CN114591528A - Foamable flame-retardant PET (polyethylene terephthalate) polyester and preparation method thereof - Google Patents
Foamable flame-retardant PET (polyethylene terephthalate) polyester and preparation method thereof Download PDFInfo
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- CN114591528A CN114591528A CN202210178484.3A CN202210178484A CN114591528A CN 114591528 A CN114591528 A CN 114591528A CN 202210178484 A CN202210178484 A CN 202210178484A CN 114591528 A CN114591528 A CN 114591528A
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- flame
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- pet polyester
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 123
- 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 116
- 229920000728 polyester Polymers 0.000 title claims abstract description 88
- -1 polyethylene terephthalate Polymers 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229920000139 polyethylene terephthalate Polymers 0.000 title abstract description 80
- 239000005020 polyethylene terephthalate Substances 0.000 title abstract description 80
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 132
- 238000005187 foaming Methods 0.000 claims abstract description 58
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 56
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 46
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000005886 esterification reaction Methods 0.000 claims description 31
- 238000006068 polycondensation reaction Methods 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 23
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 23
- 239000004246 zinc acetate Substances 0.000 claims description 23
- 239000004088 foaming agent Substances 0.000 claims description 21
- FQXGHZNSUOHCLO-UHFFFAOYSA-N 2,2,4,4-tetramethyl-1,3-cyclobutanediol Chemical compound CC1(C)C(O)C(C)(C)C1O FQXGHZNSUOHCLO-UHFFFAOYSA-N 0.000 claims description 19
- 239000011324 bead Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 17
- 238000007493 shaping process Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000007599 discharging Methods 0.000 claims description 13
- 238000011049 filling Methods 0.000 claims description 13
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 239000011574 phosphorus Substances 0.000 claims description 11
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011268 mixed slurry Substances 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- FPIGBKDVHZUQJO-UHFFFAOYSA-N 2-hydroxyethyl(phenyl)phosphinic acid Chemical compound OCCP(O)(=O)C1=CC=CC=C1 FPIGBKDVHZUQJO-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- JVLRYPRBKSMEBF-UHFFFAOYSA-K diacetyloxystibanyl acetate Chemical compound [Sb+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JVLRYPRBKSMEBF-UHFFFAOYSA-K 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- 239000004604 Blowing Agent Substances 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- SYBJZXZBVFWDAO-UHFFFAOYSA-N hydroxymethyl(phenyl)phosphinic acid Chemical compound OCP(O)(=O)C1=CC=CC=C1 SYBJZXZBVFWDAO-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 23
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 239000000155 melt Substances 0.000 abstract description 6
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 230000000694 effects Effects 0.000 description 19
- 239000006260 foam Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 12
- 229910052760 oxygen Inorganic materials 0.000 description 12
- 239000001301 oxygen Substances 0.000 description 12
- 238000002485 combustion reaction Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 238000005453 pelletization Methods 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229920001634 Copolyester Polymers 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 210000000497 foam cell Anatomy 0.000 description 3
- 239000006261 foam material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000009781 Myrtillocactus geometrizans Nutrition 0.000 description 1
- 240000009125 Myrtillocactus geometrizans Species 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 210000003608 fece Anatomy 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000012994 industrial processing Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- 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
- C08G63/02—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
- C08G63/199—Acids or hydroxy compounds containing cycloaliphatic rings
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/06—CO2, N2 or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
-
- 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'
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of polyester preparation, and discloses foamable flame-retardant PET (polyethylene terephthalate) polyester and a preparation method thereof, wherein the foamable flame-retardant PET polyester comprises the following components in parts by weight: 100 parts of terephthalic acid, 30-100 parts of ethylene glycol, 1-60 parts of comonomer, 0.02-0.12 part of catalyst, 0.005-0.3 part of antioxidant, 1-50 parts of flame retardant and 0.1-1 part of stabilizer. According to the invention, an in-situ polymerization method is adopted, and a comonomer and a flame retardant are introduced in the polyester synthesis process, so that the problem that the melt strength is low and foaming is difficult to occur due to the linear structure of a PET molecular chain is solved, the problem of inflammability of a foaming material is solved, and the lightweight flame retardance of the foaming material is realized.
Description
Technical Field
The invention relates to the technical field of polyester preparation, in particular to foamable flame-retardant PET polyester and a preparation method thereof.
Background
As a recyclable thermoplastic material, PET has excellent fatigue resistance, mechanical properties, surface retardation, wear resistance, barrier properties, stability, and high working temperature and recyclability, and is widely used in the fields of synthetic fibers, engineering plastics, films, medical care, electronics, buildings, wind power generation, and the like. The foam material prepared from PET has the advantages of light weight, high strength, moisture resistance, stable size, corrosion resistance and the like, is usually used in the fields of fan blades, train carriages, packaging materials, building interlayers and the like, but belongs to flammable materials due to the fact that the limited oxygen index is about 22%, black smoke and molten drop phenomena can be generated in the combustion process, and in addition, a large amount of smoke and toxic and harmful gases can be generated by a common halogen flame retardant, so that the application range of the PET foam is further limited.
The conventional PET molecular chain is of a linear structure, so that the melt strength is low, the viscoelasticity is poor, the molecular chain is easy to break in a high-temperature melting stage in a foaming process, foam holes are easy to merge and collapse in a foam hole growth stage, and finally a foam material with compact and uniform foam holes is difficult to form. Therefore, PET needs to be modified and reinforced, common methods include a blending addition method and a copolymerization synthesis method, the blending addition method is low in cost and high in adaptability, but the effect is unstable due to reasons such as matrix compatibility, and a modifier can be synthesized into a molecular chain in a comonomer mode by the copolymerization synthesis method, so that the durability and stability of the material can be ensured.
