CN1910263B - Process for producing phosphorus compound flame retardant, phosphorus compound flame retardant, and flame-retardant polyester - Google Patents
Process for producing phosphorus compound flame retardant, phosphorus compound flame retardant, and flame-retardant polyester Download PDFInfo
- Publication number
- CN1910263B CN1910263B CN2004800387644A CN200480038764A CN1910263B CN 1910263 B CN1910263 B CN 1910263B CN 2004800387644 A CN2004800387644 A CN 2004800387644A CN 200480038764 A CN200480038764 A CN 200480038764A CN 1910263 B CN1910263 B CN 1910263B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- phosphonium flame
- retardant
- phosphinate
- polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 153
- 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 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 47
- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- 229920000728 polyester Polymers 0.000 title abstract description 67
- 229910052698 phosphorus Inorganic materials 0.000 title abstract description 15
- 239000011574 phosphorus Substances 0.000 title abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title abstract description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000004519 manufacturing process Methods 0.000 claims abstract description 54
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 39
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 39
- -1 alkylene glycol Chemical compound 0.000 claims abstract description 37
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 23
- 150000002903 organophosphorus compounds Chemical class 0.000 claims abstract description 23
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 claims description 86
- 229940058344 antitrematodals organophosphorous compound Drugs 0.000 claims description 22
- 150000008065 acid anhydrides Chemical class 0.000 claims description 17
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 16
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- UQZPTVULCJDKIV-UHFFFAOYSA-N CCC.O[PH2]=O Chemical compound CCC.O[PH2]=O UQZPTVULCJDKIV-UHFFFAOYSA-N 0.000 claims description 4
- ISWLRMQDZDXXBC-UHFFFAOYSA-N O[PH2]=O.CCCC Chemical compound O[PH2]=O.CCCC ISWLRMQDZDXXBC-UHFFFAOYSA-N 0.000 claims description 4
- ZCAUYTYTNDUKQS-UHFFFAOYSA-N O[PH2]=O.CCCCC Chemical class O[PH2]=O.CCCCC ZCAUYTYTNDUKQS-UHFFFAOYSA-N 0.000 claims description 4
- 150000004714 phosphonium salts Chemical class 0.000 claims description 4
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- WLLLTBGMZHYHEJ-UHFFFAOYSA-N CC.O[PH2]=O Chemical compound CC.O[PH2]=O WLLLTBGMZHYHEJ-UHFFFAOYSA-N 0.000 claims description 2
- PNWNMNSPQGJNTF-UHFFFAOYSA-N O[PH2]=O.CC1=CC=CC=C1 Chemical compound O[PH2]=O.CC1=CC=CC=C1 PNWNMNSPQGJNTF-UHFFFAOYSA-N 0.000 claims description 2
- ADWBBBJRAKQOFR-UHFFFAOYSA-N O[PH2]=O.CCCCCC Chemical compound O[PH2]=O.CCCCCC ADWBBBJRAKQOFR-UHFFFAOYSA-N 0.000 claims description 2
- HVPNHVYDDAGZOE-UHFFFAOYSA-N [PH2](O)=O.C1(=CC=CC=C1)CC Chemical compound [PH2](O)=O.C1(=CC=CC=C1)CC HVPNHVYDDAGZOE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical class [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 238000006068 polycondensation reaction Methods 0.000 abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 5
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 238000001879 gelation Methods 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 238000005886 esterification reaction Methods 0.000 description 7
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005755 formation reaction Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical class CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 150000003504 terephthalic acids Chemical class 0.000 description 3
- 238000001149 thermolysis Methods 0.000 description 3
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 101000766096 Halorubrum sodomense Archaerhodopsin-3 Proteins 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229940119177 germanium dioxide Drugs 0.000 description 2
- 239000002955 immunomodulating agent Substances 0.000 description 2
- 229940121354 immunomodulator Drugs 0.000 description 2
- 230000002584 immunomodulator Effects 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- 229940059574 pentaerithrityl Drugs 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DVAVTWDOWVBESE-UHFFFAOYSA-N 1,1,3,5,6-pentachloro-1,2,2,3,4,4,5,6,6-nonafluorohexane Chemical compound FC(F)(Cl)C(F)(Cl)C(F)(F)C(F)(Cl)C(F)(F)C(F)(Cl)Cl DVAVTWDOWVBESE-UHFFFAOYSA-N 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- RUNJHCZDNSMWGF-UHFFFAOYSA-N 1-propylphosphonoylpropane Chemical compound CCCP(=O)CCC RUNJHCZDNSMWGF-UHFFFAOYSA-N 0.000 description 1
- RRTALVKXNFOACI-UHFFFAOYSA-N 2-(3-tert-butyl-4-hydroxyphenyl)butanoic acid Chemical compound CCC(C(O)=O)C1=CC=C(O)C(C(C)(C)C)=C1 RRTALVKXNFOACI-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- LXPSYLSFEIGSMD-UHFFFAOYSA-N 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoic acid Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(O)=O LXPSYLSFEIGSMD-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- WQEXBUQDXKPVHR-SNAWJCMRSA-N Dimethyl citraconate Chemical compound COC(=O)\C=C(/C)C(=O)OC WQEXBUQDXKPVHR-SNAWJCMRSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- XQESRKKYLKQLDE-UHFFFAOYSA-N OP(O)(=O)OP(=O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)CN)C(C)(C)C)C(O)C(CO)(CO)CO Chemical compound OP(O)(=O)OP(=O)(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)CN)C(C)(C)C)C(O)C(CO)(CO)CO XQESRKKYLKQLDE-UHFFFAOYSA-N 0.000 description 1
