銻等對環境不友好的無機化學阻燃劑物質。
這些使用含磷酚醛當做阻燃成分的一部分或全部所製得的覆銅板,可以達到阻燃的目的,但耐酸鹼性、耐化學藥品性、黏結性、耐熱性、加工性等存在不少的缺陷,不適合製造現代通訊需要的高多層、高 可靠性、高黏結性、良好的加工性能的需要,以及由於高成本的原因,不利於普及到如手機等要求低成本的消費電子等民用品領域。
隨著電子產業對短、小、薄、高多層化、高可靠性要求的進一步提高、民用消費電子的普及使用以及越來越嚴峻的環境污染的壓力,市場迫切需要材料具有良好的阻燃性、耐熱性、良好的機械性能的廉價阻燃性物質。
有鑑於此,本發明一方面提供一種含有酯基的磷腈化合物、製備方法及用途,其係具有良好的阻燃性、耐熱性、良好的機械性能的阻燃性材料。
針對現有技術的不足,本發明的目的之一在於提供一種含有酯基的磷腈化合物,前述含有酯基的磷腈化合物具有式(I)所示的結構:
式(I)中,Y、Z1和Z2為惰性親核基團;M為磷腈化合物中的任意1種或至少2種的組合;R’1為-X-R’3-,R’2為-X-R’4-,R’3和R’4為具有兩個斷鍵的有機基團,X 為氧原子、氮原子或硫原子;a為大於等於1的整數,例如1、2、3、4、5、6、7、8、9、10、11、14、15等,b為大於等於0的整數,例如0、1、2、3、4、5、6、7、8、9、10、13、15等,c為大於等於0的整數,例如0、1、2、3、4、5、6、7、8、9、10、13、15等,d為大於等於0的整數,例如0、1、2、3、4、5、6、7、8、9、10、13、15等,b和a之和為M中磷原子個數的2倍,c+2為M中磷原子個數的2倍,d+2為M中磷原子個數的2倍,m為小於等於10,例如1、2、3、4、5、6、7、8、9等。
一種含有酯基的磷腈化合物,前述含有酯基的磷腈化合物具有式(II)所示的結構:
式(II)中,Z1和Z2為惰性親核基團;M為磷腈化合物中的任意1種或至少2種的組合;R’1為-X-R’3-,R’2為-X-R’4-,R’3和R’4為具有兩個斷鍵的有機基團,X為氧原子、氮原子或硫原子;c為大於等於0的整數,例如0、1、2、3、4、5、6、7、8、9、10、13、15等,d為大於等於0的整數,例如0、1、2、3、4、5、6、7、8、9、10、13、15等,c+2為M中磷原子個數的2倍,d+2為M中磷原子個數的2倍,m為大於0且小於等於10的整數,例如1、2、3、4、5、6、7、8、9等。
在磷腈化合物中接入酯基基團,通過末端接枝的羥基和羧基與聚合物基體發生反應,使磷腈化合物在引入基體提高阻燃性能的同時,產生降低介電常數的效果。由於N原子和P原子是通過反應直接鍵合在前述的聚合物基體中,而非現有技術的添加組合,不存在由於阻燃劑添加,對母體造成的機械性能的降低。
在本發明中,所謂惰性親核基團是指能夠進行親核反應,在進行親核反應以後,連接在磷腈母體M(如環三磷腈,環四磷腈或線性磷腈)上,並不再具有反應活性的基團;所謂反應活性是指進行任何本領域習知的反應的能力,包括親核取代、加成反應、酸鹼反應、酯化反應,置換反應等等。
本發明所記載之含有酯基的磷腈化合物由具有至少2個羥基的磷腈化合物單體與具有至少2個羧基的磷腈化合物單體通過酯化反應得到。
本領域技術人員應該明瞭,對於酯化反應,需要有羥基和羧基,而在本發明所記載之磷腈化合物中,磷腈母體能夠連接多個羥基或多個羧基,在發生酯化的過程中,任何兩個羧基和羥基均可發生酯化,形成本發明所記載之磷腈化合物。
而對於本發明,具有羥基的磷腈化合物單體和具有羧基的磷腈化合物單體同樣有可能形成網路狀或者具有側鏈的化合物,且得到的產物均在本發明的保護範圍內。