The Chinese patent with publication number CN113512227A discloses a high flame retardant PET foam material and a preparation method thereof, organic layered silicate is added into a reaction kettle to prepare a PET composite material, and then the PET composite material, polyphosphazene derivative, chain extender and polycondensation reaction catalyst are added into a reaction extruder to prepare the PET composite foaming special material. However, the method needs to undergo a series of complex operations such as early-stage polymerization, reactive extrusion, foaming and the like, the required period is long, the influence factors are more, and the stability of the final material is deficient.
The Chinese patent with publication number CN105694386A discloses a composition of phosphorus-containing copolyester foam, general polyester, reactive phosphorus-containing flame retardant, tackifier, foaming agent and nucleating agent with formula amounts are reacted, blended and modified by an extruder at the melting temperature of the general polyester, the mixture is extruded and foamed by a neck mold to obtain the phosphorus-containing copolyester foam, and then the foam is pulled and cut to obtain the finished product. Although the method is simple and easy to operate, and the component concentration is easy to control, the components of the prepared material are easy to aggregate, the phase separation phenomenon occurs, and the uniformity of the material is difficult to ensure.
The invention patent of China with publication number CN101508770B discloses a method for preparing phosphorus halogen-free flame-retardant copolyester, which comprises the steps of preparing a flame-retardant esterified substance solution from a phosphorus halogen-free flame-retardant copolymerization agent and ethylene glycol, then adding a prepared esterified solution, a stabilizer, a catalyst and the like after dimethyl terephthalate and the ethylene glycol react to a certain degree, and carrying out polymerization reaction to obtain the phosphorus halogen-free flame-retardant copolyester. The method adopts an ester exchange method to prepare the flame-retardant copolyester, the obtained material has stronger crystallinity and lower melt strength, is mainly applied to the field of polyester films, but is not suitable for preparing the foaming flame-retardant polyester.
Disclosure of Invention
The invention aims to provide foamable flame-retardant PET polyester and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
in a first aspect, the invention provides a foamable flame-retardant PET polyester, which comprises the following components in parts by weight:
the invention adopts an in-situ copolymerization method, directly synthesizes the foaming material from the monomer in one step, has simple preparation process, and allows the flame retardant to participate in the polymerization process, so that the prepared polyester foaming material has more stable flame retardant property. In the in-situ polymerization method, comonomer is added to destroy the PET crystal structure, and compared with the conventional PET modification method in which polyol, polybasic acid and polybasic acid anhydride are introduced to carry out polyester chain extension, the method uses micromolecular dihydric alcohol as a chain extender to destroy the regularity and crystallization performance of PET polyester chain segments, so that random copolyester without a melting point is formed, and the toughness of the molecular chains is improved. Meanwhile, the processing temperature is reduced, the processing temperature range is widened, the melt strength is effectively improved, and a better foaming effect is achieved. On the other hand, the flame retardant and the stabilizer are added, so that the prepared polyester foaming material has the flame retardant characteristic. Therefore, the PET is subjected to chain extension modification to have a better foaming effect, and simultaneously, a good flame retardant effect is also given.
The polyester foaming material is simple in synthesis method, high in efficiency, good in foaming effect and low in energy consumption, the addition amount of each component must be strictly controlled, excessive or insufficient addition of the comonomer can affect the modification effect, so that the foaming and flame-retardant effects are not obvious, the foaming temperature and the foaming multiplying power can be affected to a certain extent by the existence of the flame retardant, and the content of the flame retardant needs to be controlled.
Preferably, the comonomer is one or more of neopentyl glycol, 2,4, 4-tetramethyl-1, 3-cyclobutanediol or 1, 4-cyclohexanedimethanol.
The structure of the comonomer is different from that of ethylene glycol and terephthalic acid greatly, and side groups are more, so that a branched chain structure can be introduced into a PET molecular chain to further increase toughness, and the original crystalline structure of polyester can be damaged by adding a small amount of the comonomer. In addition, the polyester modified by neopentyl glycol and 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol has good temperature resistance and wide processing window, and is beneficial to the stability of melt strength and foam molding in the foaming process. Meanwhile, the two have good reaction activity in the polymerization process, the product has high molecular weight, large intrinsic viscosity and high melt strength, and the foam cell growth in the foaming process is facilitated. The 4-cyclohexanedimethanol can also accelerate the polymerization reaction, improve the polymerization efficiency, and has higher utilization rate of raw materials and random degree of reaction products after the polymerization reaction.
Preferably, the catalyst is one or more of ethylene glycol antimony, antimony trioxide, antimony acetate, tetrabutyl titanate, tetraisopropyl titanate and zinc acetate; the stabilizer is red phosphorus.
The red phosphorus has good stability, high phosphorus content and easy addition. The phosphorus content in the system can be improved, so that the flame retardant can be added into a molecular structure more and more quickly, and the flame retardant effect is enhanced.
Preferably, the antioxidant is at least one of a phenol antioxidant and a phosphite antioxidant.
Preferably, the antioxidant is 1010, 168 or triphenyl phosphite.
Preferably, the flame retardant is at least one of halogen-free phosphorus flame retardants.
Preferably, the flame retardant is one or more of red phosphorus, 2-hydroxyethyl phenyl phosphinic acid, hydroxymethyl phenyl phosphinic acid, poly-p-phenylphosphinonitrile benzoate, diammonium hydrogen phosphate, (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid.
The flame retardant is more preferably red phosphorus or 2-hydroxyethyl phenyl hypophosphorous acid, which has less influence on the foaming performance and the expansion ratio and can obtain PET polyester with better comprehensive performance.
In a second aspect, the invention also provides a preparation method of the foamable flame retardant PET polyester, which comprises the following steps:
(1) mixing terephthalic acid, ethylene glycol and a comonomer according to a ratio, preheating, adding a catalyst, stirring, and carrying out an esterification reaction in an inert atmosphere;
(2) adding a flame retardant into ethylene glycol, heating to obtain mixed slurry, then adding the mixed slurry into the step (1) after the esterification reaction is finished, and adding a stabilizer and an antioxidant for stirring; then, carrying out a pre-polycondensation reaction, carrying out a final polycondensation reaction, discharging and granulating after the reaction is finished, and obtaining the flame-retardant PET polyester chip;
(3) and filling the flame-retardant PET polyester chips with a foaming agent, foaming, and finally cooling and shaping to obtain the flame-retardant PET polyester foamed beads.
