USRE30783E - Flame retarding linear polyesters and shaped articles thereof - Google Patents
Flame retarding linear polyesters and shaped articles thereof Download PDFInfo
- Publication number
- USRE30783E USRE30783E US06/120,465 US12046580A USRE30783E US RE30783 E USRE30783 E US RE30783E US 12046580 A US12046580 A US 12046580A US RE30783 E USRE30783 E US RE30783E
- Authority
- US
- United States
- Prior art keywords
- present
- carbon atoms
- contain
- flame
- diol
- 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 - Lifetime
Links
- 229920000728 polyester Polymers 0.000 title claims abstract description 55
- 230000000979 retarding effect Effects 0.000 title 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000009833 condensation Methods 0.000 claims abstract description 10
- 230000005494 condensation Effects 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 19
- 125000005842 heteroatom Chemical group 0.000 claims description 19
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 17
- 150000002009 diols Chemical class 0.000 claims description 17
- -1 cyclic anhydride Chemical class 0.000 claims description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims description 15
- 239000011574 phosphorus Substances 0.000 claims description 15
- PHGBTOBVWQJBKT-UHFFFAOYSA-N OC(=O)P(O)=O Chemical compound OC(=O)P(O)=O PHGBTOBVWQJBKT-UHFFFAOYSA-N 0.000 claims description 14
- 229920000642 polymer Polymers 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000000732 arylene group Chemical group 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims 10
- 125000000217 alkyl group Chemical group 0.000 claims 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims 6
- 125000001033 ether group Chemical group 0.000 claims 6
- 150000003457 sulfones Chemical class 0.000 claims 6
- 150000003462 sulfoxides Chemical class 0.000 claims 6
- 239000011593 sulfur Substances 0.000 claims 6
- 150000003568 thioethers Chemical class 0.000 claims 6
- 125000005907 alkyl ester group Chemical group 0.000 claims 2
- 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 claims 1
- 101100177155 Arabidopsis thaliana HAC1 gene Proteins 0.000 claims 1
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 claims 1
- 101100434171 Oryza sativa subsp. japonica ACR2.2 gene Proteins 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000835 fiber Substances 0.000 abstract description 20
- 239000005871 repellent Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 4
- 150000003018 phosphorus compounds Chemical class 0.000 abstract description 3
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 230000001154 acute effect Effects 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 150000007513 acids Chemical class 0.000 description 12
- 239000000654 additive Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000004043 dyeing Methods 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 229940093476 ethylene glycol Drugs 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000004434 sulfur atom Chemical group 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- QXFUBAAEKCHBQY-UHFFFAOYSA-N 3-[hydroxy(methyl)phosphoryl]propanoic acid Chemical compound CP(O)(=O)CCC(O)=O QXFUBAAEKCHBQY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910017895 Sb2 O3 Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- UCTWMZQNUQWSLP-VIFPVBQESA-N (R)-adrenaline Chemical compound CNC[C@H](O)C1=CC=C(O)C(O)=C1 UCTWMZQNUQWSLP-VIFPVBQESA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical group CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- SLWIPPZWFZGHEU-UHFFFAOYSA-N 2-[4-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=C(CC(O)=O)C=C1 SLWIPPZWFZGHEU-UHFFFAOYSA-N 0.000 description 1
- FGALVVBOIVDPLP-UHFFFAOYSA-N 2-[hydroxy(phenyl)phosphoryl]acetic acid Chemical compound OC(=O)CP(O)(=O)C1=CC=CC=C1 FGALVVBOIVDPLP-UHFFFAOYSA-N 0.000 description 1
- UNPLIEQDFJULBB-UHFFFAOYSA-N 4-[(4-carboxyphenyl)-hydroxyphosphoryl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1P(O)(=O)C1=CC=C(C(O)=O)C=C1 UNPLIEQDFJULBB-UHFFFAOYSA-N 0.000 description 1
- UTCFIWKVMIMCFB-UHFFFAOYSA-N 5-(3-sulfopropoxy)benzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(OCCCS(O)(=O)=O)=CC(C(O)=O)=C1 UTCFIWKVMIMCFB-UHFFFAOYSA-N 0.000 description 1
- CARJPEPCULYFFP-UHFFFAOYSA-N 5-Sulfo-1,3-benzenedicarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(S(O)(=O)=O)=C1 CARJPEPCULYFFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000008090 Colias interior Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- SUSAGCZZQKACKE-UHFFFAOYSA-N cyclobutane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC1C(O)=O SUSAGCZZQKACKE-UHFFFAOYSA-N 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- LWNLXVXSCCLRRZ-UHFFFAOYSA-N dichlorophosphane Chemical class ClPCl LWNLXVXSCCLRRZ-UHFFFAOYSA-N 0.000 description 1
- 150000005690 diesters Chemical class 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
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005108 dry cleaning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007706 flame test Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000009347 mechanical transmission Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000003008 phosphonic acid esters Chemical group 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000009747 press moulding Methods 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- LGZQSRCLLIPAEE-UHFFFAOYSA-M sodium 1-[(4-sulfonaphthalen-1-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=C2C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C(S([O-])(=O)=O)C2=C1 LGZQSRCLLIPAEE-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 125000003375 sulfoxide group Chemical group 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 238000010626 work up procedure Methods 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S260/00—Chemistry of carbon compounds
- Y10S260/24—Flameproof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S57/00—Textiles: spinning, twisting, and twining
- Y10S57/904—Flame retardant
Definitions
- shaped articles such as filaments and fibers can be prepared from linear polyesters which comprise in the polymer molecule phosphorus-containing compounds.
- various acids of phosphorus and their derivatives were especially used as phosphorus-containing modification-compounds, e.g. also phosphonic acids and phosphinic acids.
- the German Auslegeschrift No. 1,243,819 describes filaments and fibers made from polyesters modified with phosphonic acid esters. The filaments and fibers are well suited for dyeing with basic and disperse dyestuffs and have a low pilling tendency.
- Phosphonic and phosphinic acids or their esters are added in course of the processes for the preparation of fiber-forming linear polyesters, according to the disclosures in German Offenlegungsschrift No. 1,520,079 and German Offenlegungsschrift No. 1,595,598, and incorporated into the polymer chains.
- the main purpose of this modification is also to improve the dyeing properties of the corresponding filaments and fibers, and improvement in dyeing properties is the sole purpose of the polyester modification with bis-(p-carboxyphenyl)-phosphinic acid described by German Auslegeschrift No. 1,232,348.
- polyesters comprising phosphorus-containing compounds may have flame-repellent properties.
- French Pat. No. 1,196,971 discloses copolyesters having phosphonic acid units, and being resistant to flames and heat. These copolyester products can be used as flame-protection agents, adhesives, varnish and impregnating substances for paper and textiles as well as intermediate products.
- flame-repellent polyesters be prepared by incorporating by condensation into the polyester molecules alkylene-diphosphinic acids, arylene-di-phosphinic acids or aralkylene-di-phosphinic acids which may also contain additional hetero atoms such as F, Cl, Br, O and S.
- alkylene-diphosphinic acids arylene-di-phosphinic acids or aralkylene-di-phosphinic acids which may also contain additional hetero atoms such as F, Cl, Br, O and S.
- These polyesters can be worked up to filaments, fibers and to shaped articles (German Offenlegungsschrift Nos. 2,236,037, 2,328,343, 2,236,038 and 2,236,039).
- non-volatile oligomers of diphosphinic acids with diols are often used and incorporated in the polyester by condensation. In such cases it is, of course, necessary to first prepare the oligomers.
- the additives are often responsible for sticking together of the polymer chips during the drying process, as a consequence of the additives tending to migrate to the surface of the polymer chips.
- the quite highly-viscous polymer additives described in Belgian Pat. No. 769,229 have a viscosity such that mixing them homogeneously with the polyesters is rather difficult. Moreover, they cause undesirably high diglycol contents in cases where the additives are blended in while the polyester-forming reaction is still going on.
- the modification agent should not be volatile during the process of incorporation by condensation.
- modified linear polyesters of the present invention consist of dicarboxylic acid components and diol-components as well as of phosphorus-containing chain members and comprise phosphorus-containing chain members having structural units of the formula ##STR2## which constitute about 3 to 20 mol. % of the acid component of the polyester.
- R is a saturated open-chained or cyclic alkylene-radical having from one to 15, preferably from two to 10 carbon atoms or an arylene or aralkylene-radical for example ##STR3## and R 1 is an alkyl radical having up to six carbon atoms, an aryl radical or an aralkyl radical for example CH 3 , C 2 H 5 , n- and i-C 4 H 9 , C 5 H 11 , C 6 H 13 , C 6 H 5 , C 6 H 5 -CH 2 etc.).
- Preferred phosphorus-containing chain members are the structural units of the above formula with R being --CH 2 --CH 2 -- or C 6 H 4 and R 1 being CH 3 or C 6 H 5 , i.e., ##STR4##
- Radical R as well as radical R 1 may additionally comprise one or more hetero atoms, preferably halogen, (F, Cl, Br) atoms, oxygen atoms or sulphur atoms; they may be located in branches or in the chain, the latter being preferred.
- “In the chain” means here a member of a chian consisting of carbon atoms. Due to their monovalence, halogen atoms cannot be located in the chain. Most suitable are O atoms and S atoms only.
- the S-atoms can be present as sulfide groups, sulfoxide groups or sulfone-groups, whereas on the chain or on the aromatic ring they may be present mainly as sulfonate groups.
- radicals R containing hetero atoms ##STR5## and with O atoms and S atoms in chain position.
- R is a saturated, open-chained or cyclic alkylene radical a halogen-substitution is satisfactory only, if the compounds either do not or only slightly yield hydrogen halide under the conditions used for preparation of the polyester.
