CN111154085A - Flame-retardant PET and fiber thereof - Google Patents
Flame-retardant PET and fiber thereof Download PDFInfo
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- CN111154085A CN111154085A CN201811317685.7A CN201811317685A CN111154085A CN 111154085 A CN111154085 A CN 111154085A CN 201811317685 A CN201811317685 A CN 201811317685A CN 111154085 A CN111154085 A CN 111154085A
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- flame retardant
- sulfonate
- dopo
- pet
- fluorine
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 194
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 239000000835 fiber Substances 0.000 title claims abstract description 19
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 claims abstract description 63
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 60
- 239000011737 fluorine Substances 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 35
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 20
- -1 amine salts Chemical class 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 12
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 7
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 6
- BWRJIDMRILXEDW-UHFFFAOYSA-N 2,3,4-trichlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C(Cl)=C1Cl BWRJIDMRILXEDW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 claims description 4
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 3
- UNNNAIWPDLRVRN-UHFFFAOYSA-N 1-fluoro-4-(trifluoromethyl)benzene Chemical compound FC1=CC=C(C(F)(F)F)C=C1 UNNNAIWPDLRVRN-UHFFFAOYSA-N 0.000 claims description 3
- DDLBHIIDBLGOTE-UHFFFAOYSA-N 3-chloro-2-hydroxypropane-1-sulfonic acid Chemical compound ClCC(O)CS(O)(=O)=O DDLBHIIDBLGOTE-UHFFFAOYSA-N 0.000 claims description 3
- MLWPJXZKQOPTKZ-UHFFFAOYSA-N benzenesulfonyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OS(=O)(=O)C1=CC=CC=C1 MLWPJXZKQOPTKZ-UHFFFAOYSA-N 0.000 claims description 3
- HMPHJJBZKIZRHG-UHFFFAOYSA-N chloromethanesulfonic acid Chemical compound OS(=O)(=O)CCl HMPHJJBZKIZRHG-UHFFFAOYSA-N 0.000 claims description 3
- IKGLACJFEHSFNN-UHFFFAOYSA-N hydron;triethylazanium;trifluoride Chemical compound F.F.F.CCN(CC)CC IKGLACJFEHSFNN-UHFFFAOYSA-N 0.000 claims description 3
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019407 octafluorocyclobutane Nutrition 0.000 claims description 3
- WLGDAKIJYPIYLR-UHFFFAOYSA-M octane-1-sulfonate Chemical compound CCCCCCCCS([O-])(=O)=O WLGDAKIJYPIYLR-UHFFFAOYSA-M 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 229950011087 perflunafene Drugs 0.000 claims description 3
- UWEYRJFJVCLAGH-IJWZVTFUSA-N perfluorodecalin Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)[C@@]2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[C@@]21F UWEYRJFJVCLAGH-IJWZVTFUSA-N 0.000 claims description 3
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 3
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 3
- QBTKZDLOWUAQFF-UHFFFAOYSA-N trichloromethyl benzenesulfonate Chemical compound ClC(Cl)(Cl)OS(=O)(=O)C1=CC=CC=C1 QBTKZDLOWUAQFF-UHFFFAOYSA-N 0.000 claims description 3
- UZPUXLRDLVOKTB-UHFFFAOYSA-N trifluoromethyl benzenesulfonate Chemical compound FC(F)(F)OS(=O)(=O)C1=CC=CC=C1 UZPUXLRDLVOKTB-UHFFFAOYSA-N 0.000 claims description 3
- 241001120493 Arene Species 0.000 claims description 2
- 150000008052 alkyl sulfonates Chemical group 0.000 claims 2
- 238000009987 spinning Methods 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 82
- 229920000139 polyethylene terephthalate Polymers 0.000 description 80
- 230000000052 comparative effect Effects 0.000 description 59
- 238000004458 analytical method Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 229920000728 polyester Polymers 0.000 description 14
- 238000005886 esterification reaction Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004786 cone calorimetry Methods 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000005227 alkyl sulfonate group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000003247 decreasing effect Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 238000012661 block copolymerization Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- GLGXXYFYZWQGEL-UHFFFAOYSA-M potassium;trifluoromethanesulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)F GLGXXYFYZWQGEL-UHFFFAOYSA-M 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 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
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- MORLYCDUFHDZKO-UHFFFAOYSA-N 3-[hydroxy(phenyl)phosphoryl]propanoic acid Chemical compound OC(=O)CCP(O)(=O)C1=CC=CC=C1 MORLYCDUFHDZKO-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BFVPDUKXJIAIJR-UHFFFAOYSA-N [benzhydrylsulfonyl(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)S(=O)(=O)C(C=1C=CC=CC=1)C1=CC=CC=C1 BFVPDUKXJIAIJR-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- USJRLGNYCQWLPF-UHFFFAOYSA-N chlorophosphane Chemical class ClP USJRLGNYCQWLPF-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 1
- 238000005869 desulfonation reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000008054 sulfonate salts Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention provides flame-retardant PET and a fiber thereof, wherein the flame-retardant PET comprises a substrate PET and a flame-retardant component, the flame-retardant component comprises a fluorine-containing compound, sulfonate and a DOPO flame retardant, and the flame-retardant PET can simultaneously have excellent flame-retardant performance under the condition of keeping good spinning capacity; the invention also provides a preparation method of the flame-retardant PET, and the preparation method is simple in process and convenient to operate.