The esterification reaction is carried out firstly, and the flame retardant is added after the esterification stage is finished, so that the flame retardant is prevented from being degraded due to high temperature in the esterification stage, and the flame retardant performance is improved. And foaming the prepared flame-retardant PET polyester chip, filling a foaming agent medium, preheating to the required foaming temperature and pressure until the required foaming temperature and pressure reach a supercritical state, saturating at constant temperature and constant pressure in the foaming agent atmosphere for a period of time to complete the diffusion effect of the foaming agent, then quickly relieving pressure to normal pressure, inducing a polymer and foaming agent system to generate a thermodynamic unstable state, promoting the nucleation and growth of foam cells, finally cooling and shaping, and cooling the foaming kettle to obtain the foaming beads.
Preferably, in the step (1), the preheating temperature is 60-150 ℃; the temperature of the esterification reaction is 200-260 ℃, the pressure is 0.1-0.38MPa, and the reaction time is 1-4 h.
Preferably, in the step (2), the pre-polycondensation reaction is performed by vacuumizing for 60-120min to the absolute pressure of below 100Pa, and the temperature is 250-290 ℃; the final polycondensation reaction is carried out at the temperature of 260-290 ℃, the pressure of 0-300Pa and the reaction time of 60-150 min.
Preferably, in the step (3), the foaming agent is one or two of carbon dioxide and nitrogen; the foaming conditions are as follows: the temperature is 80-200 ℃, the pressure is 5-30MPa, the pressure is released to the normal pressure after keeping for 5-90min, and the pressure release time is 1-10 s; the cooling and shaping time is 0-30 min; the density of the expanded beads ranges from 40 to 600kg/m3The diameter of the cells is 50-300 μm.
In the foaming process, the key steps are control of pressure maintaining time and pressure relief operation, the supercritical state of the foaming agent needs to be maintained, the material is softened and bonded at high temperature due to overlong pressure maintaining time, and the material is not completely fused with the foaming agent and the foaming effect is poor due to overlong time; too fast a pressure release may result in too small foam cells with low multiplying power, too slow a pressure release may result in too large cells, a small number of cells, and low foam strength.
Compared with the prior art, the invention has the following beneficial effects:
(1) the comonomer can destroy the regularity of the original PET chain segment, thereby destroying the crystallization to form random polyester without melting point and crystallization peak, reducing the processing temperature, improving the foaming effect,
(2) the halogen-free flame retardant which accords with the environmental protection concept is used, so that toxic and harmful gas or smoke is not generated after the halogen-free flame retardant is ignited, and the halogen-free flame retardant has good cost advantage and processing advantage;
(3) the in-situ polymerization mode is adopted, the processing is convenient, the reaction rate is high, the foaming interval is wide, and the melt strength and the melt viscosity are obviously improved; and the production flow is simplified, the energy consumption is reduced, the industrial processing and production are facilitated, and the market prospect is good.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
general examples
1. Preparation of foamable flame-retardant PET polyester
The foamable flame-retardant PET polyester comprises the following components in parts by weight: 100 parts of terephthalic acid, 30-100 parts of ethylene glycol, 1-60 parts of comonomer, 0.02-0.12 part of catalyst, 0.005-0.3 part of antioxidant, 1-50 parts of flame retardant and 0.1-1 part of stabilizer.
Wherein the comonomer is one or more of neopentyl glycol, 2,4, 4-tetramethyl-1, 3-cyclobutanediol or 1, 4-cyclohexanedimethanol; the catalyst is one or more of ethylene glycol antimony, antimony trioxide, antimony acetate, tetrabutyl titanate, tetraisopropyl titanate and zinc acetate; the antioxidant is at least one of phenol antioxidant and phosphite antioxidant, including antioxidant 1010, antioxidant 168, and triphenyl phosphite; the flame retardant is at least one of halogen-free phosphorus flame retardants, including red phosphorus, 2-hydroxyethyl phenyl hypophosphorous acid, hydroxymethyl phenyl hypophosphorous acid, poly-p-phenylphenylphosphine nitrile benzoate, diammonium hydrogen phosphate, (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid; the stabilizer is red phosphorus.
The preparation method of the foamable flame-retardant PET polyester comprises the following steps:
(1) mixing terephthalic acid, ethylene glycol and a comonomer according to a ratio, preheating at the temperature of 60-150 ℃, adding a catalyst, stirring, carrying out an esterification reaction in a nitrogen atmosphere, and reacting for 1-4h under the conditions that the temperature is 200-260 ℃ and the pressure is 0.1-0.38 MPa;
(2) adding a flame retardant into ethylene glycol, heating to obtain mixed slurry, then adding the mixed slurry into the step (1) after the esterification reaction is finished, and adding a stabilizer and an antioxidant for stirring; then, firstly, carrying out a pre-polycondensation reaction at the temperature of 250-290 ℃, vacuumizing for 60-120min to the absolute pressure of below 1000Pa, then carrying out a final polycondensation reaction, reacting for 60-150min under the conditions of the temperature of 260-290 ℃ and the pressure of 0-300Pa, discharging and pelletizing after the reaction is finished, and obtaining the flame-retardant PET polyester chip;
(3) the flame-retardant PET polyester chip is filled with foaming agent (CO)2Or N2) Preheating at 80-200 deg.C under 5-30MPa for 5-90min, and rapidly relieving pressure to normal pressure for 1-10 s; finally cooling and shaping for 0-30min to obtain the flame-retardant PET polyester expanded beads, wherein the density range of the expanded beads is 40-600kg/m3The diameter of the cells is 50-300 μm.