理想地,本發明所記載之Z1和Z2均各自獨立地選自-OR14、 -SR2、、-C≡C-R6、、-O-NO2、-I或中的任意一種或者至少兩種的組合。
其中,R14、R13、R2、R3、R4、R5、R6、R15、R11和R12均獨立地為取代或未取代的直鏈烷基或支鏈烷基、取代或未取代的環烷基、取代或未取代的芳烷基、取代或未取代的烷氧基、取代或未取代的烷基硫基、取代或未取代的環烷氧基、取代或未取代的芳烷氧基、取代或未取代的烷基芳氧基、取代或未取代的碳酸酯基、取代或未取代的磺酸酯基、取代或未取代的膦酸酯基、取代或未取代的芳基或取代或未取代的雜芳基中的任意一種。
理想地,前述M選自具有式(III)結構的環狀磷腈,或具有式(IV)結構的線性磷腈;
在式(III)或式(IV)中,n1和n2均各自獨立地選自3~10的整數,n1理想為3或4,n2理想為5、6、7或8。
對於M,其可以選擇環狀磷腈,如環三磷腈或/和環四磷腈,也可以選擇線性磷腈,前述線性磷腈以P=N為重複單元,以氫原子或甲基封端;在前述M的P原子上,至少接枝-X-Y,並可選地接枝R,實現在M上接 枝偶聯劑基團的目的。
理想為前述M為環三磷腈基M1、環四磷腈基M2或非環狀聚磷腈基M3中的任意1種或至少2種的組合。
理想地,前述R’3選自取代或未取代的亞烴基,進一步理想為取代或未取代的直鏈亞烷基、取代或未取代的支鏈亞烷基、取代或未取代的亞芳香基;更進一步理想為C1~C30的取代或未取代的直鏈亞烷基、C1~C30取代或未取代的支鏈亞烷基、C6~C30取代或未取代的亞芳香基;特別理想為C1~C10的取代或未取代的直鏈亞烷基、C1~C10取代或未取代的支鏈亞烷基、C6~C16取代或未取代的亞芳香基;特別理想為亞苯基、甲基亞苯基、二甲基亞苯基、乙基亞苯基、、亞甲基、亞乙基、亞丙基、亞正丁基或亞異丙基。
理想地,前述含有酯基的磷腈化合物由具有至少2個羥基的磷腈化合物單體與具有至少2個羧基的磷腈化合物單體發生酯化反應得到。
理想地,前述含有酯基的磷腈化合物包括具有如下結構的磷腈化合物中的任意1種或者至少2種的混合物:
;其中m為大於0且小於等於10的整數。
本發明目的之二是提供一種如目的之一所記載之含有酯基的磷腈化合物的製備方法,前述方法包括如下步驟:(1)將磷腈氯化物與惰性親核原料發生親核反應,取代M上的部分氯原子為惰性親核基團,剩餘磷腈氯化物上的兩個氯原子不取代;(2)將步驟(1)的產物等莫耳分成2份,一份與H-X-R’3-OH反應,將磷腈母體上的剩餘的氯原子取代為-R’1-OH,另一份與H-X-R’4-COOH反應,將磷腈母體上的剩餘的氯原子取代為-R’2-COOH;(3)將步驟(2)分別得到的帶有羥基的磷腈化合物與帶有羧基的磷腈化合物進行酯化反應,得到含有酯基的磷腈化合物;其中,M、X、R’1、R’2、R’3和R’4具有目的之一所記載之限定範圍。
本領域技術人員應該明瞭,對於磷腈母體M,其具有不止一個P原子,每個P原子能夠接枝2個側鏈基團,在製備的過程的步驟(1)和步驟(2)中,每個氯原子取代機會幾乎是相同的,因此,在反應過程中,並不能夠完全控制取代基的個數和位置,因此,往往通過前述方法製備得到的產品是一個混合物,但是這些混合物均可用於本發明所記載之酯化反應,其酯化反應遵循的原則是羥基和羧基進行酯化反應。當然,在保證物料比例的前提下,大部分的產物都應該是按照設定的方案獲得的。
在前述化學結構中,取代基並未連接至環三磷腈的某個原子上,而是畫在了環三磷腈的環內,意指在滿足價態需求的前提下,前述取代基可以取代在環三磷腈的任意位置。
本發明目的之三是提供一種樹脂組合物,包含目的之一所記載之含有酯基的磷腈化合物。
本發明目的之四是提供一種預浸板,其由目的之三所記載之樹脂組合物含浸或塗布於基材而成。
