TWI432445B - 新穎磷系單官能、雙官能及多官能酚類與其衍生物及其製造方法 - Google Patents
新穎磷系單官能、雙官能及多官能酚類與其衍生物及其製造方法 Download PDFInfo
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- TWI432445B TWI432445B TW100123924A TW100123924A TWI432445B TW I432445 B TWI432445 B TW I432445B TW 100123924 A TW100123924 A TW 100123924A TW 100123924 A TW100123924 A TW 100123924A TW I432445 B TWI432445 B TW I432445B
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- 150000002989 phenols Chemical class 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title claims description 5
- 230000001588 bifunctional effect Effects 0.000 title description 4
- 150000001875 compounds Chemical class 0.000 claims description 98
- 238000006243 chemical reaction Methods 0.000 claims description 58
- 229910052698 phosphorus Inorganic materials 0.000 claims description 49
- 239000011574 phosphorus Substances 0.000 claims description 49
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 35
- 239000003822 epoxy resin Substances 0.000 claims description 34
- 229920000647 polyepoxide Polymers 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 30
- 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 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- XAVGNEJDRLVNOO-UHFFFAOYSA-N [P].OC1=CC=CC=C1 Chemical compound [P].OC1=CC=CC=C1 XAVGNEJDRLVNOO-UHFFFAOYSA-N 0.000 claims description 15
- 239000004848 polyfunctional curative Substances 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- -1 polyphenol compound Chemical class 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 239000003377 acid catalyst Substances 0.000 claims description 11
- 229940126062 Compound A Drugs 0.000 claims description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 229910052740 iodine Inorganic materials 0.000 claims description 8
- 235000013824 polyphenols Nutrition 0.000 claims description 8
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- BJHJDRPKLAKFSU-UHFFFAOYSA-N C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.[P] Chemical compound C1(=CC=CC=C1)O.C1(=CC=CC=C1)O.[P] BJHJDRPKLAKFSU-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229930185605 Bisphenol Natural products 0.000 claims description 5
- 150000001913 cyanates Chemical class 0.000 claims description 5
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- ZMCHBSMFKQYNKA-UHFFFAOYSA-N 2-aminobenzenesulfonic acid Chemical compound NC1=CC=CC=C1S(O)(=O)=O ZMCHBSMFKQYNKA-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000006184 cosolvent Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- DVECLMOWYVDJRM-UHFFFAOYSA-N pyridine-3-sulfonic acid Chemical compound OS(=O)(=O)C1=CC=CN=C1 DVECLMOWYVDJRM-UHFFFAOYSA-N 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 239000007810 chemical reaction solvent Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 40
- 230000015572 biosynthetic process Effects 0.000 description 33
- 238000003786 synthesis reaction Methods 0.000 description 32
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 18
- 239000005011 phenolic resin Substances 0.000 description 18
- 239000012065 filter cake Substances 0.000 description 17
- 239000003063 flame retardant Substances 0.000 description 17
- 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 16
- 238000001914 filtration Methods 0.000 description 16
- 229920001568 phenolic resin Polymers 0.000 description 16
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000007171 acid catalysis Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 230000009477 glass transition Effects 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical group C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