Description
Technical Field
The invention relates to the field of high polymer materials, and particularly relates to flame-retardant PET, a flame-retardant PET fiber and a preparation method of the flame-retardant PET fiber.
Background
Polyethylene terephthalate (PET) belongs to a high molecular compound and is prepared by esterification and Polycondensation of Terephthalic Acid (PTA) and Ethylene Glycol (EG).
Although PET polyester fibers are widely used in many fields, the research on flame retardancy of polyester fibers attracts attention worldwide because polyester fibers are flammable and cause great damage to lives and properties in case of fire.
Patent Cooperation Treaty (PCT) WO095/20593 reports a process for producing a flame retardant polyester: the method is characterized in that a compound is generated by reacting a chlorophosphine derivative with (iso) acrylic acid, and the compound is subjected to esterification and refining by using low-grade monohydric alcohol, and then is subjected to exchange reaction with glycol ester to obtain a flame-retardant comonomer, so that the block copolymerization flame-retardant polyester can be prepared by using the monomer, the stability is high, and the limit oxygen index and the fire-proof grade of the block copolymerization flame-retardant polyester are still to be improved.
Chinese patent 02109909.X reports a production method of flame-retardant polyester: after the esterification of terephthalic acid and glycol is finished, adding 2-carboxyethyl (phenyl) phosphinic acid and 1:1(mol) glycol blending solution to obtain the flame-retardant polyester through polycondensation. The polyester fibers obtained in this way had an oxygen index of 32.5% and the effect achieved by UL-94 was not mentioned.
Chinese patent CN101787579A, a flame-retardant polyester fiber and a preparation method and a device thereof, discloses that a flame retardant is one or a mixture of more of decabromodiphenyl ether, decabromodiphenylethane, tetrabromobisphenol A, red phosphorus or triphenyl phosphate, and a flame-retardant auxiliary agent is one or a mixture of more of antimony trioxide, zinc borate, hydrated alumina, hydrated magnesium oxide, silicon powder or expanded graphite; the amount of flame retardant and flame retardant aid used in this patent is high and there is no mention of fire rating and anti-dripping effect.
Therefore, it is highly desirable to provide a flame retardant PET and its fiber, and a method for preparing the flame retardant PET, so that the flame retardant PET has excellent flame retardant performance while maintaining good spinning ability.
Disclosure of Invention
In order to solve the above problems, the present inventors have conducted intensive studies and, as a result, have found that: the flame-retardant PET comprises a substrate PET and a flame-retardant component, wherein the flame-retardant component comprises a fluorine-containing compound, sulfonate and DOPO flame retardant, and can synergistically act on the flame-retardant PET, so that the flame-retardant PET has excellent anti-dripping performance and flame-retardant performance under the condition of keeping good spinning capacity; the invention also provides a preparation method of the flame-retardant PET, which is simple in process and beneficial to popularization and application, thereby completing the invention.
The object of the present invention is to provide the following:
in a first aspect, the invention provides the flame-retardant PET, which comprises 80-99 parts of base PET and 1-20 parts of flame-retardant components.
In a second aspect, the present invention also provides a process for preparing a flame retardant PET, preferably a flame retardant PET according to the first aspect, comprising the steps of:
step 1, adding monomers and/or flame retardant components, and uniformly stirring;
step 2, carrying out polymerization reaction to generate flame-retardant PET;
preferably, the first and second electrodes are formed of a metal,
the monomer comprises terephthalic acid and ethylene glycol;
the flame-retardant component comprises sulfonate, DOPO flame retardant and fluorine-containing compound;
more preferably still, the first and second liquid crystal compositions are,
the sulfonate is selected from alkyl sulfonate and aryl sulfonate;
the DOPO flame retardant is selected from DOPO-HPM, DOPO-HAM, DOPO-TRIOL, DOPO-BQ, DDP, OD-PN and DOPO-NQ;
the fluorine-containing compound is selected from fluorine-containing alkane, fluorine-containing olefin, fluorine-containing arene and fluorine-containing organic amine salt.
In a third aspect, the present invention also provides a flame retardant PET fiber, preferably spun from the flame retardant PET of the first aspect or the flame retardant PET prepared in the second aspect.