- QKCWWJIWIGOCDA-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].C(C)[Ca+].C(C)[Ca+].C(C)[Ca+] Chemical compound P(=O)([O-])([O-])[O-].C(C)[Ca+].C(C)[Ca+].C(C)[Ca+] QKCWWJIWIGOCDA-UHFFFAOYSA-K 0.000 description 1
- VYGRRCKMMADGBB-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] phosphono hydrogen phosphate Chemical compound OCC(CO)(CO)COP(O)(=O)OP(O)(O)=O VYGRRCKMMADGBB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229940069428 antacid Drugs 0.000 description 1
- 239000003159 antacid agent Substances 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- JMCNGFNJWDJIIV-UHFFFAOYSA-N dibutyl(oxo)phosphanium Chemical compound CCCC[P+](=O)CCCC JMCNGFNJWDJIIV-UHFFFAOYSA-N 0.000 description 1
- YPTLFOZCUOHVFO-VOTSOKGWSA-N diethyl (e)-2-methylbut-2-enedioate Chemical compound CCOC(=O)\C=C(/C)C(=O)OCC YPTLFOZCUOHVFO-VOTSOKGWSA-N 0.000 description 1
- ZEFVHSWKYCYFFL-UHFFFAOYSA-N diethyl 2-methylidenebutanedioate Chemical compound CCOC(=O)CC(=C)C(=O)OCC ZEFVHSWKYCYFFL-UHFFFAOYSA-N 0.000 description 1
- YVXVNGVYXSQARS-UHFFFAOYSA-N diethyl(oxo)phosphanium Chemical compound CC[P+](=O)CC YVXVNGVYXSQARS-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- FQWBKGICDYMQHJ-UHFFFAOYSA-N dioxogermane;ethane-1,2-diol Chemical compound O=[Ge]=O.OCCO FQWBKGICDYMQHJ-UHFFFAOYSA-N 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- RRZCFXQTVDJDGF-UHFFFAOYSA-N dodecyl 3-(3-octadecoxy-3-oxopropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC RRZCFXQTVDJDGF-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Natural products OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229940038384 octadecane Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- QOOLLUNRNXQIQF-UHFFFAOYSA-N sodium;5-sulfobenzene-1,3-dicarboxylic acid Chemical compound [Na].OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 QOOLLUNRNXQIQF-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Fireproofing Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A phosphorus compound flame retardant which is to be copolymerized in polyester production and does not arouse problems, for example, that it undergoes pyrolysis, flies out of the system, or causes polymer gelation in the polyester-yielding reaction, under the high-temperature reduced-pressure conditions used for the polycondensation for polyester production. The flame-retardant polyester thus produced has a satisfactory color tone. Also provided are: a process for producing the flame retardant; and a flame-retardant polyester produced through copolymerization with the phosphorus compound flame retardant. The process for producing a phosphorus compound flame retardant comprises reacting an organophosphorus compound with an unsaturated carboxylic acid and/or an anhydride thereof in an alkylene glycol, wherein the reaction is conducted in the presence of at least one antioxidant incorporated in a total amount of 0.001 to 10 wt.% based on the organophosphorus compound.
Description
Technical field
The present invention relates to the manufacture method, phosphonium flame retardant of phosphonium flame retardant and with the fire-retardant polyester of this phosphonium flame retardant as structural unit.
Background technology
In recent years from the position of respect people life, as can enumerating flame retardant resistance, and various researchs have been carried out with regard to it with the desired characteristic of various molding headed by the fiber.In for the molding made from linear polyesters, someone proposes when polymkeric substance is made to add the fire retardant copolymerization or with the method for its blend, mediate the method enter in the polyester during with moulding, and molding is carried out the method etc. that post-treatment is given flame retardant resistance and resistivity against fire.In these methods, considering under the situation of its industrial value that from the simplest and without detriment to the viewpoint of all performances of gained molding, the interpolation fire retardant makes the method for its copolymerization the most favourable when polymkeric substance is made.Make the fire retardant of its copolymerization when making, use phosphorus compound mostly as polyester.Yet, under the high temperature of many phosphorus compounds when polycondensation of polyester, the reduced pressure since exist produce thermolysis, outside system, disperse and in the formation reaction of polyester problem such as polymer gel, so require to its improvement.
As the phosphonium flame retardant that does not produce described problem can with the phosphorus compound of polyethylene terephthalate copolymer, with 9, the 10-dihydro-9-oxy is assorted-P contained compound of 10-phospho hetero phenanthrene-10-oxide compound and methylene-succinic acid manufacturing is known (referring to patent documentation 1) in the presence of ethylene glycol.
