CN101186689A - Manufacturing method of flame retardant polyester polymer, polyester polymer and fiber therefrom - Google Patents
Manufacturing method of flame retardant polyester polymer, polyester polymer and fiber therefrom Download PDFInfo
- Publication number
- CN101186689A CN101186689A CNA2007101871866A CN200710187186A CN101186689A CN 101186689 A CN101186689 A CN 101186689A CN A2007101871866 A CNA2007101871866 A CN A2007101871866A CN 200710187186 A CN200710187186 A CN 200710187186A CN 101186689 A CN101186689 A CN 101186689A
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- Prior art keywords
- flame retardant
- polymkeric substance
- amount
- oligopolymer
- phosphorus
- Prior art date
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- 229920000728 polyester Polymers 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- 229920000642 polymer Polymers 0.000 title claims abstract description 35
- 239000000835 fiber Substances 0.000 title claims abstract description 29
- 239000003063 flame retardant Substances 0.000 title claims description 122
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 86
- 239000000126 substance Substances 0.000 claims abstract description 79
- 238000000034 method Methods 0.000 claims abstract description 57
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 150000002696 manganese Chemical class 0.000 claims abstract description 22
- 239000012963 UV stabilizer Substances 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 128
- 229910052698 phosphorus Inorganic materials 0.000 claims description 49
- 239000011574 phosphorus Substances 0.000 claims description 49
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 35
- 238000006068 polycondensation reaction Methods 0.000 claims description 25
- 239000002002 slurry Substances 0.000 claims description 21
- 238000005886 esterification reaction Methods 0.000 claims description 20
- 230000032050 esterification Effects 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 17
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- -1 alicyclic diol Chemical class 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 150000001263 acyl chlorides Chemical class 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 150000001261 hydroxy acids Chemical group 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 238000009987 spinning Methods 0.000 description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 230000000704 physical effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229940071125 manganese acetate Drugs 0.000 description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000002085 persistent effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 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
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QPKOBORKPHRBPS-UHFFFAOYSA-N bis(2-hydroxyethyl) terephthalate Chemical compound OCCOC(=O)C1=CC=C(C(=O)OCCO)C=C1 QPKOBORKPHRBPS-UHFFFAOYSA-N 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000010036 direct spinning Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 230000000176 photostabilization Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000000326 ultraviolet stabilizing agent Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
-
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- 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
- C08G63/78—Preparation processes
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
-
- 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
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/59—Stability
- C08G2261/594—Stability against light, i.e. electromagnetic radiation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/78—Stabilisers against oxidation, heat, light or ozone
- C08L2666/82—Phosphorus-containing stabilizers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/66—Substances characterised by their function in the composition
- C08L2666/84—Flame-proofing or flame-retarding additives
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
The invention discloses a method for producing a flame-resistance polymer through the following steps: a phosphor-series flame-resistance agent expressed in the following chemical formula I is added into the second esterifying reaction process so that the phosphor quantity in the phosphor-series flame-resistance agent is 500ppm to 50000ppm relative to the quantity of the polymer; and manganese salt and phosphor-included compound (both are UV stabilizers) are added into the second esterifying reaction process so that the quantities of Mg and phosphor in the manganese salt and phosphor-included compound are both 0.1ppm to 500ppm. The invention also discloses a polyester polymer produced through the method, and a polyester fiber produced through the polyester polymer. The polyester polymer and the polyester fiber both have a permanent flame-resistance property and an excellent UV stability.
Description
Technical field
The present invention relates to a kind of polymkeric substance and fiber of making the method for polyester polymers and using this method to make, more particularly, the present invention relates to make the method for flame-retardant polymer: in second esterification reaction process, add the represented phosphorus flame retardant of following Chemical formula 1 by following step, make that the amount of the phosphorus in the above-mentioned phosphorus flame retardant is 500ppm～50000ppm with respect to the amount of polymkeric substance, add manganese salt and P contained compound (they are UV stabilizer) then, make the manganese in above-mentioned manganese salt and the P contained compound and the amount of phosphorus be 0.1ppm～500ppm; The polyester fiber that the invention still further relates to the polyester polymers that uses this method manufacturing and use this polyester polymers to make.
Background technology
Usually, polyester (particularly polyethylene terephthalate (hereinafter being called " PET ")) is widely used in fiber, film, engineering plastics etc. owing to having excellent mechanical property and favorable chemical resistance.Yet the weak point of the polyester of this routine is its easy burning.In recent years, law is strictly stipulated dry goods (as cloth for baby etc.) and technical fabric (such as automobile with sheet material, curtain, carpet etc.).Therefore, for the fp purpose, the demand of fire-retardant fibre is strengthened.