- Suitable halogen-substituted alkylene radicals of this kind are, for example, the radical ##STR7## or perfluorinated alkylene radicals.
- Radical R 1 may also contain hetero atoms in similar manner.
- the most suitable substituents are halogen atoms or the sulfonate group, for example,
- the linear polyesters comprising the above, special structural units as chain members are obtained as follows:
- the usual starting materials which are known to be most suitable for preparing high-molecular and particularly fiber-forming and film-forming linear polyesters are reacted in known manner, while prior to, during or shortly before the end of the polycondensation bifunctional carboxy-phosphinic acids which may optionally contain further hetero atoms and/or their esters with a lower alcohol of especially from one to four carbon atoms or with diol are added, the latter also forming the diol component of the polyester.
- It is further possible to use the cyclic anhydrides of phosphinic-carboxylic acids which form easily and are readily accessible.
- the quantity of the carboxy-phosphinic acid component may be from about 3-20 mol. % of the total acid component.
- the dicarboxylic acids used as starting materials may be free acids or may be esterified with lower aliphatic alcohols having preferably from one to four carbon atoms, especially CH 3 OH, Terephthalic acid is preferred and may be used with other dicarboxylic acids as co-components.
- acids are, for example, isophthalic acid, 5-sulfo-isophthalic acid, 5-sulfopropoxy-isophthalic acid, naphthalene-2,6-dicarboxylic acid, diphenyl-p, p-dicarboxylic acid, p-phenylenediacetic acid, diphenyloxide-p, p'-dicarboxylic acid, diphenoxy-alkane-dicarboxylic acids, transhexahydroterephthalic acid, adipic acid, sebacic acid, 1,2-cyclobutane-dicarboxylic acid etc.
- Suitable diol-components are, besides ethylene-glycol, e.g. propane-diol-1,3, butane-diol-1,4 and the higher homologues of butane-diol-1,4 as well as, 2,2-dimethyl-propanediol-1,3, 1,4-cyclohexane-dimethanol etc., as well as co-componets.
- ethylene-glycol e.g. propane-diol-1,3, butane-diol-1,4 and the higher homologues of butane-diol-1,4 as well as, 2,2-dimethyl-propanediol-1,3, 1,4-cyclohexane-dimethanol etc., as well as co-componets.
- the additional acid constitute not much more than 10 mol. % of the total acid used. Similar considerations apply to the composition of the diol component. For example, if further diols besides the ethylene-glycol are used as components, their quantity preferably should not substantially exceed 10 mol. % of the total diol component.
- the first step is the esterification, followed by polycondensation. If the starting materials are dicarboxylic acid esters, and especially dimethyl esters, instead of free dicarboxylic acids, the first step is also transesterification which is followed by polycondensation, each of these steps using the usual catalysts.
- Bifunctional carboxyphosphinic acids which are added prior to, during or shortly before termination of the polycondensation and which contain still further hetero atoms, or their esters or their cyclic anhydrides can be prepared as follows:
- Carboxyphosphinic acids having but one carbon atom inserted between the P-atom and the COOH-group are obtained, for example, according to the reaction described by H. G. Hennig and G. Hilgetag in J. Prakt. Chem. 29, 86 ff (1965), starting from ⁇ -Cl or ⁇ -Br-acetic acid alkyl esters and phosphonous acid alkyl esters.
- a carboxymethyl-phenyl-phosphinic acid having e.g. the formula ##STR9## is obtainable by this method.
- R is an alkylene group having two or more carbon atoms
- unsaturated acids preference is given to the use of acrylic acid, methacrylic acid and crotonic acid.
- That latter process consists in reacting halogenobenzoic acid esters with phosphoneous acid diesters according to the guidelines of an Arbusov reaction.
- the carboxylalkyl-phosphinic acid esters can be saponified e.g. by means of strong inorganic acids or bases.
- Carboxyphosphinic acids with R being aralkylene can be prepared by analogy to Belgian Pat. No. 601,710 from carboxybenzylhalides and phosphoneous acid esters and subsequent saponification of the ester groups to yield free acids.
- carboxyphosphinic acids or their esters or cyclic anhydrides are not volatile under the conditions of the polyester-forming reaction--contrary to e.g. various diphosphinic acids--so that the former may be incorporated well and completely by condensation.
- the phosphorus-organic structural unit is randomly distributed in the macromolecule of the polyester final product. Occasionally the carboxyphosphinic acid units may also be present as terminal groups, due to their random distribution.
- moulding compositions should contain at least approx. 0,5 wt. % of phosphorus in the polyester, whilst the amount in filaments and fibers should be at least 1 wt. %.
- the flame-retarding qualities are further improved, if the P-containing chain members in the polyesters include halides as hetero atoms.
- the completely condensed polyesters are spun to filaments and fibers as usual, stretched and submitted to additional treatment or extruded to yield sheets or, in known manner, worked-up to obtain shaped articles by press-moulding, injection-moulding or extrusion.
- Particularly suitable are filaments, fibers, sheets and shaped articles the dicarboxylic acid component of which contains mainly terephthalic acid and the diol component of which comprises essentially ethylene-glycol. All these shaped articles are also an object of the present invention.
- the fibers and filaments have very good and permanent flame-repellent and self-extinguishing properties. Since they have a good degree of whiteness, they have very good dyeing properties for disperse dyestuffs and their receptivity includes acid dyestuffs in colour shades of average to deep intensity. If the P-containing chain members additionally include sulfonate groups, the receptivity also extends to basic dyestuffs. The diglycol portion of the polyesters increases only slightly. The tensile strength of the filaments and fibers, second order transition temperature, melting point, etc. approximately correspond to the values of the non-modified polyesters.
- Such fibers and filaments are generally useful, for applications where readily ignitible textiles and technical articles cannot be tolerated, for example for awning cloths, carpets, curtains etc. It is also possible to use these filaments as one of the components in bi-component-filaments in combination with other polymers.
- the sheets and shaped articles as well are used whereever serious risks of ignition and fire exist. If the transparency of the shaped articles is not a matter of concern, their solidity can be enhanced by imbedding therein e.g. inorganic fiber materials such as glass fibers, fibers from quartz, asbestos and carbon in the usual quantities.
- inorganic fiber materials such as glass fibers, fibers from quartz, asbestos and carbon in the usual quantities.
- 1,000 g of dimethylterephthalate are transesterified with 720 ml of ethylene-glycol in the presence of 230 mg of manganacetate 4 H 2 O as catalyst, the transesterification taking place under nitrogen at temperatures of from 170°-220° C.
- 100 g of 2-carboxy-ethyl-methylphosphinic acid (preparation according to V. K. Chajrullin et al, Z. obsc. Chim 37 (1967) No. 3, pg. 710-714) are added at 220° C. and esterified.
- reaction mixture After having added 350 mg of Sb 2 O 3 the reaction mixture is further heated and, simultaneously, evacuated slowly so that a pressure of 1 torr at 250° C. interior temperature is built up.
- the polycondensation is carried out at 0.2 torr and at 275° C. until a relative viscosity (1% solution in dichloroacetic acid at 25°) of 1,85 is attained. Melting point 244°-248° C., phosphorus contents: 1.85%.
- the condensation product was spun from the melt under the usual conditions and, subsequently, stretched in a proportion of 1:3.65.
- the threads obtained showed a resistance of 33 g/tex at an elongation at break of 35%. They were worked up to a tubular knit which was used for dyeing and flame tests.
- the flammability test was carried out according to the oxygen-index method as per the test regulation ASTM D 2863-70.
- ASTM D 2863-70 The tubular knit was fitted vertically into the apparatus and flamed from above.
- An artificial oxygen/nitrogen atmosphere was created with a quantity of oxygen which was just enough to allow the test knit to burn.
- Example 1 was repeated with the difference that instead of 100 g of 2-carboxy-ethyl-methyl-phosphinic acid there are used 75 g of its cyclic anhydride 2-methyl-2,5-dioxo-1-oxa-2-phospholane having formula ##STR17## and, instead of 350 mg of Sb 2 O 3 of example 1, the present example 10 used 300 mg of GeHPO 3 .
- the purely white polyester containing 1.5 % of phosphorus was crushed in the cold.
- the viscosity of the granules was increased to 1.36 by condensation of the solid matter in a rotating vessel at 230° C. and at 0.2 torr, condensation period 8 hours.
- the granules were worked up to plates on an injection moulding machine, the cylinder having temperatures of 260°/270°/260° C., the moulding temperature being 20° C.
- the plates measuring 60 ⁇ 60 ⁇ 2 mm were transparent and completely colorless, their reduced specific viscosity was 1.25.
- the impact strength of the plates was examined by means of the drop hammer test, exposing the plates to the vertical impact of a dropping object (drop hammer) from various heights, the plates being clamped onto a frame.
- the tip of the drop hammer was shaped as a hemisphere having a radius of 10 mm and a weight of 1 kg. For each height 10 plates were submitted to the test. For example, at a given dropping height of 150 cm the impact was strong enough to break 50% of the plates.
- the impact strength of the plates of the example was 200 cm.
- Plates being obtained under the same conditions but without the phosphorus modification compound and having a reduced specific viscosity of 1.32, showed an impact strength of 190 cm when submitted to impact under the same conditions.
- Example 10 was repeated with the difference that instead of 75 g of 2-methyl-2,5-dioxo-1-oxa-2-phospholane only 35 g of this compound were used. The phosphorus portion was then 0.7%. The flammability test according to ASTM D 635-68 showed the material to be "self-extinguishing.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Textile Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Flame-repellant linear polyesters are obtained by incorporating by condensation phosphorus-compounds having the formula ##STR1## wherein R and R1 are organic radicals which may also contain hereto atoms into the linear polyesters, preferably those from terephthalic acid and ethylene glycol. These polyesters are materials of which flame-repellent filaments, fibers, sheets, press-moulded and injection-moulded articles may be made. Products of the invention can be used whereever especially acute risks of ignition and fire exist.
