GB1575157A - Flame retardant polycondensation products derived from phosphorus-containing dicarboxylic acids - Google Patents
Flame retardant polycondensation products derived from phosphorus-containing dicarboxylic acids Download PDFInfo
- Publication number
- GB1575157A GB1575157A GB14830/78A GB1483078A GB1575157A GB 1575157 A GB1575157 A GB 1575157A GB 14830/78 A GB14830/78 A GB 14830/78A GB 1483078 A GB1483078 A GB 1483078A GB 1575157 A GB1575157 A GB 1575157A
- Authority
- GB
- United Kingdom
- Prior art keywords
- resins
- phosphorus
- formula
- flame retardant
- mols
- 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.)
- Expired
Links
- 238000006068 polycondensation reaction Methods 0.000 title claims abstract description 28
- 239000003063 flame retardant Substances 0.000 title claims abstract description 15
- 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 11
- 229910052698 phosphorus Inorganic materials 0.000 title description 17
- 239000011574 phosphorus Substances 0.000 title description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title description 16
- 150000001991 dicarboxylic acids Chemical class 0.000 title description 6
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 239000004417 polycarbonate Substances 0.000 claims description 15
- 229920000515 polycarbonate Polymers 0.000 claims description 15
- 229920005992 thermoplastic resin Polymers 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 13
- 239000004800 polyvinyl chloride Substances 0.000 claims description 12
- 239000004793 Polystyrene Substances 0.000 claims description 11
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 11
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 11
- 229920001893 acrylonitrile styrene Polymers 0.000 claims description 10
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052794 bromium Inorganic materials 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920000193 polymethacrylate Polymers 0.000 claims description 5
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 9
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 9
- 150000001298 alcohols Chemical class 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- -1 o-phenylphenol compound Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 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 5
- 150000002763 monocarboxylic acids Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical class C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- PQYJRMFWJJONBO-UHFFFAOYSA-N Tris(2,3-dibromopropyl) phosphate Chemical compound BrCC(Br)COP(=O)(OCC(Br)CBr)OCC(Br)CBr PQYJRMFWJJONBO-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012433 hydrogen halide Substances 0.000 description 3
- 229910000039 hydrogen halide Inorganic materials 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229940046892 lead acetate Drugs 0.000 description 2
- 150000004682 monohydrates Chemical class 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 150000002903 organophosphorus compounds Chemical class 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 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 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- JHJUYGMZIWDHMO-UHFFFAOYSA-N 2,6-dibromo-4-(3,5-dibromo-4-hydroxyphenyl)sulfonylphenol Chemical compound C1=C(Br)C(O)=C(Br)C=C1S(=O)(=O)C1=CC(Br)=C(O)C(Br)=C1 JHJUYGMZIWDHMO-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- QEJPOEGPNIVDMK-UHFFFAOYSA-N 3-bromo-2,2-bis(bromomethyl)propan-1-ol Chemical compound OCC(CBr)(CBr)CBr QEJPOEGPNIVDMK-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- CVWPQQDMHILNGI-UHFFFAOYSA-N Brc1cc(Br)c2OP(=O)c3ccccc3-c2c1 Chemical compound Brc1cc(Br)c2OP(=O)c3ccccc3-c2c1 CVWPQQDMHILNGI-UHFFFAOYSA-N 0.000 description 1
- YKJMVLPPQVHDOR-UHFFFAOYSA-N C=1CCC=C2C3=CC=CC=C3OP(C12)=O Chemical compound C=1CCC=C2C3=CC=CC=C3OP(C12)=O YKJMVLPPQVHDOR-UHFFFAOYSA-N 0.000 description 1
- HZJGWADURBZRRM-UHFFFAOYSA-N CC(C)(C)c1cccc-2c1OP(=O)c1ccccc-21 Chemical compound CC(C)(C)c1cccc-2c1OP(=O)c1ccccc-21 HZJGWADURBZRRM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- BORHNRMYZHUKQM-UHFFFAOYSA-N O=P1Oc2ccc(cc2-c2ccccc12)-c1ccccc1 Chemical compound O=P1Oc2ccc(cc2-c2ccccc12)-c1ccccc1 BORHNRMYZHUKQM-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 108010085672 beta-lactamase PSE-2 Proteins 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 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
- CVFJNXQOIZKPMG-UHFFFAOYSA-L dipotassium;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [K+].[K+].[O-]P([O-])(=O)C1=CC=CC=C1 CVFJNXQOIZKPMG-UHFFFAOYSA-L 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N ortho-phenyl-phenol Natural products OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 238000004816 paper chromatography Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 238000004809 thin layer chromatography Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- 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
- C09K21/14—Macromolecular materials
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Fireproofing Substances (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Flame retardant, of high molecular weight, comprising phosphorous-containing products of polycondensation of a dicarboxylic acid which has the formula: <IMAGE> in which each of R1, R2 and R3 denotes a hydrogen, a halogen or an alkyl, cycloalkyl, aryl or aralkyl group, with a polyalcohol.