理想地,前述基材為玻璃纖維基材、聚酯基材、聚醯亞胺基材、陶瓷基材或碳纖維基材。
本發明目的之五是提供一種複合金屬基板,其包括一張以上如目的之四所記載之預浸板依次進行表面覆金屬層、重疊、壓合而成。
理想地,前述表面覆金屬層的材質為鋁、銅、鐵及其任意組合的合金。
理想地,前述複合金屬基板為CEM-1覆銅板、CEM-3覆銅板、FR-4覆銅板、FR-5覆銅板、CEM-1鋁基板、CEM-3鋁基板、FR-4鋁基板或FR-5鋁基板。
本發明目的之六是提供一種線路板,於目的之五前述的複合金屬基板的表面加工線路而成。
本發明目的之七是提供一種柔性覆銅板,前述柔性覆銅板包含一張以上如目的之四所記載之預浸板以及覆於疊合後的預浸板一側或兩側的銅箔。
本發明目的之八是提供一種如目的之一所記載之含有酯基的磷腈化合物的用途,前述含有酯基的磷腈化合物用於IC封裝板、HDI封裝板、汽車板或覆銅板。
與現有技術相比,本發明具有如下功效:在磷腈化合物中接入酯基基團,通過末端接枝的羥基和羧基與聚合物基體發生反應,使磷腈化合物在引入基體提高阻燃性能的同時,產生降低 介電常數的效果。由於N原子和P原子是通過反應直接鍵合在前述的聚合物基體中,而非現有技術的添加組合,不存在由於阻燃劑添加,對母體造成的機械性能的降低。
為便於理解本發明,本發明列舉實施例如下。本領域技術人員應該明瞭,前述實施例僅僅是幫助理解本發明,不應視為對本發明的具體限制。
為了方便描述結構和方法,本發明所記載之實施例製備的磷腈化合物的結構式中,沒有標出取代基在磷腈母體上的具體位置,意指任何位置均可以取代前述取代基;另外,對於實施例中描述的化合物的結構式中取代基的個數,也只是示意性的表示前述方法製備得到的產物,其取代基的數量是前述產物中取代基的平均值,並不表示得到的產物是一個結構的化合物。
實施例1
一種含有酯基的磷腈化合物,具有如下的結構:,其中,環三磷腈上平均被4個苯氧基取代;m為3; 製備方法為:(1)帶有攪拌裝置的三口2000mL玻璃反應器裡投入六氯環三磷腈1mol、丙酮200mL,苯酚鈉4mol,一邊攪拌、一邊通氮氣,升溫到60℃,用60min滴入20%氫氧化鈉溶液至pH值中性,保持60℃溫度,攪拌反應15個小時;(2)將步驟(1)的產物等分2份;一份與2mol甲二醇反應,一邊攪拌、一邊通氮氣,升溫到40℃,用30min滴入20%氫氧化鈉溶液至pH值中性,保持40℃溫度,攪拌反應15個小時,得到含有羥甲基氧基的磷腈化合物;另一份與2mol 2-羥基乙酸反應,一邊攪拌、一邊通氮氣,升溫到40℃,用30min滴入20%氫氧化鈉溶液至pH值中性,保持40℃溫度,攪拌反應15個小時,得到含有羧乙基氧基的磷腈化合物;(3)將步驟(2)得到的含有氧甲基氧基取代的磷腈化合物和含有羧乙基氧基的磷腈化合物進行酯化反應,共聚得到含有酯基的磷腈化合物。
反應後,用物理的方法去除體系中無機成分和水分,蒸餾掉體系中溶劑,得到含有酯基的磷腈化合物。
對得到的含有酯基的磷腈化合物進行核磁共振氫譜表徵,結果如下:1H NMR(CDCl3,500MHz):6.7~6.8,7.0~7.15,6.8~6.9(苯環上的氫),5.75~5.80(O-C-O上的氫),6.30~6.35(O-C-O-C=O上的氫),4.45~4.55(O=C-C-O上的氫),11.0(羧基的氫),2.0(羥基的氫)。
紅外譜圖特徵峰的位置:磷腈骨架中P=N鍵的特徵吸收峰1217cm-1, 磷腈骨架中P-N 874cm-1,P-O-C鍵吸收峰1035cm-1,苯環骨架震動1500~1600cm-1,酯基吸收峰1200~1300cm-1。