Description
.Iadd.This is a continuation of application Ser. No. 880,866 filed Feb. 23, 1978, now abandoned. .Iaddend.
It is an object of the present invention to provide flame retarded synthetic linear polyesters modified with carboxy-phosphinic acids, as well as articles shaped from these modified polyesters.
It is known that shaped articles, such as filaments and fibers can be prepared from linear polyesters which comprise in the polymer molecule phosphorus-containing compounds. In these cases, various acids of phosphorus and their derivatives were especially used as phosphorus-containing modification-compounds, e.g. also phosphonic acids and phosphinic acids. Thus, the German Auslegeschrift No. 1,243,819 describes filaments and fibers made from polyesters modified with phosphonic acid esters. The filaments and fibers are well suited for dyeing with basic and disperse dyestuffs and have a low pilling tendency.
Phosphonic and phosphinic acids or their esters are added in course of the processes for the preparation of fiber-forming linear polyesters, according to the disclosures in German Offenlegungsschrift No. 1,520,079 and German Offenlegungsschrift No. 1,595,598, and incorporated into the polymer chains. The main purpose of this modification is also to improve the dyeing properties of the corresponding filaments and fibers, and improvement in dyeing properties is the sole purpose of the polyester modification with bis-(p-carboxyphenyl)-phosphinic acid described by German Auslegeschrift No. 1,232,348.
However, it is also known that polyesters comprising phosphorus-containing compounds may have flame-repellent properties. Thus, French Pat. No. 1,196,971 discloses copolyesters having phosphonic acid units, and being resistant to flames and heat. These copolyester products can be used as flame-protection agents, adhesives, varnish and impregnating substances for paper and textiles as well as intermediate products. On the other hand, it is not possible to spin these polyesters to yield filaments or fibers, since their phosphorus content imparts brittleness to the products.
Furthermore, it has been suggested that flame-repellent polyesters be prepared by incorporating by condensation into the polyester molecules alkylene-diphosphinic acids, arylene-di-phosphinic acids or aralkylene-di-phosphinic acids which may also contain additional hetero atoms such as F, Cl, Br, O and S. These polyesters can be worked up to filaments, fibers and to shaped articles (German Offenlegungsschrift Nos. 2,236,037, 2,328,343, 2,236,038 and 2,236,039). But, due to their occasionally rather considerable volatility at the condensation temperatures, it is quite difficult to incorporate the diphosphinic acids by condensation. Therefore, non-volatile oligomers of diphosphinic acids with diols are often used and incorporated in the polyester by condensation. In such cases it is, of course, necessary to first prepare the oligomers.
Another method for preparation of flame-repellent polyesters has also been plasticized which involves incorporating phosphorus compounds into the polyester in such a way that they are not built into the polymer chains. According to the two Japanese Pat. Nos. 7,142,230 and 7,142,231 certain esters of phosphoric acid and halogen-containing aromatic dihydroxy-compounds have been used as such additives and according to Belgian Pat. No. 769,229 special polyphosphonates and poly(phosphonate-phosphates) have been similarly used. While the use of these additives provides good flame-protection properties, the flame-protection is not permanent and the products are subject to certain other disadvantages. These advantages are especially a consequence of the considerable tendency of the additives to migrate as a result of which the polymer products have a certain toxicity and the additives can be washed out relatively easily, e.g. in the course of dry cleaning of articles made of corresponding fibers. When the additives are washed out of the articles, the polymer products, of course, lose their flame-repellent properties.
In the course of the preparation of such fibers, the additives are often responsible for sticking together of the polymer chips during the drying process, as a consequence of the additives tending to migrate to the surface of the polymer chips. The quite highly-viscous polymer additives described in Belgian Pat. No. 769,229 have a viscosity such that mixing them homogeneously with the polyesters is rather difficult. Moreover, they cause undesirably high diglycol contents in cases where the additives are blended in while the polyester-forming reaction is still going on.
A comparison of these polymers with polymers in which, phosphorus compounds are incorporated into the chain molecules shows the polymers with the additives in question have poorer dyeing properties. Even red phosphorus has been used as an additive for producing flame-repellent and self-extinguishing properties of polyester fibers and filaments (German Offenlegungsschrift No. 2,148,348).
Even though such filaments and fibers are sufficiently flame-repellent or self-extinguishing, the addition of red phosphorus does not permit white products to be obtained. Thus the products obtained are of limited use only.
Therefore, it is an object of the present invention to produce permanently flame-retarding linear polyesters by using an appropriate modify agent which imparts flame-repellent properties to filaments and fibers spun therefrom the textile properties of which compare favorably with those of filaments and fibers made of the corresponding non-modified polyesters, and which also permit a work-up to yield useful sheets and shaped articles. Moreover, the modification agent should not be volatile during the process of incorporation by condensation.
The problems outlined above have been solved by the modified linear polyesters of the present invention. These modified polyesters consist of dicarboxylic acid components and diol-components as well as of phosphorus-containing chain members and comprise phosphorus-containing chain members having structural units of the formula ##STR2## which constitute about 3 to 20 mol. % of the acid component of the polyester.
In this formula R is a saturated open-chained or cyclic alkylene-radical having from one to 15, preferably from two to 10 carbon atoms or an arylene or aralkylene-radical for example ##STR3## and R1 is an alkyl radical having up to six carbon atoms, an aryl radical or an aralkyl radical for example CH3, C2 H5, n- and i-C4 H9, C5 H11, C6 H13, C6 H5, C6 H5 -CH2 etc.).
Preferred phosphorus-containing chain members are the structural units of the above formula with R being --CH2 --CH2 -- or C6 H4 and R1 being CH3 or C6 H5, i.e., ##STR4##
Radical R as well as radical R1 may additionally comprise one or more hetero atoms, preferably halogen, (F, Cl, Br) atoms, oxygen atoms or sulphur atoms; they may be located in branches or in the chain, the latter being preferred. "In the chain" means here a member of a chian consisting of carbon atoms. Due to their monovalence, halogen atoms cannot be located in the chain. Most suitable are O atoms and S atoms only. Though N-atoms are also possible chain members as --NH-- or --NR'-- groups (R'=an organic radical), they are less desirable, since N-compounds, as is well known to those skilled in the art are often responsible for producing undesirable discoloration in course of the polycondensation process.
Within the chain the S-atoms can be present as sulfide groups, sulfoxide groups or sulfone-groups, whereas on the chain or on the aromatic ring they may be present mainly as sulfonate groups.
The following examples may be cited to illustrate radicals R containing hetero atoms: ##STR5## and with O atoms and S atoms in chain position. --(CH2)3 --O--(CH2)3 -, --(CH2)2 --O--(CH2)2 --O--(CH2)2 --, --(CH2)4 --O--(CH2)4 -, --(CH2)4 --S--(CH2)4 --, --CH2)4 --S--(CH2)4 --, ##STR6##
In cases where R is a saturated, open-chained or cyclic alkylene radical a halogen-substitution is satisfactory only, if the compounds either do not or only slightly yield hydrogen halide under the conditions used for preparation of the polyester. Suitable halogen-substituted alkylene radicals of this kind are, for example, the radical ##STR7## or perfluorinated alkylene radicals.
Radical R1 may also contain hetero atoms in similar manner. In this case, however, the most suitable substituents are halogen atoms or the sulfonate group, for example,
CH2 Cl, C6 H4 Cl, C6 H4 Br, C6 H4 SO3 Na, etc.
The linear polyesters comprising the above, special structural units as chain members are obtained as follows: The usual starting materials which are known to be most suitable for preparing high-molecular and particularly fiber-forming and film-forming linear polyesters are reacted in known manner, while prior to, during or shortly before the end of the polycondensation bifunctional carboxy-phosphinic acids which may optionally contain further hetero atoms and/or their esters with a lower alcohol of especially from one to four carbon atoms or with diol are added, the latter also forming the diol component of the polyester. It is also possible to use the oligomers of the above carboxy-phosphinic acid-diol esters. It is further possible to use the cyclic anhydrides of phosphinic-carboxylic acids which form easily and are readily accessible. The quantity of the carboxy-phosphinic acid component may be from about 3-20 mol. % of the total acid component.
The carboxy-phosphinic acids used here have the formula ##STR8## wherein R and R1 have the aforesaid meaning.
The dicarboxylic acids used as starting materials may be free acids or may be esterified with lower aliphatic alcohols having preferably from one to four carbon atoms, especially CH3 OH, Terephthalic acid is preferred and may be used with other dicarboxylic acids as co-components. Other suitable acids are, for example, isophthalic acid, 5-sulfo-isophthalic acid, 5-sulfopropoxy-isophthalic acid, naphthalene-2,6-dicarboxylic acid, diphenyl-p, p-dicarboxylic acid, p-phenylenediacetic acid, diphenyloxide-p, p'-dicarboxylic acid, diphenoxy-alkane-dicarboxylic acids, transhexahydroterephthalic acid, adipic acid, sebacic acid, 1,2-cyclobutane-dicarboxylic acid etc.
Suitable diol-components are, besides ethylene-glycol, e.g. propane-diol-1,3, butane-diol-1,4 and the higher homologues of butane-diol-1,4 as well as, 2,2-dimethyl-propanediol-1,3, 1,4-cyclohexane-dimethanol etc., as well as co-componets.