Description
(54) FLAME RETARDANT POLYCONDENSATION PRODUCTS
DERIVED FROM PHOSPHORUS -CONTAINING DICARBOXYLIC ACIDS
(71) We, SANKO KAIHATSU
KAGAKU KENKYUSHO, a Japanese Cor
poration, of 40, 3-chome, Andojibashi-dori,
Minami-ku, Osaka-shi, Japan, do hereby de
clare the invention, for which we pray that a
patent may be granted to us, and the method
by which it is to be performed, to be par
ticularly described in and by the following statement:- This invention relates to flame retardants
comprising phosphorus-containing polycon
densation products having a high molecular
weight.
Organophosphorus or organohalogen compounds have been used as flame retardnts for thermoplastic resins, as disclosed in, for
example, U.S. Patent Specifications Nos.
3,247,135; 3,262,894; 3,278,464; 3,359,220;
3,368,916 and 3,372,141; British Patent
Specifications Nos. 1,015,212; 1,094,723 and
1,108,064; and Belgian Patent Specification
No. 709,417. On the one hand, when known
organophosphorus compounds are added to
thermoplastic resins in an amount sufficient to impart flame retardancy, disadvantages are observed in that the softening point of the resin is lowered and its heat resistance is reduced. On the other hand, conventional flame retardants containing halogen atoms such as bromine or chlorine have low thermal stability. For example, tetrabromobisphenol A
decomposes at 220"C., generating bromine.
According to a first aspect of the present
invention, a polycondensation product which can be used as a flame retardant is of a dicarboxylic acid represented by Formula I
wherein R1, R2 and R, are the same or different and are each hydrogen, halogen, alkyl, cycloalkyl, aryl or aralkyl, with a polyhydric alcohol and, if desired, a monocarboxylic acid or a monohydric alcohol.
In accordance with a second aspect of this invention, a flame retardant resin compoosition comprises a normally inflammable thermoplastic resin and a suitable amount of a phosphorus-containing polycondensation product as defined above.
The phosphorus-containing polycondensation products wherein any one or more of
R1, R2 and R3 of Formula I are halogen, preferably bromine, exhibit excellent flameretardancy and have thermal stability good enough not to generate halogen even at temperatures above 300"C.
Dicarboxylic acids of Formula I may be prepared by heating a compound represented by Formula II,
wherein Rl, R2 and R3 are as defined above, with itaconic acid.
Generally, this reaction may be effected at temperatures of 100"C to 2500C without any catalysts. The reaction is effected quantitatively and no by-products are formed. Therefore, using the stoichiometric amounts, the pure dicarboxylic acid of Formula I can be obtained. This can be normally confirmed by paper chromatography, thin layer chromatography or liquid chromatography. From an infrared absorption spectrum, end products can be easily identified to be compounds of
Formula I from the disappearance of the P-H bond (wave number 2340) and double bond (wave number 1630) and the formation of CH2 and CH groups and the P-C bond (wave number about 718).
Compounds of Formula II are known and may be prepared by the method disclosed in
U.S. Patent Specification No. 3,702,878 or
Japanese Patent Publication No. 17979/75, or methods similar thereto.
For example, compounds of Formula III,
wherein R1, R2 and Ra are as defined above, are obtained by reaction of 1 mol of a substituted o-phenylphenol compound of Formula
IV,
wherein Rl, R2 and R3 are as defined above, with 1.3 mols of phosphorus trichloride in the presence of 0.003 mols of zinc chloride at temperatures of 1300C to 2000C for about 20 hours. The compound of Formula III thus obtained is purified by distillation and hydrolyzed by adding an excess of water. The remaining water is then removed under reduced pressure (about 10 mm Hg), to form a compound of Formula II.
R1, R2 and Ra are preferably hydrogen, chlorine, bromine, methyl, tert-butyl, cyclohexyl, phenyl or benzyl. More preferably, R1 and R3 are each hydrogen, chlorine or bromine and R2 is chlorine or bromine.
Examples of compounds of Formula II include 9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide; 6 - bromo9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide; 6,8 - dibromo9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide; 8 - tert - butvl9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide; 2,6,8 - trichloro9,10 - dihydro - 9 - oxa - 10 - phospnaphenanthrene - 10 - oxide; and 6 - phenyl9,10 - dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide.
Dicarboxylic acids of Formula I can be condensed with alcohols to form esters in the same manner as other carboxylic acids.
Polyhydric alcohols which may be used in this invention are, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 1,3propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,10 - decanediol, 1,4 - di hydroxymethylcyclohexane, hydrogenated bisphenol A, ethylene oxide adducts of bisphenol
A, ethylene oxide adducts of tetrabromobisphenol S, 2,2-dibromomethyl-1,3-propanediol, glycerine, trimethylol ethane, trimethylol propane or pentaerythritol.
In the polycondensation reaction according to this invention, monocarboxylic acids or monohydric alcohols may also be used, if desired, to obtain polycondensation products having further improved compatibility with thermoplastic resins. Polycondensation products having hydroxyl or carboxyl groups at the molecular chain terminals generally exhibit less compatibility with resins.
Monocarboxylic acids or monohydric alcohols can act to improve the compatibility through reaction with such terminal groups.