Patent documentation 1: the spy opens clear 52-97981 communique
But the ethylene glycol solution of disclosed P contained compound is significantly painted in the patent documentation 1, has the problem of tonal difference with the fire-retardant polyester of its manufacturing, requires further to be improved.
Summary of the invention
The phosphonium flame retardant of copolymerization when the object of the invention is to provide a kind of polyester to make, under high temperature when polycondensation of polyester, the reduced pressure, can not produce problems such as causing thermolysis, outside system, disperse and in the polyester formation reaction, occur polymer gel, and the good phosphonium flame retardant of the fire-retardant polyester tone of making and manufacture method thereof and with the fire-retardant polyester of this phosphonium flame retardant copolymerization.
The inventor etc. find through deep result of study, organo phosphorous compounds and unsaturated carboxylic acid and/or its acid anhydrides are reacted in alkylene glycol, in the method for making phosphonium flame retardant, employing makes antioxidant contains the phosphonium flame retardant of specified proportion with respect to organo phosphorous compounds manufacture method can solve above-mentioned problem, thereby has finished the present invention.
That is to say, the manufacture method of phosphonium flame retardant of the present invention, it is characterized in that organo phosphorous compounds and unsaturated carboxylic acid and/or its acid anhydrides are reacted in alkylene glycol, make in the method for phosphonium flame retardant, make at least a antioxidant with respect to organo phosphorous compounds, add up to and contain 0.001～10 weight %, make its reaction.
With the phosphonium flame retardant that related manufacture method obtains, be the composition that contains phosphor-containing flame-proof immunomodulator compounds, antioxidant and alkylene glycol, the phosphor-containing flame-proof immunomodulator compounds contains carboxyl, constitutes the copolymer structure unit of flame retardance poly ester polymer after the polymerization.
Phosphonium flame retardant of the present invention, it is characterized in that wherein containing phosphonium flame retardant, antioxidant and alkylene glycol, tone (APHA) is in below 120. and related fire retardant is preferably obtained by the manufacture method of phosphonium flame retardant of the present invention. and the composition of phosphonium flame retardant will be directly used in the manufacturing fire-retardant polyester.
Related phosphonium flame retardant under the high temperature when polycondensation of polyester, the reduced pressure, can not produce problems such as causing thermolysis, disperse and occur polymer gelization outside system in the polyester formation reaction, and the fire-retardant polyester tone of making is good.
And fire-retardant polyester of the present invention, it is characterized in that with phosphonium flame retardant manufacturing of the present invention, and contain it as constitutional unit.
Utilize the alkylene glycol solution of the phosphonium flame retardant of manufacture method manufacturing of the present invention, can prevent effectively that it is painted.And, be the improved product of tone with the fire retardant polyester that the alkylene glycol solution of resulting phosphonium flame retardant is made.
Embodiment
The manufacture method of phosphonium flame retardant of the present invention, it is characterized in that in the reaction system that organo phosphorous compounds and unsaturated carboxylic acid and/or its acid anhydrides (below be called the unsaturated carboxylic acid class) are reacted in alkylene glycol, making phosphonium flame retardant contain at least a antioxidant.There is no particular restriction to make when making phosphonium flame retardant reaction system contain the method for antioxidant, for example can enumerate:
1) organo phosphorous compounds, unsaturated carboxylic acid class and alkylene glycol are reacted containing under the situation of antioxidant, make the method for phosphonium flame retardant;
2) organo phosphorous compounds and unsaturated carboxylic acid class are reacted containing under the situation of antioxidant, so with the alkylene glycol reaction, make the method for phosphonium flame retardant;
3) unsaturated carboxylic acid class and alkylene glycol are reacted containing under the situation of antioxidant, and then add organo phosphorous compounds and react, make the method for phosphonium flame retardant etc.
The described organo phosphorous compounds that can use in the present invention, so long as can react with the unsaturated carboxylic acid class, the P contained compound that forms the phosphorus compound with carboxyl does not just have special the restriction, for example can enumerate:
1) phosphine oxide derivatives such as dimethyl oxidation phosphine, diethyl phosphine oxide, dipropyl phosphine oxide, dibutyl phosphine oxide, diphenyl phosphine oxide,
2) 9, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound, methylmethane phosphinate, ethyl methane phosphinate, methyl ethane phosphinate, ethyl ethane phosphinate, methylpropane phosphinate, ethyl propane phosphinic acid esters, methylbutane phosphinate, ethyl butane phosphinate, methylbenzene phosphinate, ethylbenzene phosphinate grade phosphate derivatives.In these illustrative compounds,, preferably using 9 from the good viewpoint of fire retardant effect, the 10-dihydro-9-oxy is assorted-10-phospho hetero phenanthrene-10-oxide compound (below be called DOP).