The method of giving the polyester fiber flame retardant properties is following listed.At first, there is the method for using fire retardant to handle fiber surface.This method is favourable aspect production cost, but has problems aspect weather resistance.Secondly, a kind of like this method is arranged: fire retardant material is added in the fiber, when spinning, this fiber is carried out spinning then.This method comprises: with fire retardant material (being fire retardant) and fiber blend, fiber is carried out the method for spinning and with flame-retardant master batch (containing excessive fire retardant) blend, this masterbatch is carried out the method for spinning then then.In these two kinds of methods, the problem of the method for front is that spinning property reduces, and also variation of the physicals of raw yarn, and the problem of the method for back is to be difficult for flame-retardant master batch is formed the polymkeric substance with desired physical properties (for example viscosity, color etc.).The 3rd, also there is a kind of like this method: fire retardant material is added in the fiber, when polymerization, make fire retardant material and fiber carry out copolymerization then.The advantage of this method is that weather resistance is good, and is similar to the ordinary method of making polyester.In above-mentioned the third method (it is a method of making flame retardant polyester by copolyreaction), mainly use halogenated flame retardant (particularly bromine (Br) flame retardant) and phosphorus (P) flame retardant.
Japanese unexamined patent open No.Sho62-6912, Sho53-46398 and Sho51-28894 disclose bromide fire retardant.Herein, because therefore bromine-containing compound pyrolysis easily at high temperature must add a large amount of fire retardants to obtain effective flame retardant properties.The result produces the tone deterioration of polymkeric substance, photostabilization reduces and produce toxic gas when burning problem.
In addition, U.S. Patent No. 3,941,752,5,399,428 and 5,180,793 and the open No.Sho50-56488 of Japanese unexamined patent and Sho52-47891 disclosed phosphorus flame retardant.As the result that the inventor tests the physicals of the flame retardant polyester that uses this phosphorus flame retardant manufacturing, find that the physicals of the flame retardant polyester of manufacturing greatly reduces.In addition, use phosphorus flame retardant to make in the method for PET at great majority, have such problem: with by making the method for PET and compare, by to make the cost of method of PET higher to carry out polymerization as the dimethyl terephthalate (DMT) (hereinafter being called " DMT ") of raw material to carry out polymerization as the terephthalic acid (hereinafter being called " TPA ") of raw material.
Summary of the invention
[technical problem that will solve]
Therefore, consider the problems referred to above of the prior art and obtain the present invention, and the purpose of this invention is to provide the manufacture method of polyester polymers with persistent flame retardant properties and good UV (ultraviolet ray) stability.
The polyester fiber that another object of the present invention provides the polyester polymers that uses this method manufacturing and uses this polyester polymers to make.
[technical scheme]
In order to achieve the above object, one aspect of the present invention provides the method for using terephthalic acid to make the flame retardant polyester polymkeric substance, and this method may further comprise the steps: use the terephthalic acid (TPA) and ethylene glycol (EG) the preparation slurry that are reactant; Described slurry is added in first esterifier, thereby form oligopolymer by first esterification; Through following step, prepare fire-retardant oligopolymer: will add in second esterifier by the described oligopolymer that first esterification forms by second esterification, to wherein adding the phosphorus flame retardant that following Chemical formula 1 is represented, make that the amount of the phosphorus in the above-mentioned phosphorus flame retardant is 500ppm～50000ppm with respect to polyester polymers, then to wherein adding manganese salt and P contained compound (they all are UV stabilizer), make the manganese in above-mentioned manganese salt and the P contained compound and the amount of phosphorus be 0.1ppm～500ppm; And, will add in the polycondensation reactor by the oligopolymer of described second esterification preparation, in this polycondensation reactor, make this oligopolymer polycondensation then.
Wherein, R
1Be hydrogen or hydroxyalkyl with 1 to 10 carbon atom, R
2Be hydrogen or have the alkyl of 1 to 10 carbon atom or have the aryl of 6 to 24 carbon atoms, and R
3Be hydrogen or have the alkyl or the hydroxyalkyl of 1 to 10 carbon atom or be used to form the functional group of ester.
Description of drawings
Fig. 1 is the schematic process diagram according to embodiment of the present invention.
The explanation of each parts in the＜accompanying drawing 〉
1: the pulp preparation device
2: the slurry storage tank
3: the first esterifiers (DE-1)
4: the first strainers
5: the second esterifiers (DE-2)
6: the second strainers
7: polycondensation reactor
8: tablets press
Embodiment
Hereinafter, describe the present invention with reference to the accompanying drawings.
Fig. 1 is the indicative flowchart according to embodiment of the present invention.With reference to Fig. 1, slurry preparation step is to use the step of the terephthalic acid and the ethylene glycol slurry that are reactant in pulp preparation device 1.In slurry preparation step, can be provided with the slurry storage tank 2 that is used to store prepared slurry.
First step of esterification is to add described slurry to first esterifier, and uses this slurry to form the step of oligopolymer.First esterifier 3 contains basic oligopolymer (it is a product) always.Can in the transfer lime that is used for the oligopolymer that first esterifier 3 forms is transferred in second esterifier 5, first strainer 4 be set.Strainer 4 can be basket filter.