Examples of suitable monocarboxylic acids are acetic acid, propionic acid, benzoic acid, naphthoic acid, palmitic acid and (meth)acrylic acid adducts of compounds of Formula
II. Examples of suitable monohydric alcohols are methanol ethanol, propanol, butanol, ethylene glycol monomethylether, ethylene glycol monobutylether, ethylene glycol monophenylether, ethylene oxide adducts of tribromophenol, 2,2,2 - tribromomethylethanol, palmityl alcohol and stearyl alcohol.
The polycondensation reaction may be carried out in the presence of or in the absence of catalysts. The catalysts which may be used are, for example, acidic catalysts such as sulfuric acid, paratoluenesulfonic acid or phosphoric acid, or metal compounds such as zinc acetate, lead acetate, germanium oxide, antimony trioxide, sodium alcoholates or potassium phenylphosphonate.
The polycondensation products of this invention may also be prepared by effecting alcoholysis between polyhydric alcohols and dicarboxylic acids of Formula I (and, if desired, monocarboxylic acids) which have previously been esterified with volatile lower alcohols.
The dehydration- or dealcoholization condensation may be carried out at temperatures of 1500 to 290"C. When dihydric alcohols are used as the polyhydric alcohol, linear polycondensation products are obtained. When polyhydric alcohols having three or more hydroxy groups are used, it results in the formation of polycondensation products with branched chains.
The molecular weight of the polycondensation products is an important factor for their utility, because it has a great influence on their softening point and their compatibility with thermoplastic resins. The average molecular weight depends on the degree to which polycondensation is allowed to advance and the molar ratio of the phosphorus-containing dicarboxylic acid, monocarboxylic acid, polyhydric alcohol and monohydric alcohol. The lower the molecular weight, the better is the compatibility with thermoplastic resins, but the heat resistance of the resins is apt to be reduced. The molecular weight of the polycondensation products of this invention is preferably from 1,000 to 20,000, and more preferably from 2,000 to 13,000. Within the preferred range good compatibility with various types of thermoplastic resins can be achieved without any appreciable reduction in heat resistance. The compatibility may vary depending on the nature of R1, R2 and/or R3 in Formula I and the type of polyhydric alcohols, monocarboxylic acids and/or monohydric alcohols, both of which may be varied as appropriate to prepare polycondensation products having good compatibility with any given resin.
Alternatively, the polycondensation products of this invention may be prepared by effecting the polycondensation reaction with polyhydric alcohols simultaneously with the formation of the compounds of Formula I by the reaction. of compounds of Formula II with itaconic acid.
The polycondensation products of this invention which have a phosphorus content of 3.5% to 8.5% by weight usually have a high softening point and good compatibility with various thermoplastic resins, so that a flame retardant resin composition can be obtained without lowering its heat resistance.
Examples of the thermoplastic resins include polystyrenes, acrylonitrile-styrene copolymers, polycarbonates, polytetraphthalate resins (e.g.
polyethylene terephthalate, polybutylene terephthalate and polyarylene terephthalates),
ABS resins, polyphenylene oxide resins, polymethcarylate resins (e.g. polymethylmethacrylate) and polyvinyl chloride.
In accordance with this invention, a flame retardant resin composition is obtained by compounding the phosphorus-containing polycondensation product with the thermoplastic resin so as to give a phosphorus content of 0.15% to 2.5% by weight based on the weight of the resin. This phosphorus content normally corresponds to adding 2 to 30 parts of the polycondensation product to 100 parts by weight of the thermoplastic resin.
This invention will be illustrated by the following examples. Softening points are measured by a capillary tube method.
Example 1.
432 g (2 mols) of 3,10 - dihydro - 9 - oxa10 - phosphaphenanthrene - 10 - oxide (hereinafter referred to as HCA), 260 g (2 mols) of itaconic acid and 1,300 g of dimethyl sulfoxide are fed into a four-necked flask of 2,000 ml capacity provided with a thermometer, a gas inlet, a stirrer and a reflux condenser.
While slowly introducing nitrogen gas through the gas inlet, the flask is heated until the dimethyl sulfoxide slowly refluxes. Reaction is effected at 1900C for about 2 hours.
After cooling the reaction mixture, white crystals are deposited, which are then filtered and washed with 700 ml of dioxane. After drying, about 620 g of white crystals are obtained.
M.P.: 2030C
Acid Value: 325 (Calculated, 323.7)
Saponification Value: 488 (Calculated,
485.5)
Elementary Analysis:
Found:
C 60.2%, H 4.5%
Calculated:
C 59.0%, H 4.3%
The foregoing shows that the end product is a compound of Formula I wherein R,, R2 and Ra are each hydrogen.
588 g (1.7 mols) of the above compound and 210 g of ethylene glycol are charged into a 1000 ml three-necked flask provided with a thermometer, a stirrer and a packed column type rectifier, 3 cm in diameter and 20 cm in filler height. On heating the flask, a polycondensation reaction occurs and water from the top of the rectifier is distilled out.
While slowly removing water, the temperature of the contents is elevated to 200"C and this temperature is maintained for about 3 hours.