As operable unsaturated carboxylic acid among the present invention, can enumerate:
1) unsaturated monocarboxylic acids such as vinylformic acid, methacrylic acid, butenoic acid,
2) unsaturated monocarboxylic acid alkyl esters such as methyl acrylate, ethyl propenoate, methyl methacrylate, Jia Jibingxisuanyizhi, M Cr, butenoic acid ethyl,
3) unsaturated dicarboxylic acids such as toxilic acid, fumaric acid, methylfumaric acid, citraconic acid, methylene-succinic acid,
4) unsaturated dicarboxylic acid alkyl esters such as dimethyl maleate, ethyl maleate, dimethyl fumarate, DEF, methylfumaric acid dimethyl ester, methylfumaric acid diethyl ester, citraconic acid dimethyl ester, lemon diethyl phthalate, dimethyl itaconate, diethyl itaconate
5) acid anhydrides of unsaturated dicarboxylic acids such as maleic anhydride, citraconic anhydride, itaconic anhydride etc.
In the above-mentioned illustrative compound, preferably use at least a compound of from the acid anhydrides of unsaturated dicarboxylic acid and unsaturated dicarboxylic acid, selecting, more preferably use methylene-succinic acid, itaconic anhydride.
The antioxidant that can use in phosphonium flame retardant manufacture method of the present invention is not particularly limited, and for example can enumerate 1) sterically hindered phenol is antioxidant, 2) phosphoric acid is antioxidant and 3) sulphur is antioxidant etc.
As sterically hindered phenol is antioxidant; can enumerate the 4-tert-butyl catechol; 3; 5-di-t-butyl-4-hydroxytoluene; Octadecane base-β-(4 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl) propionic ester; four [methylene radical-3-(3 '; 5 '-di-t-butyl-4 '-hydroxyl-phenyl) propionic ester] methane; 1; 3; 5-trimethylammonium-2; 4; 6 '-three (3 '; 5 '-di-t-butyl-4 '-hydroxyl-benzyl) benzene; 3 '; 5 '-di-t-butyl-4-hydroxyl-benzyl-single ethyl-calcium phosphate; triglycol-two [3-(the 3-tertiary butyl-5-methyl-4-hydroxy phenyl) propionic ester]; [3-(3 for tetramethylolmethane four; 5-di-tert-butyl amido)]-1; 3; the 5-triazine; 3; 9-two [1; 1-dimethyl-2-{ β-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy } ethyl] 2; 4,8,10-four oxaspiros (5.5) hendecane; two (3; two (4 '-hydroxyl-3 '-tert-butyl-phenyl) butyric acid of 3-) diol ester; trisphenol; 2; 2 '-ethylidene two (4, the 6-DI-tert-butylphenol compounds); N, N-is two, and (3-(3; the 5-di-tert-butyl-hydroxy phenyl) hydrazine propionyl); 2; 2 '-oxalyl amido two (ethyl-3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester); 1,1; 3-three (3 '; 5 '-di-tert-butyl-4-hydroxyl benzyl)-along triazine-2,4,6-(1H; 3H; 5H) triketone; 1,3,5-three (the 4-tertiary butyl-3-hydroxyl-2; the 6-dimethyl benzyl) isocyanuric acid ester; 3; 5-di-t-butyl-4-hydroxycinnamic acid three ester ウ イ ズ-1,3,5-three (hydroxyethyl)-along triazine-2; 4; 6-(1H, 3H, 5H); N; N-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl cinnamide) etc.
And as phosphorous antioxidant, can enumerate tricresyl phosphate (blended, single and two nonyl phenyl) ester, tricresyl phosphate (2, the 3-di-tert-butyl-phenyl) ester, 4, two (the 3-methyl-6-tert butyl phenyl-two-tridecyl) phosphoric acid ester of 4 '-Ding fork, 1,1,3-(2-methyl-4-two-tridecyl phosphoric acid ester-5-tert-butyl-phenyl) butane, tricresyl phosphate (2, the 4-di-tert-butyl-phenyl) ester, two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphate, four (2, the 4-di-tert-butyl-phenyl)-4,4 '-biphenylene phosphinate, two (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate, four (2, the 4-di-tert-butyl-phenyl)-4,4 '-biphenylene, two phosphinates, triphenylphosphate, di(2-ethylhexyl)phosphate phenyl decyl ester, the tricresyl phosphate decyl ester, tricresyl phosphate octyl group ester, tricresyl phosphate (dodecyl) ester, tricresyl phosphate (octadecyl) ester, tricresyl phosphate (nonyl phenyl) ester, trithio tricresyl phosphate (dodecyl) ester etc.
And be antioxidant as sulphur, can enumerate dilauryl-3,3 '-thiodipropionate, myristyl-3,3 '-thiodipropionate, distearyl-3,3 '-thiodipropionate, lauryl stearyl-3,3 '-thiodipropionate, dilauryl thiodipropionate, sulfuric acid two (octadecyl) ester, tetramethylolmethane four (β-lauryl thiopropionate) etc.Wherein from the painted viewpoint that prevents that effect is good of the alkylene glycol solution of phosphonium flame retardant, preferred sterically hindered phenol is an antioxidant, more preferably the 4-tert-butyl catechol.