2. Performance testing
1) Vertical combustion
And carrying out copolymerization flame-retardant modification on PET, and characterizing the flame-retardant property of a sample by vertically burning the modified sample. In the experiment, a horizontal and vertical combustion tester is adopted to carry out combustion test on the flame-retardant sample, and the flame-retardant sample is compared with the UL94V-0 standard to carry out flame-retardant grade classification. The measured sample meets the standard technical index, wherein the ignition distance of the sample is required to be 20mm +/-2 mm from the height of 150mm blue flame, the length of the sample is 125mm +/-5 mm, the width is 13.0mm +/-0.3 mm, the thickness is 3.0mm +/-0.2 mm, and the used gas is methane.
In the test, one end of the prepared standard sample is fixed on a vertical fixture, the other end is exposed in a specified test flame, and the vertical burning behavior of the sample is evaluated by observing and recording the burning time, the dropping of the comburent particles and whether the absorbent cotton is burnt or not, and is classified according to the UL94V-0 standard. During the test, 5 bars were prepared per group, measured several times and the mean value calculated. Absorbent cotton was placed at the lower end of the sample by 12cm, the flame height was adjusted to 20. + -.1 mm, the flame was continuously applied to the sample for 10 seconds, and then the flame was withdrawn. Performing combustion test on the sample for 10 seconds twice, extinguishing the flame within 10 seconds, enabling no combustible to fall off, and evaluating the grade as V-0; performing combustion test on the sample for 10 seconds twice, extinguishing the flame within 30 seconds, allowing the comburent to fall off, but not igniting the absorbent cotton at the lower end of the sample strip, and evaluating as V-1 grade; the sample was subjected to two 10 second burn tests, the flame was extinguished within 30 seconds, and any combustible falling, allowing the droppings to ignite cotton wool, rated V-2, and the sample was not allowed to burn onto the fixture for each burn.
2) Limiting oxygen index
The flame retardant modified sample was subjected to determination of Limiting Oxygen Index (LOI) by a limiting oxygen index instrument, which is the minimum volume fraction of oxygen in a mixed gas of nitrogen and oxygen that provides sufficient combustion of the material. For materials with an LOI value less than 22%, defining as combustible materials; an LOI value between 22% and 27%, defined as combustible material; LOI values greater than 27% are defined as flame retardant materials. The selection of the test sample and the instrument is required to meet the standard sample specification of GB2406-80, the length is 80-120 mm, the width is 10mm, and the thickness is 4 mm. In the testing process, a test sample strip is vertically fixed in a combustion cylinder, then oxygen and nitrogen mixed gas flows through the combustion cylinder from bottom to top, the sample strip is ignited from the top end, meanwhile, the combustion length of the sample is observed and recorded, and compared with the specified length, when the oxygen concentration just maintains the stable combustion of the plastic, the oxygen concentration at the moment is expressed by the volume percentage of the oxygen content in the mixed gas, and the oxygen concentration is the limit oxygen index of the sample.
3) Density of foam
The actual density of the foam beads is measured by adopting a drainage method, the average value of 3 samples is taken, the density of the foam beads is obtained mainly by comparing the mass of the foam samples in the air and the mass of the foam samples in the water, and the foaming ratio can be obtained by knowing the density of the foaming material and the density of the raw materials.
The density of the foamed sample can be determined according to the calculation formula:
wherein alpha is the mass of the foaming sample in the air; b is the total mass of the bob and the sample immersed in the water; w is the mass of the suspension hammer immersed in water; ρ f is the density of the sample to be measured; ρ water is the density of water.
The volume expansion ratio (expansion ratio) can be obtained from the ratio of the density of the raw material to the density of the expanded polymer:
wherein Rv is the expansion ratio; ρ is the density of the polymer before foaming; ρ f is the density of the foamed polymer.
Example 1
The expandable flame-retardant PET polyester comprises: 100 parts of terephthalic acid, 75 parts of ethylene glycol, 30 parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, 0.05 part of ethylene glycol antimony, 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 10 parts of 2-hydroxyethyl phenyl hypophosphorous acid and 0.1 part of red phosphorus.
The preparation method comprises the following steps:
(1) adding 100 parts of terephthalic acid, 70 parts of ethylene glycol, 30 parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol and 0.05 part of ethylene glycol antimony into a 2.5L reaction kettle, preheating and stirring at 100 ℃ for 15min, introducing nitrogen, starting esterification reaction for 3h at 230 ℃ and 0.38MPa, and stirring and collecting condensed water until water outlet is finished;
(2) adding 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 10 parts of slurry prepared from 2-hydroxyethyl phenyl hypophosphorous acid and 5 parts of ethylene glycol and 0.1 part of red phosphorus into the step (1) after the esterification reaction is finished, and stirring for 10 min; then, carrying out a pre-polycondensation reaction at 280 ℃ and vacuumizing for 100min to the absolute pressure of below 100Pa, carrying out a final polycondensation reaction, recording the stirring torque, starting the reaction for 90min from the rise of the stirring torque, at 280 ℃ and under the pressure of 60Pa, discharging and pelletizing after the reaction is finished, and obtaining the flame-retardant PET polyester chips;
(3) placing the flame-retardant PET polyester chip into a foaming kettle, and filling foaming agent CO2Preheating to 180 deg.C under 15MPa, maintaining at constant temperature and pressure for 20min, and rapidly heatingReleasing the pressure for 3s to normal pressure; finally, cooling and shaping for 10min to obtain the flame-retardant PET polyester foamed beads.
Example 2
The expandable flame-retardant PET polyester comprises: 100 parts of terephthalic acid, 85 parts of ethylene glycol, 20 parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, 0.02 part of ethylene glycol antimony, 0.04 part of zinc acetate, 0.1 part of triphenyl phosphite, 20 parts of 2-hydroxyethyl phenyl hypophosphorous acid and 0.3 part of red phosphorus.