Thereafter, 0.2 g of zinc acetate and 0.1 g of germanium oxide are added. The rectifier is then removed and a vacuum distillation port provided with a cold trap is connected thereto.
While slowly distilling out ethylene glycol, the inside of the flask is put under reduced pressure of 1 mm Hg. Reaction is carried out at 230"C for 2 hours.
The reaction products are poured into a stainless vat and cooled to solidify them. A colorless, transparent glassy solid is thus ob
tained.
Content of Phosphorus: 8.2% by weight
Softening Point: ca. 600C
Approximate Molecular Weight: 4,500
(According to a terminal group determi
nation).
The linear polycondensate above obtained has a good compatibility with acrylonitrilestyrene copolymers, polymethacrylate resins, polyterephthalate resins, polyvinyl chloride resins and ABS resins.
Next, 10 parts by weight of the above polycondensate are added to 100 parts by weight of each of bisphenol A/terephthalic acid polycondensate (PAT) and polyvinyl chloride (PVC), and blended in a Brabender mill at an appropriate blending temperature for the respective resin. Samples for burning test, 3.2 mm thick, 12.2 mm wide and 152.4 mm long, are obtained by subjecting the compounds to compression moulding. A flame retardancy rating is obtained by measuring the burning time of a test sample according to the standard of Underwriters Laboratories
Inc., Subject 94.
As a result of the burning test, both samples of the flame-retarded PAT and PVC are rated V-O.
Example 2.
864 g (4 mols) of HCA, 520 g (4 mols) of itaconic acid and 520 g (4 X 1.25 mols) of neopentyl glycol are charged into a fournecked 200 ml flask provided with a thermometer, a gas inlet, a stirrer and a water outlet.
The flask is heated while slowly introducing nitrogen gas through the gas inlet. When the temperature of the contents reaches 120"C, the reactants melt and water is formed.
The temperature is then slowly elevated while stirring and maintained at 2000C for an hour. The water outlet is connected to a vacuum distillation port equipped with a cold trap and the inside of the flask is put under reduced pressure of 18 mm Hg. This pressure is maintained for an hour to distill out water and neopentyl glycol. Thereafter, the reaction is continued under reduced pressure (1 mm
Hg) at 2200C for a further two hours.
The reaction products are poured into a stainless vat and cooled to solidify them. A light yellow, transparent glassy solid is thus obtained.
Content of Phosphorus: 7.2%
Softening Point: 960C
Approximate Molecular Weight: 3,800
The linear polycondensate above obtained has good compatibility with polystyrene, polycarbonates, polyphenylene oxides and polyvinyl chloride.
Further, the above polycondensate is saponified and decomposed by a methanol solution of potassium hydroxide and then rendered acidic by hydrochloric acid.
After evaporation of methanol, precipitates appear which are then recrystallized from dimethyl sulfoxide simultaneously with dehydration. The product thus obtained, according to the melting point and liquid chromatography, is identical with the compound of
Formula I obtained in Example 1.
The foregoing shows that the polycondensation reaction can be effected simultaneously with the formation of compounds of Formula
I through the reaction of compounds of
Formula II with itaconic acid.
Next, the burning test and flame retardancy rating are effected in the same manner as in
Example 1.
Amounts of Poly
Resins condensate Added* Rating
Polycarbonate
(PC) 8 V-2 PAT 10 V-0 Polyphenylene Oxide 7 V--O (PPO)
PVC 10 V--O 8) Parts per 100 parts by weight of resins.
Example 3.
180 g (4 mols) of 6 - bromo - 9,10dihydro - 9 - oxa - 10 - phosphaphenanthrene - 10 - oxide (MP 1970C, hereinafter referred to as 6-bromo-HCA), 520 g (4 mols) of itaconic acid and 520 g (4 X 1.25 mols) of neopentyl glycol are charged into the same four-necked flask as in Example 2 and, similarly, a light yellow, transparent glassy solid is obtained.
Content of Phosphorus: 6.2%
Softening Point: 1190C
Approximate Molecular Weight: 4,200
The linear polycondensate above obtained has a good compatibility with polystyrenes, polycarbonates, polytetraphthalate resins, polyphenylene oxides and polyvinyl chloride.
Example 4.
A light yellow, transparent glassy solid is obtained by the same procedure as Example 2 except using 1,176 g (3 mols) of monohydrate of 6,8-dibromo-HCA (MP 210"C), 390 g (3 mols) of itaconic acid and 390 g (3 X 1.25 mols) of neopentyl glycol.
Content of Phosphorus: 5.3%
Softening Point: 1260C Approximate Molecular Weight: 5,500
The linear polycondensate above obtained has a good compatibility with polystyrenes, pofyterephthalate resins, polycarbonates, polyphenylene oxides, polymethacrylate resins and polyvinyl chloride.
Example 5.
1,294 g (3 X 1.1 mols) of monohydrate of 6,8-dibromo-HCA, 390 g (3 mols) of itaconic acid, 21.6 (3 X 0.1 mols) of acrylic acid, 312 g (3 mols) of neopentyl glycol and 75 g (3 X 0.4 mols) of ethylene glycol are charged into the same flask as in Example 2.