Use though above-mentioned antioxidant can be in reaction system directly adds, also it can be dissolved in the alkylene glycol and be added in the reaction system with the solution form.And antioxidant both may be used alone, used in two or more.Among the present invention, the proportional total for organo phosphorous compounds that contain of antioxidant is decided to be 0.001～10 weight %.In case antioxidant contain the proportional 0.001 weight % that is lower than, abundant inhibited reaction resultant solution painted just.And contain proportional if use above 10 weight %, then not only can not see corresponding effects, otherwise, become the reason that the molten resin strainability is worsened sometimes because of becoming the foreign matter in the polyester behind the importing antioxidant.Containing of antioxidant is proportional, and more preferably total amount is decided to be 0.05～1 weight % for organo phosphorous compounds.
Among the present invention, add the period of antioxidant when making phosphonium flame retardant, though, preferably before organo phosphorous compounds and unsaturated carboxylic acid and/or its acid anhydrides and alkylene glycol reaction, add so long as can suppress the special restriction of the painted just nothing of the alkylene glycol solution of phosphonium flame retardant.
The alkylene glycol that uses among the present invention, the preferred alkylene glycol that uses as the polyester constituent specifically can be enumerated ethylene glycol, 1, ammediol, 1, the glycol of 2～5 carbon atoms such as 4-butyleneglycol, neopentyl glycol.
As the manufacture method of phosphonium flame retardant of the present invention, preferably utilize an operation to make the manufacture method of phosphonium flame retardant.Specifically, in the presence of antioxidant, in inert gas atmosphere, undertaken by the mode that makes the reaction of organo phosphorous compounds and unsaturated carboxylic acid and/or its acid anhydrides and alkylene glycol.This is reflected under the situation about being heated to more than 100 ℃ and can carries out, but need be for a long time owing to react completely under the mistake low temperature, and too high organo phosphorous compounds and the unsaturated carboxylic acid of can causing of Heating temperature decomposes, so temperature of reaction preferably is decided to be 120～200 ℃.Though the reaction between organo phosphorous compounds and unsaturated carboxylic acid or its acid anhydrides than in fact with etc. mol ratio carry out, preferred is that 1.0～1.1 times mode adds with unsaturated carboxylic acid and/or its acid anhydrides according to the mol ratio with respect to phosphorus compound.
The consumption of alkylene glycol is in 1.5～20 times of scopes according to molar ratio computing with respect to unsaturated carboxylic acid or its acid anhydrides, preferably is in 2～5 times of scopes.The consumption of alkylene glycol, with respect to unsaturated carboxylic acid and/or its acid anhydrides according to molar ratio computing less than under 1.5 the situation, with the esterification that comes from carboxyl in unsaturated carboxylic acid and/or its acid anhydrides will be insufficient, the viscosity increased of reaction soln thereby bad.When the consumption of alkylene glycol surpasses under 20 times the situation, the viscosity of reaction soln reduces, though handle easily, uneconomical.
The fire retardant of the present invention that utilizes the phosphonium flame retardant manufacture method of the invention described above to obtain is the alkylene glycol solution that the phosphonium flame retardant of one or two hydroxyl is arranged in the molecule, contains antioxidant.Phosphonium flame retardant of the present invention by adding above-mentioned antioxidant thereby painted few, is extremely useful as the material of the polyester that requires the height whiteness being given flame retardant resistance.There is no particular restriction for the alkylene glycol strength of solution of phosphonium flame retardant of the present invention, is 10～90 weight %.
Fire-retardant polyester of the present invention is to use phosphonium flame retardant of the present invention with the form of making at least a portion raw material that the fire retardant polyester uses.Under the situation about using with the raw material form of making the fire retardant polyester, preferably use with the alkylene glycol solution form of phosphonium flame retardant of the present invention.As making fire retardant polyester raw material, can from the known starting compound of past that uses as polyester raw material, suitably select.For example, diatomic alcohol compounds such as ethylene glycol, propylene glycol, neopentyl glycol, di-carboxylic acid such as phthalic acid, terephthalic acid, m-phthalic acid, 5-sulfoisophthalic acid sodium, hexanodioic acid, the ester of di-carboxylic acid such as dimethyl phthalate, dimethyl terephthalate (DMT), dimethyl isophthalate, dimethyl isophthalate-5-sodium sulfonate, dimethyl adipate formation property compound etc.And as the polycondensation of making the fire retardant polyester, the suitably known method of employing own.
Fire-retardant polyester of the present invention contains the structural unit that is formed by phosphonium flame retardant with respect to polyester with 0.1～5.0 weight % phosphorus concentration.Phosphorus concentration is lower than under the situation of 0.1 weight %, can not obtain sufficient flame retardant effect, and in case surpass 5.0 weight % fire retardant effects and not only also can correspondingly not increase, and sometimes the intensity of polyester etc. is exerted an influence on the contrary.
The manufacture method of phosphonium flame retardant of the present invention, in phosphonium flame retardant and fire-retardant polyester, also appropriate combination is used additives such as photostabilizer, static inhibitor, lubricant, molecular weight regulator, metal inerting agent, organic and inorganic nucleator, neutralizing agent, antacid, antiseptic-germicide, white dyes, weighting agent, fire retardant, flame retardant, organic and inorganic series pigments etc. as required.