Drawings
FIG. 1(a) shows an infrared spectrum of a product obtained in comparative example 4;
FIG. 1(b) shows an infrared spectrum of the product obtained in example 1;
FIGS. 2(a) and 2(b) show DSC temperature rise curves and temperature fall curves of comparative examples 1 to 6, respectively;
FIGS. 3(a) and 3(b) show DSC graphs of temperature rise and temperature fall in comparative example 1, examples 1 to 5;
FIGS. 4(a) and 4(b) show TG analysis graphs of comparative examples 1 to 6;
FIGS. 5(a) and 5(b) show TG analysis graphs of comparative example 1 and examples 1 to 5;
FIGS. 6(a) and 6(b) show cone calorimetry plots for the products of comparative examples 1 to 6;
fig. 7(a) and 7(b) show cone calorimetry plots for the products of comparative example 1 and examples 1-5.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The present invention is described in detail below.
According to a first aspect of the present invention, there is provided the flame retardant PET comprising:
80-99 parts of matrix PET,
1-20 parts of flame retardant component.
Preferably, the first and second electrodes are formed of a metal,
85-95 parts of matrix PET,
5-15 parts of flame retardant component.
Wherein the flame retardant component comprises a sulfonate salt and a DOPO flame retardant;
in a preferred embodiment, the sulfonate is selected from alkyl sulfonates, aryl sulfonates;
further preferably selected from octane sulfonate, monochloromethyl sulfonate, trifluoromethyl sulfonate, trichlorophenyl sulfonate, trifluoromethyl benzene sulfonate, 3-chloro-2-hydroxypropane sulfonate, benzenesulfonyl benzene sulfonate, trichloromethyl benzene sulfonate, diphenylmethanesulphone sulfonate;
more preferably, the sulfonate is a trichlorophenyl sulfonate or a trifluoromethyl sulfonate.
In still further preferred embodiments, the sulfonate is a triflate, such as potassium triflate, sodium triflate; more preferably sodium triflate.
Wherein the dosage of the sulfonate is that the mass ratio of the sulfonate to the DOPO flame retardant is (0.1-25): 100.
in one embodiment, the DOPO-based flame retardant is selected from DOPO-HPM, DOPO-HAM, DOPO-TRIOL, DOPO-BQ, DDP, OD-PN and DOPO-NQ;
preferably, the DOPO flame retardant is DOPO-BQ or DDP,
further preferably, the DOPO-based flame retardant is DDP.
The inventors believe, without being bound by any theory, that DDP is a cyclic phosphate flame retardant containing pendant phosphorus groups, and that the O ═ P — O groups on the molecule are located on the pendant groups of the polymer when such flame retardant monomer is polymerized into the PET molecular chain. When the polymer is heated, the weak bond O-P-C is broken without causing the decomposition of the main chain of the polymer, namely, the integrity of the main chain of the polymer molecule is not damaged when the chemical bond is broken by the oxidation of phosphorus of the flame retardant element, so that the flame retardant can play a flame retardant role and simultaneously cannot damage the thermal stability of the polymer. When the flame retardant is used together with sulfonate for flame retardant PET, the flame retardant has excellent effect of synergistic flame retardant.
Generally, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, abbreviated as DOPO, has a P-H bond in its structure and is very active for olefins, epoxy compounds and carbonyl compounds.
The DOPO flame retardant refers to DOPO and derivatives thereof, and the molecular structure of the DOPO flame retardant contains a biphenyl ring, a phenanthrene ring and an O ═ P-O bond, so that the DOPO flame retardant has stronger flame retardant performance than common organic phosphate.
In the invention, the molecular formula structures of DOPO-TRIOL, DOPO-NQ, DOPO-HPM, DOPO-HAM, DOPO-BQ, DDP and OD-PN are as follows:
in one embodiment, the flame retardant component further comprises a fluorine-containing compound selected from the group consisting of fluorine-containing alkanes, fluorine-containing alkenes, fluorine-containing arenes, and fluorine-containing organic amine salts.
Preferably, the fluorine-containing compound is selected from triethylamine trifluoride, tetrabutylammonium fluoride, tetramethylammonium fluoride, trifluoromethylbenzene, 4-fluorotrifluoromethylbenzene, perfluorocyclobutane, perfluorodecalin, polytetrafluoroethylene, vinylidene fluoride, and polychlorotrifluoroethylene.
Further preferably, the fluorine-containing compound is one of tetramethylammonium fluoride, tetrabutylammonium fluoride, trifluoromethylbenzene and polytetrafluoroethylene;
still more preferably, the fluorine-containing compound is tetramethylammonium fluoride.
In one embodiment, the mass ratio of the fluorine-containing compound to the DOPO-based flame retardant is (0.25-45): 100.
Generally, the DOPO flame retardant is used for polycarbonate and polyolefin, and has the disadvantages of large addition amount and high cost when used alone, and is not beneficial to industrial popularization and application.
In the invention, a flame retardant component containing the DOPO flame retardant is adopted, namely, the fluorine-containing compound, the sulfonate and the DOPO flame retardant are compounded, so that the using amount of the DOPO flame retardant can be reduced, the synergistic flame retardant effect is achieved, and the anti-dripping performance of the flame retardant PET is improved;
this is probably because the addition of the fluorine-containing compound and the sulfonate lowers the thermal crystallization temperature of the PET system to a certain extent, further increases the residual carbon quality of the PET system, and improves the flame retardancy of PET.