The preparation method comprises the following steps:
(1) adding 100 parts of terephthalic acid, 80 parts of ethylene glycol, 20 parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol and 0.02 part of ethylene glycol antimony into a 2.5L reaction kettle, preheating and stirring at the temperature of 110 ℃ for 15min, introducing nitrogen, starting esterification reaction for 2h at the temperature of 250 ℃ and under the pressure of 0.35MPa, and stirring and collecting condensed water until water outlet is finished;
(2) adding 0.04 part of zinc acetate, 0.1 part of triphenyl phosphite, 20 parts of slurry prepared from 2-hydroxyethyl phenyl hypophosphorous acid and 5 parts of ethylene glycol and 0.3 part of red phosphorus into the step (1) after the esterification reaction is finished, and stirring for 10 min; then, carrying out a pre-polycondensation reaction at the temperature of 250 ℃ for 100min under the absolute pressure of 100Pa, carrying out a final polycondensation reaction, recording the stirring torque, starting the reaction for 100min from the rise of the stirring torque at the temperature of 290 ℃ under the pressure of 70Pa, discharging and dicing after the reaction is finished, and obtaining the flame-retardant PET polyester chips;
(3) placing the flame-retardant PET polyester chip into a foaming kettle, and filling foaming agent CO2Preheating to 130 ℃, keeping the pressure at 20MPa, keeping the constant temperature and the constant pressure for 20min, and then quickly releasing the pressure for 3s to the normal pressure; finally, cooling and shaping for 10min to obtain the flame-retardant PET polyester foamed beads.
Example 3
The difference from example 1 is that: the comonomer is neopentyl glycol.
The expandable flame-retardant PET polyester comprises: 100 parts of terephthalic acid, 75 parts of ethylene glycol, 30 parts of neopentyl glycol, 0.05 part of ethylene glycol antimony, 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 15 parts of 2-hydroxyethyl phenyl hypophosphorous acid and 0.1 part of red phosphorus.
The preparation method comprises the following steps:
(1) adding 100 parts of terephthalic acid, 70 parts of ethylene glycol, 30 parts of neopentyl glycol and 0.05 part of ethylene glycol antimony into a 2.5L reaction kettle, preheating and stirring at the temperature of 100 ℃ for 15min, introducing nitrogen, starting esterification reaction at the temperature of 230 ℃ and the pressure of 0.38MPa for 3h, stirring, and collecting condensed water until water outlet is finished;
(2) adding 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 15 parts of slurry prepared from 2-hydroxyethyl phenyl hypophosphorous acid and 5 parts of ethylene glycol and 0.1 part of red phosphorus into the step (1) after the esterification reaction is finished, and stirring for 10 min; then, carrying out a pre-polycondensation reaction at 280 ℃ and vacuumizing for 100min to the absolute pressure of below 100Pa, carrying out a final polycondensation reaction, recording the stirring torque, starting the reaction for 90min from the rise of the stirring torque, at 280 ℃ and under the pressure of 60Pa, discharging and pelletizing after the reaction is finished, and obtaining the flame-retardant PET polyester chips;
(3) placing the flame-retardant PET polyester chip into a foaming kettle, and filling foaming agent CO2Preheating to 180 ℃, keeping the pressure at 15MPa at constant temperature and constant pressure for 20min, and then quickly relieving the pressure for 3s to normal pressure; finally, cooling and shaping for 10min to obtain the flame-retardant PET polyester foamed beads.
Example 4
The difference from example 1 is that: the comonomers are 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol and neopentyl glycol.
The expandable flame-retardant PET polyester comprises: 100 parts of terephthalic acid, 75 parts of ethylene glycol, 20 parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, 10 parts of neopentyl glycol, 0.05 part of ethylene glycol antimony, 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 10 parts of 2-hydroxyethyl phenylphosphinic acid and 0.1 part of red phosphorus.
The preparation method comprises the following steps:
(1) adding 100 parts of terephthalic acid, 70 parts of ethylene glycol, 20 parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, 10 parts of neopentyl glycol and 0.05 part of ethylene glycol antimony into a 2.5L reaction kettle, preheating and stirring at the temperature of 100 ℃ for 15min, introducing nitrogen, starting esterification reaction at the temperature of 230 ℃ and the pressure of 0.38MPa for 3h, stirring, and collecting condensed water until water outlet is finished;
(2) adding 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 10 parts of slurry prepared from 2-hydroxyethyl phenyl hypophosphorous acid and 5 parts of ethylene glycol and 0.1 part of red phosphorus into the step (1) after the esterification reaction is finished, and stirring for 10 min; then, carrying out a pre-polycondensation reaction at the temperature of 280 ℃ for 100min under the absolute pressure of 100Pa, then carrying out a final polycondensation reaction, recording the stirring torque, starting the reaction for 90min from the rise of the stirring torque at the temperature of 280 ℃ under the pressure of 60Pa, discharging and pelletizing after the reaction is finished, and obtaining the flame-retardant PET polyester chips;
(3) placing the flame-retardant PET polyester chip into a foaming kettle, and filling foaming agent CO2Preheating to 180 ℃ and 15MPa, keeping constant temperature and pressure for 20min, and quickly releasing pressure for 3s to normal pressure; finally, cooling and shaping for 10min to obtain the flame-retardant PET polyester foamed beads.
Example 5
The difference from example 1 is that: the comonomer is 1, 4-cyclohexanedimethanol.
The expandable flame-retardant PET polyester comprises: 100 parts of terephthalic acid, 75 parts of ethylene glycol, 30 parts of 1, 4-cyclohexanedimethanol, 0.05 part of ethylene glycol antimony, 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 15 parts of 2-hydroxyethyl phenyl hypophosphorous acid and 0.1 part of red phosphorus.