The particularly preferred embodiment of the manufacture method of phosphonium flame retardant of the present invention and phosphonium flame retardant is as following 1)～3) shown in.
1) DOP and methylene-succinic acid are reacted in the method for making phosphonium flame retardant, with the 4-tert-butyl catechol as antioxidant, make it add up to the manufacture method of the phosphonium flame retardant contain 0.01 weight % with respect to DOP, and the phosphonium flame retardant that obtains with this method.
2) DOP and methylene-succinic acid are reacted in the method for making phosphonium flame retardant, with the 4-tert-butyl catechol as antioxidant, make it add up to the manufacture method of the phosphonium flame retardant contain 0.1 weight % with respect to DOP, and the phosphonium flame retardant that obtains with this method.
3) DOP and methylene-succinic acid are reacted in the method for making phosphonium flame retardant, with the 4-tert-butyl catechol as antioxidant, make it add up to the manufacture method of the phosphonium flame retardant contain 1 weight % with respect to DOP, and the phosphonium flame retardant that obtains with this method.
The preferred implementation of fire-retardant polyester of the present invention is characterized in that the structural unit as polyester, will be by above-mentioned 1)～3) the structural unit that forms of phosphonium flame retardant, contain 0.1～5.0 weight % in phosphorus concentration with respect to polyester.
Below enumerate embodiment etc. formation of the present invention and effect are done more specifically explanation, but the present invention is not subjected to any restriction of these embodiment etc.In addition, in following embodiment and reference examples, umber is represented weight part, and % represents weight %.
In the present invention and following embodiment, the tone of phosphonium flame retardant (APHA) is to measure with the mode of the APH reference liquid comparison of JIS K 1557-1970 record.
Embodiment
The Production Example of＜phosphonium flame retardant 〉
The manufacturing of (embodiment 1) phosphonium flame retardant (P-1)
Add 300 gram ethylene glycol (4.83 moles), 187 gram DOP (0.87 mole), 113 gram methylene-succinic acids (0.87 mole) and 0.06 in 1 liter of four-hole reaction flask of pipe and restrain 4-tert-butyl catechol (antioxidant (A-1)) (0.01 weight %) to having whipping appts, thermometer, nitrogen ingress pipe and distillating, heated and stirred is to carry out esterification under nitrogen atmosphere.Temperature of reaction rose to 190 ℃ from room temperature after about 6 hours, further continue reaction 4 hours under the equality of temperature, had obtained containing the ethylene glycol solution of the phosphonium flame retardant (P-1) of 66 weight %.The water yield that generates because of esterification in this reaction is about 32 milliliters.The tone of ethylene glycol (EG) solution of resulting phosphonium flame retardant (P-1), with the result of APHA color standard visual valuation, tone (APHA) is 90.
The manufacturing of (embodiment 2,3) phosphonium flame retardant (P-2), (P-3)
Except the kind of addition, the antioxidant of change antioxidant, carried out the manufacturing of phosphonium flame retardant (P-2), (P-3) (embodiment 2,3) similarly to Example 1.With regard to the tone (APHA) of ethylene glycol (EG) solution of the phosphonium flame retardant (P-2) of gained, (P-3), be 70 (P-2), (P-2) be 60.The result collects among the table 1.
The manufacturing of (embodiment 4) phosphonium flame retardants (P-4)
Remove added 0.6 gram (0.1 weight %) four [methylene radical-3-(3, ' 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane (antioxidant (A-2)) in addition, carried out the manufacturing of phosphonium flame retardant (P-4) (embodiment 4) similarly to Example 1.The tone (APHA) of ethylene glycol (EG) solution of resultant phosphonium flame retardant (P-4) is 100.The result collects among the table 1.
The manufacturing of (reference examples 1) phosphonium flame retardant (R-1)
To have whipping appts, thermometer, nitrogen ingress pipe and distillate add 300 gram ethylene glycol (4.83 moles) in 1 liter of four-hole reaction flask of pipe, 187 gram DOP (0.87 mole) and 113 restrain methylene-succinic acids (0.87 mole), heated and stirred under nitrogen atmosphere.Temperature of reaction rose to 190 ℃ from room temperature after about 6 hours, further continue reaction 4 hours under the equality of temperature, had obtained containing the ethylene glycol solution of the phosphonium flame retardant (R-1) of 66 weight %.This reaction system heats with regard to finding immediately painted at the beginning.The water yield that esterification generates in this reaction is about 32 milliliters.The tone (APHA) 200 of ethylene glycol (EG) solution of resulting phosphonium flame retardant (R-1), painted remarkable.