The inventor of the invention has found through a great deal of research and experiments that when the fluorine-containing compound is selected to be tetramethyl ammonium fluoride, the sulfonate is selected to be trifluoromethyl sulfonate, the DOPO flame retardant is selected to be DDP, and the DOPO flame retardant is matched with the flame retardant for PET according to a certain amount, the obtained flame-retardant PET has the best performance.
According to a second aspect of the present invention, there is also provided a process for the preparation of a flame retardant PET, preferably a flame retardant PET according to the first aspect, comprising the steps of:
step 1, adding monomers and/or flame retardant components, and uniformly stirring;
and 2, carrying out polymerization reaction to generate the flame-retardant PET.
Preferably, the first and second electrodes are formed of a metal,
the monomer comprises terephthalic acid and ethylene glycol;
the flame-retardant component comprises sulfonate, DOPO flame retardant and fluorine-containing compound;
more preferably still, the first and second liquid crystal compositions are,
the sulfonate is selected from alkyl sulfonate and aryl sulfonate;
the DOPO flame retardant is selected from DOPO-HPM, DOPO-HAM, DOPO-TRIOL, DOPO-BQ, DDP, OD-PN and DOPO-NQ;
the fluorine-containing compound is selected from fluorine-containing alkane, fluorine-containing olefin, fluorine-containing arene and fluorine-containing organic amine salt.
It is further preferred that the first and second liquid crystal compositions,
the sulfonate is selected from octane sulfonate, chloromethylsulfonate, trifluoromethyl sulfonate, trichlorophenyl sulfonate, trifluoromethyl benzene sulfonate, 3-chloro-2-hydroxypropane sulfonate, benzenesulfonyl benzene sulfonate, trichloromethyl benzene sulfonate and diphenylmethylsulfone sulfonate;
the DOPO flame retardant is DOPO-BQ or DDP;
the fluorine-containing compound is selected from triethylamine trifluoride, tetrabutylammonium fluoride, tetramethylammonium fluoride, trifluoromethylbenzene, 4-fluorotrifluoromethylbenzene, perfluorocyclobutane, perfluorodecalin, polytetrafluoroethylene, vinylidene fluoride and polychlorotrifluoroethylene;
it is still further preferred that the first and second substrates are,
the sulfonate is trichlorophenyl sulfonate or trifluoromethyl sulfonate;
the DOPO flame retardant is DDP;
the fluorine-containing compound is one of tetramethyl ammonium fluoride, tetrabutyl ammonium fluoride, trifluoromethyl benzene and polytetrafluoroethylene;
still further preferably, the first and second substrates are,
the sulfonate is a triflate, such as potassium triflate or sodium triflate;
the fluorine-containing compound is tetramethyl ammonium fluoride.
In one embodiment, the mass ratio of the sulfonate to the DOPO flame retardant is (0.1-25): 100;
in one embodiment, the mass ratio of the fluorine-containing compound to the DOPO-based flame retardant is (0.25-45): 100.
In a preferred embodiment, in step 1, the monomers terephthalic acid and ethylene glycol are subjected to esterification reaction; during the esterification reaction, DOPO flame retardant in the flame retardant component is also added; after the esterification reaction is finished, adding sulfonate and fluorine-containing compounds into the esterification reaction solution; then, the polymerization reaction is carried out.
In the invention, the reaction equation for preparing the flame-retardant PET is as follows:
further, the flame-retardant PET according to the first aspect or the flame-retardant PET prepared according to the second aspect is characterized, for example, infrared spectrum analysis, thermal stability analysis, combustion performance analysis, flame-retardant performance analysis and the like are performed.
The obtained infrared spectrogram is 925cm-1Nearby, 1180cm-1，1400cm-1～1500cm-1，1740cm-1The presence of characteristic peaks;
the combustion performance analysis result shows that the ignition time of the polymer shows an increasing trend along with the increase of the DOPO flame retardant, and the peak value of the heat release rate, the average heat release rate and the total heat release amount show a decreasing trend; on the other hand, the addition of the fluorine-containing compound and the sulfonate can further reduce the average heat release rate in the burning process of the PET polymer, and plays a role in synergistic flame retardance.
The limiting oxygen index LOI of the flame-retardant PET can reach 34 percent, and the fire-retardant grade UL-94 reaches V-0 grade.
According to a third aspect of the present invention, there is also provided a flame retardant PET fiber, preferably spun from the flame retardant PET of the first aspect or the flame retardant PET prepared in the second aspect.
The flame-retardant PET fiber provided by the invention has the spinning temperature of 265-275 ℃, the fiber fineness of 110dtex/f and good spinnability.