The preparation method comprises the following steps:
(1) adding 100 parts of terephthalic acid, 70 parts of ethylene glycol, 30 parts of 1, 4-cyclohexanedimethanol and 0.05 part of ethylene glycol antimony into a 2.5L reaction kettle, preheating and stirring at 100 ℃ for 15min, introducing nitrogen, starting esterification reaction for 3h at 230 ℃ and 0.38MPa, and stirring and collecting condensed water until water outlet is finished;
(2) adding 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 15 parts of slurry prepared from 2-hydroxyethyl phenyl hypophosphorous acid and 5 parts of ethylene glycol and 0.1 part of red phosphorus into the step (1) after the esterification reaction is finished, and stirring for 10 min; then, carrying out a pre-polycondensation reaction at 280 ℃ and vacuumizing for 100min to the absolute pressure of below 100Pa, carrying out a final polycondensation reaction, recording the stirring torque, starting the reaction for 90min from the rise of the stirring torque, at 280 ℃ and under the pressure of 60Pa, discharging and pelletizing after the reaction is finished, and obtaining the flame-retardant PET polyester chips;
(3) placing the flame-retardant PET polyester chip into a foaming kettle, and filling foaming agent CO2Preheating to 180 ℃ and 15MPa, keeping constant temperature and pressure for 20min, and quickly releasing pressure for 3s to normal pressure; finally, cooling and shaping for 10min to obtain the flame-retardant PET polyester foamed beads.
Example 6
The difference from example 1 is that: the comonomers are 1, 4-cyclohexanedimethanol and neopentyl glycol.
The expandable flame-retardant PET polyester comprises: 100 parts of terephthalic acid, 75 parts of ethylene glycol, 20 parts of 1, 4-cyclohexanedimethanol, 10 parts of neopentyl glycol, 0.05 part of ethylene glycol antimony, 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 15 parts of 2-hydroxyethyl phenyl hypophosphorous acid and 0.1 part of red phosphorus.
The preparation method comprises the following steps:
(1) adding 100 parts of terephthalic acid, 70 parts of ethylene glycol, 20 parts of 1, 4-cyclohexanedimethanol, 10 parts of neopentyl glycol and 0.05 part of ethylene glycol antimony into a 2.5L reaction kettle, preheating and stirring at 100 ℃ for 15min, introducing nitrogen, starting esterification reaction for 3h at 230 ℃ and 0.38MPa, stirring, and collecting condensed water until water outlet is finished;
(2) adding 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 15 parts of slurry prepared from 2-hydroxyethyl phenyl hypophosphorous acid and 5 parts of ethylene glycol and 0.1 part of red phosphorus into the step (1) after the esterification reaction is finished, and stirring for 10 min; then, carrying out a pre-polycondensation reaction at 280 ℃ and vacuumizing for 100min to the absolute pressure of below 100Pa, carrying out a final polycondensation reaction, recording the stirring torque, starting the reaction for 90min from the rise of the stirring torque, at 280 ℃ and under the pressure of 60Pa, discharging and pelletizing after the reaction is finished, and obtaining the flame-retardant PET polyester chips;
(3) placing the flame-retardant PET polyester chip into a foaming kettle, and filling foaming agent CO2Preheating to 180 ℃ and 15MPa, keeping constant temperature and pressure for 20min, and quickly releasing pressure for 3s to normal pressure; finally, cooling and shaping for 10min to obtain the flame-retardant PET polyester foamed beads.
Comparative example 1
The difference from example 1 is that: the 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol was replaced by the same mass parts of ethylene glycol.
The expandable flame-retardant PET polyester comprises: 100 parts of terephthalic acid, 105 parts of ethylene glycol, 0.05 part of ethylene glycol antimony, 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 10 parts of 2-hydroxyethyl phenyl hypophosphorous acid and 0.1 part of red phosphorus.
The preparation method comprises the following steps:
(1) adding 100 parts of terephthalic acid, 100 parts of ethylene glycol and 0.05 part of ethylene glycol antimony into a 2.5L reaction kettle, preheating and stirring at the temperature of 100 ℃ for 15min, introducing nitrogen, starting an esterification reaction at the temperature of 230 ℃ and the pressure of 0.38MPa for 3h, stirring, and collecting condensed water until water outlet is finished;
(2) adding 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 10 parts of slurry prepared from 2-hydroxyethyl phenyl hypophosphorous acid and 5 parts of ethylene glycol and 0.1 part of red phosphorus into the step (1) after the esterification reaction is finished, and stirring for 10 min; then, carrying out a pre-polycondensation reaction at 280 ℃ and vacuumizing for 100min to the absolute pressure of below 100Pa, carrying out a final polycondensation reaction, recording the stirring torque, starting the reaction for 90min from the rise of the stirring torque, at 280 ℃ and under the pressure of 60Pa, discharging and pelletizing after the reaction is finished, and obtaining the flame-retardant PET polyester chips;
(3) placing the flame-retardant PET polyester chip into a foaming kettle, and filling foaming agent CO2Preheating to 180 ℃ and 15MPa, keeping constant temperature and pressure for 20min, and quickly releasing pressure for 3s to normal pressure; finally, cooling and shaping for 10min to obtain the flame-retardant PET polyester foamed beads.
Comparative example 2
The difference from example 1 is that: the ethylene glycol was replaced with the same mass parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol.
The expandable flame-retardant PET polyester comprises: 100 parts of terephthalic acid, 5 parts of ethylene glycol, 100 parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, 0.05 part of ethylene glycol antimony, 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 10 parts of 2-hydroxyethyl phenyl hypophosphorous acid and 0.1 part of red phosphorus.
The preparation method comprises the following steps:
(1) adding 100 parts of terephthalic acid, 20 parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol and 0.05 part of ethylene glycol antimony into a 2.5L reaction kettle, preheating and stirring at 100 ℃ for 15min, introducing nitrogen, starting esterification reaction at 230 ℃ and 0.38MPa for 3h, stirring, and collecting condensed water until water outlet is finished;
(2) adding 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 10 parts of slurry prepared from 2-hydroxyethyl phenyl hypophosphorous acid and 5 parts of ethylene glycol and 0.1 part of red phosphorus into the step (1) after the esterification reaction is finished, and stirring for 10 min; then, carrying out a pre-polycondensation reaction at 280 ℃ and vacuumizing for 100min to the absolute pressure of below 100Pa, carrying out a final polycondensation reaction, recording the stirring torque, starting the reaction for 90min from the rise of the stirring torque, at 280 ℃ and under the pressure of 60Pa, discharging and pelletizing after the reaction is finished, and obtaining the flame-retardant PET polyester chips;
(3) placing the flame-retardant PET polyester chip into a foaming kettle, and filling foaming agent CO2Preheating to 180 ℃ and 15MPa, keeping constant temperature and pressure for 20min, and quickly releasing pressure for 3s to normal pressure; finally, cooling and shaping for 10min to obtain the flame-retardant PET polyester foamed beads.