[table 1]
*): with respect to the addition of organo phosphorous compounds
The Production Example of＜fire-retardant polyester 〉
The manufacturing of (embodiment 5) fire-retardant polyesters (AP-1)
To having whipping appts, add 1242 gram terephthalic acids (7.48 moles) in 5 liters of stainless steel autoclaves of distillation tower and pressure-regulator, the ethylene glycol solution (containing 0.3 mole of phosphonium flame retardant) of the fire retardant (P-1) that 200 grams are made in the fire retardant Production Example and 850 gram (13.71 moles) ethylene glycol, and then adding ANTIMONY TRIOXIDE SB 203 99.8 PCT concentration is ethylene glycol solution 2.41 grams of 14 grams per liters, after germanium dioxide concentration is ethylene glycol solution 15 grams and 5.2 gram triethylamines of 8 grams per liters, dephlegmate on one side under the condition of 2.5 kilograms/square centimeter of 230 ℃ and gauge pressures is Yi Bian carry out 2 hours esterifications.Then be warmed up to 275 ℃, slowly system pressure be decompressed to 0.1 mmhg with 1 hour temperature with reaction system, carry out polycondensation in 1 hour with this understanding after, obtained fire-retardant polyester (AP-1).The fire-retardant polyester that obtains (AP-1) the analysis showed that it is to contain the structural unit that is formed by phosphonium flame retardant in phosphorus concentration with the ratio of 0.60 weight % for polyester.And the L value and the b value measured with Ha Application タ-type colour-difference meter of resulting fire-retardant polyester (AP-1), be respectively the L value and be 75 and the b value be 10.3.Wherein the whiteness of the big more expression polyester of L value is high more, and the yellow tone of the big more expression polyester of b value is strong more.That is to say that the L value is big more and b is more little, tone is good more.
The manufacturing of (embodiment 6～8) fire-retardant polyesters (AP-2)～(AP-4)
Except the phosphonium flame retardant EG solution that change is used, same with the Production Example of fire-retardant polyester (AP-1), carried out the manufacturing of fire-retardant polyester (AP-2)～(AP-4) (embodiment 6～8).The result collects among the table 2.
The manufacturing of (reference examples 2) fire-retardant polyester (AR-1)
To having whipping appts, add 1242 gram terephthalic acids (7.48 moles) in 5 liters of stainless steel autoclaves of distillation tower and pressure-regulator, the ethylene glycol solution of the phosphonium flame retardant of making in 200 gram (0.30 mole) phosphonium flame retardant Production Examples (R-1) and 850 gram (13.71 moles) ethylene glycol, and then adding ANTIMONY TRIOXIDE SB 203 99.8 PCT concentration is ethylene glycol solution 24.1 grams of 14 grams per liters, after germanium dioxide concentration is ethylene glycol solution 15 grams and 5.2 gram triethylamines of 8 grams per liters, dephlegmate on one side under the condition of 2.5 kilograms/square centimeter of 230 ℃ and gauge pressures is Yi Bian carry out 2 hours esterifications.Then temperature of reaction system is warmed up to 275 ℃, slowly system pressure is decompressed to 0.1 mmhg with 1 hour, carry out polycondensation in 1 hour with this understanding after, obtained fire-retardant polyester (AR-1).The fire-retardant polyester that obtains (AR-1) the analysis showed that, contains the structural unit that by phosphonium flame retardant formed according to the phosphorus concentration meter with the ratio of 0.60 weight % with respect to polyester.And the L value and the b value measured with Ha Application タ-type colour-difference meter of resulting fire-retardant polyester (AR-1), respectively the L value be 74 and the b value be 19.7.
The manufacturing of (reference examples 3) fire-retardant polyester (AR-2)
To having whipping appts, in 5 liters of stainless steel autoclaves of distillation tower and pressure-regulator, add 1242 gram terephthalic acids (7.48 moles), the ethylene glycol solution of the phosphonium flame retardant (R-1) that 200 grams (0.30 mole) are made in the phosphonium flame retardant Production Example and 850 gram (13.71 moles) ethylene glycol, and 1.32 the gram (is 1% with respect to the phosphor-containing flame-proof agent content) 4-tert-butyl catechol as antioxidant, and then add 24.1 the gram concentration be the ANTIMONY TRIOXIDE SB 203 99.8 PCT ethylene glycol solution of 14 grams per liters, after 15 gram concentration are the germanium dioxide ethylene glycol solution and 5.2 gram triethylamines of 8 grams per liters, dephlegmate on one side under the condition of 2.5 kilograms/square centimeter of 230 ℃ and gauge pressures, carry out 2 hours esterifications on one side. then temperature of reaction system is warmed up to 275 ℃ with 1 hour, system pressure slowly is decompressed to 0.1 mmhg, after carrying out polycondensation in 1 hour with this understanding, obtained fire-retardant polyester (AR-2). the fire-retardant polyester that obtains (AR-2), the analysis showed that, contain the structural unit that by fire retardant form according to the phosphorus concentration meter with 0.60 weight % ratio with respect to polyester. and the L value and the b value measured with Ha Application タ-type colour-difference meter of resulting fire-retardant polyester (AR-2), respectively the L value be 74 and the b value be 18.6.
The manufacturing of (reference examples 4) fire-retardant polyester (AR-3)
Except [methylene radical-3-(3 ' with 1.32 grams four, 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester] methane, replace having carried out the manufacturing of fire-retardant polyester (AR-3) equally with reference examples 3 beyond the gram of 1.5 in the fire-retardant polyester (AR-2) the 4-tert-butyl catechol.The tone evaluation result of the fire-retardant polyester that obtains collects among the table 2.