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- 238000000921 elemental analysis Methods 0.000 description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- JQKFLNWRTBPECK-UHFFFAOYSA-N methoxymethane;propane-1,2-diol Chemical compound COC.CC(O)CO JQKFLNWRTBPECK-UHFFFAOYSA-N 0.000 description 4
- 239000005022 packaging material Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
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- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 2
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 2
- JAGRUUPXPPLSRX-UHFFFAOYSA-N 4-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=C(O)C=C1 JAGRUUPXPPLSRX-UHFFFAOYSA-N 0.000 description 2
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- AKUPIABWVUYZPX-UHFFFAOYSA-N 1,2,3,4-tetrabromodibenzo-p-dioxin Chemical compound C1=CC=C2OC3=C(Br)C(Br)=C(Br)C(Br)=C3OC2=C1 AKUPIABWVUYZPX-UHFFFAOYSA-N 0.000 description 1
- QLPZYYOHERFPKO-UHFFFAOYSA-N 1,2,3,4-tetrabromodibenzofuran Chemical compound C1=CC=C2C3=C(Br)C(Br)=C(Br)C(Br)=C3OC2=C1 QLPZYYOHERFPKO-UHFFFAOYSA-N 0.000 description 1
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 1
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- BRPSWMCDEYMRPE-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 BRPSWMCDEYMRPE-UHFFFAOYSA-N 0.000 description 1
- QJDOMYJEKGFUDS-UHFFFAOYSA-N 4-[1,1-bis(4-hydroxyphenyl)ethyl]phenol;phenol Chemical compound OC1=CC=CC=C1.C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=C(O)C=C1 QJDOMYJEKGFUDS-UHFFFAOYSA-N 0.000 description 1
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 description 1
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- 239000000057 synthetic resin Substances 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
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Description
本發明係提供一種磷系單酚、雙酚及多酚類化合物及其環氧樹脂,氧代氮代苯并環己烷(benzoxazine)及氰酸酯衍生物之新穎化合物及其製備方法。該等磷系化合物可進一步用於製備難燃樹脂硬化物。
環氧樹脂具有優良的電氣性質、尺寸安定性、耐高溫、耐溶劑性、低成本及高接著性等優點,適合做印刷電路板及積體電路封裝材料。然而,以碳、氫、氧原子鍵結的環氧樹脂與一般塑膠材料一樣容易燃燒進而危害生命,因此全世界對於使用電子、資訊用材料,其難燃性有嚴格要求。
在阻燃技術上,過去以環氧樹脂中導入溴原子為主。含溴環氧樹脂因優異的難燃特性,廣泛地被應用於具有難燃特性需求的電子材料上。然而,這些含溴環氧樹脂在燃燒過程會釋出溴化氫、四溴二聯苯戴奧辛(tetrabromodibenzo-p-dioxin)與四溴二聯苯呋喃(tetrabromodibenzofuran)等具有腐蝕性及毒性物質。
除了含鹵素的化合物外,有機磷化合物亦具有高度阻燃性;磷系難燃劑在燃燒時會促使高分子材料先行脫水,使碳氫化合物之氫與空氣中氧形成水,藉以降低周遭環境的溫度,使其低於燃燒溫度而達到難燃效果;另一方面在高溫加熱下會分解出磷酸促進高分子化合物的碳化,而形成不燃性焦炭層。此外,磷酸在高溫下會進一步脫水酯化形成聚磷酸覆蓋於燃燒物的表面形成保護作用,阻止氧氣進入高分子未燃燒的內層以及抑制揮發性裂解物的釋放。
導入磷元素的方法有二種,一種是直接合成含磷之環氧樹脂,另一種是將含磷硬化劑與環氧樹脂均勻混合。本發明則提供含磷硬化劑,使其與環氧樹脂混合硬化後,便可達到難燃的效果。
在含磷衍生物中,具反應性的9,10-二氫-9-氧雜-10-磷菲-10-氧化物(9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide,DOPO)深受矚目,因其可與缺電子化合物如苯二酮(benzoquinone)[1]
、環氧乙烷(oxirane)[2]
、馬來酸(maleic acid)[3]
、雙馬來亞醯胺(bismaleimide)[4
]、二胺基二苯甲酮(diaminobenzophenone)[5-6]
及對苯二甲醛(terephthaldicarboxaldehyde)[7]
等進行親核加成反應。
王等人在2001年提出可利用DOPO中的活性氫以附加型的方式,直接和雙官能或多官能的環氧樹脂的環氧基反應,而形成具有高玻璃轉移溫度(Tg)、高熱裂解溫度及高彈性率,而且對環境無害的難燃環氧樹脂半固化物[2
]。林等人也在2005年揭露三官能硬化劑(dopotriol[8
]與dopo-ta[9
])的合成方法與應用,成功得到難燃且具有高玻璃轉移溫度的環氧樹脂。然而,文獻中合成dopotriol的原料薔薇酸(rosolic acid)非常昂貴,於工業應用上不符合經濟效益,於是林等人接著於2008年以較便宜的4,4'-二羥基二苯基甲酮(4,4'-dihydroxy benzophenone,DHBP)與DOPO及苯酚/苯胺反應,成功合成含磷難燃劑dopotriol以及dopodiolamine[10]
。經由硬化所得之環氧樹脂具有優異玻璃轉移溫度、熱穩定性、尺寸安定性及難燃性。但dopotriol以及dopodiolamine有溶解度不佳的加工性的問題。
酚醛樹脂是最早工業化的合成樹脂,由於原料易得,吸水率低,加工性良好以及樹脂固化後性能能滿足很多使用要求,因此在模塑膠、絕緣材料、塗料、木材黏接等方面得到廣泛應用。近年來隨著人們對安全等要求的提高,具有阻燃、少煙、無毒等特性的酚醛樹脂重新引起人們重視,尤其在飛機場、火車站、學校、醫院等公共建築設施及飛機的內部裝飾材料等方面的應用越來越多。
文獻指出,雙酚A會在酸催化下裂解成酚及不安定的4-異丙烯基酚(4-isopropenylphenol)[11]
。本發明即利用DOPO與雙酚A,在酸催化下進行反應,使DOPO鍵結於剛形成之4-異丙烯基酚上,合成單官能酚類化合物。接著利用DOPO與三官能酚1,1,1-三(4-羥基苯基)乙烷(1,1,1-tris(4-hydroxyphenyl)ethane),在酸催化下進行反應,形成雙官能酚類化學物。此外,本申請案亦將DOPO與多官能雙酚A酚醛樹脂(BPA novolac)在酸催化下合成磷系多官能雙酚A酚醛樹脂。本發明亦將磷系酚類進一步反應形成環氧樹脂,氧代氮代苯并環己烷(benzoxazine)及氰酸酯衍生物。
[1] Wang, C.S. and Lin, C.H. Polymer 1999; 40; 747.