Second step of esterification is that the oligopolymer that will form in first step of esterification is transferred in second esterifier 5 and forms the step of fire-retardant oligopolymer.In second step of esterification, add the phosphorus flame retardant that following Chemical formula 1 is represented, thereby make that the amount of the phosphorus in the above-mentioned phosphorus flame retardant is 500ppm～50000ppm with respect to the amount of polyester polymers, and add manganese salt and P contained compound, thereby make the manganese in above-mentioned manganese salt and the P contained compound and the amount of phosphorus be 0.1ppm～500ppm.
Can in the transfer lime that is used for the oligopolymer that second esterifier 5 forms is transferred in the polycondensation reactor 7, second strainer 6 be set.Strainer 6 can be basket filter.
Condensation polymerization step is to shift oligopolymer that forms in second step of esterification and the step that makes the oligopolymer generation polycondensation that is changed under high vacuum condition.
The polymer formation that herein can be provided for manufacturing is the tablets press 8 of bits sheet.
Prepare through the following steps that the method for the oligopolymer of bishydroxyethyl terephthalate and oligomerization thereof is known in the art: make terephthalic acid (TPA) and ethylene glycol (EG) direct reaction, under high vacuum condition, make them carry out polycondensation then as reactant.Yet, in order to make polyester polymers with persistent flame retardant properties, the invention provides a kind of method of making the flame retardant polyester polymkeric substance, this method comprises the steps: to add the phosphorus flame retardant that above-mentioned Chemical formula 1 is represented in second step of esterification, and in second esterification reaction process, add manganese salt and P contained compound (it is ultra-violet stabilizer), make the manganese in above-mentioned manganese salt and the P contained compound and the amount of phosphorus be 0.1ppm～500ppm with respect to polyester polymers.
To constitute characteristic of the present invention below and be explained in more detail.
1. selection of fire retardant
Result as physical property (as, fire-retardant behavior of environmental hazard, flame retardant properties, polymerization process, production cost, flame-retardant yarn etc.) is considered generally determines that the phosphorus flame retardant of above-mentioned chemical formulation is suitable as fire retardant of the present invention.
Because phosphorus flame retardant comprises a large amount of phosphorus with respect to its molecular weight, so it can show sufficient flame retardant effect, and also is favourable from the angle of processing stability.In addition, compare with the fire retardant with phosphorus phenanthryl group of routine, because described phosphorus flame retardant has more a spot of aromatic group, so it produces more a spot of cigarette and poison gas.
2. determine to be included in the amount of the phosphorus flame retardant in the polymkeric substance
The inventor has carried out the phosphorus flame retardant that adds is determined in various tests in polymkeric substance amount.Found that no matter the structure of the phosphorus flame retardant represented of above-mentioned Chemical formula 1 how, the amount of the phosphorus in the phosphorus flame retardant that adds is preferably 500ppm～50000ppm in polymkeric substance.Particularly, consider the manufacturing of polymerization process performance and raw yarn, the amount of phosphorus of finding the phosphorus flame retardant added is with respect to the amount of polymkeric substance 1000ppm～20000ppm more preferably.When the amount of phosphorus flame retardant is lower than 500ppm with respect to polymkeric substance, can not expect to obtain required flame retardant effect.On the other hand, when the amount of phosphorus flame retardant is higher than 50, during 000ppm, be difficult for making the polyester height polymerization of manufacturing, and be difficult for making the polyester of manufacturing to form fiber, this is that this is disadvantageous because the crystallinity of the polyester of manufacturing excessively reduces.
3. the method that phosphorus flame retardant is added reactor
The method that adds the represented phosphorus flame retardant of above Chemical formula 1 to reactor is difference along with the difference of phosphorus flame retardant state.When the represented phosphorus flame retardant of above Chemical formula 1 is solid, its form with ethylene glycol (EG) solution or ethylene glycol (EG) disperse phase can be added in the reactor.In addition, when the represented phosphorus flame retardant of above Chemical formula 1 is liquid, it directly can be added in the reactor, perhaps the form with the mixing solutions of EG and phosphorus flame retardant adds in the reactor.Wherein, when adding in reactor with the form of ethylene glycol (EG) solution or ethylene glycol (EG) disperse phase phosphorus flame retardant, preferably the amount of EG meets following mathematical expression 1:
0.2*FR(g)*(FN
FR*62)/(MW
FR)*(1+α)≤EG(g)
≤ 3*FR (g) * (FN
FR* 62)/(MW
FR) * (1+ α)-------mathematical expression 1,
Wherein, FR is a fire retardant, FN
FRBe the quantity of 1 mole of hydroxy-acid group in the fire retardant, MW
FR(g/ mole) is the molecular weight of fire retardant, and α is constant, and when fire retardant was solid, α was 1, and when fire retardant was liquid, α was 0.
The reactive ratio of the oligopolymer in transferring to second esterifier is 95% or when higher, the acid number of oligopolymer is lower, can be left in the basket thus.On the other hand, when its reactive ratio is lower than 95%, must add the corresponding EG of acid number with oligopolymer, and the amount of the EG that is added can meet following mathematical expression 2 according to the acid number of oligopolymer.
AV
Oligopolymer* 31/1000≤EG (g)≤AV
Oligopolymer* the 62/1000------mathematical expression 2,
Wherein, AV
OligopolymerBe the acid number of oligopolymer, and the unit of acid number is (KOH equivalents)/(a 1kg polymkeric substance).
