CN114644656A - Preparation method of cyclic phosphorus-boron flame retardant and flame-retardant smoke-suppressing polyester film - Google Patents
Preparation method of cyclic phosphorus-boron flame retardant and flame-retardant smoke-suppressing polyester film Download PDFInfo
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- CN114644656A CN114644656A CN202210179673.2A CN202210179673A CN114644656A CN 114644656 A CN114644656 A CN 114644656A CN 202210179673 A CN202210179673 A CN 202210179673A CN 114644656 A CN114644656 A CN 114644656A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 221
- 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 220
- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 122
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229920006267 polyester film Polymers 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920000728 polyester Polymers 0.000 claims abstract description 72
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 52
- 239000010452 phosphate Substances 0.000 claims abstract description 52
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 41
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 38
- 239000000779 smoke Substances 0.000 claims abstract description 35
- -1 cyclic boric acid ester Chemical class 0.000 claims abstract description 33
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 31
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004327 boric acid Substances 0.000 claims abstract description 20
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 13
- 238000009998 heat setting Methods 0.000 claims description 12
- 238000005266 casting Methods 0.000 claims description 10
- 230000002401 inhibitory effect Effects 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 claims 1
- 150000001263 acyl chlorides Chemical class 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 26
- 229960001701 chloroform Drugs 0.000 description 22
- 150000002148 esters Chemical class 0.000 description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 229910052796 boron Inorganic materials 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 238000011056 performance test Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000835 fiber Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 125000003003 spiro group Chemical group 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003867 O—B—O Inorganic materials 0.000 description 1
- 229910003873 O—P—O Inorganic materials 0.000 description 1
- PHXNQAYVSHPINV-UHFFFAOYSA-N P.OB(O)O Chemical compound P.OB(O)O PHXNQAYVSHPINV-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65742—Esters of oxyacids of phosphorus non-condensed with carbocyclic rings or heterocyclic rings or ring systems
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08K5/55—Boron-containing compounds
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention relates to a preparation method of a cyclic phosphorus-boron flame retardant and a flame-retardant smoke-suppressing polyester film, wherein the chemical structural formula of the cyclic phosphorus-boron flame retardant is shown in the specification
Wherein n is 1-2, m is 1-2, and n + m is 2-3; the preparation method comprises the following steps: preparing a cyclic phosphorus-boron flame retardant by nucleophilic substitution reaction of cyclic phosphate alcohol and cyclic boric acid ester monoacyl chloride; the cyclic phosphate alcohol is prepared by reacting cyclic phosphate monoacyl chloride with ethylene glycol, and the cyclic phosphate monoacyl chloride is prepared by performing nucleophilic substitution reaction on phosphorus trichloride and 2-methyl-1, 3-propylene glycol; cyclic boronic acid ester monoThe acyl chloride is prepared by adopting boron trichloride and 2-methyl-1, 3-propanediol through nucleophilic substitution reaction; and uniformly mixing the annular phosphorus-boron flame retardant and the polyester master batch, putting the mixture into a double-screw extruder for melt blending, and extruding to obtain the flame-retardant polyester master batch, thereby preparing the flame-retardant smoke-suppressing polyester film. The cyclic phosphorus boron flame retardant prepared by the invention has good compatibility with polyester, and the flame-retardant polyester film prepared by the cyclic phosphorus boron flame retardant has excellent flame-retardant property and lower smoke release.
Description
Technical Field
The invention belongs to the technical field of polyester films, and relates to a preparation method of a cyclic phosphorus-boron flame retardant and a flame-retardant smoke-suppressing polyester film.