In cases where terephthalic acid is used with additional dicarboxylic acids as disclosed above, it is preferable that the additional acid constitute not much more than 10 mol. % of the total acid used. Similar considerations apply to the composition of the diol component. For example, if further diols besides the ethylene-glycol are used as components, their quantity preferably should not substantially exceed 10 mol. % of the total diol component.
If the starting materials are free dicarboxylic acids and diols, the first step, as usual for these reaction partners, is the esterification, followed by polycondensation. If the starting materials are dicarboxylic acid esters, and especially dimethyl esters, instead of free dicarboxylic acids, the first step is also transesterification which is followed by polycondensation, each of these steps using the usual catalysts.
Of course usual additives (cross-linking agents, delusterants and stabilizers, nucleating agents, coloring agent and fillers etc.) can be added during the preparation of polyesters, in addition to the usual catalysts.
Bifunctional carboxyphosphinic acids which are added prior to, during or shortly before termination of the polycondensation and which contain still further hetero atoms, or their esters or their cyclic anhydrides can be prepared as follows:
Carboxyphosphinic acids having but one carbon atom inserted between the P-atom and the COOH-group are obtained, for example, according to the reaction described by H. G. Hennig and G. Hilgetag in J. Prakt. Chem. 29, 86 ff (1965), starting from α-Cl or α-Br-acetic acid alkyl esters and phosphonous acid alkyl esters. A carboxymethyl-phenyl-phosphinic acid having e.g. the formula ##STR9## is obtainable by this method.
If R is an alkylene group having two or more carbon atoms, it is useful to follow the reaction scheme described by V. K. Chajrullin et al aprox. in Z. Obsc. Chim. 37 (1967) No. 3, pg. 710-714, starting from dichlorophosphines and unsaturated carboxylic acids, such as, for example: ##STR10## Among the unsaturated acids preference is given to the use of acrylic acid, methacrylic acid and crotonic acid.
Carboxyphosphinic acids having an aromatic radical (R=arylene) inserted between the P and COOH-groups can be prepared for instance according to the guidelines of the process described by L. D. Quin et al in J. Org. Chem. 27, 4120 (1962) or according to the process disclosed in Application serial No. (German Patent Application No. P 2346657.1) filed concurrently herewith.
That latter process consists in reacting halogenobenzoic acid esters with phosphoneous acid diesters according to the guidelines of an Arbusov reaction. The carboxylalkyl-phosphinic acid esters can be saponified e.g. by means of strong inorganic acids or bases.
Carboxyphosphinic acids with R being aralkylene can be prepared by analogy to Belgian Pat. No. 601,710 from carboxybenzylhalides and phosphoneous acid esters and subsequent saponification of the ester groups to yield free acids.
The carboxyphosphinic acids or their esters or cyclic anhydrides are not volatile under the conditions of the polyester-forming reaction--contrary to e.g. various diphosphinic acids--so that the former may be incorporated well and completely by condensation.
The phosphorus-organic structural unit is randomly distributed in the macromolecule of the polyester final product. Occasionally the carboxyphosphinic acid units may also be present as terminal groups, due to their random distribution. In order to guarantee the desired flame-repellent properties, moulding compositions should contain at least approx. 0,5 wt. % of phosphorus in the polyester, whilst the amount in filaments and fibers should be at least 1 wt. %. The flame-retarding qualities are further improved, if the P-containing chain members in the polyesters include halides as hetero atoms.
Subsequently, the completely condensed polyesters are spun to filaments and fibers as usual, stretched and submitted to additional treatment or extruded to yield sheets or, in known manner, worked-up to obtain shaped articles by press-moulding, injection-moulding or extrusion. Particularly suitable are filaments, fibers, sheets and shaped articles the dicarboxylic acid component of which contains mainly terephthalic acid and the diol component of which comprises essentially ethylene-glycol. All these shaped articles are also an object of the present invention.
The fibers and filaments have very good and permanent flame-repellent and self-extinguishing properties. Since they have a good degree of whiteness, they have very good dyeing properties for disperse dyestuffs and their receptivity includes acid dyestuffs in colour shades of average to deep intensity. If the P-containing chain members additionally include sulfonate groups, the receptivity also extends to basic dyestuffs. The diglycol portion of the polyesters increases only slightly. The tensile strength of the filaments and fibers, second order transition temperature, melting point, etc. approximately correspond to the values of the non-modified polyesters.
Such fibers and filaments are generally useful, for applications where readily ignitible textiles and technical articles cannot be tolerated, for example for awning cloths, carpets, curtains etc. It is also possible to use these filaments as one of the components in bi-component-filaments in combination with other polymers.
The sheets and shaped articles as well are used whereever serious risks of ignition and fire exist. If the transparency of the shaped articles is not a matter of concern, their solidity can be enhanced by imbedding therein e.g. inorganic fiber materials such as glass fibers, fibers from quartz, asbestos and carbon in the usual quantities. As examples of such shaped articles there can be cited casings, structural parts, electric machinery, mechanical transmission parts in automates, hollow articles, structural units in large-scale computers and sensitive electronic apparatus.
The following examples illustrate the present invention
1,000 g of dimethylterephthalate are transesterified with 720 ml of ethylene-glycol in the presence of 230 mg of manganacetate 4 H2 O as catalyst, the transesterification taking place under nitrogen at temperatures of from 170°-220° C. After completion of the separation of methanol 100 g of 2-carboxy-ethyl-methylphosphinic acid (preparation according to V. K. Chajrullin et al, Z. obsc. Chim 37 (1967) No. 3, pg. 710-714) are added at 220° C. and esterified.
After having added 350 mg of Sb2 O3 the reaction mixture is further heated and, simultaneously, evacuated slowly so that a pressure of 1 torr at 250° C. interior temperature is built up. The polycondensation is carried out at 0.2 torr and at 275° C. until a relative viscosity (1% solution in dichloroacetic acid at 25°) of 1,85 is attained. Melting point 244°-248° C., phosphorus contents: 1.85%.
The condensation product was spun from the melt under the usual conditions and, subsequently, stretched in a proportion of 1:3.65. The threads obtained showed a resistance of 33 g/tex at an elongation at break of 35%. They were worked up to a tubular knit which was used for dyeing and flame tests.
Dyeing with the acid dyestuffs having the commercial names of
"Supranol Echtrot" (C.I. No. 24,790) (Red)
"Alphanol Echtblau FGLL" (C.I. 62,155) and (Blue)
"Lanaperlgelb 3 G" (C.I. No. 19,025) (Yellow) yielded deep colour shades.
The flammability test was carried out according to the oxygen-index method as per the test regulation ASTM D 2863-70. For that purpose the tubular knit was fitted vertically into the apparatus and flamed from above. An artificial oxygen/nitrogen atmosphere was created with a quantity of oxygen which was just enough to allow the test knit to burn.
A value of 29 vol. % of O2 had been found. A corresponding tubular knit made of non-modified polyethylene-terephthalate started burning at an oxygen concentration of 20 vol. %.
The test according to example 1 was repeated with different carboxyphosphinic acids or their derivatives suitable for incorporation into polyester molecules. The following table shows the results.
TABLE __________________________________________________________________________ characteristics of Examples 2-8: polyester Oxygen-test Ex. Modification Preparation quantity rel..sup.+ P- on tubular No. agent according to: added viscosity melting point content knit __________________________________________________________________________ ##STR11## V. K. Chajrullin et al. Z.obsc. Chim. 38 (1968) Nr. 2, S. 288-292 100 g 1.75 240-242° C. 1.9% 30 Vol.% 3 ##STR12## V. K. Chajrullin et al. Z obsc. Chim. 37 (1967) Nr. 3, S. 710-714 80 g 1.89 241-245° C. 1.6% 30 Vol. % 4 5 ##STR13## U.S. Pat. No. 3,974,243 90 g 100 g 1.54 1.37 243-245° C. 241-243.d egree. C. 1.25% 1.4% 28 Vol.% 29 Vol. % 6 ##STR14## 100 g 1.81 247-249° C. 1.4% 29 Vol. % 7 ##STR15## V. K. Chajrullin et al. Z obsc. Chim. 37 (1967) Nr. 2, S. 455-460 125 g 1.79 240-244° C. 1.7% 30 Vol. % 8 ##STR16## V. K. Chajrullin et al. Doklady Akad. SSSR 162 (1965) Nr. 4, S. 827-828 or Z obsc. Chim. 42 (1972) Nr. 8 S. 1730-1733 75 g 1.77 245-247° C. 1.3% 27.5 Vol. __________________________________________________________________________ % .sup.+ measured or carried out according to the description of Example 1
The experiment as per example 1 was repeated, except that 6 mol. % of the DMT was replaced by dimethyl-isophthalate in the transesterification step. The polymer melting point was then 236°-238° C. The relative viscosity was 1.82. Tubular knits made of this material have an oxygen index value of 30%.
Example 1 was repeated with the difference that instead of 100 g of 2-carboxy-ethyl-methyl-phosphinic acid there are used 75 g of its cyclic anhydride 2-methyl-2,5-dioxo-1-oxa-2-phospholane having formula ##STR17## and, instead of 350 mg of Sb2 O3 of example 1, the present example 10 used 300 mg of GeHPO3.
The purely white polyester containing 1.5 % of phosphorus was crushed in the cold. The reduced specific viscosity of the granules was 1.08 (measured in phenol/tetrachloroethane=3:2 at 25° C.). The viscosity of the granules was increased to 1.36 by condensation of the solid matter in a rotating vessel at 230° C. and at 0.2 torr, condensation period 8 hours.