The amount (g) of the EG that is added when adding fire retardant is lower than FR (g) * (FN
FR* 62)/(MW
FR) during * (1+ α), the viscosity of fire retardant increases, difficult like this fire retardant is added in the reactor, and be difficult for making the fire retardant esterification.On the other hand, the amount (g) of the EG that is added when adding fire retardant is greater than FR (g) * (FN
FR* 62)/(2*MW
FR) during * (1+ α), though can be easily to wherein adding fire retardant, DEG can produce more and more, and thermotolerance reduces thus.
4. adjust the amount of glycol ether (hereinafter being called " DEG ")
Using TPA to make in the method for polyester polymers, when the amount of DEG increases, there is the problem of the thermotolerance decline of polymkeric substance.Owing to the increase along with the acidity of reactant of the generation of DEG improves, therefore need to reduce the method for its acidity.
In order to reduce acidity, the inventor has carried out basic material is added test in second esterifier 5 shown in Figure 1, or carries out to the test that wherein adds the P contained compound that above Chemical formula 1 represents.As a result, they find that the test of back is favourable when considering quality stability.Yet what do not exceed the scope of the invention is that imagination adds basic material in first esterifier 3 or second esterifier, perhaps basic material is added in the represented P contained compound of above Chemical formula 1.
Under the P contained compound that above Chemical formula 1 is represented will be gone into situation in second esterifier 5 (as shown in fig. 1), preferably, the amount of the relative polymkeric substance of DEG is reduced to 3.0 weight %, keep constant then, the physicals that suppresses the polyester polymers of manufacturing thus descends, and successfully carry out spinning, false twisting, dyeing etc., and and no problem.
When the P contained compound that above Chemical formula 1 is represented adds the slurry storage tank 2 or first esterifier 3, have such problem: the acidity of reactant increases, and the amount of DEG constantly increases thus.
5. selection UV stabilizer
Because the flame retardant polyester series fiber is used for interior finish product (as, curtain), therefore requirement has UV stable.So the inventor has studied UV stable.Usually with organic stabilizer and inorganic stabilizers as UV stabilizer, but the inventor have been found that and consider effect and cost, the most suitable with manganous phosphate as UV stabilizer.
Yet find that because manganous phosphate is insoluble to EG, therefore, when directly manganous phosphate being added reaction system, it condenses, the result forms a large amount of impurity in polymkeric substance, thereby increases dwell pressure when spinning.Therefore, the inventor tests the various methods that form the manganese compounds in polymerization system.As a result, they find can address the above problem by adding manganese salt and P contained compound respectively.
In addition, the amount of the manganese in the manganese salt (it is as UV stabilizer) can be 0.1ppm～500ppm, more preferably 0.2ppm to 200ppm with respect to the amount of polymkeric substance.When the amount of the manganese in the manganese salt is lower than 0.1ppm, be difficult to obtain required UV stable.On the contrary, when the amount of the manganese in the manganese salt is higher than 500ppm, the dispersed reduction, therefore dwell pressure increases when spinning.
In addition and the manganese salt amount that adds phosphorus in the P contained compound in the polymkeric substance together can be 0.1ppm～500ppm, more preferably 0.2ppm to 200ppm with respect to polymkeric substance.As long as the reaction of P contained compound and manganese salt is no problem, just can add P contained compound.Yet when the amount of P contained compound was higher than 500ppm, activity of such catalysts reduced, so polymerization process decline.
6. the other comonomer that adds
Usually use comonomer to give multiple function to polyester polymers.According to the present invention, can also use comonomer to give multiple function for the flame retardant polyester polymkeric substance.Operable in the present invention comonomer comprises dicarboxylic acid and can form the derivative and the glycol of ester.
Dicarboxylic acid and the derivative that can form ester thereof can comprise: aromatic dicarboxylic acid, and as m-phthalic acid, biphenyl dicarboxylic acid, 2,6-naphthalic acid, 1,5-naphthalic acid etc. and can form the derivative of ester; The alicyclic dicarboxylic acid is as 1,4 cyclohexanedicarboxylic acid etc.; With alkyl dicarboxylic aid and can form derivative or its acyl chlorides of ester with 2 to 6 carbon atoms.
Wherein, for the economical efficiency and the physicals of not obvious reduction flame retardant polyester polymkeric substance, terephthalic acid can be 70% or higher with the mol ratio of whole dicarboxylic acid.When their mol ratio was lower than 70%, the fusing point of flame retardant polyester polymkeric substance or second-order transition temperature descended, so its moldability has problems, and perhaps in addition, when using expensive comonomer, its production cost excessively increases.
Glycol can comprise: alkanediol, and as 1,2-propylene glycol, 1, ammediol, 1,3 butylene glycol, 1,5-pentanediol, 1,6-hexylene glycol etc.; Alicyclic diol, as 1,4-cyclohexanediol, 1,4 cyclohexane dimethanol etc.; Aromatic diol is as dihydroxyphenyl propane, bisphenol S etc.; And the oxyethane of aromatic diol or propylene oxide adduct.Wherein, in order suitably to show the physicals of flame retardant polyester polymkeric substance, ethylene glycol can be 70% with the mol ratio of whole polymer diols.