While slowly blowing in nitrogen gas, the flask is heated.
When the temperature of the contents reaches 1200C, they melt and water formation starts. The temperature is then slowly elevated while stirring and reaction is effected at 200"C for 2 hours. Thereafter 0.02 g of sodium methoxide are added. The water outlet is connected to a vacuum distillation port equipped with a cold trap and the flask is put under reduced pressure of 18 mm Hg.
This pressure is maintained for 2 hours ro distill out water, ethylene glycol and neopentyl glycol. Thereafter, the reaction is continued under reduced pressure of 1 mm Hg at 240"C for further two hours. The reaction products are poured into a stainless vat and cooled to solidify them. A slightly yellowish, glassy solid is thus obtained.
Content of Phosphorus: 5 5:5% Softening Point: 1210C
Approximate Molecular Weight: 5,400
(According to a viscosity method)
The linear polycondensate above obtained has a good compatibility with polystyrenes, polycarbonates, polyphenylene oxides, polymethacrylate resins, poly ( terephthalate 'type) resins, ABS resins and polyvinyl chloride.
Moreover, the above polycondensate is saponified and decomposed by a methanol solution of lithium hydroxide and then rendered acidic by hydrochloric acid. According to liquid chromatography, the presence of a compound of Formula I wherein R1 and R2 are bromine, the acrylic acid adduct of the compound of Formula II wherein R, and R.
are bromine, neopentyl glycol and ethylene glycol are confirmed.
Example 6.
816 g (3 mols) of 8-tert-butyl-HCA, 558 g (3 mols) of diethyl itaconate, 629 g (3 X 0.8 mols) of 2,2-dibromomethyl-1,3-propane- diol, 29 g (3 X 0.07 mols) of trimethylolpropane and 0.1 g of lead acetate are charged into the same flask as in Example 2. The flask is heated while slowly blowing in nitrogen gas. When the temperature of the contents reaches 120"C, stirring is effected and ethanol is distilled out while elevating the temperature. After reaching 1500 C, the contents are maintained at this temperature for an hour.
The water outlet is connected to a vacuum distillation port and reaction is effected under reduced pressure of 18 mm Hg for 6 hours.
The reaction products are poured into a stainless vat and cooled until solid. The yellow glassy product thus obtained is a slightly branched polycondensate.
Content of Phosphorus: 5.0 /O Softening Point: 115"C The above polycondensate has a good com
patibility with polystyrene (PS) polycarbon
ates (PC) and polyphenylene oxides (PPO)
Moreover, the burning test and rating on
the flame retardancy are effected in the same
manner as in Example 1.
Amounts of Poly
Resins condensate Added Rating PS 15 V-2
PS 15 V-2 PC 7 V-O PPO 5
Example 7.
958.5 g (3 mols) of 2,6,8-trichloro-HCA,
390 g (3 molt) of itaconic acid and 390 g (3 X 1.25 mols) of neopentyl glycol are charged into the same flask as in Example 2.
A light yellow, glassy product is obtained in the same manner as Example 2 except that polycondensation is effected finally at 2500C under reduced pressure of 1 mm Hg for 3 hours.
Content of Phosphorus: 6.0% Softening Molecular Point: l120C Approximate Molecular Weight: 12,000 (According to a terminal group determi- nation)
The linear polycondensate above obtained has a good compatibility with polystyrene, polycarbonates, polyphenylene oxides, poly terephthalate resins, polymethacrylate resins,
ABS resins, acrylonitrile-styrene copolymers and polyvinyl chloride.
Example 8.
Using rhe polycondensates of Examples 3 to 5 and 7, burning tests and flame retardancy ratings are effected in the same manner as in Example 1, using inter alia 100 parts by weight of each of acrylonitrile-styrene (AS) copolymer, polymethylmethacrylate (PMM) and ABS resin as the thermoplastic resin.
The results are given in Table 1, where in each instance the upper figure of a pair shows the amount of the polycondensate which was added (in parts by weight) and the lower symbol is the flame retardancy rating.
TABLE 1
Example Resin 3 4 5 7 10 10 10 10 PS V-2 V-i. V-i V-2 10 10 10 15 AS V-I V-0 V-10 V-I 8 4 4 5 PC V-0 V-0 V-0 V-1 8 4 4 5 PAT V-0 V-0 V-0 V-0 6 3 3 5 PPO V-0 V-0 V-0 V-0 15 10 10 10 PMM V-1 V-1 V-1 V-2 7 5 5 10 PVC V-0 V-0 V-0 V-0 15 15 15 20 ABS V-1 V-0 V-0 V-0 Example 9.
To each of polystyrene (PS), acrylonitrilestyrene copolymer (AS), polycarbonate (PC) and ABS resin (ABS) are added varying amounts of various flame retardants such that the average burning times are of the same order.
Average Burning
Resin Time (sec.)
PS 20
PS 20
PC 10
ABS 20
As the flame retardants, the polycondensates
of Examples 3 to 7 and, for comparison, tris
(2,3-dibromopropyl) phosphate (TBP) and a
composite flame retardant of antimony trioxide and tetrabromobisphenol A (Sb-TBA) are used.