The granules were worked up to plates on an injection moulding machine, the cylinder having temperatures of 260°/270°/260° C., the moulding temperature being 20° C. The plates measuring 60×60×2 mm were transparent and completely colorless, their reduced specific viscosity was 1.25. The impact strength of the plates was examined by means of the drop hammer test, exposing the plates to the vertical impact of a dropping object (drop hammer) from various heights, the plates being clamped onto a frame. The tip of the drop hammer was shaped as a hemisphere having a radius of 10 mm and a weight of 1 kg. For each height 10 plates were submitted to the test. For example, at a given dropping height of 150 cm the impact was strong enough to break 50% of the plates. The impact strength of the plates of the example was 200 cm.
Plates being obtained under the same conditions but without the phosphorus modification compound and having a reduced specific viscosity of 1.32, showed an impact strength of 190 cm when submitted to impact under the same conditions.
For the flammability test the granules were pressed to plates 1.3 mm thick at a temperature between 230° and 250° C. and under a pressure of 80 atm. From these plates were cut test specimens measuring 127×12.7 mm. The result of the flammability test according to ASTM D 635-68 was "non-ignitible," the flammability test being carried out according to Underwriters Laboratories (UL) Subject 94 "SE O."
Example 10 was repeated with the difference that instead of 75 g of 2-methyl-2,5-dioxo-1-oxa-2-phospholane only 35 g of this compound were used. The phosphorus portion was then 0.7%. The flammability test according to ASTM D 635-68 showed the material to be "self-extinguishing.
Claims (13)
1. A linear polyester which is the polycondensation product of a dicarboxylic acid, a diol and a flame-retarding carboxy-phosphinic acid monomer, said monomer being used in an amount of from 3 to 20 mol percent, based on the total amount of dicarboxylic acid and monomer, said monomer being a source of structural units in said polyester of the formula ##STR18## wherein R is saturated, open-chain or cyclic alkylene, arylene or aralkylene having one to 15 carbon atoms, and may contain one or more hetero atoms selected from F, Cl, Br, O and S, and R1 is alkyl having up to six carbon atoms, aryl, or aralkyl and may contain one or more hetero atoms selected from F, Cl, Br, O and S, provided that in the R and R1 groups the O, if present, is the oxygen of an ether group, and the S, if present, is the sulfur of a thioether, sulfoxide, sulfone or sulfonate group.
2. A linear polyester according to claim 1 wherein
R is --CH2 --CH2 -- or --C6 H4 - and
R1 is CH3 -- or C6 H5 --.
3. A linear polyester according to claim 1 wherein the radical R or R1 contains a hetero atom O or S.
4. A linear polyester according to claim 1 wherein the units derived from dicarboxylic acid are essentially terephthalic acid units and the units derived from the diol are essentially units of a diol of the formula
HO (CH2)n OH
wherein n is 2 to 10, or the diol units are derived from 1,4-cyclohexane-dimethanol.
5. A linear polyester according to claim 1 wherein the units derived from dicarboxylic acid are essentially terephthalic acid units and the units derived from diol are essentially ethylene glycol units.
6. A method of making a linear polyester which comprises polycondensing a dicarboxylic acid or a lower alkyl ester thereof with a diol in the presence of a flame-retarding phosphorus containing monomer of the general formula ##STR19## or a lower alkyl ester or cyclic anhydride of said monomer in an amount of about 3 to 20 mole percent of the total acid components wherein the symbol R of said formula is saturated, open-chain or cyclic alkylene having one to 15 carbon atoms, arylene or aralkylene, and R1 of the formula is alkyl having up to 6 carbon atoms, aryl or aralkyl, and wherein R and R1 may further contain one or more hetero atoms selected from F, Cl, Br, O and S, provided that in the R and R1 groups the O, if present, is the oxygen of an ether group, and the S, if present, is the sulfur of a thioether, sulfoxide, sulfone or sulfonate group.
7. A process according to claim 6 wherein the dicarboxylic acid is terephthalic acid and the diol is ethylene glycol.
8. Shaped articles made by molding or extrusion of the linear polyester of claim 1. .Iadd.
9. A linear polyester which is effectively a polycondensation product of a dicarboxylic acid, a diol and a flame-retarding amount of a carboxy-phosphinic acid monomer, said monomer being a source of structural units in said polyester of the formula ##STR20## wherein R is saturated, open-chain or cyclic alkylene, arylene or aralkylene having one to 15 carbon atoms, and may contain one or more hetero atoms selected from F, Cl, Br, O and S and R1 is alkyl having up to six carbon atoms, aryl, or aralkyl and may contain one or more hetero atoms selected from F, Cl, Br, O and S, provided that in the R and R1 groups the O, if present, is the oxygen of an ether group, and the S, if present, is the sulfur of a thioether, sulfoxide, sulfone or sulfonate group. .Iaddend. .Iadd.
10. A flame-repellant linear polyester obtained by incorporating in said polyester by condensation a phosphorus-containing compound having the formula: ##STR21## wherein R is saturated, open-chain or cyclic alkylene, arylene or aralkylene having one to 15 carbon atoms, and may contain one or more hetero atoms selected from F, Cl, Br, O and S, and
R1 is alkyl having up to six carbon atoms, aryl or aralkyl and may contain one or more hetero atoms selected from F, Cl, Br, O and S, provided that in the R and R1 groups the O, if present, is the oxygen of an ether group, and the S, if present, is the sulfur of a thioether, sulfoxide, sulfone or sulfonate group. .Iaddend. .Iadd.
11. A flame-retarding linear polymer which comprises a modified polyethylene terephthalate having structural units of the formula ##STR22## present in an amount sufficient to impart flame-repellant properties thereof, wherein R is saturated, open-chain or cyclic alkylene, arylene or aralkylene having one to 15 carbon atoms and may contain one or more hetero atoms selected from F, Cl, Br, O and S, and R1 is alkyl having up to six carbon atoms, aryl or aralkyl and may contain one or more hetero atoms selected from F, Cl, Br, O and S, provided that in the R and R1 groups the O, if present, is the oxygen of an ether group and the S, if present, is the sulfur of a thioether, sulfoxide, sulfone or sulfonate group. .Iaddend. .Iadd.
12. A flame-retarded linear polyester which is effectively a polycondensation product of a dicarboxylic acid, a diol and a carboxy-phosphinic acid monomer present in an amount sufficient to impart flame-retardant properties to said polyester, said monomer being a source of structural units in said polyester of the formula ##STR23## wherein R is saturated, open-chain or cyclic alkylene, arylene or aralkylene having one to 15 carbon atoms, and may contain one or more hetero atoms selected from F, Cl, Br, O and S and R1 is alkyl having up to six carbon atoms, aryl or aralkyl and may contain one or more hetero atoms selected from F, Cl, Br, O and S, provided that in the R and R1 groups the O, if present, is the oxygen of an ether group, and the S, if present, is the sulfur of a thioether, sulfoxide, sulfone or sulfonate group. .Iaddend. .Iadd.
13. The polyester as defined in claim 12 which comprises a polyethylene terephthalate. .Iaddend.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2346787 | 1973-09-17 | ||
DE2346787A DE2346787C3 (en) | 1973-09-17 | 1973-09-17 | Flame retardant linear polyesters, processes for their manufacture and their use |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/505,686 Reissue US3941752A (en) | 1973-09-17 | 1974-09-13 | Flame retarding linear polyesters and shaped articles thereof |
US05880866 Continuation | 1978-02-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
USRE30783E true USRE30783E (en) | 1981-10-27 |
Family
ID=5892839
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/505,686 Expired - Lifetime US3941752A (en) | 1973-09-17 | 1974-09-13 | Flame retarding linear polyesters and shaped articles thereof |
US06/120,465 Expired - Lifetime USRE30783E (en) | 1973-09-17 | 1980-02-11 | Flame retarding linear polyesters and shaped articles thereof |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/505,686 Expired - Lifetime US3941752A (en) | 1973-09-17 | 1974-09-13 | Flame retarding linear polyesters and shaped articles thereof |
Country Status (24)
Country | Link |
---|---|
US (2) | US3941752A (en) |
JP (1) | JPS5313479B2 (en) |
AT (1) | AT338529B (en) |
BE (1) | BE820010A (en) |
BR (1) | BR7407703D0 (en) |
CA (1) | CA1037194A (en) |
CH (1) | CH571030A5 (en) |
DD (2) | DD120208A5 (en) |
DE (1) | DE2346787C3 (en) |
DK (1) | DK136158C (en) |