7. be used for improving the mol ratio of reactive glycol (comprising EG) Yu the dicarboxylic acid (comprising TPA) of reactor
The mol ratio of glycol and dicarboxylic acid (glycol/dicarboxylic acid) can be 1.01 to 2.0.When its mol ratio less than 1.01 the time, have such problem owing to can not successfully carry out the esterification of glycol and dicarboxylic acid, so reactive ratio is lower; Because a large amount of unreacted dicarboxylic acid are retained in the reactor, the time of therefore changing strainer in polymerization process shortens; And because residual unreacted dicarboxylic acid plays the effect of impurity, optical property (for example transparency, mist degree etc.) descends, and dwell pressure increases fast in polymerization process.On the other hand, when mol ratio greater than 2.0 the time, have such problem, owing to exceeded the ability of reflux, therefore, processing characteristics reduces, and owing to form the DEG of the thermotolerance decline that causes polymkeric substance and product in a large number, so the aftertreatment of polymkeric substance becomes difficult.
8. polycondensation catalyzer
Can will be used for the catalyzer of normal polyester polyreaction as the polycondensation catalyzer.The compound (for example ANTIMONY TRIOXIDE SB 203 99.8 PCT, Antimony Triacetate etc.) of antimony and the compound of titanium (for example four butyric acid titaniums, four isopropyl acid titaniums etc.) can be used for the polycondensation catalyzer.
The amount of the metal in the polycondensation usefulness catalyzer can be 10ppm～1000ppm with respect to the amount of polymkeric substance.When its amount was lower than 10ppm, activity of such catalysts was low excessively.On the other hand, when its amount was higher than 1000ppm, catalyzer caused that impurity forms, and the cost of making polyester polymers is increased.
9. additive
In order to make the flame retardant polyester polymkeric substance, can add various additives according to the purposes of flame retardant polyester polymkeric substance.Specifically, in order to improve the tone of polyester polymers, can be with inorganic metal salt (for example Cobaltous diacetate etc.) and pigment dyestuff as tinting material.In addition, for polyester polymers is used for fiber, can be to the titanium dioxide that wherein adds 100ppm～30000ppm, perhaps to silicon-dioxide that wherein adds 100ppm～30000ppm and barium sulfate.The addition of inorganic additives and addition means thereof can be respectively common addition and the conventional addition means when normal polyester is used for fiber usually.
Hereinafter, with reference to example the present invention is explained in more detail.But the present invention is not limited to these examples.
Before describing example, will the method for evaluating performance of the fiber that provided in the test be described.
Limiting viscosity (IV): after fiber being dissolved in phenol and sym.-tetrachloroethane mixes the solution that forms with 6: 4 weight ratio, use Ubbelohde viscometer to measure its limiting viscosity.
Fusing point (Tm): the differential scanning calorimeter (DSC-7) that uses Perkin Elmer company to make is measured fusing point.
DEG: after making polymer unwinds, use vapor-phase chromatography to analyze DEG with trolamine.
The color of polymkeric substance: use automatic colour difference meter to measure L, a and b value.
UV stable: with estimating UV stable: the polymkeric substance of manufacturing is placed on the sheet glass through the limiting viscosity conservation rate after the following step, be exposed to 48 hours (QUV that uses Q-Panel company to make) in the ultraviolet ray, measure its limiting viscosity then.
(limiting viscosity after initial intrinsic viscosity-aftertreatment)/initial intrinsic viscosity * 100
Flame retardant properties: estimate flame retardant properties by measuring establishment fiber limiting oxygen index(LOI) (LOI) afterwards.
Use the TPA of 1300kg and the EG of 560kg to prepare slurry.Prepared slurry is added in the DE-1 reactor 3 (wherein, when the temperature with DE-1 reactor 3 remains under 260 ℃ the temperature, 1.5 tons of bishydroxyethyl terephthalates and low-molecular-weight oligomer thereof being stirred 3 hours under 260 ℃ temperature).With the backflow of slurry that adds in it, and stirred simultaneously 30 minutes, the esterification yield of slurry reaches 97% thus.In prepared oligopolymer, 1.5 tons of oligopolymer are stayed in the DE-1 reactor 3, and remaining oligopolymer is transferred in the DE-2 reactor 5.At room temperature, with 68kg by above Chemical formula 1 (R wherein
1Be hydrogen, R
2Be phenyl, R
3Being hydrogen) fire retardant and the 68kg EG of expression mix, and add in the DE-2 reactor 5 and go.In addition, manganese acetate (it is the manganese salt that is used for preparing UV stabilizer) is added DE-2 reactor 5, make that the amount of the manganese in the manganese acetate is 22ppm with respect to the amount of polymkeric substance; In it, add phosphoric acid (its for P contained compound), make that the amount of the phosphorus in the phosphoric acid is 100ppm with respect to the amount of polymkeric substance; And in it, add titanium dioxide (it is used as matting agent), make that the amount of titanium dioxide is 0.3 weight % with respect to the amount of polymkeric substance, then these additives are stirred under 260 ℃ temperature.Subsequently, the oligopolymer that all are stored in the DE-2 reactor 5 is transferred in the polycondensation reactor.Then 200g ANTIMONY TRIOXIDE SB 203 99.8 PCT solution (wherein, ANTIMONY TRIOXIDE SB 203 99.8 PCT is dissolved among the EG with the concentration of 2 weight %) is added in the polycondensation reactor.Subsequently, products therefrom is carried out polycondensation by the polycondensation of polyester method of routine, thereby make the flame retardant polyester polymkeric substance.Use identical method to repeat to make the flame retardant polyester polymkeric substance five times, and table 1 provide the mean value and the scope of analytical results of the flame retardant polyester polymkeric substance of manufacturing.