The flame retardant resin compositions thus obtained are tested for three criteria. These are set out in each case in order in Table 2 beneath the amount (in parts by weight per 100 parts by weight of resin) of flame retardant and are, respectively: the reduction (in C. degrees) in thermal deformation temperature, the transparency of the composition to the naked eye, and the formation of hydrogen halide at a moulding temperature (2000 2800 C) suitable for each composition. The degree of hydrogen halide release is characterised as zero, slight (indicating a response to a pH test paper after a long period), fair (indicating a response to a pH test paper after a short period), or great (indicating both quick reesponse to a pH test paper and a strong odour of hydrogen halide).
TABLE 2
Resin Flame PS AS | PC ABS Retardants (760C) (820C) (1350C) (820C) Example 3 15.0 16.0 4.0 16.0 .16 17 8 17 Transparent Transparent Transparent Transparent zero zero zero zero Example 4 8.0 7.5 1.8 8.0 9 6.5 3.5 9 Transparent Transparent Transparent Transparent zero zero zero zero Example 5 7.5 8.0 1.8 8.5 7 8 3.5 9 Transparent Transparent Transparent Semi-trans. zero zero zero zero Example 6 9.0 9.0 2.0 10.0 10 8.5 5 10.5 Transparent Transparent Transparent Transparent Slight Slight Slight Slight Example 7 12.0 11.0 3.5 12.0 12 10 6 13 Transparent Transparent Trans parent Transparent zero zero zero zero TBP 7.0 7.5 2.5 9.0 21 20 18 25 Transparent Transparent Transparent Semi-trans.
great great great great Sb-TBA 10.5 12.0 6.0 10.5 19 20 23 17 Opaque Opaque Opaque Opaque Slight Slight Fair Fair
Claims (7)
1. A polycondensation product of a dicarboxylic acid of Formula I
wherein Rl, R2 and Ra are the same or different and are each hydrogen, halogen, alkyl, cycloalkyl, aryl or aralkyl, with a polyhydric alcohol and, if desired, a monocarboxylic acid or a monohydric alcohol.
2. A product as claimed in claim 1 wherein at least one of R1, Ra and Ra is halogen.
3. A product as claimed in claim 2 wherein
R1 and Ra are each bromine and Ra is hydrogen.
4. A flame retardant composition comprising 100 parts by weight of a thermoplastic resin and 2 to 30 parts by weight of a polycondensation product as claimed in any preceding claim.
5. A composition according to claim 4 in which the thermoplastic resin is selected from polystyrene, acrylonitrile-styrene copolymers, polycarbonates, polyterephthalate resins, polyphenylene oxides, polymethacrylate resins, polyvinyl chloride and ABS resins.
6. A product as claimed in claim 1 substantially as described in any of Examples 1 to 7.
7. A composition according to claim 4 substantially as described in Example 8 or
Example 9.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4259977A JPS53128195A (en) | 1977-04-15 | 1977-04-15 | Flame retarder |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1575157A true GB1575157A (en) | 1980-09-17 |
Family
ID=12640510
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB14830/78A Expired GB1575157A (en) | 1977-04-15 | 1978-04-14 | Flame retardant polycondensation products derived from phosphorus-containing dicarboxylic acids |
Country Status (8)
Country | Link |
---|---|
JP (1) | JPS53128195A (en) |
BE (1) | BE866005A (en) |
CH (1) | CH632775A5 (en) |
DE (1) | DE2816100A1 (en) |
FR (1) | FR2387276A1 (en) |
GB (1) | GB1575157A (en) |
IT (1) | IT1095605B (en) |
NL (1) | NL183654C (en) |
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5693842A (en) * | 1994-01-29 | 1997-12-02 | Hoechst Ag | Process for preparing phosphorus-containing dicarboxylic acids alkyl esters thereof |
US5847184A (en) * | 1994-10-10 | 1998-12-08 | Hoechst Aktiengesellschaft | Process for preparing phosphorus-containing dicarboxylic acids |
WO2002070587A1 (en) * | 2001-03-07 | 2002-09-12 | Ucb, S.A. | Phosphorus containing materials, their preparation and use |
US8389901B1 (en) | 2010-05-27 | 2013-03-05 | Awds Technologies Srl | Welding wire guiding liner |
CN101287797B (en) * | 2005-09-30 | 2013-03-20 | 株式会社钟化 | Flame-retardant polyester resin composition |
US8470916B2 (en) | 2008-03-06 | 2013-06-25 | Schill + Seilacher Ag | Halogen-free flame retardants |
US8674263B2 (en) | 2009-07-20 | 2014-03-18 | Awds Technologies Srl | Wire guiding liner, in particular a welding wire liner, with biasing means between articulated guiding bodies |
US8882018B2 (en) | 2011-12-19 | 2014-11-11 | Sidergas Spa | Retainer for welding wire container and welding wire container with retainer |