According to the invention, the application of the fluorine-containing compound in polyester PET as a flame retardant and the flame retardant component containing the fluorine-containing compound have the following beneficial effects:
(1) the LOI of the flame-retardant PET can reach 34%, and UL-94 reaches V-0 level;
(2) the flame retardant component provided by the invention can be used as a PET flame retardant, so that PET has excellent flame retardant performance under the condition of keeping the spinning capacity;
(3) the flame retardant component provided by the invention can reduce the using amount of DOPO flame retardants and reduce the cost;
(4) the preparation method of the flame-retardant PET is simple and is beneficial to popularization and application.
Examples
Example 1
Adding terephthalic acid TPA700g, ethylene glycol 330g and DDP62g into a reaction kettle, stirring and uniformly mixing;
heating to 260 ℃ for esterification reaction, controlling the reaction pressure at 330kpa, slightly opening a valve to reduce the pressure until the pressure is normal when the water yield reaches one third of the theoretical water yield, and controlling the reaction time to be about 2-2.5 hours based on the theoretical water yield reaching 150 milliliters;
and then adding 13.5g of tetramethylammonium fluoride and 2.5g of sodium trifluoromethanesulfonate into the esterified solution, introducing nitrogen for protection, continuing stirring, finally reaching the polymerization temperature of 280-285 ℃, the polymerization pressure of less than 100pa, the polymerization time of 2-3h, discharging the polymer with the required molecular weight, and after the reaction is finished, carrying out tape injection and grain cutting to obtain the flame-retardant PET slice.
Example 2
The same procedure as in example 1 was followed, except that 70g of DDP was used, to obtain a flame-retardant PET.
Example 3
The same procedure as in example 1, except that 87.6g of DDP was used, gave a flame-retardant PET.
Example 4
The same procedure as in example 1, except that 95g of DDP was used, gave a flame-retardant PET.
Example 5
The same procedure as in example 1, except that 118.3g of DDP was used, gave a flame-retardant PET.
Example 6
Drying the flame-retardant PET slices obtained in the embodiments 1-5 and blank pure PET slices (drying at 120 ℃ for 10h and drying at 140 ℃ for 2 h);
and then respectively carrying out melt spinning on an SJ-120 type single screw spinning machine at the spinning temperature of 265-280 ℃ and the spinning speed of 3300m/min to obtain nascent fibers, and then drafting the obtained nascent fibers on a drafting machine.
Comparative example
Comparative example 1
Stirring and uniformly mixing terephthalic acid TPA700g and ethylene glycol 330 g;
heating to 260 ℃, controlling the pressure of the esterification reaction at 330kpa, slightly opening a valve to reduce the pressure until the pressure is normal when the water yield reaches one third of the theoretical water yield, and controlling the reaction time to be about 2-2.5 hours based on the theoretical water yield reaching 150 milliliters; and then introducing nitrogen for protection, continuing stirring, finally reaching the polymerization temperature of 280-285 ℃, the polymerization pressure of less than 100pa, the polymerization time of 2-3h, discharging when the required polymer molecular weight is reached, and after the reaction is finished, performing tape injection and grain cutting to obtain the flame-retardant PET slice.
Comparative example 2
Adding terephthalic acid TPA700g, ethylene glycol 330g and DDP62g into a reaction kettle, stirring and uniformly mixing;
heating to 260 ℃, controlling the pressure of the esterification reaction at 330kpa, slightly opening a valve to reduce the pressure until the pressure is normal when the water yield reaches one third of the theoretical water yield, and controlling the reaction time to be about 2-2.5 hours based on the theoretical water yield reaching 150 milliliters; and then introducing nitrogen for protection, continuing stirring, finally reaching the polymerization temperature of 280-285 ℃, the polymerization pressure of less than 100pa, the polymerization time of 2-3h, discharging when the required polymer molecular weight is reached, and after the reaction is finished, performing tape injection and grain cutting to obtain the flame-retardant PET slice.
Comparative example 3
The same procedure as in comparative example 2, except that 70g of DDP was used; obtaining the flame-retardant PET.
Comparative example 4
The same procedure as in comparative example 2, except that 87.6g of DDP was used; obtaining the flame-retardant PET.
Comparative example 5
The same procedure as in comparative example 2, except that 95g of DDP was used; obtaining the flame-retardant PET.
Comparative example 6
The same procedure as in comparative example 2, except that 118.3g of DDP was used; obtaining the flame-retardant PET.
Comparative example 7
Pure PET767g and polytetrafluoroethylene 33g are melted and blended, extruded and cut into granules, and the flame-retardant PET is obtained.
Examples of the experiments
Infrared spectroscopic analysis of sample of Experimental example 1
The products obtained in comparative example 4 and example 1 were measured and subjected to infrared spectroscopic analysis, and the results are shown in FIG. 1(a) and FIG. 1(b), respectively.