Comparative example 3
The difference from example 1 is that: the pressure maintaining time is reduced by half to 10 min.
The expandable flame-retardant PET polyester comprises: 100 parts of terephthalic acid, 75 parts of ethylene glycol, 30 parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, 0.05 part of ethylene glycol antimony, 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 10 parts of 2-hydroxyethyl phenylphosphinic acid and 0.1 part of red phosphorus.
The preparation method comprises the following steps:
(1) adding 100 parts of terephthalic acid, 70 parts of ethylene glycol, 30 parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol and 0.05 part of ethylene glycol antimony into a 2.5L reaction kettle, preheating and stirring at the temperature of 100 ℃ for 15min, introducing nitrogen, starting esterification reaction at the temperature of 230 ℃ and the pressure of 0.38MPa for 3h, stirring, and collecting condensed water until water outlet is finished;
(2) adding 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 10 parts of slurry prepared from 2-hydroxyethyl phenyl hypophosphorous acid and 5 parts of ethylene glycol and 0.1 part of red phosphorus into the step (1) after the esterification reaction is finished, and stirring for 10 min; then, carrying out a pre-polycondensation reaction at 280 ℃ and vacuumizing for 100min to the absolute pressure of below 100Pa, carrying out a final polycondensation reaction, recording the stirring torque, starting the reaction for 90min from the rise of the stirring torque, at 280 ℃ and under the pressure of 60Pa, discharging and pelletizing after the reaction is finished, and obtaining the flame-retardant PET polyester chips;
(3) placing the flame-retardant PET polyester chip into a foaming kettle, and filling foaming agent CO2Preheating to 180 ℃ and 15MPa, keeping constant temperature and pressure for 10min, and quickly releasing pressure for 3s to normal pressure; finally, cooling and shaping for 10min to obtain the flame-retardant PET polyester foamed beads.
Comparative example 4
The difference from example 1 is that: the amount of the flame retardant added was increased to 50 parts.
The expandable flame-retardant PET polyester comprises: 100 parts of terephthalic acid, 75 parts of ethylene glycol, 30 parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol, 0.05 part of ethylene glycol antimony, 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 50 parts of 2-hydroxyethyl phenyl hypophosphorous acid and 0.1 part of red phosphorus.
The preparation method comprises the following steps:
(1) adding 100 parts of terephthalic acid, 70 parts of ethylene glycol, 30 parts of 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol and 0.05 part of ethylene glycol antimony into a 2.5L reaction kettle, preheating and stirring at 100 ℃ for 15min, introducing nitrogen, starting esterification reaction for 3h at 230 ℃ and 0.38MPa, and stirring and collecting condensed water until water outlet is finished;
(2) adding 0.02 part of zinc acetate, 0.3 part of triphenyl phosphite, 50 parts of slurry prepared from 2-hydroxyethyl phenyl hypophosphorous acid and 5 parts of ethylene glycol and 0.1 part of red phosphorus into the step (1) after the esterification reaction is finished, and stirring for 10 min; then, carrying out a pre-polycondensation reaction at 280 ℃ and vacuumizing for 100min to the absolute pressure of below 100Pa, carrying out a final polycondensation reaction, recording the stirring torque, starting the reaction for 90min from the rise of the stirring torque, at 280 ℃ and under the pressure of 60Pa, discharging and pelletizing after the reaction is finished, and obtaining the flame-retardant PET polyester chips;
(3) placing the flame-retardant PET polyester chip into a foaming kettle, and filling foaming agent CO2Preheating to 180 ℃, keeping the pressure at 15MPa at constant temperature and constant pressure for 20min, and then quickly relieving the pressure for 3s to normal pressure; finally, cooling and shaping for 10min to obtain the flame-retardant PET polyester foamed beads.
TABLE 1 results of Performance test of samples of examples and comparative examples
As shown in Table 1, the invention can overcome the problem that the melt strength is low and foaming is difficult due to the linear structure of the PET molecular chain, and simultaneously solve the problem of inflammability of the foaming material, thereby realizing light-weight flame retardance of the foaming material. With the combination of the embodiments 1 to 6, when a single comonomer is added, 1, 4-cyclohexanedimethanol forms a completely random structure, compared with other comonomers, the molecular structure has better flexibility, weakened rigidity, greatly reduced foaming temperature and high foaming ratio, and can exert the flame retardant effect of the flame retardant to a greater extent and enhance the flame retardant property; compared with the addition of a single comonomer, the addition of the composite comonomer can effectively enhance the foaming effect and increase the polyester branched structure, thereby improving the foaming effect. As is clear from comparative example 1 and example 1, the addition of no comonomer at all causes the polyester to retain a crystal structure, and hence the polyester cannot be foamed or has an extremely high foamable temperature and an extremely low ratio. From comparative example 2 and example 1, it is clear that the complete replacement of ethylene glycol with comonomer allows the polyester to continue to maintain the crystal structure and the foaming effect is extremely poor. It is understood from comparative example 3 and example 1 that the pressure holding time during foaming is reduced, the blowing agent is not uniformly diffused, and the foaming effect is greatly affected. From comparative example 4 and example 1, it is understood that increasing the amount of the flame retardant can effectively enhance the flame retardant effect, but at the same time, greatly reduces the foaming effect.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The foamable flame-retardant PET polyester is characterized by comprising the following components in parts by weight:
terephthalic acid 100 parts
30-100 parts of ethylene glycol
1-60 parts of comonomer
0.02-0.12 part of catalyst
0.005-0.3 part of antioxidant
1-50 parts of fire retardant
0.1-1 part of stabilizer.