[2] Lin,C.H. and Wang,C.S. Polymer.,2001,42,1869.
[3] Wang,C.S.;Lin,C.H. and Wu,C.Y. J. Appl. Polym. Sci. 2000,78,228.
[4] Lin,C.H. and Wang,C.S. J. Polym. Sci. Part A: Polym. Chem. 2000,38,2260.
[5] Liu,Y.L. and Tsai,S.H. Polymer 2002;43;5757.
[6] Wu,C.S.;Liu,Y.L. and Chiu,Y.S. Polymer 2002;43;1773.
[7] Liu,Y.L.;Wang,C.S.;Hsu,K.Y. and Chang,T.C. J. Polym. Sci. Part A: Polym. Chem. 2002,40,2329.
[8] Lin,C.H.;Cai,S.X. and Lin,C.H. J. Polym. Sci. Polym. Chem. 2005,43,5971.
[9] Cai,S.X. and Lin,C.H. J. Polym. Sci. Polym. Chem. 2005,43,2862.
[10] Lin,C.H.;Lin,T.L.;Chang S.L.;Dai,S.H. A.;Cheng,R.J.;Hwang,K.U.;Tu,A.P.;Su,W.C. J. Polym. Sci. Part A: Polym. Chem. 2008,46,7898.
[11] Andrew J.C. and Julia L.L. J. Org. Chem. 1997,62,1058.
本發明係提供新穎製造磷系單酚、雙酚及多酚類化合物及其環氧樹脂,BENZOXAZINE及氰酸酯衍生物的方法。可進一步製備一難燃樹脂硬化物。
新穎磷系單酚、雙酚化合物及酚醛樹脂
本發明揭示具有下列化學式之磷系酚類化合物結構如下:
其中Y1
至Y4
各獨立為H,C1
-C6
烷基或苯基,較佳為甲基;R0
及R4
各獨立為H、C1
-C6
烷基、C3
-C6
環烷基、F、Cl、Br或I;及n為1至10之整數。
當上述式(I)化合物之Y1
及Y2
為CH3
,R1
及R2
為H時,該式(I)化合物之結構式可為磷系單酚化合物A
當上述式(II)化合物之Y1
至Y4
為CH3
,R1
及R2
為H,且中間苯環上之取代基呈間位關係時,該式(II)化合物之結構式可為磷系單酚化合物B
當上述式(II)化合物之Y1
至Y4
為CH3
,R1
及R2
為CH3
,且中間苯環上之取代基呈對位關係時,該式(II)化合物之結構式可為磷系單酚之化合物C
當上述式(III)化合物之Y1
至Y3
均為CH3
,該式(III)化合物之結構式可為磷系雙酚之化合物D
當上述式(IV)化合物之Y1
為CH3
,R1
至R4
為H時,該式(IV)化合物之結構式可為磷系雙酚之化合物E(此為已知化合物)
當上述式(V)化合物之R0
為H時,該式(V)化合物之結構式可為式P-BPN之磷系酚醛樹脂
並由本發明實施例可知,當P-BPN分子量較高時,其所對應硬化物的玻璃轉移溫度也較高。
本發明係提供一種製造磷系單酚、雙酚或多酚的方法,其包含將如下式之DOPO化合物
與選自由下列各式酚類化合物所組成之群在酸觸媒存在下進行反應:
其中Y1
至Y4
各獨立為H,C1
-C6
烷基或苯基,較佳為甲基;R0
至R6
各獨立為H、C1
-C6
烷基、C3
-C6
環烷基、F、Cl、Br或I,及m為1至10之整數。
本發明上述方法中,該酸觸媒可選自由醋酸、對-甲基苯璜酸(p-Toluenesulfonic acid,PTSA)、甲基磺酸(Methanesulfonic acid)、氟磺酸(Fluorosulfonic acid)、三氟甲磺酸(Trifluoromethanesulfonic acid)、硫酸(Sulfuric acid)、2-胺基苯磺酸(Orthanilic acid)、3-啶磺酸(3-Pyridinesulfonic acid)、對胺基苯磺酸(Sulfanilic acid)、氯化氫(HCl)、溴化氫(HBr)、碘化氫(HI)、氟化氫(HF)、三氟乙酸(CF3
COOH)、硝酸(HNO3
)、磷酸(H3
PO4
)所組成之群。
本發明上述方法中,該酸觸媒之量為該酚類化合物的0.1 wt%至10 wt%間,較佳為1 wt%至5 wt%。
本發明上述方法中,該反應時間為6至24小時,較佳為12至20小時。
本發明上述方法中,該反應溫度為60℃至150℃間。
本發明上述方法中,反應可在使用或不使用溶劑下進行。若在溶劑下進行,選用的溶劑可為選用的溶劑可為乙氧基乙醇(ethoxyethanol)、甲氧基乙醇(methoxyethanol)、1-甲氧基-2-丙醇(1-methoxy-2-propanol)、單甲基醚丙二醇(propylene glycol monomethyl ether,DOW PM)、二氧陸圜(dioxane)、或上述溶劑所組成的共溶劑。