From the analysis in FIG. 1(a), it can be seen that: 925cm-1The vicinity is a P-O-Ar absorption peak of 1180cm-1Is a characteristic absorption peak of the P ═ O group, 1400cm-1-1500cm-1Near P-C stretching vibration absorption peak, 1740cm-1Is the peak of the carboxyl group vibration of the ester group. The analysis shows that the DOPO flame retardant, the PTA and the EG have copolymerization reaction. As can be seen from FIG. 1(b), the resulting FIG. 1(b) is not significantly changed from FIG. 1(a) because the added fluorine-containing compound and sulfonate are added to the polymer in the form of a blend, and the peak positions of C-F bond and sulfonic acid group are 1000-1500 cm--1The flame retardant polyester is covered by a characteristic peak of the flame retardant polyester, and the addition amount is small, so that the flame retardant polyester has no obvious change.
Experimental example 2 DSC analysis of thermal stability of sample
DSC temperature rise and fall analysis was performed on comparative examples 1 to 6 and examples 1 to 5, and the relevant data are shown in tables 1 and 2, and DSC graphs are shown in FIG. 2(a), FIG. 2(b), FIG. 3(a), and FIG. 3 (b).
Table 1 is a data table of DSC temperature rise and drop of comparative examples 1 to 6;
table 2 is a table of DSC temperature rise and fall data of comparative example 1, example 1 to example 5;
FIG. 2(a) is a DSC temperature rise curve of comparative examples 1 to 6;
FIG. 2(b) is a DSC cooling curve of comparative examples 1 to 6;
FIG. 3(a) is a DSC temperature increase curve of examples 1 to 5;
FIG. 3(b) is a DSC melting curve of examples 1 to 5;
TABLE 1 DSC test results of comparative examples 1 to 6
| Sample numbering | Tg/℃ | Tm/℃ | Tcc/℃ | Tmc/℃ |
| Comparative example 1 | 64 | 250 | 106 | 199 |
| Comparative example 2 | 64 | 238 | 118 | 197 |
| Comparative example 3 | 65 | 234 | 120 | 188 |
| Comparative example 4 | 65 | 233 | 121 | 189 |
| Comparative example 5 | 64 | 226 | 122 | 188 |
| Comparative example 6 | 65 | 226 | 130 | 187 |
TABLE 2 DSC test results of comparative example 1, example 1 to example 5 products
| Sample (I) | Tg/℃ | Tm/℃ | Tcc/℃ | Tmc/℃ |
| Comparative example 1 | 64 | 250 | 106 | 199 |
| Example 1 | 61 | 224 | 118 | 172 |
| Example 2 | 62 | 220 | 121 | 157 |
| Example 3 | 61 | 210 | 122 | 142 |
| Example 4 | 61 | 211 | 123 | 140 |
| Example 5 | 61 | 200 | 122 | 145 |
As can be seen from the data of Table 1 and FIGS. 2(a) and 2(b), as the content of the DOPO-based flame retardant (e.g., DDP) increases, the cold crystallization temperature (T) of the blend increasescc) Gradually increased, when the amount of the DOPO based flame retardant added reached 118.3g (comparative example 6), TccThe temperature is increased from 106 ℃ of pure PET to 130 ℃ because the DOPO flame retardant is polymerized on the PET molecular chain, and because the side chain of the DOPO flame retardant has large steric hindrance, the rearrangement of the molecular chain is hindered, and the crystallization can be carried out at higher temperature. It can also be seen from the figure that the melting temperature (T) of the DOPO-based flame retardant PET is comparable to that of pure PETm) The Tm is reduced along with the increase of the content of the DOPO flame retardant, the Tm is in a descending trend, because the side chain of the DOPO flame retardant is in an intrinsic ring structure, the crystallization of a system is difficult, the Tm is reduced due to the reduction of the crystallinity, and the Tm of the DOPO flame retardant-PET is reduced along with the increase of the content of the DOPO flame retardant.
As is clear from the data in Table 1 and FIGS. 2(a) and 2(b), the thermal crystallization temperature (T) of the system increases with the DOPO-based flame retardant content as compared with that of pure PETmc) Gradually decreased, and when the DOPO based flame retardant content reached 87.6g (comparative example 4), T was hardly observedmcThe reason is that the side chain of the DOPO flame retardant has large steric hindrance, which prevents the rearrangement of the molecular chain to reduce the crystallization temperature, and when the addition amount of the DOPO flame retardant is more and reaches a certain condition, the polymer can not be crystallized.
As is clear from Table 2 and FIGS. 3(a) and 3(b), the addition of the fluorine-containing compound and the sulfonate led to T in the systemccThe increase amplitude is reduced because the added fluorine-containing compound and the sulfonate play the role of a plasticizer in the whole system, and under the combined action of the DOPO flame retardant, the fluorine-containing compound and the sulfonate,so that TccThe growth amplitude is slowed down, and in addition, the added fluorine-containing compound and sulfonate are used as plasticizers to reduce the glass transition temperature (T) of the system to a certain extentg) And melting temperature (T)m). In the cooling crystallization process, fluorine-containing compounds and sulfonate are used as plasticizers to be unfavorable for the production of crystal nuclei, so that the thermal crystallization temperature is further reduced.