[table 2]
The possibility of utilizing on the industry
Phosphonium flame retardant of the present invention can be used in the polyester manufacturing, and this phosphonium flame retardant can adopt the manufacture method manufacturing of phosphonium flame retardant of the present invention.
Claims (7)
1. the manufacture method of a phosphonium flame retardant, it is characterized in that organo phosphorous compounds and unsaturated carboxylic acid and/or its acid anhydrides are reacted in alkylene glycol, make in the method for phosphonium flame retardant, with respect to described organo phosphorous compounds, at least a antioxidant is added up to contain 0.001～10 weight %, described antioxidant is the 4-tert-butyl catechol.
2. according to the manufacture method of the described phosphonium flame retardant of claim 1, it is characterized in that described organo phosphorous compounds, be to be selected from 9, the 10-dihydro-9-oxy is assorted-the phosphinate derivative of 10-phospho hetero phenanthrene-10-oxide compound, methylmethane phosphinate, ethyl methane phosphinate, methyl ethane phosphinate, ethyl ethane phosphinate, methylpropane phosphinate, ethyl propane phosphinic acid esters, methylbutane phosphinate, ethyl butane phosphinate, methylbenzene phosphinate, ethylbenzene phosphinate.
3. according to the manufacture method of claim 1 or 2 described phosphonium flame retardants, it is characterized in that described organo phosphorous compounds, is 9, and the 10-dihydro-9-oxy is mixed-10-phospho hetero phenanthrene-10-oxide compound.
4. according to the manufacture method of claim 1 or 2 described phosphonium flame retardants, it is characterized in that described unsaturated carboxylic acid and/or its acid anhydrides, is unsaturated dicarboxylic acid and/or its acid anhydrides.
5. according to the manufacture method of claim 1 or 2 described phosphonium flame retardants, it is characterized in that described unsaturated carboxylic acid is a methylene-succinic acid, the acid anhydrides of described unsaturated carboxylic acid is an itaconic anhydride.
6. phosphonium flame retardant, it is characterized in that it being to make by 9, the 10-dihydro-9-oxy is assorted-organo phosphorous compounds, unsaturated carboxylic acid and/or its acid anhydrides that 10-phospho hetero phenanthrene-10-oxide compound constitutes and be that the antioxidant that is made of the 4-tert-butyl catechol of 0.001～10 weight % reacts the phosphonium flame retardant that makes in ethylene glycol with respect to described organo phosphorous compounds, and the tone of this phosphonium flame retardant is in below 120, and wherein said tone is to obtain according to measuring with the mode of the APH reference liquid comparison of JIS K 1557-1970 record.
7. according to the described phosphonium flame retardant of claim 6, adopt the manufacture method manufacturing of any one described phosphonium flame retardant in the claim 1～5 and get.
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| JP2003431692 | 2003-12-26 | ||
| JP431692/2003 | 2003-12-26 | ||
| PCT/JP2004/019363 WO2005063922A1 (en) | 2003-12-26 | 2004-12-24 | Process for producing phosphorus compound flame retardant, phosphorus compound flame retardant, and flame-retardant polyester |
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| CN1910263B true CN1910263B (en) | 2010-05-05 |
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| JP5115172B2 (en) * | 2007-12-13 | 2013-01-09 | 株式会社カネカ | Resin composition |
| CN101613374B (en) * | 2009-07-22 | 2012-03-14 | 中国科学技术大学 | Polymeric phosphorus-containing flame retardant with DOPO as lateral group and preparation method thereof |
| DE102009037631A1 (en) * | 2009-08-14 | 2011-02-17 | Schill + Seilacher "Struktol" Gmbh | Phosphorus-containing flame retardant |
| CN101792530A (en) * | 2010-03-19 | 2010-08-04 | 苏州兰特纳米材料科技有限公司 | Polymer type halogen-free flame retardant (PDPTP) and preparation method thereof |
| CN103333205A (en) * | 2013-06-28 | 2013-10-02 | 青岛富斯林化工科技有限公司 | Phosphorus flame retardant 2,3-dicarboxylic propyl diphenyl phosphine oxide, preparation method and flame-retardant polyester composition thereof |
| CN110343413B (en) * | 2019-07-17 | 2021-01-08 | 烟台大学 | Nitrogen-phosphorus intumescent flame retardant and preparation method thereof in application of waterborne polyurethane coating |
| CN110903512B (en) * | 2019-11-21 | 2021-12-17 | 浙江大学宁波理工学院 | Efficient halogen-free phosphorus gas-phase flame retardant and high polymer material containing same |
| CN112812285B (en) * | 2020-12-28 | 2022-05-06 | 湖南美莱珀科技发展有限公司 | Macromolecular flame retardant and preparation method and application thereof |
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| WO2005063922A1 (en) | 2005-07-14 |
| CN1910263A (en) | 2007-02-07 |
| JPWO2005063922A1 (en) | 2007-12-20 |
| JP4835975B2 (en) | 2011-12-14 |
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