Comparative Examples 1
Use 68kg by above Chemical formula 1 (R wherein
1Be hydrogen, R
2Be phenyl, R
3Be hydrogen) expression fire retardant, 1300kg TPA and 560kg EG prepare slurry.Prepared slurry is added in the DE-1 reactor 3 (wherein, when the temperature with DE-1 reactor 3 remains under 260 ℃ the temperature, will using the oligopolymer (as polymkeric substance) of above-mentioned identical component preparation to stir 3 hours under 260 ℃ temperature).With the backflow of slurry that adds in it, and stirred simultaneously 30 minutes, the esterification yield of slurry reaches 96.7% thus.In prepared oligopolymer, 1.5 tons of oligopolymer are stayed in the DE-1 reactor 3, and remaining oligopolymer is transferred in the DE-2 reactor 5.Subsequently, manganese acetate (it is the manganese salt that is used for preparing UV stabilizer) is added DE-2 reactor 5, make that the amount of the manganese in the manganese acetate is 22ppm with respect to the amount of polymkeric substance; In it, add phosphoric acid (its for P contained compound), make that the amount of the phosphorus in the phosphoric acid is 30ppm with respect to the amount of polymkeric substance; And in it, add titanium dioxide (it is used as matting agent), make that the amount of titanium dioxide is 0.3 weight % with respect to the amount of polymkeric substance, then these additives are stirred under 260 ℃ temperature.Subsequently, the oligopolymer that all are stored in the DE-2 reactor 5 is transferred in the polycondensation reactor.Then 200g ANTIMONY TRIOXIDE SB 203 99.8 PCT solution (wherein, ANTIMONY TRIOXIDE SB 203 99.8 PCT is dissolved among the EG with the concentration of 2 weight %) is added in the polycondensation reactor.Subsequently, products therefrom is carried out polycondensation by the polycondensation of polyester method of routine, thereby make the flame retardant polyester polymkeric substance.Use identical method to repeat to make the flame retardant polyester polymkeric substance five times, and table 1 provide the mean value and the scope of analytical results of the flame retardant polyester polymkeric substance of manufacturing.
By table 1 as seen, the variation of the amount of DEG is bigger, so the variation of fusing point is also bigger.
Use the method manufacturing flame retardant polyester polymkeric substance identical with embodiment 1, difference is phosphorus flame retardant and EG were reacted 4 hours under 190 ℃ temperature, adds then in the DE-2 reactor.
Use the method manufacturing flame retardant polyester polymkeric substance identical with embodiment 1, difference is phosphorus flame retardant and EG were reacted 4 hours under 190 ℃ temperature, adds in the polycondensation reactor then.
Comparative Examples 2
Use the method manufacturing flame retardant polyester polymkeric substance identical with embodiment 1, difference is 68kg by above Chemical formula 1 (R wherein
1Be hydrogen, R
2Be phenyl, R
3Being hydrogen) fire retardant of expression with under the EG blended state adds in second esterifier (DE-2 reactor) separately at it.
Use the method manufacturing flame retardant polyester polymkeric substance identical with embodiment 1, difference is to add 82kg by above Chemical formula 1 (R wherein
1Be hydrogen, R
2Be phenyl, R
3Be hydroxyethyl (CH
2CH
2OH)) Biao Shi fire retardant.
Comparative Examples 3
Use the method manufacturing flame retardant polyester polymkeric substance identical with embodiment 1, difference is not use manganese salt and P contained compound.
Use vacuum drier with dry 24 hours of the flame retardant polyester polymkeric substance made among the embodiment 2.Subsequently, use internal diameter the polyester polymers of drying to be extruded under 280 ℃ spinning temperature as the forcing machine of 95mm, (it is heated to 80 ℃ to use the first seal wire rod then, and rotating speed is 1350m/ minute) and the second seal wire rod (it is heated to 120 ℃, and rotating speed is 4100m/ minute), by the direct spinning stretching method polyester polymers of extruding is formed the fiber of 75 dawn/72 rhizoids.It is knitting and weave that the fiber of manufacturing is carried out sebific duct, estimates its limiting oxygen index(LOI) (LOI) then.LOI is 32, therefore shows excellent flame-retardant.