CN104211954A (en) * | 2013-05-30 | 2014-12-17 | 辽宁银珠化纺集团有限公司 | Preparation method of halogen-free flame retardant nylon 66 polymer |
US9950857B1 (en) | 2016-10-17 | 2018-04-24 | Sidergas Spa | Welding wire container |
US10010962B1 (en) | 2014-09-09 | 2018-07-03 | Awds Technologies Srl | Module and system for controlling and recording welding data, and welding wire feeder |
US10294065B2 (en) | 2013-06-06 | 2019-05-21 | Sidergas Spa | Retainer for a welding wire container and welding wire container |
US10343231B2 (en) | 2014-05-28 | 2019-07-09 | Awds Technologies Srl | Wire feeding system |
US10350696B2 (en) | 2015-04-06 | 2019-07-16 | Awds Technologies Srl | Wire feed system and method of controlling feed of welding wire |
US11174121B2 (en) | 2020-01-20 | 2021-11-16 | Awds Technologies Srl | Device for imparting a torsional force onto a wire |
US11278981B2 (en) | 2020-01-20 | 2022-03-22 | Awds Technologies Srl | Device for imparting a torsional force onto a wire |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5912693B2 (en) * | 1978-05-24 | 1984-03-24 | 株式会社三光開発科学研究所 | Flame retardants |
DE2916136A1 (en) * | 1979-04-20 | 1980-10-30 | Bayer Ag | ABS MOLDS WITH IMPROVED SURFACE |
JPS60126293A (en) * | 1983-12-09 | 1985-07-05 | Sanko Kaihatsu Kagaku Kenkyusho:Kk | Cyclic organic phosphorus compound and production thereof |
JP2001122977A (en) * | 1999-10-27 | 2001-05-08 | Sanko Chem Co Ltd | Flame-retardant polyacrylonitrile-based resin molded product |
US20090253837A1 (en) * | 2005-03-31 | 2009-10-08 | Kaneka Corporation | Flame Retardant Polyester Resin Composition |
JP5347211B2 (en) * | 2005-10-19 | 2013-11-20 | 株式会社カネカ | Flame retardant polyester resin composition |
JP5048268B2 (en) * | 2006-04-28 | 2012-10-17 | 株式会社カネカ | Flame retardant conductive thermoplastic resin composition |
US20100069599A1 (en) | 2006-11-29 | 2010-03-18 | Toyo Boseki Kabushiki Kaisha | Oxetane-containing resin, as well as an adhesive and a resist agent using the same |
JP5115172B2 (en) * | 2007-12-13 | 2013-01-09 | 株式会社カネカ | Resin composition |
JP5557383B2 (en) * | 2010-05-18 | 2014-07-23 | 竹本油脂株式会社 | Polycarbonate resin composition |
JP2013023632A (en) * | 2011-07-25 | 2013-02-04 | Mitsubishi Plastics Inc | Flame retardant polyester resin composition |
DE202013103502U1 (en) | 2013-08-05 | 2013-10-04 | Carl Weiske Gmbh & Co.Kg | Plastic composition and fibers containing it having high light fastness and flame resistance |
KR102237222B1 (en) | 2013-09-26 | 2021-04-08 | 도요보 가부시키가이샤 | Polyurethane resin composition and adhesive composition, laminate, and printed wiring board using same |
US9975728B2 (en) | 2015-09-10 | 2018-05-22 | Sidergas Spa | Wire container lid, wire container and wire feeding system |
CN111607053B (en) * | 2019-02-26 | 2022-06-07 | 三晃股份有限公司 | Thermoplastic polyurethane and molded article thereof |
US11396575B2 (en) | 2019-09-19 | 2022-07-26 | Sunko Ink Co., Ltd. | Polyester polyol, thermoplastic polyurethane and article thereof |
DE102021002539A1 (en) | 2021-05-14 | 2022-11-17 | Schill + Seilacher Gmbh | Process for making a flame retardant polyester |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4127590A (en) * | 1975-10-14 | 1978-11-28 | Toyo Boseki Kabushiki Kaisha | Phosphorus-containing compounds |
-
1977
- 1977-04-15 JP JP4259977A patent/JPS53128195A/en active Pending
-
1978
- 1978-04-12 FR FR7810789A patent/FR2387276A1/en active Granted
- 1978-04-13 CH CH394778A patent/CH632775A5/en not_active IP Right Cessation
- 1978-04-13 NL NLAANVRAGE7803914,A patent/NL183654C/en not_active IP Right Cessation
- 1978-04-13 DE DE19782816100 patent/DE2816100A1/en active Granted
- 1978-04-14 GB GB14830/78A patent/GB1575157A/en not_active Expired
- 1978-04-14 IT IT22314/78A patent/IT1095605B/en active
- 1978-04-14 BE BE186810A patent/BE866005A/en not_active IP Right Cessation
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5693842A (en) * | 1994-01-29 | 1997-12-02 | Hoechst Ag | Process for preparing phosphorus-containing dicarboxylic acids alkyl esters thereof |
US5847184A (en) * | 1994-10-10 | 1998-12-08 | Hoechst Aktiengesellschaft | Process for preparing phosphorus-containing dicarboxylic acids |
WO2002070587A1 (en) * | 2001-03-07 | 2002-09-12 | Ucb, S.A. | Phosphorus containing materials, their preparation and use |
US6984717B2 (en) | 2001-03-07 | 2006-01-10 | Surface Specialties, S.A. | Phosphorous containing materials, their preparation and use |