本發明上述方法中,當酚類化合物選自式(I)-a化合物,其中Y1
及Y2
為CH3
,R1
至R4
為H時,則該化學反應式可如下所示,而反應所得產物則為磷系單酚化合物A
本發明上述方法中,當酚類化合物選自式(II)-a化合物,其中Y1
至Y4
為CH3
,R1
至R4
為H時,且中間苯環上之取代基呈間位關係時,則該化學反應式可如下所示,而反應所得產物則為磷系單酚化合物B
本發明上述方法中,當酚類化合物選自式(II)-a化合物,其中Y1
至Y4
為CH3
,R1
至R4
為CH3
時,且中間苯環上之取代基呈對位關係時,則該化學反應式可如下所示,而反應所得產物則為磷系單酚化合物C
本發明上述方法中,當酚類化合物選自式(III)-a化合物,其中Y1
至Y3
為CH3
,則該化學反應式可如下所示,而反應所得產物則為磷系單酚化合物D
本發明上述方法中,當酚類化合物選自式(IV)-a化合物,其中Y1
為CH3
,R1
至R6
為H時,則該化學反應式可如下所示,而反應所得產物則為磷系雙酚化合物E
本發明上述方法中,當酚類化合物選自式(V)-a化合物,其中R0
為H時,則反應所得產物則為式P-BPN之磷系酚醛樹脂
由本發明實施例可知,在不同觸媒、觸媒量及反應溫度等反應環境中,可生成不同分子量之P-BPN化合物,當減少觸媒使用量由4%降為2%時,可得較高分子量之P-BPN化合物,當使用DOW PM作為溶劑時,則可得更高分子量之P-BPN化合物。
本發明應用例中,進一步使用上述不同分子量之磷系P-BPN化合物作為環氧樹脂之硬化劑,而其硬化物皆符合UL-94燃燒性測試中的難燃等級V-0,相對而言,僅使用非磷系BPN化合物作為硬化劑時,其硬化物在UL-94燃燒性測試中會全部燃燒。另,當P-BPN分子量較高時,其所對應硬化物的玻璃轉移溫度也較高。
本發明另揭示一種具有下列化學式之P-BPN衍生物:
其中R0
為H、C1
-C6
烷基、C3
-C5
環烷基、F、Cl、Br或I,R係選自C1
-C12
烷基、苯基、丙烯基、N≡C-C6
H4
-及HC≡C-O-C6
H4
-所組成之群,n為1至10之整數。
當上述式P-BPN-EP化合物之R0
為H時,該式P-BPN-EP化合物之結構式可為式P-BPN-EP-1化合物
當上述式P-BPN-BZ化合物之R為CH3
時,該式P-BPN-BZ化合物之結構式可為式P-BPN-BZ-1化合物
當上述式P-BPN-OCN化合物之R0
為H時,該式P-BPN-OCN化合物之結構式可為式P-BPN-OCN-1化合物
本發明提供一種新穎P-BPN衍生物之製備方法,該衍生物可為環氧樹脂(P-BPN-EP)、或氧代氮代苯并環己烷(benzoxazine)(P-BPN-BZ)、或氰酸酯衍生物(P-BPN-OCN),其化學反應係如下所示:
其中,R0
為H、C1
-C6
烷基、C3
-C5
環烷基、F、Cl、Br或I,R係選自C1
-C12
烷基、苯基、丙烯基、N≡C-C6
H4
-及HC≡C-O-C6
H4
-所組成之群,n為1至10之整數。
本發明上述方法中,該P-BPN之R0
為H時,其反應產物分別可為如下式之P-BPN-EP-1之環氧樹脂衍生物、或P-BPN-BZ-1之氧代氮代苯并環己烷衍生物、或P-BPN-OCN-1氰酸酯衍生物
本發明另提供一種含有硬化劑之環氧樹脂,其中該硬化劑系選自上述磷系單酚、雙酚、多酚或酚醛樹脂之化合物或式P-BPN之衍生物之任一化合物。
以上之相關發明之實施將以下列之具體實施例說明。
磷系單官能酚類(化合物A)以雙酚A(bisphenol A,BPA)與過量的DOPO(9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide)在酸觸媒催化下反應而得,其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入22.83克(0.1莫耳)的BPA、63.85克(0.3莫耳)的DOPO、0.92克(BPA的4 wt%)的甲苯磺酸及升高反應溫度達140℃,將反應系統溫度維持在140℃,反應12小時後,滴入乙醇攪拌析出,抽氣過濾後,過濾分離,濾餅用真空烘箱在110℃下真空烘乾即為化合物A,產率為75%。化合物A之分子式為C21
H19
O3
P,高解析質譜儀鑑定其分子量為350.3522。元素分析:C:71.65%,H:5.65%。化合物A的1
H NMR圖譜標示於圖1。
磷系單官能酚類(化合物B)是以BHPB(1,3-Bis[2-(4-hydroxyphenyl)-2-propyl]benzene)與過量的DOPO在酸觸媒催化下反應而得,其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入34.65克(0.1莫耳)的BHPB、64.85克(0.3莫耳)的DOPO、1.39克(BHPB的4 wt%)的硫酸及升高反應溫度達150℃,將反應系統溫度維持在150℃,反應18小時後,滴入乙醇攪拌析出,抽氣過濾後,過濾分離,濾餅用真空烘箱在110℃下真空烘乾即為化合物B,產率為53%。化合物B之分子式為C30