Experimental example 3 analysis of sample for thermal stability TG
TG analyses were performed on comparative examples 1 to 6 and examples 1 to 5, and the relevant data are shown in tables 3 and 4, and TG curves are shown in FIG. 4(a), FIG. 4(b), and FIG. 5(a), FIG. 5 (b).
Table 3 shows the decomposition temperature tables of comparative examples 1 to 6;
table 4 shows the decomposition temperature tables of comparative example 1 and examples 1 to 5;
fig. 4(a) and 4(b) show TG analysis graphs;
fig. 5(a), 5(b) show TG analysis graphs.
TABLE 3 decomposition temperature chart of products of comparative examples 1 to 6
Note: t is5wt％5 wt% of thermal weight loss corresponding to temperature, Tmax: maximum rate of thermal weight loss versus temperature
TABLE 4 decomposition temperature chart of comparative example 1 and examples 1 to 5
Note: t is5wt％5 wt% of thermal weight loss corresponding to temperature, Tmax: maximum rate of thermal weight loss versus temperature
From tables 3, 4 and fig. 4(a), 4(b), and 5(a), 5(b) can be derivedIt was found that, in comparative examples 2 to 6, the DOPO based flame retardant-PET had an initial decomposition temperature (T)5％) Slightly decreased because the P-C bond of the phenyl phosphate ester on the side chain of the DOPO based flame retardant was broken, and its influence on the main chain was small.
The maximum thermal weight loss rate is reduced by adding the DOPO flame retardant, and the temperature corresponding to the maximum thermal weight loss rate is increased along with the increase of the content of the DOPO flame retardant, so that the degradation of PET molecular chains is inhibited by the existence of phosphorus; the residual carbon at 800 ℃ increases with the increase of the content of the DOPO flame retardant;
in examples 1 to 5, after the addition of the fluorine-containing compound and the sulfonate, the initial decomposition temperature was further lowered and the residual carbon at 800 ℃ was further increased as compared with the DOPO-based flame retardant-PET system in comparative examples 2 to 6, indicating that the added fluorine-containing compound and the sulfonate started to act before the decomposition of PET, further increasing the residual carbon mass. The maximum rate of thermal weight loss of the system after adding the fluorine-containing compound and the sulfonate is slightly increased, which is probably because the sulfonate can perform desulfonation reaction at 400 ℃ to generate SO2And H2O, wherein H2The O molecules can promote the degradation of the PET, increasing the maximum rate of thermal weight loss, accelerating thermal degradation to promote the formation of the insulating carbon layer.
Experimental example 4 analysis of Combustion Performance of sample
Comparative examples 1 to 6 and examples 1 to 5 were subjected to combustion performance analysis, i.e., cone calorimetry test, and the relevant data are shown in tables 5 and 6, and cone calorimetry graphs are shown in fig. 6(a), 6(b), and 7(a), 7 (b).
Wherein,
table 5 shows cone calorimetry test results of the products of comparative examples 1 to 6;
table 6 shows cone calorimetry test results of the products of comparative example 1 and examples 1 to 5;
FIGS. 6(a) and 6(b) show cone calorimetry plots for the products of comparative examples 1 to 6;
FIGS. 7(a) and 7(b) show cone calorimetry plots for the products of comparative example 1 and examples 1-5;
TABLE 5 Cone calorimeter test results for the products of comparative examples 1 to 6
TABLE 6 Cone calorimeter test results for the products of comparative example 1 and examples 1-5
From tables 5 and 6, it can be seen that when the DOPO-based flame retardant is added alone, the ignition time of the polymer tends to increase with an increase in the content of the flame retardant, and the peak heat release rate, the average heat release rate, and the total heat release amount all tend to decrease. This is because the DOPO-based flame retardant-formed PO. during the combustion of the polymer, which can bond with hydrogen atoms in the flame zone and act to suppress the flame. In addition, the moisture generated in the combustion process of the DOPO flame retardant PET can reduce the temperature of a condensed phase on one hand and can dilute the concentration of combustible substances in a gas phase on the other hand, thereby playing a good flame-retardant role. Compared with a DOPO flame retardant-PET system, the addition of the fluorine-containing compound and the sulfonate can further reduce the average heat release rate in the combustion process of the polymer and play a role in synergistic flame retardance.
Experimental example 5 flame retardancy analysis of sample
Performing flame retardant performance analysis on comparative examples 1 to 6 and examples 1 to 5, wherein relevant data are shown in tables 7 and 8, including LOI and UL-94 test results;
wherein, table 7 shows the flame retardant property analysis data of the products of comparative examples 1 to 6; table 8 shows the flame retardant performance analysis data for the products of comparative example 1 and examples 1-5.