CN101287797B (en) * | 2005-09-30 | 2013-03-20 | 株式会社钟化 | Flame-retardant polyester resin composition |
US8470916B2 (en) | 2008-03-06 | 2013-06-25 | Schill + Seilacher Ag | Halogen-free flame retardants |
US8674263B2 (en) | 2009-07-20 | 2014-03-18 | Awds Technologies Srl | Wire guiding liner, in particular a welding wire liner, with biasing means between articulated guiding bodies |
US8389901B1 (en) | 2010-05-27 | 2013-03-05 | Awds Technologies Srl | Welding wire guiding liner |
US8882018B2 (en) | 2011-12-19 | 2014-11-11 | Sidergas Spa | Retainer for welding wire container and welding wire container with retainer |
CN104211954A (en) * | 2013-05-30 | 2014-12-17 | 辽宁银珠化纺集团有限公司 | Preparation method of halogen-free flame retardant nylon 66 polymer |
CN104211954B (en) * | 2013-05-30 | 2016-10-05 | 辽宁银珠化纺集团有限公司 | A kind of preparation method of halogen-free flame-proof nylon 66 having polymer |
US10294065B2 (en) | 2013-06-06 | 2019-05-21 | Sidergas Spa | Retainer for a welding wire container and welding wire container |
US10343231B2 (en) | 2014-05-28 | 2019-07-09 | Awds Technologies Srl | Wire feeding system |
US10010962B1 (en) | 2014-09-09 | 2018-07-03 | Awds Technologies Srl | Module and system for controlling and recording welding data, and welding wire feeder |
US10350696B2 (en) | 2015-04-06 | 2019-07-16 | Awds Technologies Srl | Wire feed system and method of controlling feed of welding wire |
US9950857B1 (en) | 2016-10-17 | 2018-04-24 | Sidergas Spa | Welding wire container |
US11174121B2 (en) | 2020-01-20 | 2021-11-16 | Awds Technologies Srl | Device for imparting a torsional force onto a wire |
US11278981B2 (en) | 2020-01-20 | 2022-03-22 | Awds Technologies Srl | Device for imparting a torsional force onto a wire |
Also Published As
Publication number | Publication date |
---|---|
CH632775A5 (en) | 1982-10-29 |
JPS53128195A (en) | 1978-11-08 |
FR2387276B1 (en) | 1984-01-27 |
BE866005A (en) | 1978-07-31 |
IT7822314A0 (en) | 1978-04-14 |
IT1095605B (en) | 1985-08-10 |
NL183654C (en) | 1988-12-16 |
NL7803914A (en) | 1978-10-17 |
DE2816100C2 (en) | 1989-08-24 |
NL183654B (en) | 1988-07-18 |
DE2816100A1 (en) | 1978-10-19 |
FR2387276A1 (en) | 1978-11-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
GB1575157A (en) | Flame retardant polycondensation products derived from phosphorus-containing dicarboxylic acids | |
US4280951A (en) | Flame retardants | |
CA1118543A (en) | Flame-retardant polycarbonate compositions | |
US4086206A (en) | Organophosphorus compounds and process for the production thereof | |
US4134876A (en) | Phosphorus and linear polyester compositions and products containing them | |
JPS6038420B2 (en) | Flame retardant polymer composition | |
EP0235266B1 (en) | Tetrahalophthalate esters as flame retardants for polyphenylene ether resins | |
US4087408A (en) | Bromine and phosphorus containing polyester | |
US4142904A (en) | Flame retardant polycarboxy alkyl and aryl phosphonates | |
JP3557792B2 (en) | Resin composition | |
US3305608A (en) | Phenolic phosphites | |
CA1188034A (en) | Process for the preparation of thermoplastic polyphosphonatophenyl ester carbonates | |
US4067934A (en) | Condensation products of phosphine oxides | |
DE2253207C2 (en) | Flame-retardant thermoplastic polyester molding compounds | |
EP0244393B1 (en) | Flame retardant polyphenylene ether molding compositions | |
JPH01115955A (en) | Fire retardant polyphenylene ether molding composition | |
US4711931A (en) | Flame retarded polycarbonate polymers | |
AU623369B2 (en) | Halophenyl ester flame retardants for polyphenylene ether resins | |
US4206296A (en) | Polyester composition containing a benzene phosphorus oxydichloride, a diphenol and POCl3 | |
EP0057441B1 (en) | Mixed ether compositions containing oligomers of polyfunctional phosphine oxides and method for their manufacture | |
US3161687A (en) | Phosphine oxide polymers | |
AU631358B2 (en) | Halogenated polyester flame retardants for polyphenylene ether resins | |
CA1080397A (en) | Polymers of benzene phosphorus oxydichloride and 4,4'-thiodiphenol | |
US3809678A (en) | Polylauryllactam with improved resistance to the effects of heat,oxygen and light | |
JP3484802B2 (en) | Flame retardant polymer composition and molded article |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PS | Patent sealed [section 19, patents act 1949] | ||
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19930414 |