H29
O3
P,高解析質譜儀鑑定其分子量為468.5211。元素分析:C:76.61%,H:6.45%。
磷系單官能酚類(化合物C)是以BHDMP(alpha,alpha'-Bis(4-hydroxy-3,5-dimethylphenyl)-1,4-diisopropylbenzene)與過量的DOPO在酸觸媒催化下反應而得,其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入40.26克(0.1莫耳)的BHDMP、64.85克(0.3莫耳)的DOPO、3.22克(BHDMP的8 wt%)的甲基磺酸及升高反應溫度達180℃,將反應系統溫度維持在180℃,反應20小時後,滴入乙醇攪拌析出,抽氣過濾後,過濾分離,濾餅用真空烘箱在110℃下真空烘乾即為化合物C,產率為65%。化合物C之分子式為C32
H33
O3
P,高解析質譜儀鑑定其分子量為496.5823。元素分析:C:77.21%,H:6.87%。
磷系雙官能酚類(化合物D)是以三酚單體(Trisphenol,PA)與過量的DOPO在酸觸媒催化下反應而得,其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入42.45克(0.1莫耳)的PA、63.85克(0.3莫耳)的DOPO、1.82克(PA的4 wt%)的甲苯磺酸及升高反應溫度達140℃,將反應系統溫度維持在140℃,反應16小時後,滴入乙醇攪拌析出,抽氣過濾後,過濾分離,濾餅用真空烘箱在110℃下真空烘乾即為化合物D,產率為78%。化合物D之分子式為C35
H31
O4
P,高解析質譜儀鑑定其分子量為546.5928。元素分析:C:76.77%,H:5.88%。
磷系雙官能酚類(化合物E)是以三酚單體THPE(1,1,1-Tris(4-hydroxyphenyl)ethane)與過量的DOPO在酸觸媒催化下反應而得,其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入30.64克(0.1莫耳)的THPE、63.85克(0.3莫耳)的DOPO、1.23克(THPE的4wt%)的甲苯磺酸及升高反應溫度達130℃,將反應系統溫度維持在130℃,反應12小時後,滴入乙醇攪拌析出,抽氣過濾後,過濾分離,濾餅用真空烘箱在110℃下真空烘乾即為化合物E,產率為58%。化合物E之分子式為C26
H21
O4
P,高解析質譜儀鑑定其分子量為428.4213。元素分析:C:72.98%,H:5.01%。化合物E的1
H NMR圖譜標示於圖2。
磷含量2%的磷系酚醛樹酯(P-BPN-2a)係將雙酚A酚醛樹酯(Bisphenol A Novolac,BPN)與DOPO在酸催化下反應而得其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入50克BPN、8.102克DOPO及2克(BPN的4wt%)的甲苯磺酸,將反應系統溫度維持在140℃,反應12小時後,利用甲醇水將黏稠物洗去殘餘的甲苯磺酸,抽氣過濾後,過濾分離,濾餅用真空烘箱在100℃下真空烘乾。
圖3為31
P NMR反應追蹤光譜圖,由圖可知在5分鐘就可以明顯看出產物生成在43ppm左右,未完全反應完的DOPO位置在16~23ppm,而在25分鐘即可看到DOPO的特徵峰完全消失,進而觀察到產物為一支peak,代表此化合物有成功合成出來的。產物的GPC分析結果如表1所示。
磷含量3%的磷系酚醛樹酯(P-BPN-3a)係將BPN與DOPO在酸催化下反應而得。其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入50克BPN、13.227克DOPO、及2克(BPN的4 wt%)的甲苯磺酸將反應系統溫度維持在140℃,反應12小時後,利用甲醇水將黏稠物洗去殘餘的甲苯磺酸,抽氣過濾後,過濾分離,濾餅用真空烘箱在100℃下真空烘乾得化合物P-BPN-3a。產物的GPC分析結果如表1所示。
磷含量5%的磷系酚醛樹酯(P-BPN-5a)係將BPN與DOPO在酸催化下反應而得。其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入50克BPN、26.765克DOPO、及2克(BPN的4 wt%)的甲苯磺酸將反應系統溫度維持在140℃,反應12小時後,利用甲醇水將黏稠物洗去殘餘的甲苯磺酸,抽氣過濾後,過濾分離,濾餅用真空烘箱在100℃下真空烘乾真空烘乾得化合物P-BPN-5a。產物的GPC分析結果如表1所示。