以上述含有酯基的磷腈化合物100g作為偶聯固化劑加入環氧當量為200g/eq的鄰甲酚醛環氧樹脂100g,固化促進劑2-甲基咪唑0.1g,製備環氧樹脂組合物。採用該環氧樹脂組合物按照通用的覆銅板製作程序製得符合國標、UL等標準的標準覆銅板樣品,命名為a覆銅板,測試a覆銅板的性能,其結果在表-1中表示。
實施例2
一種含有酯基的磷腈化合物,具有如下的結構:,其中,環三磷腈上平均被4個甲氧基取代;m為2;製備方法為:(1)帶有攪拌裝置的三口2000mL玻璃反應器裡投入六氯環三磷腈1mol、丙酮200mL,甲醇鈉4mol,一邊攪拌、一邊通氮氣,升溫到60℃,用60min滴入20%氫氧化鈉溶液至pH值中性,保持60℃溫度,攪拌反應15個小時;(2)將步驟(1)的產物等分2份;一份與2mol甲二醇反應,一邊攪拌、一邊通氮氣,升溫到40℃,用30min滴入20%氫氧化鈉溶液至pH值中性,保持40℃溫度,攪拌反應15個小時, 得到含有羥甲基氧基的磷腈化合物;另一份與2mol 2-羥基乙酸反應,一邊攪拌、一邊通氮氣,升溫到40℃,用30min滴入20%氫氧化鈉溶液至pH值中性,保持40℃溫度,攪拌反應15個小時,得到含有羧乙基氧基的磷腈化合物;(3)將步驟(2)得到的含有氧甲基氧基取代的磷腈化合物和含有羧乙基氧基的磷腈化合物進行酯化反應,共聚得到含有酯基的磷腈化合物。
對得到的含有酯基的磷腈化合物進行核磁共振氫譜表徵,結果如下:1H NMR(CDCl3,500MHz):5.75~5.80(O-C-O上的氫),6.30~6.35(O-C-O-C=O上的氫),4.45~4.55(O=C-C-O上的氫),11.0(羧基的氫),2.0(羥基的氫),3.35(甲基上的氫)。
紅外譜圖特徵峰的位置:磷腈骨架中P=N鍵的特徵吸收峰1217cm-1,磷腈骨架中P-N 874cm-1,P-O-C鍵吸收峰1035cm-1,烴基C-H伸縮振動2850~3000cm-1,C=O伸縮振動1680~1630cm-1,酯基吸收峰1200~1300cm-1。
以上述含有酯基的磷腈化合物100g作為偶聯固化劑加入環氧當量為200g/eq的鄰甲酚醛環氧樹脂100g,固化促進劑2-甲基咪唑0.1g,製備環氧樹脂組合物。採用該環氧樹脂組合物按照通用的覆銅板製作程序製得符合國標、UL等標準的標準覆銅板樣品,命名為b覆銅板,測試b覆銅板的性能,其結果在表-1中表示。
實施例3
一種含有酯基的磷腈化合物,具有如下的結構: ,其中,環三磷腈上平均被4個甲氧基取代,m為10;製備方法為:(1)帶有攪拌裝置的三口2000mL玻璃反應器裡投入六氯環三磷腈1mol、丙酮200mL,甲醇鈉4mol,一邊攪拌、一邊通氮氣,升溫到60℃,用60min滴入20%氫氧化鈉溶液至pH值中性,保持60℃溫度,攪拌反應15個小時;(2)將步驟(1)的產物等分2份;一份與2mol間苯二酚反應,一邊攪拌、一邊通氮氣,升溫到60℃,用30min滴入20%氫氧化鈉溶液至pH值中性,保持60℃溫度,攪拌反應15個小時,得到含有羥苯基氧基的磷腈化合物;另一份與2mol間羥基苯甲酸反應,一邊攪拌、一邊通氮氣,升溫到60℃,用30min滴入20%氫氧化鈉溶液至pH值中性,保持60℃溫度,攪拌反應15個小時,得到含有羧基的磷腈化合物;(3)將步驟(2)得到的含有氧苯基氧基的磷腈化合物和含有羧基的磷腈化合物進行酯化反應,共聚得到含有酯基的磷腈化合物。
對得到的含有酯基的磷腈化合物進行核磁共振氫譜表徵,結果如下:1H NMR(CDCl3,500MHz):6.15~6.25,6.90~7.05(HO-O-Ar-O-P上的 氫),7.65~7.75,7.20~7.50(O-Ar-C=O上的氫),3.39(甲基上的氫),6.6~6.8,7.1~7.7(Ar-O-C(=O)-Ar上的氫)。