Table 1
| | Embodiment | 1 | Comparative Examples 1 | |
|
Comparative Examples 2 | |
Comparative Examples 3 |
| Time | 190/9 | 190/16 | 185/10 | 200/12 | 185/14 | 190/8 | 190/10 | |
| IV | 0.645/0.015 | 0.636/0.045 | 0.639/0.011 | 0.635/0.018 | 0.63 8/0.021 | 0.643/0.013 | 0.646/0.015 | |
| DEG | 2.1/0.3 | 3.8/3.2 | 2.3/0.3 | 1.8/0.4 | 3.1/0.9 | 2.4/0.4 | 2.1/0.4 | |
| Temperature (℃) | 242/1.8 | 239/11.7 | 237/1.6 | 244/1.9 | 235/2.2 | 238/2.7 | 242/2.0 | |
| IV conservation rate (%) | 97/0.3 | 97/0.4 | 96/0.4 | 96/0.3 | 96/0.4 | 97/0.3 | 88/0.2 |
(representing scope=maximum value-minimum value with mean value/scope)
*Time (minute) be polycondensation reaction time, this time is from adding the time of catalyzer when polycondensation is finished.
*2.IV be limiting viscosity, and its unit is the dl/ gram.
*3.DEG: unit is weight %.
By table 1 as seen, the amount of DEG in an embodiment remains 3% weight or lower, and the amount of the DEG in the Comparative Examples 3 is 3% weight or lower.Yet owing to do not add manganese salt and P contained compound, the limiting viscosity conservation rate significantly reduces.
[beneficial effect]
Flame retardant polyester polymer and use the polyester fiber of this flame retardant polyester polymers manufacturing to have the fire resistance of good color harmony excellence, and when they form final products in spinning process, show excellent UV stable.
Claims (8)
1. method of using terephthalic acid to make the flame retardant polyester polymkeric substance, this method comprises:
Use prepares slurry as the terephthalic acid (TPA) and the ethylene glycol (EG) of reactant;
Described slurry is added in first esterifier, thereby form oligopolymer by first esterification;
Through following step, prepare fire-retardant oligopolymer: will add in second esterifier by the described oligopolymer that described first esterification forms by second esterification, to wherein adding the phosphorus flame retardant that following Chemical formula 1 is represented, make that the amount of the phosphorus in the described phosphorus flame retardant is 500ppm～50000ppm with respect to polyester polymers, then to wherein adding manganese salt and the P contained compound be UV stabilizer, make the manganese in described manganese salt and the described P contained compound and the amount of phosphorus be 0.1ppm～500ppm; And,
To add in the polycondensation reactor by the described oligopolymer of described second esterification preparation, in this polycondensation reactor, make described oligopolymer polycondensation then,
Wherein, R
1Be hydrogen or hydroxyalkyl with 1 to 10 carbon atom, R
2Be hydrogen or have the alkyl of 1 to 10 carbon atom or have the aryl of 6 to 24 carbon atoms, and R
3Be hydrogen or have the alkyl or the hydroxyalkyl of 1 to 10 carbon atom or be used to form the functional group of ester.
2. the method for manufacturing flame retardant polyester polymkeric substance according to claim 1, wherein the amount of glycol ether (DEG) remains 3 weight % or lower with respect to the amount of polyester polymers.
3. the method for manufacturing flame retardant polyester polymkeric substance according to claim 1 wherein adds fashionablely when the described phosphorus flame retardant that above Chemical formula 1 is represented with the form of solution or disperse phase, the amount of ethylene glycol (EG) meets following mathematical expression 1:
0.2*FR(g)*(FN
FR*62)/(MW
FR)*(1+α) ≤EG(g)
≤ 3*FR (g) * (FN
FR* 62)/(MW
FR) * (1+ α)-------mathematical expression 1,
Wherein, FR is a fire retardant, FN
FRBe the quantity of 1 mole of hydroxy-acid group in the fire retardant, MW
FR(g/ mole) is the molecular weight of described fire retardant, and α is constant, and when described fire retardant was solid, α was 1, and when described fire retardant was liquid, α was 0.
4. the method for manufacturing flame retardant polyester polymkeric substance according to claim 1, wherein add as comonomer, be selected from one or more dicarboxylic acid in the following material or it can form the derivative of ester: aromatic dicarboxylic acid, as m-phthalic acid, biphenyl dicarboxylic acid, 2,6-naphthalic acid, 1,5-naphthalic acid and can form the derivative of ester; The alicyclic dicarboxylic acid; With alkyl dicarboxylic aid and can form derivative or its acyl chlorides of ester with 2 to 6 carbon atoms.
5. the method for manufacturing flame retardant polyester polymkeric substance according to claim 1, wherein add as comonomer, be selected from one or more glycol in the following material: alkanediol, alicyclic diol, aromatic diol and propylene oxide adduct.
6. the method for manufacturing flame retardant polyester polymkeric substance according to claim 1, wherein ethylene glycol is 1.01 to 2.0 with the mol ratio that comprises the dicarboxylic acid of TPA.