磷含量2%的磷系酚醛樹酯(P-BPN-2b)係將BPN與DOPO在酸催化下反應而得。其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入50克BPN、8.102克DOPO、及1克(BPN的2wt%)的甲苯磺酸將反應系統溫度維持在130℃,反應12小時後,利用甲醇水將黏稠物洗去殘餘的甲苯磺酸,抽氣過濾後,過濾分離,濾餅用真空烘箱在100℃下真空烘乾得化合物P-BPN-2b。產物的GPC分析結果如表1所示。
磷含量3%的磷系酚醛樹酯(P-BPN-3b)係將BPN與DOPO在酸催化下反應而得。其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入50克BPN、13.227克DOPO、及1克(BPN的2wt%)的甲苯磺酸將反應系統溫度維持在130℃,反應12小時後,利用甲醇水將黏稠物洗去殘餘的甲苯磺酸,抽氣過濾後,過濾分離,濾餅用真空烘箱在100℃下真空烘乾得化合物P-BPN-3b。產物的GPC分析結果如表1所示。
磷含量5%的磷系酚醛樹酯(P-BPN-5b)係將BPN與DOPO在酸催化下反應而得。其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入50克BPN、26.765克DOPO、及1克(BPN的4 wt%)的甲苯磺酸將反應系統溫度維持在130℃,反應12小時後,利用甲醇水將黏稠物洗去殘餘的甲苯磺酸,抽氣過濾後,過濾分離,濾餅用真空烘箱在100℃下真空烘乾真空烘乾得化合物P-BPN-5b。產物的GPC分析結果如表1所示。
磷含量2%的磷系酚醛樹酯(P-BPN-2PM)係將BPN與DOPO在酸催化下反應而得。其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入50克BPN、8.102克DOPO、1克(BPN的2 wt%)的甲苯磺酸及溶劑單甲基醚丙二醇升高反應溫度達100℃,反應12小時後,滴入水中攪拌析出,抽氣過濾後,濾餅再用大量的去離子水洗滌,抽氣過濾後,過濾分離,濾餅用真空烘箱在100℃下真空烘乾得化合物P-BPN-2PM。產物的GPC分析結果如表1所示。
磷含量3%的磷系酚醛樹酯(P-BPN-3PM)係將BPN與DOPO在酸催化下反應而得。其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入50克BPN、13.227克DOPO、1克(BPN的2 wt%)的甲苯磺酸及溶劑單甲基醚丙二醇升高反應溫度達100℃,反應12小時後,滴入水中攪拌析出,抽氣過濾後,濾餅再用大量的去離子水洗滌,抽氣過濾後,過濾分離,濾餅用真空烘箱在100℃下真空烘乾得化合物P-BPN-3PM。產物的GPC分析結果如表1所示。
磷含量5%的磷系酚醛樹酯(P-BPN-5PM)係將BPN與DOPO在酸催化下反應而得。其合成步驟如下:在一附有溫度指示裝置之0.5升三頸反應器中,加入50克BPN、26.765克DOPO、1克(BPN的2 wt%)的甲苯磺酸及溶劑單甲基醚丙二醇升高反應溫度達100℃,反應12小時後,滴入水中攪拌析出,抽氣過濾後,濾餅再用大量的去離子水洗滌,抽氣過濾後,過濾分離,濾餅用真空烘箱在100℃下真空烘乾得化合物P-BPN-5PM。產物的GPC分析結果如表1所示。
由實施例6-14產物的GPC結果顯示,觸媒的量從4%降為2%時,對應P-BPN化合物之分子量明顯增加,意即減少觸媒有助於維持較高分子量。當加入單甲基醚丙二醇(DOW PM)為溶劑,並降低反應溫度至100℃,可維持較前二者更高的分子量。
取21.4克的P-BPN-5b、92.5克的環氧氯丙烷加入1公升反應器中,常壓下攪拌成均勻混合溶液後,於190mmHg絕對壓力下升高反應溫度至70℃並於4小時內分批加入14.6克之20%氫氧化鈉溶液,加入同時並把反應器內的水共沸蒸出。反應完後利用減壓蒸餾將環氧氯丙烷及溶劑蒸餾乾淨,將產物以甲基乙基酮及去離子水溶解、水洗樹脂中氯化鈉,再用減壓蒸餾將溶劑蒸餾乾淨即得磷系磷氧樹脂P-BPN-EP-1。
將甲醛13.98克溶於dioxane 12毫升,配製成溶液A。再將甲基胺2.68克溶於dioxane 3毫升,配製成溶液B。於100毫升反應瓶內放置溶液A,冰浴下通氮氣。再將溶液B以每秒一滴的方式滴入反應器內,溫度控制在10℃以下,滴完後再反應30分鐘。將磷系化合物P-BPN-5b 11.98克加入反應器內後,開始升溫至回流,反應10小時。反應完成後,用真空濃縮機抽乾溶劑,將產物溶於CH2
Cl2
,用0.1M氫氧化鈉萃取並用去離子水沖洗三次,加入無水硫酸鎂除水後過濾,用真空烘箱烘乾,得到P-BPN-5-BZ-1固體,產率85%。
加入無水丙酮(70克)於1升三頸反應器中。將反應器冷卻至-15℃後,加入BrCN 3.102克並攪拌之,同時將溫度降至-25℃以下。另將2.39克的P-BPN-5b及Et3
N 2.62克充分混合溶解於無水丙酮(100克)後,以進料漏斗緩慢滴入反應器中,且溫度維持在-30℃,反應維持2小時。當反應溫度回到-30℃時,將反應液滴入去離子水中洗滌以去除溴化銨鹽。過濾後,將所得之沈澱物以CH2