TABLE 7 LOI and UL-94 test results for the products of comparative examples 1-6
TABLE 8 LOI and UL-94 test results for the products of comparative example 1 and examples 1-5
As can be seen from tables 7 and 8, the LOI results show that the LOI value of the polymer is significantly improved by adding the DOPO based flame retardant alone, the LOI reaches 33% and the UL-94 reaches V-0 when the DOPO based flame retardant is added in an amount of 118.3g (comparative example 6), and only 87.6g of the DOPO based flame retardant is required when a very small amount of the fluorine-containing compound and the sulfonate is added (example 3), at which time the LOI reaches 34% and the UL-94 reaches V-0. Therefore, the DOPO flame retardant plays a main role in the flame retardant system of the polymer, but the added fluorine-containing compound and sulfonate can further reduce the dosage of the flame retardant, and the synergistic flame retardant effect is achieved.
Experimental example 6 spinnability analysis of sample
Spinning performance tests were performed on the products of comparative example 7 and examples 1-5, as shown in Table 9.
TABLE 9 spinning Performance test results for the products of comparative example 7 and examples 1-5
As can be seen from Table 9, under reasonable spinning process conditions, the prepared flame-retardant copolyester PET has good spinnability, and the obtained flame-retardant fibers can meet the requirements of clothing and home textile. The spinning performance of the flame retardant PET of the present invention has significant advantages over the spinning performance of flame retardant PET produced from other flame retardants (comparative example 7). More importantly, the flame-retardant PET provided by the invention has excellent flame-retardant performance.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A flame retardant PET, characterized in that it comprises:
80-99 parts of matrix PET,
1-20 parts of flame retardant component.
2. The flame retardant PET according to claim 1,
85-95 parts of matrix PET,
5-15 parts of flame retardant component.
3. The flame retardant PET of claim 1 or 2, wherein the flame retardant component comprises sulfonate and DOPO based flame retardants;
the sulfonate is selected from alkyl sulfonate and aryl sulfonate; preferably selected from octane sulfonate, monochloromethyl sulfonate, trifluoromethyl sulfonate, trichlorophenyl sulfonate, trifluoromethyl benzene sulfonate, 3-chloro-2-hydroxypropane sulfonate, benzenesulfonyl benzene sulfonate, trichloromethyl benzene sulfonate, diphenylmethanesulphone sulfonate; more preferably, the sulfonate is a trichlorophenyl sulfonate or a trifluoromethyl sulfonate.
4. The flame retardant PET of claim 3, wherein the DOPO based flame retardant is selected from DOPO-HPM, DOPO-HAM, DOPO-TRIOL, DOPO-BQ, DDP, OD-PN and DOPO-NQ; preferably selected from DOPO-BQ or DDP.
5. The flame retardant PET as recited in any one of claims 1 to 4, further comprising a fluorine-containing compound selected from the group consisting of fluorine-containing alkanes, fluorine-containing alkenes, fluorine-containing arenes, and fluorine-containing organic amine salts.
6. The flame retardant PET according to claim 5 wherein the fluorine containing compound is selected from triethylamine trifluoride, tetrabutylammonium fluoride, tetramethylammonium fluoride, trifluoromethylbenzene, 4-fluorotrifluoromethylbenzene, perfluorocyclobutane, perfluorodecalin, polytetrafluoroethylene, vinylidene fluoride and polychlorotrifluoroethylene.
7. The flame retardant PET according to claim 6,
the fluorine-containing compound is one of tetramethyl ammonium fluoride, tetrabutyl ammonium fluoride, trifluoromethyl benzene and polytetrafluoroethylene; preferably, the fluorine-containing compound is tetramethylammonium fluoride.
8. A method for preparing a flame retardant PET, preferably a flame retardant PET as claimed in any one of claims 1 to 7, comprising the steps of:
step 1, adding monomers and/or flame retardant components, and uniformly stirring;
step 2, carrying out polymerization reaction to generate flame-retardant PET;
preferably, the first and second electrodes are formed of a metal,
the monomer comprises terephthalic acid and ethylene glycol;
the flame-retardant component comprises sulfonate, DOPO flame retardant and fluorine-containing compound;
more preferably still, the first and second liquid crystal compositions are,
the sulfonate is selected from alkyl sulfonate and aryl sulfonate;
the DOPO flame retardant is selected from DOPO-HPM, DOPO-HAM, DOPO-TRIOL, DOPO-BQ, DDP, OD-PN and DOPO-NQ;
the fluorine-containing compound is selected from fluorine-containing alkane, fluorine-containing olefin, fluorine-containing arene and fluorine-containing organic amine salt.
9. The flame retardant PET according to any one of claims 1 to 7 or the flame retardant PET produced by the production method according to claim 8,
in the infrared spectrogram, 925cm-1Nearby, 1180cm-1，1400cm-1～1500cm-1，1740cm-1Characteristic peaks exist nearby.
10. A flame retardant PET fiber, preferably spun from the flame retardant PET of claim 9.
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