紅外譜圖特徵峰的位置:磷腈骨架中P=N鍵的特徵吸收峰1217cm-1,磷腈骨架中P-N 874cm-1,P-O-C鍵吸收峰1035cm-1,烴基C-H伸縮振動2850~3000cm-1,C=O伸縮振動1680~1630cm-1,酯基吸收峰1200~1300cm-1。
以上述含有酯基的磷腈化合物100g作為偶聯固化劑加入環氧當量為200g/eq的鄰甲酚醛環氧樹脂100g,固化促進劑2-甲基咪唑0.1g,製備環氧樹脂組合物。採用該環氧樹脂組合物按照通用的覆銅板製作程序製得符合國標、UL等標準的標準覆銅板樣品,命名為c覆銅板,測試c覆銅板的性能,其結果在表-1中表示。
比較例1
環氧當量為200g/eq的鄰甲酚醛環氧樹脂200g,加入酚羥基當量為105g/eq的線型酚醛樹脂固化劑105g和作為阻燃劑的六苯氧基環三磷腈70g以及0.2g的2-甲基咪唑,用適量的丁酮溶解成溶液,用標準玻璃布,按照常規的製作方法,得到含樹脂量為50%的覆銅板d,覆銅板d的各項性能在表-1中表示。
比較例2
環氧當量為200g/eq的鄰甲酚醛環氧樹脂200g,加入具有如式(1)結構的樹脂化合物220g,酯當量為220g/eq以及作為阻燃劑的六苯氧基環三磷腈70g和0.2g的吡啶,用適量的丁酮溶解成溶液,用標準玻璃布,按照常規的製作方法,得到含樹脂量為50%的覆銅板e。覆銅板e的各項性能在表-1中表示。
實施例和比較例的測試結果如下表-1所示:表-1各種覆銅板的性能比較
測試方法:
(1)吸水率
將100mm×100mm×1.6mm板材置於105℃的烘箱中乾燥1h,冷卻後稱重並放置在105kPa的蒸汽壓下蒸煮120min,最後擦乾稱重並計算出吸水率。
(2)玻璃化轉變溫度Tg
製備測試樣品的寬度約為8-12mm,長度為60mm,在德國耐馳DMA Q800上設置測量模式為彎曲模式,掃描溫度為室溫至200℃,讀取損耗角正切值最大時對應的溫度為該試樣的玻璃化轉變溫度Tg。
(3)彎曲強度
製備25.4mm×63.5m的試樣,使用遊標卡尺測量其厚度,將萬能材料試驗機的測試模式調為彎曲測試模式,設置間距為15.9mm,試驗速度為0.51mm/min,取3次平行測試的平均值,測試溫度分別為室溫和180℃。
(4)剝離強度測定
將覆銅層疊板切成100mm×3mm的試驗片,使用抗剝儀試驗裝置,以速度50.8mm/min對銅箔進行剝離分層,測試銅箔與樹脂的剝離強度,數值越大說明樹脂與銅箔間的黏合力越好。
(5)按照標準ANSL UL94-1985測試燃燒性;
(6)按照標準ASTM D150介電常數測試介電常數和介電損耗。
申請人聲明,本發明透過上述實施例來說明本發明的工藝方法,但本發明並不侷限於上述工藝步驟,即不意味著本發明必須依賴上述工藝步驟才能實施。所屬技術領域的技術人員應該明瞭,對本發明的任何改進,對本發明所選用原料的等效替換及輔助成分的添加、具體方式的選擇等,均落在本發明的保護範圍和公開範圍之內。
Claims (11)
- 一種含有酯基的磷腈化合物,其特徵在於,前述含有酯基的磷腈化合物具有式(I)所示的結構:
- 如申請專利範圍第1項所記載之含有酯基的磷腈化合物,其中,前述含有酯基的磷腈化合物具有式(II)所示的結構:
- 如申請專利範圍第2項所記載之含有酯基的磷腈化合物,其中,Z 1和Z 2均各自獨立地選自-OR 14、-SR 2、 、-C≡C-R 6、 、-O-NO 2、-I或 中的任意一種或者至少兩種的組合;R 14、R 13、R 2、R 3、R 4、R 5、R 6、R 15、R 11和R 12均獨立地為取代或未取代的直鏈烷基或支鏈烷基、取代或未取代的環烷基、取代或未取代的芳烷基、取代或未取代的烷氧基、取代或未取代的烷基硫基、取代或未取代的環烷氧基、取代或未取代的芳烷氧基、取代或未取代的烷基芳氧基、取代或未取代的碳酸酯基、取代或未取代的磺酸酯基、取代或未取代的膦酸酯基、取代或未取代的芳基或取代或未取代的雜芳基中的任意一種;理想地,前述M選自具有式(III)結構的環狀磷腈,或具有式(IV)結構的線性磷腈;