Cl2
/H2
O進行萃取。收集有機相,再以無水硫酸鎂乾燥。將硫酸鎂去除後,於室溫下利用旋轉蒸發器將CH2
Cl2
移除,得到氰酸酯P-BPN-OCN-1固體。
將實施例6~8三種硬化劑作為環氧樹脂的硬化劑,使用的環氧樹脂分別為雙酚A環氧樹脂(DGEBA)與磷甲基酚醛環氧樹脂(CNE)。將環氧樹脂與硬化劑以當量比為1:1的比例下在模具中均勻混合,另外添加了咪唑(Imidazole)(添加量為環氧樹脂的0.2 wt%)當作反應的硬化促進劑。利用DMA所測得玻璃轉移溫度以及在UL-94測試上皆整理在表2中。由表中可知,所有的硬化物組成皆符合UL-94燃燒性測試中的難燃等級V-0。
將實施例9~11三種硬化劑作為環氧樹脂的硬化劑,使用的環氧樹脂分別為雙酚A環氧樹脂(DGEBA)與磷甲基酚醛環氧樹脂(CNE)。將環氧樹脂與硬化劑以當量比為1:1的比例下在模具中均勻混合,另外添加了咪唑(添加量為環氧樹脂的0.2 wt%)當作反應的硬化促進劑。利用DMA所測得玻璃轉移溫度以及在UL-94測試上皆整理在表2中。由表中可知,所有的硬化物組成皆符合UL-94燃燒性測試中難燃等級V-0。
將實施例12~14三種硬化劑作為環氧樹脂的硬化劑,使用的環氧樹脂分別為雙酚A環氧樹脂(DGEBA)與磷甲基酚醛環氧樹脂(CNE)。將環氧樹脂與硬化劑以當量比為1:1的比例下在模具中均勻混合,另外添加了咪唑(添加量為環氧樹脂的0.2 wt%)當作反應的硬化促進劑。利用動態機械分析儀(Dynamic Mechanical Analysis,DMA)所測得玻璃轉移溫度以及在UL-94測試上皆整理在表2中。由表中可知,所有的硬化物組成皆符合UL-94燃燒性測試中的難燃等級V-0。
由表2可知,當使用P-BPN作為難燃劑時,所有的硬化物皆符合UL-94燃燒性測試中的難燃等級V-0,相對而言,僅使用非磷系BPN化合物作為硬化劑時,其硬化物則在UL-94燃燒性測試中會全部燃燒。另,當P-BPN分子量較高時,其所對應硬化物的玻璃轉移溫度也較高。
圖1為化合物A的1
H NMR光譜圖。
圖2為化合物E的1
H NMR光譜圖。
圖3為化合物P-BNP-2a的31
P NMR反應追跡光譜圖,其中所時間分別為(a)5分鐘(b)10分鐘(c)15分鐘(d)20分鐘(e)25分鐘。
(無元件符號說明)
Claims (13)
- 一種如下列各式之磷系單酚或多酚化合物,
- 如請求項1之化合物,其中當式(I)化合物之Y1 及Y2 為CH3 ,R1 及R2 為H時,該式(I)化合物之結構式可為磷系單酚化合物A
- 一種製造如下列各式之磷系單酚、雙酚或多酚化合物的方法,
- 如請求項3之方法,其中當式(I)-a化合物之Y1 及Y2 為CH3 ,R1 及R2 為H時,該磷系單酚產物可為下式之化合物A
- 如請求項3或4之方法,其中該酸觸媒係選自由醋酸、對-甲基苯璜酸(p-Toluenesulfonic acid,PTSA)、甲基磺酸(Methanesulfonic acid)、氟磺酸(Fluorosulfonic acid)、三氟甲磺酸(Trifluoromethanesulfonic acid)、硫酸(Sulfuric acid)、2-胺基苯磺酸(Orthanilic acid)、3-啶磺酸(3-Pyridinesulfonic acid)、對胺基苯磺酸(Sulfanilic acid)、氯化氫(HCl)、溴化氫(HBr)、碘化氫(HI)、氟化氫(HF)、三氟乙酸(CF3 COOH)、硝酸(HNO3 )、磷酸(H3 PO4 )所組成之群。
- 如請求項3或4之方法,其中該酸觸媒之量為該酚類化合 物的0.1wt%至10wt%間。
- 如請求項3或4之方法,其中反應溫度為60至150℃之間。
- 如請求項3或4之方法,其中該反應溶劑係選自由下列所組成之群:乙氧基乙醇(ethoxyethanol)、甲氧基乙醇(methoxyethanol)、1-甲氧基-2-丙醇(1-methoxy-2-propanol)、單甲基醚丙二醇(propylene glycol monomethyl ether,DOW PM)、或二氧陸圜(dioxane)、或上述溶劑所組成的共溶劑。
- 一種如下列各式之P-BPN衍生物,
- 如請求項9之式P-BPN衍生物,其中當式P-RPN-EP化合 物之R0 為H時,該式P-BPN-EP化合物之結構式可為式P-BPN-EP-1化合物
- 一種新穎P-BPN衍生物之製備方法,該衍生物可為環氧樹脂(P-BPN-EP)、或氧代氮代苯并環己烷(benzoxazine) (P-BPN-BZ)、或氰酸酯衍生物(P-BPN-OCN),其化學反應係如下所示
- 如請求項11之方法,其中當該P-BPN之R0 為H時,其反應產物分別可為如下式之P-BPN-EP-1之環氧樹脂衍生物、或P-BPN-BZ-1之氧代氮代苯并環己烷衍生物、或P-BPN-OCN-1氰酸酯衍生物:
- 一種含有硬化劑之環氧樹脂,其中該硬化劑為請求項1或2之磷系單酚或多酚之化合物或請求項9或10之式P-BPN衍生物。
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CN201210230287.8A CN103122010B (zh) | 2011-07-06 | 2012-07-04 | 磷系单官能、双官能及多官能酚类与其衍生物及其制备方法 |
JP2012151251A JP5788835B2 (ja) | 2011-07-06 | 2012-07-05 | 一官能性、二官能性、および多官能性ホスフィン化フェノール、その誘導体、ならびにその調製方法 |
US13/542,556 US8841388B2 (en) | 2011-07-06 | 2012-07-05 | Monofunctional, bifunctional, and multifunctional phosphinated phenols and their derivatives and preparation method thereof |
KR20120073934A KR101483821B1 (ko) | 2011-07-06 | 2012-07-06 | 일작용성, 이작용성 및 다작용성 포스핀 화합물 및 이의 유도체 및 이의 제조 방법 |
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TWI498334B (zh) * | 2012-01-16 | 2015-09-01 | Univ Nat Chunghsing | 磷系化合物、含有磷系化合物之混摻物及其製備方法 |
CN103382242B (zh) | 2013-06-25 | 2015-06-24 | 江苏雅克科技股份有限公司 | 含磷阻燃酚醛树脂及以其为原料制备的阻燃环氧树脂固化物 |
CN103450421A (zh) * | 2013-07-27 | 2013-12-18 | 梁劲捷 | 磷改性酚醛树脂的制备方法 |
CN103450426A (zh) * | 2013-07-27 | 2013-12-18 | 广西藤县通轩立信化学有限公司 | 磷改性酚醛树脂及其制备方法 |
CN106750226B (zh) * | 2014-11-11 | 2019-01-08 | 江苏雅克科技股份有限公司 | 含磷聚酯化合物组成及含磷阻燃环氧树脂固化物的制备方法 |
TWI494297B (zh) * | 2014-11-21 | 2015-08-01 | Univ Nat Chunghsing | 乙烯苯基化磷系酚類、環氧樹脂固化物及其製法 |
CN105801814B (zh) * | 2014-12-29 | 2018-05-04 | 广东生益科技股份有限公司 | 一种无卤热固性树脂组合物及使用它的预浸料和印制电路用层压板 |
US10723747B2 (en) * | 2015-09-29 | 2020-07-28 | Nan Ya Plastics Corporation | Low DK phosphorous containing hardener useful for halogen free, flame retardant polymers and use |
US9546262B1 (en) * | 2015-11-04 | 2017-01-17 | Chang Chun Plastics Co. Ltd. | Phosphorous containing compounds and process for synthesis |
CN106905561B (zh) * | 2017-03-02 | 2019-08-23 | 张家港市山牧新材料技术开发有限公司 | 一种含氟的dopo衍生物阻燃剂及其制备方法 |
CN110733093B (zh) * | 2019-10-25 | 2021-01-19 | 福建省顺昌县升升木业有限公司 | 一种杉木阻燃改性处理方法 |
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JP5788835B2 (ja) | 2015-10-07 |
KR101483821B1 (ko) | 2015-01-16 |
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CN103122010B (zh) | 2017-12-12 |
US8841388B2 (en) | 2014-09-23 |
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JP2013018772A (ja) | 2013-01-31 |
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