Background
The polyester material has the characteristics of low price, excellent physical property and processability and the like, and is widely applied to the fields of textile and clothing, decoration, packaging materials and the like. However, polyester materials are flammable, have a serious molten drop phenomenon in the combustion process, and have a large smoke emission (particularly recycled polyester), so that the application of the polyester materials is greatly limited. The cyclic phosphate ester flame retardant has the characteristics of no halogen, good compatibility with materials, lasting flame retardant effect and the like, plays roles of flame retardance, plasticization and the like in high polymer materials, and has good development prospect. The currently reported types of cyclic phosphate ester flame retardants are more, wherein the Antiblaze 19 product (also called Amgard CU) developed by the American Mobil company and the domestic FRC-1 product have better flame retardant effect, and can effectively inhibit the melting and dripping phenomena of polyester. However, the cyclic phosphate ester flame retardant has the defects of large smoke generation amount, large toxicity and the like, and still has large fire hazard, so the application of the cyclic phosphate ester flame retardant is limited to a certain extent. In recent years, along with the enhancement of environmental protection consciousness and safety consciousness of people, boron-containing flame retardants have attracted extensive attention due to the advantages of no toxicity, smoke suppression and the like. The Chinese patent CN 103046336A discloses a phosphorus-boron composite flame retardant, phosphorus oxychloride and pentaerythritol are firstly adopted to react in acetonitrile at 80 ℃ for 7 hours to synthesize spiro phosphate diacid chloride, boric acid and glycerol are reacted at 130 ℃ for 3 hours to synthesize boric acid diglyceride, and then the spiro phosphate diacid chloride and the boric acid diglyceride are reacted at 150-180 ℃ for 12-14 hours to synthesize the phosphorus-boron composite flame retardant which is a product in ethnic groups.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of a cyclic phosphorus-boron flame retardant and a flame-retardant smoke-suppressing polyester film. According to the invention, boron trichloride, phosphorus trichloride, 2-methyl-1, 3-propylene glycol and ethylene glycol are used as raw materials to prepare the cyclic phosphorus-boron flame retardant through reaction, and the cyclic phosphorus-boron flame retardant is used for preparing the flame-retardant smoke-suppressing polyester film, and has good compatibility with polyester, good combination and high flame-retardant efficiency. The polyester film prepared by the method has the advantages of excellent flame retardant effect, no molten drop, lower smoke release, good washing resistance and important practical application value.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a cyclic phosphorus boron flame retardant has a chemical structure shown as follows;
wherein n is 1 to 2, m is 1 to 2, and n + m is 2 to 3.
Specifically, the cyclic phosphorus boron flame retardant is one of the following chemical structures:
the cyclic structure in the cyclic phosphorus-boron flame retardant is a six-membered ring structure, the six-membered ring structure in the cyclic phosphorus-boron flame retardant is 2-3, at least one phosphorus-containing six-membered ring and at least one boron-containing six-membered ring are provided, boron and phosphorus are connected with oxygen atoms to form O-B-O and O-P-O structures, and the molecular chain segment of the cyclic phosphorus-boron flame retardant has good linearity.
The invention also provides a preparation method of the cyclic phosphorus boron flame retardant, wherein the cyclic phosphorus boron flame retardant is prepared by the nucleophilic substitution reaction of cyclic phosphate alcohol and cyclic boric acid ester monoacyl chloride;
the cyclic phosphate alcohol is prepared by reacting cyclic phosphate monoacyl chloride with ethylene glycol, and the cyclic phosphate monoacyl chloride is prepared by performing nucleophilic substitution reaction on phosphorus trichloride and 2-methyl-1, 3-propylene glycol;
the cyclic boric acid ester monoacyl chloride is prepared by adopting boron trichloride and 2-methyl-1, 3-propylene glycol through nucleophilic substitution reaction.
As a preferred technical scheme:
according to the preparation method of the cyclic phosphorus-boron flame retardant, the nucleophilic substitution reaction temperature of the cyclic phosphate alcohol and the cyclic borate monoacid chloride is 30-35 ℃, and the time is 1-3 hours;
the molar ratio of the cyclic boronic acid ester monoacyl chloride to the cyclic phosphate ester alcohol is 1: 1-1.2.
According to the preparation method of the cyclic phosphorus boron flame retardant, the reaction temperature of the cyclic phosphate ester monoacyl chloride and the glycol is 25-30 ℃, and the reaction time is 2-3 hours;
the molar ratio of the cyclic phosphate monoacyl chloride to the glycol is 1: 1-1.3, and the glycol is slightly excessive, so that the residual active chlorine is ensured to be completely reacted.
According to the preparation method of the cyclic phosphorus boron flame retardant, the nucleophilic substitution reaction temperature of phosphorus trichloride and 2-methyl-1, 3-propylene glycol is 20-25 ℃, and the time is 2-4 hours;
the molar ratio of phosphorus trichloride to 2-methyl-1, 3-propanediol is 1: 1-1.1, 2-methyl-1, 3-propanediol is slightly excessive, so that two active chlorides in phosphorus trichloride molecules react with two hydroxyl groups of 2-methyl-1, 3-propanediol to generate a cyclic phosphate ester structure.
According to the preparation method of the cyclic phosphorus boron flame retardant, the nucleophilic substitution reaction temperature of boron trichloride and 2-methyl-1, 3-propylene glycol is 25-35 ℃, and the time is 3-4 hours;
the molar ratio of boron trichloride to 2-methyl-1, 3-propylene glycol is 1: 1-1.25, the nucleophilic substitution reaction temperature is not too high, otherwise, boron trichloride is volatilized, and the nucleophilic substitution reaction is not facilitated.