7. flame retardant polyester polymkeric substance, this flame retardant polyester polymkeric substance are to use that in the claim 1 to 6 any described method is made.
8. fiber, this fiber are to utilize to use the flame retardant polyester polymkeric substance that any described method is made in the claim 1 to 6 to make.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060115769A KR100764378B1 (en) | 2006-11-22 | 2006-11-22 | Manufacturing method of flame retardant polyester polymer, polyester polymer and fiber therefrom |
| KR1020060115769 | 2006-11-22 | ||
| KR10-2006-0115769 | 2006-11-22 |
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| Publication Number | Publication Date |
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| CN101186689A true CN101186689A (en) | 2008-05-28 |
| CN101186689B CN101186689B (en) | 2012-10-03 |
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| CN2007101871866A Active CN101186689B (en) | 2006-11-22 | 2007-11-21 | Manufacturing method of flame retardant polyester polymer, polyester polymer and fiber therefrom |
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| Country | Link |
|---|---|
| JP (1) | JP5132271B2 (en) |
| KR (1) | KR100764378B1 (en) |
| CN (1) | CN101186689B (en) |
| DE (1) | DE102007056179B4 (en) |
| TW (1) | TWI368625B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101735578B (en) * | 2008-11-24 | 2011-08-03 | 中国石油天然气股份有限公司 | Flame-retardant uvioresistant polyester composite material and preparation method thereof |
| CN102691130A (en) * | 2012-06-19 | 2012-09-26 | 福建经纬新纤科技实业有限公司 | Process for manufacturing fire-retardant polyester fiber |
| CN102691131A (en) * | 2012-06-19 | 2012-09-26 | 福建经纬新纤科技实业有限公司 | Manufacturing equipment system of flame-retardant polyester fiber |
| CN104178838A (en) * | 2013-05-23 | 2014-12-03 | 东丽纤维研究所（中国）有限公司 | Flame-retardant polyester false-twisted fiber and manufacturing method thereof |
| CN105985514A (en) * | 2015-03-03 | 2016-10-05 | 东丽纤维研究所（中国）有限公司 | Preparation method of flame-retardant polyester composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105177754B (en) * | 2015-10-21 | 2017-08-01 | 东华大学 | A kind of preparation method of high-strength fire-retarding polyester filament |
| CN116515094B (en) * | 2023-07-04 | 2023-09-29 | 中国天辰工程有限公司 | Preparation method of flame-retardant degradable polyester and degradable copolymerized flame retardant |
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-
2006
- 2006-11-22 KR KR1020060115769A patent/KR100764378B1/en active IP Right Grant
-
2007
- 2007-10-30 TW TW096140660A patent/TWI368625B/en active
- 2007-11-16 JP JP2007297651A patent/JP5132271B2/en active Active
- 2007-11-21 DE DE102007056179.4A patent/DE102007056179B4/en active Active
- 2007-11-21 CN CN2007101871866A patent/CN101186689B/en active Active
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735578B (en) * | 2008-11-24 | 2011-08-03 | 中国石油天然气股份有限公司 | Flame-retardant uvioresistant polyester composite material and preparation method thereof |
| CN102691130A (en) * | 2012-06-19 | 2012-09-26 | 福建经纬新纤科技实业有限公司 | Process for manufacturing fire-retardant polyester fiber |
| CN102691131A (en) * | 2012-06-19 | 2012-09-26 | 福建经纬新纤科技实业有限公司 | Manufacturing equipment system of flame-retardant polyester fiber |
| CN102691130B (en) * | 2012-06-19 | 2014-10-29 | 福建经纬新纤科技实业有限公司 | Process for manufacturing fire-retardant polyester fiber |
| CN104178838A (en) * | 2013-05-23 | 2014-12-03 | 东丽纤维研究所（中国）有限公司 | Flame-retardant polyester false-twisted fiber and manufacturing method thereof |
| CN104178838B (en) * | 2013-05-23 | 2018-01-02 | 东丽纤维研究所（中国）有限公司 | Flame retardant polyester false twist fibers and its manufacture method |
| CN105985514A (en) * | 2015-03-03 | 2016-10-05 | 东丽纤维研究所（中国）有限公司 | Preparation method of flame-retardant polyester composition |
| CN105985514B (en) * | 2015-03-03 | 2018-11-30 | 东丽纤维研究所（中国）有限公司 | A kind of preparation method of flame-retardant polyester composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008127570A (en) | 2008-06-05 |
| KR100764378B1 (en) | 2007-10-08 |
| DE102007056179B4 (en) | 2017-11-09 |
| CN101186689B (en) | 2012-10-03 |
| JP5132271B2 (en) | 2013-01-30 |
| DE102007056179A1 (en) | 2008-12-04 |
| TW200833734A (en) | 2008-08-16 |
| TWI368625B (en) | 2012-07-21 |
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Effective date of registration: 20181210 Address after: Seoul, South Kerean Patentee after: Xiaoxing Tianxi (Zhu) Address before: Seoul, South Korea Patentee before: Hyosung Corp. |