ES (1) | ES429952A1 (en) |
FI (1) | FI58784C (en) |
FR (1) | FR2243958B1 (en) |
GB (1) | GB1469349A (en) |
HK (1) | HK58278A (en) |
IE (1) | IE40029B1 (en) |
IT (1) | IT1021374B (en) |
LU (1) | LU70911A1 (en) |
MY (1) | MY7800435A (en) |
NL (1) | NL167180C (en) |
NO (1) | NO139351C (en) |
SE (1) | SE415023B (en) |
SU (1) | SU850010A3 (en) |
ZA (1) | ZA745811B (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4517355A (en) | 1982-04-22 | 1985-05-14 | Anic S.P.A. | Flameproof linear polyester, a process for its preparation, and articles formed from said polyester |
US5102424A (en) * | 1989-06-30 | 1992-04-07 | Hoechst Aktiengesellschaft | Pigment printing process for flame-retardant, low-flammability or nonflammable fibers: polymer or copolymer of vinylidene chloride as pigment binder |
US5145941A (en) * | 1991-01-04 | 1992-09-08 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
US5151494A (en) * | 1991-01-04 | 1992-09-29 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
US5374707A (en) * | 1993-02-18 | 1994-12-20 | Monsanto Company | Hydroxy ethyl bibenzoate |
US5399429A (en) * | 1994-03-11 | 1995-03-21 | Monsanto Company | Flame retardant recycled polyester copolymers |
US5399428A (en) * | 1994-03-11 | 1995-03-21 | Monsanto Company | Flame retardant polyester copolymers |
US5464694A (en) * | 1992-09-05 | 1995-11-07 | Hoechst Aktiengesellschaft | Spinnable polyester based on modified polyethylene terephthalate and aliphatic dicarboxylic acids |
US5550207A (en) * | 1991-12-18 | 1996-08-27 | Enichem Synthesis S.P.A. | Linear copolyester containing phosphorous, procedure for its preparation and its use as a flame-resistant additive |
US5703134A (en) * | 1994-03-11 | 1997-12-30 | Monsanto Company | Copolymers of recycled polyester |
US20060110613A1 (en) * | 2004-11-24 | 2006-05-25 | Toray Plastics (America), Inc. | Flame retardant metallized polyester films having anti-dripping properties |
WO2024146954A1 (en) | 2023-01-08 | 2024-07-11 | Indorama Ventures Public Company Limited | Flame retardant copolymer with one or more non-virgin fossil components and methods of making the same |
Families Citing this family (96)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2454189C3 (en) * | 1974-11-15 | 1980-08-14 | Hoechst Ag, 6000 Frankfurt | Process for the production of flame-retardant linear polyesters |
GB1522081A (en) * | 1975-01-17 | 1978-08-23 | Toyo Boseki | Flame resistant polyesters |
JPS51136792A (en) * | 1975-05-22 | 1976-11-26 | Toyobo Co Ltd | Flame resistant polyester preparation |
DE2526689C2 (en) * | 1975-06-14 | 1983-08-11 | Hoechst Ag, 6230 Frankfurt | Process for the preparation of 2,5-dioxo-1,2-oxa-phospholanes |
US4073829A (en) * | 1976-06-14 | 1978-02-14 | Monsanto Company | Phosphorus flame retardant compositions |
NL7710873A (en) * | 1976-10-15 | 1978-04-18 | Rhone Poulenc Textile | FIRE-RESISTANT COPOLYESTERS WITH PHOSPHONE GROUPS. |
DE2726189A1 (en) * | 1977-06-10 | 1978-12-21 | Hoechst Ag | FLAME RESISTANT, BIAXIAL ORIENTED POLYESTER FILM |
US4193914A (en) * | 1977-09-09 | 1980-03-18 | Monsanto Company | Phosphorus-containing propionates |
JPS54168554U (en) * | 1978-05-18 | 1979-11-28 | ||
JPS55111816A (en) * | 1979-02-22 | 1980-08-28 | Kanai Hiroyuki | Air filter |
DE7915593U1 (en) * | 1979-05-30 | 1979-08-30 | Hoechst Ag, 6000 Frankfurt | LIGHT SHIELD SLATS |
DE3200824C2 (en) * | 1982-01-14 | 1984-03-01 | Hoechst Ag, 6230 Frankfurt | Hardly combustible coated textile fabric |
DE3361701D1 (en) * | 1982-07-29 | 1986-02-13 | Vianova Kunstharz Ag | Process for the preparation of polyester resins containing phosphoric-acid groups, and their use |
US4596583A (en) * | 1983-11-10 | 1986-06-24 | Hoechst Aktiengesellschaft | Process for dyeing low-flammable linear polyester fiber textile material |
JPS6257984A (en) * | 1985-08-29 | 1987-03-13 | 帝人株式会社 | Flame-proof synthetic fiber |
DE8907506U1 (en) * | 1989-06-20 | 1989-08-10 | Hoechst Ag, 6230 Frankfurt | Synthetic hair made from a flame-retardant polyester monofilament |
DE8907504U1 (en) * | 1989-06-20 | 1989-09-14 | Hoechst Ag, 65929 Frankfurt | Textile closure made of flame-retardant polyester monofilaments |
DE8907505U1 (en) * | 1989-06-20 | 1989-11-02 | Hoechst Ag, 65929 Frankfurt | Textile surface sheet with flame-retardant polyester monofilaments |
DE3927505A1 (en) * | 1989-08-21 | 1991-03-14 | Hoechst Ag | Spun bond non woven |
DE4007299A1 (en) * | 1990-03-08 | 1991-09-12 | Hoechst Ag | METHOD FOR THE ONE-BATH DYEING AND FLAME-RETARDANT FINISHING OF FLAT-SHAPED TEXTILE MATERIALS |
DE4129188A1 (en) * | 1991-09-03 | 1993-03-04 | Spinnstoffabrik Zehlendorf Ag | MELT FIBER-ADHESIVE LAMINATE, METHOD AND INTERMEDIATE PRODUCT FOR THE PRODUCTION AND USE THEREOF |
US5180793A (en) * | 1991-12-31 | 1993-01-19 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
DE4327616A1 (en) * | 1993-08-17 | 1995-02-23 | Hoechst Ag | Process for the production of polyesters with improved whiteness |
DE4344691A1 (en) | 1993-12-27 | 1995-06-29 | Hoechst Ag | High tenacity, flame retardant polyester yarn, process for its manufacture and its use |
DE19631068B4 (en) * | 1996-08-01 | 2006-06-01 | Zimmer Ag | Process for accelerating the polycondensation of polyester |
US5750603A (en) * | 1997-05-23 | 1998-05-12 | Solutia Inc. | Polymer-bound non-halogen fire resistant compositions |
US5952406A (en) * | 1997-05-27 | 1999-09-14 | Solutia Inc. | Fire retarded polyamide |
DE19739852B4 (en) * | 1997-09-11 | 2006-03-16 | Zimmer Ag | Process for the preparation of flame-resistant polyesters |
KR19990070137A (en) * | 1998-02-17 | 1999-09-15 | 한형수 | Manufacturing method of flame retardant polyester |
DE60034449T2 (en) * | 1999-01-19 | 2008-01-03 | Toyo Boseki K.K. | FLAME DELAYING POLYESTER FIBERS, FABRICS, KNITWEAR, NONWOVENS AND SUEDE WOVEN OR KNITTED TEXTILE PRODUCTS FROM THESE FIBERS |
KR100457767B1 (en) * | 1999-11-09 | 2004-11-17 | 에스케이씨 주식회사 | flame retardant and Heat-shrinkable polyester film |
DE10002161A1 (en) | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | Co-extruded, biaxially oriented polyester film, useful for interior and exterior purposes and as printable, release or embossing film or label, contains soluble flame retardant and polymer with sulfonate group |
JP2003524691A (en) | 2000-01-20 | 2003-08-19 | ミツビシ ポリエステル フィルム ジーエムビーエイチ | Thermoformed white film made of crystalline thermoplastic resin and having flame retardancy and UV resistance, its use, and method for producing the same |
DE10002165A1 (en) | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | Clear, thermoformable, oriented thermoplastic film, used for interior and exterior purposes, e.g. cladding, advertising, display and lighting, contains flame retardant |
DE10002160A1 (en) | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | Co-extruded, biaxially oriented polyester film, useful for interior and exterior purposes and as printable, release of embossing film or label, contains flame retardant, ultraviolet stabilizer and polymer with sulfonate group |
DE10002171A1 (en) | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | Transparent, flame-retardant, UV-stable film made of a crystallizable thermoplastic, process for its production and its use |
DE10002163A1 (en) | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | White thermo formable film useful in displays, for labels, illumination, and electronics, contains a white pigment, a crystalline thermoplastic, and a UV stabilizer |
DE10002173A1 (en) | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | Clear, thermoformable oriented film, used for interior and exterior purposes, e.g. cladding, advertising, display and lighting, based on crystallizable thermoplastics, contains flame retardant and ultraviolet stabilizer |
DE10002153A1 (en) * | 2000-01-20 | 2001-07-26 | Mitsubishi Polyester Film Gmbh | Amorphous, white, UV-stable thermoformable film, useful in interior or exterior applications, formed from crystallizable resin, e.g. polyester, contains white pigment and soluble flame retardant and UV stabilizer |
DE10007672A1 (en) | 2000-02-19 | 2001-08-23 | Mitsubishi Polyester Film Gmbh | White-opaque, flame-retardant, UV-stabilized film with low transparency made of a crystallizable thermoplastic |
DE10007723A1 (en) | 2000-02-19 | 2001-08-23 | Mitsubishi Polyester Film Gmbh | Coextruded and biaxially oriented polyester film comprises a thermoplastic polyester base layer sandwiched between a heat-sealable layer and a matt layer and includes a flame retardant |
DE10007725A1 (en) | 2000-02-19 | 2001-08-23 | Mitsubishi Polyester Film Gmbh | One-sided matt, sealable, UV stabilized and flame-retardant, coextruded, biaxially oriented polyester film, process for its production, its use |
DE10007730A1 (en) | 2000-02-19 | 2001-08-23 | Mitsubishi Polyester Film Gmbh | Transparent, sealable, flame-retardant polyester film, process for its production and its use |