2. The foamable, flame retardant PET polyester of claim 1, wherein the comonomer is one or more of neopentyl glycol, 2,4, 4-tetramethyl-1, 3-cyclobutanediol, or 1, 4-cyclohexanedimethanol.
3. The foamable flame retardant PET polyester of claim 1, wherein the catalyst is one or more of ethylene glycol antimony, antimony trioxide, antimony acetate, tetrabutyl titanate, tetraisopropyl titanate and zinc acetate; the stabilizer is red phosphorus.
4. The foamable flame retardant PET polyester of claim 1, wherein the antioxidant is at least one of a phenolic antioxidant and a phosphite antioxidant.
5. The foamable flame retardant PET polyester of claim 4, wherein the antioxidant is 1010, 168, triphenyl phosphite.
6. The foamable flame retardant PET polyester according to claim 1, wherein the flame retardant is at least one of halogen-free phosphorus flame retardants.
7. The foamable flame retardant PET polyester of claim 6, wherein the flame retardant is one or more of red phosphorus, 2-hydroxyethylphenylphosphinic acid, hydroxymethylphenylphosphinic acid, polyparaphenylphosphine benzoate, diammonium hydrogen phosphate, (6-oxo-6H-dibenzo [ C, E ] [1,2] oxaphosphorin-6-yl) methyl ] succinic acid.
8. A process for the preparation of the expandable flame retardant PET polyester according to any one of claims 1 to 7, characterized in that it comprises the following steps:
(1) mixing terephthalic acid, ethylene glycol and a comonomer according to a ratio, preheating, adding a catalyst, stirring, and carrying out an esterification reaction in an inert atmosphere;
(2) adding a flame retardant into ethylene glycol, heating to obtain mixed slurry, then adding the mixed slurry into the step (1) after the esterification reaction is finished, adding a stabilizer and an antioxidant, and stirring; then, carrying out a pre-polycondensation reaction, carrying out a final polycondensation reaction, discharging and granulating after the reaction is finished, and obtaining the flame-retardant PET polyester chip;
(3) and filling the flame-retardant PET polyester chips with a foaming agent, foaming, and finally cooling and shaping to obtain the flame-retardant PET polyester foamed beads.
9. The method according to claim 8, wherein in the step (1), the temperature of the preheating is 60 to 150 ℃; the temperature of the esterification reaction is 200-260 ℃, the pressure is 0.1-0.38MPa, and the reaction time is 1-4 h;
in the step (2), the pre-polycondensation reaction is performed by vacuumizing for 60-120min to the absolute pressure of below 100Pa and at the temperature of 250-290 ℃; the final polycondensation reaction is carried out at the temperature of 260-290 ℃, the pressure of 0-300Pa and the reaction time of 60-150 min.
10. The production method according to claim 8 or 9, wherein in the step (3), the blowing agent is one or both of carbon dioxide and nitrogen; the foaming conditions are as follows: the temperature is 80-200 ℃, the pressure is 5-30MPa, the pressure is released to the normal pressure after keeping for 5-90min, and the pressure release time is 1-10 s; the cooling and shaping time is 0-30 min; the density of the expanded beads ranges from 40 to 600kg/m3The diameter of the cells is 50-300 μm.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731758A (en) * | 2012-03-13 | 2012-10-17 | 蓝海永乐（江苏）新材料有限公司 | Foamable flame-retarding polyester capable of being used for supercritical CO2 and preparation method and application thereof |
| CN105778066A (en) * | 2016-02-24 | 2016-07-20 | 扬州众研新材料科技有限公司 | Low-melting-point copolyester and preparing method thereof |
| US20200308363A1 (en) * | 2019-03-29 | 2020-10-01 | DDP Specialty Electronic Materials US, Inc. | Chemically modified polyesters and process for making |
| US20200308396A1 (en) * | 2019-03-29 | 2020-10-01 | DDP Specialty Electronic Materials US, Inc. | Amorphous polyester composition and method of making |
| CN111748084A (en) * | 2020-06-30 | 2020-10-09 | 四川东材科技集团股份有限公司 | Antibacterial flame-retardant polyester resin and preparation method thereof |
| CN113136028A (en) * | 2021-03-24 | 2021-07-20 | 浙江恒澜科技有限公司 | Foamable modified polyester and preparation method thereof |
| CN113150256A (en) * | 2021-04-21 | 2021-07-23 | 浙江恒澜科技有限公司 | Branched copolyester for bead foaming and preparation method thereof |
-
2022
- 2022-02-25 CN CN202210178484.3A patent/CN114591528A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731758A (en) * | 2012-03-13 | 2012-10-17 | 蓝海永乐（江苏）新材料有限公司 | Foamable flame-retarding polyester capable of being used for supercritical CO2 and preparation method and application thereof |
| CN105778066A (en) * | 2016-02-24 | 2016-07-20 | 扬州众研新材料科技有限公司 | Low-melting-point copolyester and preparing method thereof |
| US20200308363A1 (en) * | 2019-03-29 | 2020-10-01 | DDP Specialty Electronic Materials US, Inc. | Chemically modified polyesters and process for making |
| US20200308396A1 (en) * | 2019-03-29 | 2020-10-01 | DDP Specialty Electronic Materials US, Inc. | Amorphous polyester composition and method of making |
| CN111748084A (en) * | 2020-06-30 | 2020-10-09 | 四川东材科技集团股份有限公司 | Antibacterial flame-retardant polyester resin and preparation method thereof |
| CN113136028A (en) * | 2021-03-24 | 2021-07-20 | 浙江恒澜科技有限公司 | Foamable modified polyester and preparation method thereof |
| CN113150256A (en) * | 2021-04-21 | 2021-07-23 | 浙江恒澜科技有限公司 | Branched copolyester for bead foaming and preparation method thereof |
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