All the reactions adopt trichloromethane as a solvent, and after the reaction is finished, the trichloromethane is purified by reduced pressure distillation.
The invention also provides a method for preparing the flame-retardant smoke-suppressing polyester film by adopting the annular phosphorus-boron flame retardant, which comprises the steps of uniformly mixing the annular phosphorus-boron flame retardant and the polyester master batch, putting the mixture into a double-screw extruder for melt blending, extruding the mixture to obtain the flame-retardant polyester master batch, putting the flame-retardant master batch into a die for sheet casting, and stretching, heat setting and cooling the die to obtain the flame-retardant smoke-suppressing polyester film.
As a preferable technical scheme:
the method for preparing the flame-retardant smoke-suppressing polyester film by using the cyclic phosphorus-boron flame retardant comprises the following specific steps:
(1) respectively drying the cyclic phosphorus-boron flame retardant and the polyester master batch to remove water, mixing the cyclic phosphorus-boron flame retardant and the polyester master batch, and putting the mixture into a double-screw extruder for melt blending;
(2) extruding and cooling the melt after melt blending, and then carrying out grain cutting to obtain flame-retardant polyester master batches;
(3) and introducing the flame-retardant polyester master batch into a mold for casting, and stretching, heat setting and cooling to obtain the flame-retardant smoke-suppressing polyester film.
In the above method, the polyester masterbatch is a virgin polyester masterbatch or a recycled polyester masterbatch.
According to the method, the drying temperature of the polyester master batch is 140-160 ℃, and the time is 2-4 h; the drying temperature of the cyclic phosphorus boron flame retardant is 70-90 ℃, the drying time is 5-7 h, and the final moisture of the polyester master batch and the cyclic phosphorus boron flame retardant is lower than 250 ppm.
According to the method, the processing temperature of the double-screw extruder is 240-280 ℃, the processing temperature is too low, the flame retardant and the polyester master batch cannot be uniformly mixed, granulation is not facilitated, energy waste is caused when the temperature is too high, and the uniform flame-retardant polyester master batch can be smoothly prepared within the temperature range provided by the invention.
The method has the advantages that the stretching temperature is 100-140 ℃, and the heat setting temperature is 200-250 ℃.
According to the method, the cyclic phosphorus-boron flame retardant is used in an amount of 5-10% based on the total mass of the cyclic phosphorus-boron flame retardant and the polyester master batch.
The method has the advantage that the thickness of the flame-retardant smoke-suppressing polyester film is 10-200 mu m.
The method described above, the flame retardant rating according to UL94 standard is V-0; maximum smoke emission D measured according to ISO 5659.2 standardsmaxLess than or equal to 68; the damage length of the flame-retardant smoke-suppression polyester film is 10.2-13.9 cm without being washed by water, and the damage length of the flame-retardant smoke-suppression polyester film after being washed by water for 30 times is 10.5-14.2 cm.
The invention mechanism is as follows:
active chlorine atoms in the boron trichloride and phosphorus trichloride molecules can perform nucleophilic substitution reaction with hydroxyl of polyhydric alcohol, and the reaction conditions are controlled to prepare the cyclic phosphorus boron flame retardant. The hexabasic structure of the cyclic phosphorus boron flame retardant molecule is similar to that of polyester, so that the cyclic phosphorus boron flame retardant molecule and the polyester have good compatibility, the negative effect in the flame retardant adding process is small, the flame retardant can not be separated out, the adverse effect on the mechanical property of the polyester film is avoided, and the cyclic phosphorus borate flame retardant can be combined with the polyester through the similar intermiscibility principle, so that the washing resistance of the flame-retardant polyester film is good; in the thermal decomposition process, the phosphorus-containing flame-retardant groups are decomposed into phosphorus-containing volatile substances, hydrogen free radicals are eliminated, the phosphorus-containing volatile substances play a role in a gas phase, and the boron-containing groups are decomposed to form a boron-rich residual carbon layer which plays a role in a solid phase and covers the surface of the polyester to isolate heat and oxygen. The positions of the P-O group and the B-O group in the cyclic phosphorus-boron flame retardant are close, only a short C-C chain segment is separated in the middle, the structure is easy to generate thermal decomposition, and in the combustion process, the flame retardant is easy to decompose to form complex carbon residue containing P-O-B. Therefore, the phosphorus-containing group and the boron-containing group have a synergistic flame retardant effect, not only act in a gas phase, but also generate P-O-B complex carbon residue in a solid phase, and the carbon residue has good thermal stability and can effectively isolate the supply of heat and oxygen. In the invention, the thermal stability of the P-O-B complex carbon residue is better than that of P-O and B-O carbon residues, and the heat insulation and the supply of oxygen can be more effectively blocked, so that a better flame retardant effect is achieved, and the flame retardant polyester film prepared by the method has a good flame retardant effect and does not generate molten drops; the flame retardant forms P-O-B complex carbon residue with good thermal stability in the pyrolysis process, covers the surface of the polyester matrix, can promote the polyester matrix to generate carbon residue, reduces smoke release and has lower fire hazard.