DE10007726A1 (en) | 2000-02-19 | 2001-08-23 | Mitsubishi Polyester Film Gmbh | Transparent, sealable, UV-stabilized and flame-retardant polyester film, process for its production and its use |
DE10007728A1 (en) | 2000-02-19 | 2001-08-23 | Mitsubishi Polyester Film Gmbh | White, sealable, flame-retardant, biaxially oriented polyester film, process for its production and its use |
DE10009295A1 (en) | 2000-02-28 | 2001-08-30 | Mitsubishi Polyester Film Gmbh | White, biaxially-oriented, fire-resistant polyester film, used e.g. for packaging light- or air-sensitive food, has at least one layer containing cyclo-olefin copolymer and fire retardant |
DE10009286A1 (en) * | 2000-02-28 | 2001-08-30 | Mitsubishi Polyester Film Gmbh | White, biaxially-oriented, fire-resistant, UV-stabilised polyester film, used e.g. for packaging light- or air-sensitive food, has at least one layer containing cyclo-olefin copolymer, UV stabiliser and fire retardant |
KR100355807B1 (en) * | 2000-05-17 | 2002-10-19 | 박홍수 | Modified polyester pre-polymer containing phospate, preparing method thereof, and method for preparing rapid curing type two-component polyurethane flame retardant coatings including the same |
KR20020030007A (en) | 2000-09-29 | 2002-04-22 | 힐커트 | Hydrolysis-Resistant, Transparent, Biaxially Oriented Film Made From a Crystallizable Thermoplastic, and Process for Its Production |
DE10112493A1 (en) | 2001-03-15 | 2002-09-19 | Mitsubishi Polyester Film Gmbh | White biaxially oriented film of thickness 10-500 microns used for displays, buildings, furniture and packaging comprises a crystallizable thermoplastic and rutile-type titanium oxide |
DE10116751C2 (en) * | 2001-04-04 | 2003-05-22 | Trevira Gmbh | Bioactive fiber products |
DE10243231B4 (en) * | 2002-09-17 | 2004-10-28 | Clariant Gmbh | Fire protection coating |
US20050164582A1 (en) * | 2002-11-18 | 2005-07-28 | Western Nonwovens, Inc. | High binder flame-retardant nonwovens |
KR20050037854A (en) * | 2003-10-20 | 2005-04-25 | 에스케이씨 주식회사 | Flame-retardant polyester film |
JPWO2005100650A1 (en) * | 2004-04-13 | 2008-03-06 | 株式会社カネカ | Flame retardant polyester artificial hair |
US8211542B2 (en) | 2004-09-07 | 2012-07-03 | Kaneka Corporation | Artificial hair made of flame-retardant polyester |
WO2006057228A1 (en) * | 2004-11-24 | 2006-06-01 | Toyo Boseki Kabushiki Kaisha | Flame-retardant polyester and process for producing the same |
KR100615781B1 (en) * | 2004-12-31 | 2006-08-25 | 주식회사 효성 | Polyester Fiber Having Excellent Light-Shielding and Flame Retardant Characteristic and Textile Goods Using the Same |
KR100615782B1 (en) * | 2004-12-31 | 2006-08-25 | 주식회사 효성 | Dope dyed flame retardant polyester fiber and textile products therefrom |
CN101104963B (en) * | 2006-07-12 | 2011-04-20 | 东丽纤维研究所(中国)有限公司 | Phosphor series polyester flame-proof fiber and producing method |
TW200831738A (en) | 2006-11-22 | 2008-08-01 | Hyosung Corp | Dope dyed flame retardant polyester fiber and blackout fabric produced therefrom |
KR100764378B1 (en) | 2006-11-22 | 2007-10-08 | 주식회사 효성 | Manufacturing method of flame retardant polyester polymer, polyester polymer and fiber therefrom |
KR101297912B1 (en) | 2006-12-08 | 2013-08-22 | 에스케이케미칼주식회사 | Flame retardant copolyester resin composition including 1,4-cyclohexanedimethanol and preparation method thereof |
CN101200820B (en) * | 2006-12-13 | 2010-05-19 | 中国石油天然气集团公司 | Method for preparing flame-proof polyester fiber |
EP2169110B1 (en) | 2008-09-25 | 2013-06-05 | Trevira Gmbh | Fire-resistant hollow fibres with silicon-free soft hand finish comprising a polyether and a condensation product of fatty acid |
DE102008055914A1 (en) * | 2008-11-05 | 2010-05-06 | Clariant International Limited | A process for the preparation of mono-hydroxy-functionalized dialkylphosphinic acids, esters and salts by means of acroleins and their use |
US9139714B2 (en) * | 2008-11-05 | 2015-09-22 | Clariant Finance (Bvi) Limited | Method for producing dialkylphosphinic acids and esters and salts thereof by means of allyl alcohols-acroleins and use thereof |
DE102008055916A1 (en) * | 2008-11-05 | 2010-05-06 | Clariant International Limited | Process for the preparation of mono-hydroxy-functionalized dialkylphosphinic acids, esters and salts by means of allyl alcohols and their use |
DE102008056234A1 (en) * | 2008-11-06 | 2010-05-12 | Clariant International Ltd. | Process for the preparation of momo-carboxy-functionalized dialkylphosphinic acids, esters and salts by means of vinyls / nitriles and their use |
US8664418B2 (en) * | 2008-11-07 | 2014-03-04 | Clariant Finance (Bvi) Limited | Method for producing dialkylphosphinic acids and esters and salts thereof by means of acrylic acid derivatives and use thereof |
DE102008056342A1 (en) * | 2008-11-07 | 2010-05-12 | Clariant International Limited | Process for the preparation of dialkylphosphinic acids, esters and salts by means of acrylonitriles and their use |
DE102008056339A1 (en) * | 2008-11-07 | 2010-05-12 | Clariant International Limited | Process for the preparation of mono-amino-functionalized dialkylphosphinic acids, esters and salts and their use |
DE102008056341A1 (en) * | 2008-11-07 | 2010-05-12 | Clariant International Limited | Process for the preparation of mono-amino-functionalized dialkylphosphinic acids, esters and salts by means of acrylonitriles and their use |
EP2367835B1 (en) | 2008-11-11 | 2013-12-11 | Clariant Finance (BVI) Limited | Process for preparing mono-allyl-functionalized dialkylphosphinic acids, salts and esters thereof with allylic compounds, and the use thereof |
DE102008060035A1 (en) * | 2008-12-02 | 2010-06-10 | Clariant International Limited | Process for the preparation of monohydroxy-functionalized dialkylphosphinic acids, esters and salts by means of vinyl esters of a carboxylic acid and their use |
DE102008060036A1 (en) * | 2008-12-02 | 2010-06-10 | Clariant International Limited | Process for the preparation of mono-carboxy-functionalized dialkylphosphinic acids, esters and salts by means of vinyl esters of a carboxylic acid and their use |
DE102008060535A1 (en) * | 2008-12-04 | 2010-06-10 | Clariant International Limited | Process for the preparation of mono-carboxy-functionalized dialkylphosphinic acids, esters and salts by means of vinyl ethers and their use |
DE102008063627A1 (en) | 2008-12-18 | 2010-06-24 | Clariant International Limited | Process for the preparation of monohydroxy-functionalized dialkylphosphinic acids, esters and salts by means of ethylene oxide and their use |
DE102008063642A1 (en) * | 2008-12-18 | 2010-06-24 | Clariant International Limited | Process for the preparation of monocarboxy-functionalized dialkylphosphinic acids, esters and salts by means of alkylene oxides and their use |
CN103724372B (en) | 2008-12-18 | 2017-03-01 | 科莱恩金融(Bvi)有限公司 | The purposes of ethylene alkyl phosphinic acid, ethylene alkyl phosphinates and ethylene alkyl phosphinate |
DE102008063668A1 (en) | 2008-12-18 | 2010-07-01 | Clariant International Limited | Process for the preparation of alkylphosphonic acids, esters and salts by oxidation of alkylphosphonous acids and their use |
DE102008064003A1 (en) | 2008-12-19 | 2010-06-24 | Clariant International Limited | Process for the preparation of monofunctionalized dialkylphosphinic acids, esters and salts and their use |
DE102008064012A1 (en) | 2008-12-19 | 2010-06-24 | Clariant International Limited | Halogen-free adducts of alkylphosphonous acid derivatives and diester-forming olefins, halogen-free processes for their preparation and their use |
DE102010007139A1 (en) | 2010-02-05 | 2011-08-11 | Mitsubishi Polyester Film GmbH, 65203 | Multilayer polyester film of high optical density with a total thickness of maximum 60 μm with two white layers and a soot-containing outer layer |
US9050785B2 (en) | 2010-02-05 | 2015-06-09 | Mitsubishi Polyester Film Gmbh | Multilayer polyester film with high optical density with a total thickness of max. 60 μm with two white outer layers and a carbon-black containing base layer |
DE102010007140A1 (en) | 2010-02-05 | 2011-08-11 | Mitsubishi Polyester Film GmbH, 65203 | Multilayer polyester film with a maximum thickness of 60 μm with two white outer layers and a soot-containing base layer with high optical density |
US9074407B2 (en) | 2010-02-05 | 2015-07-07 | Mitsubishi Polyester Film Gmbh | Multilayer polyester film with high optical density with a total thickness of max. 60 μm two white layers and a carbon-black containing outer layer |
DE102011114237A1 (en) | 2011-09-23 | 2013-03-28 | Trevira Gmbh | Pillarm polyester fiber |
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 |
DE102016200875A1 (en) | 2016-01-22 | 2017-07-27 | Mitsubishi Polyester Film Gmbh | Biaxially oriented, UV-stabilized, single or multi-layer polyester film with a combination of silicon dioxide particles as light scattering particles and a UV stabilizer as well as processes for their production and their use in greenhouse shade mats |