- 如申請專利範圍第2項所記載之含有酯基的磷腈化合物,其中,前述含有酯基的磷腈化合物包括具有如下結構的磷腈化合物中的任意1種或者至少2種的混合物:
- 一種如申請專利範圍第2~4項中任一項所記載之含有酯基的磷腈化合物的製備方法,其特徵在於,前述方法包括如下步驟:(1)將磷腈氯化物 與惰性親核原料發生親核反應,取代M上的部分氯原子為惰性親核基團,剩餘磷腈氯化物上的兩個氯原子不取代;(2)將步驟(1)的產物等莫耳分成2份,一份與H-X-R’ 3-OH反應,將磷腈母體上的剩餘的氯原子取代為-R’ 1-OH,另一份與H-X-R’ 4-COOH反應,將磷腈母體上的剩餘的氯原子取代為-R’ 2-COOH;(3)將步驟(2)分別得到的帶有羥基的磷腈化合物與帶有羧基的磷腈化合物進行酯化反應,得到含有酯基的磷腈化合物;其中,M、X、R’ 1、R’ 2、R’ 3和R’ 4具有如申請專利範圍第2~4項中任一項所記載之限定範圍。
- 一種樹脂組合物,其特徵在於,包含如申請專利範圍第2~4項中任一項所記載之含有酯基的磷腈化合物。
- 一種預浸板,其特徵在於,其由如申請專利範圍第6項所記載之樹脂組合物含浸或塗布於基材而成;理想地,前述基材為玻璃纖維基材、聚酯基材、聚醯亞胺基材、陶瓷基材或碳纖維基材。
- 一種複合金屬基板,其特徵在於,其包括一張以上如申請專利範圍第7項所記載之預浸板依次進行表面覆金屬層、重疊、壓合而成;理想地,前述表面覆金屬層的材質為鋁、銅、鐵及其任意組合的合金;理想地,前述複合金屬基板為CEM-1覆銅板、CEM-3覆銅板、FR-4覆銅板、FR-5覆銅板、CEM-1鋁基板、CEM-3鋁基板、FR-4鋁基板或FR-5鋁基 板。
- 一種線路板,其特徵為其係於申請專利範圍第8項所記載之複合金屬基板的表面加工線路而成。
- 一種柔性覆銅板,其特徵在於,前述柔性覆銅板包含一張以上如申請專利範圍第7項所記載之預浸板以及覆於疊合後的預浸板一側或兩側的銅箔。
- 一種如申請專利範圍第2~4項中任一項所記載之含有酯基的磷腈化合物的用途,其特徵在於,前述含有酯基的磷腈化合物用於IC封裝板、HDI封裝板、汽車板或覆銅板。
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CN113024605A (zh) * | 2019-12-24 | 2021-06-25 | 中蓝晨光化工研究设计院有限公司 | 一种六苯氧基环三磷腈阻燃剂的合成方法 |
CN112142985B (zh) * | 2020-08-19 | 2022-07-12 | 四川中物材料股份有限公司 | 一种有机硅/苯氧基磷腈高分子共聚物及制备方法和应用 |
CN113234103B (zh) * | 2021-05-28 | 2023-07-25 | 青岛大学 | 磷腈阻燃剂及其制备方法和应用 |
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TWI656129B (zh) | 2019-04-11 |
EP3263576A1 (en) | 2018-01-03 |
US20180002360A1 (en) | 2018-01-04 |
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