ES2792078T3 (en) | 2016-01-22 | 2020-11-10 | Svensson Ludvig Ab | Greenhouse display |
DK3462839T4 (en) | 2016-05-30 | 2023-06-06 | Svensson Ludvig Ab | ENERGY-SAVING GREENHOUSE SHIELDING |
DE102016209294A1 (en) | 2016-05-30 | 2017-11-30 | Mitsubishi Polyester Film Gmbh | Biaxially oriented, UV stabilized, single or multilayer polyester film with at least one antireflective coating on one side and a transparency of at least 93.5% |
EP3681268B1 (en) | 2017-09-14 | 2022-01-26 | AB Ludvig Svensson | Greenhouse screen |
TWI664203B (en) * | 2017-10-11 | 2019-07-01 | 遠東新世紀股份有限公司 | Flame-retardant polyester and preparation method thereof |
CN109749080B (en) * | 2018-12-26 | 2020-06-09 | 浙江新和成特种材料有限公司 | Semi-aromatic polyamide resin and preparation method thereof |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1196971A (en) | 1956-11-30 | 1959-11-27 | Hoechst Ag | Phosphorus polyesters and their preparation |
US3092606A (en) * | 1958-09-30 | 1963-06-04 | Bayer Ag | Flame-resistant unsaturated polyestervinylidene monomer reaction product containing the dimethyl ester of 2-hydroxyisopropyl-phosphonic acid |
US3169944A (en) * | 1959-02-18 | 1965-02-16 | Ici Ltd | Process for reacting a dialkyl ester of terephthalate acid with a glycol and polycondensing the product thereof |
DE1232348B (en) | 1958-11-05 | 1967-01-12 | Ici Ltd | Process for the production of polyesters |
US3853819A (en) * | 1972-07-22 | 1974-12-10 | Hoechst Ag | Flame resistant thermoplastic polyesters |
US3962194A (en) * | 1972-07-22 | 1976-06-08 | Hoechst Aktiengesellschaft | Polyesters containing structural units derived from phosphonic acids or estere |
US4033936A (en) * | 1974-11-15 | 1977-07-05 | Hoechst Aktiengesellschaft | Process for the manufacture of flame retarding linear polyesters |
-
1973
- 1973-09-17 DE DE2346787A patent/DE2346787C3/en not_active Expired
-
1974
- 1974-09-11 ES ES429952A patent/ES429952A1/en not_active Expired
- 1974-09-12 ZA ZA00745811A patent/ZA745811B/en unknown
- 1974-09-12 CH CH1243974A patent/CH571030A5/xx not_active IP Right Cessation
- 1974-09-12 NL NL7412116.A patent/NL167180C/en not_active IP Right Cessation
- 1974-09-13 US US05/505,686 patent/US3941752A/en not_active Expired - Lifetime
- 1974-09-13 IT IT27284/74A patent/IT1021374B/en active
- 1974-09-13 FI FI2685/74A patent/FI58784C/en active
- 1974-09-13 JP JP10511174A patent/JPS5313479B2/ja not_active Expired
- 1974-09-13 SU SU742060555A patent/SU850010A3/en active
- 1974-09-16 DD DD186157A patent/DD120208A5/xx unknown
- 1974-09-16 DD DD181121A patent/DD114827A5/xx unknown
- 1974-09-16 GB GB4028074A patent/GB1469349A/en not_active Expired
- 1974-09-16 CA CA209,323A patent/CA1037194A/en not_active Expired
- 1974-09-16 DK DK487074A patent/DK136158C/en not_active IP Right Cessation
- 1974-09-16 NO NO743328A patent/NO139351C/en unknown
- 1974-09-16 AT AT744474A patent/AT338529B/en not_active IP Right Cessation
- 1974-09-16 BR BR7703/74A patent/BR7407703D0/en unknown
- 1974-09-16 SE SE7411623A patent/SE415023B/en not_active IP Right Cessation
- 1974-09-16 LU LU70911A patent/LU70911A1/xx unknown
- 1974-09-16 IE IE1916/74A patent/IE40029B1/en unknown
- 1974-09-17 FR FR7431338A patent/FR2243958B1/fr not_active Expired
- 1974-09-17 BE BE148611A patent/BE820010A/en not_active IP Right Cessation
-
1978
- 1978-10-05 HK HK582/78A patent/HK58278A/en unknown
- 1978-12-30 MY MY435/78A patent/MY7800435A/en unknown
-
1980
- 1980-02-11 US US06/120,465 patent/USRE30783E/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1196971A (en) | 1956-11-30 | 1959-11-27 | Hoechst Ag | Phosphorus polyesters and their preparation |
US3092606A (en) * | 1958-09-30 | 1963-06-04 | Bayer Ag | Flame-resistant unsaturated polyestervinylidene monomer reaction product containing the dimethyl ester of 2-hydroxyisopropyl-phosphonic acid |
DE1232348B (en) | 1958-11-05 | 1967-01-12 | Ici Ltd | Process for the production of polyesters |
US3169944A (en) * | 1959-02-18 | 1965-02-16 | Ici Ltd | Process for reacting a dialkyl ester of terephthalate acid with a glycol and polycondensing the product thereof |
US3853819A (en) * | 1972-07-22 | 1974-12-10 | Hoechst Ag | Flame resistant thermoplastic polyesters |
US3962194A (en) * | 1972-07-22 | 1976-06-08 | Hoechst Aktiengesellschaft | Polyesters containing structural units derived from phosphonic acids or estere |
US4033936A (en) * | 1974-11-15 | 1977-07-05 | Hoechst Aktiengesellschaft | Process for the manufacture of flame retarding linear polyesters |
Non-Patent Citations (2)
Title |
---|
Henning, Chemical Abstracts, vol. 67:3124n (1967). * |
Khairullin et al., Chemical Abstracts, vol. 68:105, 302g (1968). * |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4517355A (en) | 1982-04-22 | 1985-05-14 | Anic S.P.A. | Flameproof linear polyester, a process for its preparation, and articles formed from said polyester |
US5102424A (en) * | 1989-06-30 | 1992-04-07 | Hoechst Aktiengesellschaft | Pigment printing process for flame-retardant, low-flammability or nonflammable fibers: polymer or copolymer of vinylidene chloride as pigment binder |
US5145941A (en) * | 1991-01-04 | 1992-09-08 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
US5151494A (en) * | 1991-01-04 | 1992-09-29 | Hoechst Celanese Corporation | Flame resistant, low pilling polyester fiber |
US5602212A (en) * | 1991-12-18 | 1997-02-11 | Enichem Synthesis S.P.A. | Linear copolyester containing phosphorous, procedure for its preparation and its use as a flame-retardant additive |
US5550207A (en) * | 1991-12-18 | 1996-08-27 | Enichem Synthesis S.P.A. | Linear copolyester containing phosphorous, procedure for its preparation and its use as a flame-resistant additive |
US5464694A (en) * | 1992-09-05 | 1995-11-07 | Hoechst Aktiengesellschaft | Spinnable polyester based on modified polyethylene terephthalate and aliphatic dicarboxylic acids |
US5374707A (en) * | 1993-02-18 | 1994-12-20 | Monsanto Company | Hydroxy ethyl bibenzoate |
US5847070A (en) * | 1993-02-18 | 1998-12-08 | Monsanto Company | Hydroxy ethyl bibenzoate |
US5399429A (en) * | 1994-03-11 | 1995-03-21 | Monsanto Company | Flame retardant recycled polyester copolymers |
US5399428A (en) * | 1994-03-11 | 1995-03-21 | Monsanto Company | Flame retardant polyester copolymers |
US5703134A (en) * | 1994-03-11 | 1997-12-30 | Monsanto Company | Copolymers of recycled polyester |
US20060110613A1 (en) * | 2004-11-24 | 2006-05-25 | Toray Plastics (America), Inc. | Flame retardant metallized polyester films having anti-dripping properties |
WO2024146954A1 (en) | 2023-01-08 | 2024-07-11 | Indorama Ventures Public Company Limited | Flame retardant copolymer with one or more non-virgin fossil components and methods of making the same |
Also Published As
Similar Documents
Publication | Publication Date | Title |
---|---|---|
USRE30783E (en) | Flame retarding linear polyesters and shaped articles thereof | |
US3962194A (en) | Polyesters containing structural units derived from phosphonic acids or estere | |
US4033936A (en) | Process for the manufacture of flame retarding linear polyesters | |
US4127590A (en) | Phosphorus-containing compounds | |
US4157436A (en) | Phosphorus-containing polyesters | |
US3900444A (en) | Flame resistant thermoplastic polyesters | |
KR100404666B1 (en) | Flame Retardant Polyester Copolymer | |
US4035343A (en) | Flame resistant synthetic linear polyesters and shaped structures made thereof | |
US3794617A (en) | Copolyester fiber compositions having improved flame retardant properties | |
US3932351A (en) | Method of preparing phosphorus-bromine containing fire retardant polyester fibers | |
US3412070A (en) | Fibers of a terephthalate/ethylene glycol polyester containing less than 0.5 percent by weight of phosphorus incorporated therein by phosphonic acid ester linkages | |
US4087408A (en) | Bromine and phosphorus containing polyester | |
US3853819A (en) | Flame resistant thermoplastic polyesters | |
US4094926A (en) | Polymeric phosphorus compounds and flame retardant polyethyleneterephthalate containing said polymers | |
US4104259A (en) | Fireproof polyesters from brominated dihydroxy alkoxy-diphenyl sulfones | |
US3931099A (en) | Fire retardant polyester fibers | |
US4028330A (en) | Fire retardant polyester fibers | |
US3849522A (en) | Bis((1-oxo-2,6,7-trioxa-1-phospha bicyclo(2.2.2)oct-4-yl)methyl)2,5 dibromoterephthalate | |
US3947423A (en) | Polyesters containing bicyclic phosphate flame retardant | |
US4181646A (en) | Phosphorus-containing flame retardant compositions | |
US4210740A (en) | Copolyesters prepared from phosphorus compounds which can be shaped and which have reduced flammability | |
KR950002610B1 (en) | Method of producing polyester-composition | |
JPH09510245A (en) | Flame-retardant recycled polyester composition | |
JP3051586B2 (en) | Flame retardant polyester copolymer | |
US3879351A (en) | Flame-resistant high molecular weight linear polyesters |