Has the beneficial effects that:
(1) the raw materials of boron trichloride, phosphorus trichloride, 2-methyl-1, 3-propylene glycol and ethylene glycol used in the invention have sufficient sources and low toxicity, and the synthesized cyclic phosphorus boron flame retardant belongs to an environment-friendly halogen-free flame retardant;
(2) the phosphorus content and the boron content of the prepared cyclic phosphorus-boron flame retardant are high, the phosphorus content and the boron content of the cyclic phosphorus-boron flame retardant are both high, the flame retardant performance of the polyester film is improved through a synergistic flame retardant mechanism, the prepared polyester film not only has excellent flame retardant performance, but also has lower smoke release, and the fire hazard is obviously reduced;
(3) the structure of the prepared cyclic phosphorus boron flame retardant is similar to that of polyester, the compatibility of the cyclic phosphorus boron flame retardant and the polyester is good, the mechanical property of the prepared flame-retardant polyester film is not obviously influenced, the flame-retardant durability is excellent, and the application prospect is wide.
Drawings
FIG. 1 is a scheme for synthesizing the cyclic phosphorus boron flame retardant of example 1.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The method for testing the performance of the polyester film comprises the following steps:
the tensile property of the polyester film is tested according to the GB/T13022-1991 standard;
the flame retardant property of the polyester film is tested according to the UL94 standard;
the smoke generation performance of the polyester film was tested with reference to ISO 5659.2 using a NBS smoke density box and a maximum smoke emission DsmaxCarrying out characterization;
the washing method of the flame-retardant polyester film is referred to AATCC 61-2006 accelerated test of washing fastness for household and commercial use.
Example 1
A preparation method of a cyclic phosphorus boron flame retardant is shown in figure 1 and comprises the following specific steps:
(1) uniformly mixing phosphorus trichloride, 2-methyl-1, 3-propylene glycol and chloroform, reacting at 25 ℃ for 3h to obtain cyclic phosphate ester monoacyl chloride, adding ethylene glycol, continuing to react for 3h to obtain cyclic phosphate ester alcohol, and distilling under reduced pressure at 110 ℃ for purification; wherein the molar ratio of phosphorus trichloride to 2-methyl-1, 3-propylene glycol is 1:1.1, the molar ratio of cyclic phosphate ester monoacyl chloride to ethylene glycol is 1:1.3, and the mass ratio of trichloromethane to phosphorus trichloride is 3: 1;
(2) boron trichloride, 2-methyl-1, 3-propylene glycol and trichloromethane are uniformly mixed and react for 4 hours at the temperature of 30 ℃ to prepare cyclic boric acid ester monoacyl chloride, and the cyclic boric acid ester monoacyl chloride is purified by reduced pressure distillation at the temperature of 70 ℃; wherein the molar ratio of boron trichloride to 2-methyl-1, 3-propanediol is 1:1, and the mass ratio of trichloromethane to boron trichloride is 3: 1;
(3) uniformly mixing cyclic phosphate alcohol, cyclic boric acid ester monoacyl chloride and trichloromethane, reacting at 35 ℃ for 2 hours to prepare a cyclic phosphorus-boron flame retardant, and carrying out reduced pressure distillation at 70 ℃ for purification; wherein the molar ratio of the cyclic boric acid ester monoacyl chloride to the cyclic phosphate ester alcohol is 1:1, and the mass ratio of the trichloromethane to the cyclic phosphate ester alcohol is 3: 1.
The structural formula of the finally prepared cyclic phosphorus boron flame retardant is shown in the specification
Comparative example 1
A preparation method of a cyclic phosphate ester flame retardant comprises the steps of uniformly mixing phosphorus trichloride, 2-methyl-1, 3-propylene glycol and chloroform, reacting at 25 ℃ for 3 hours to prepare cyclic phosphate ester monoacyl chloride, adding ethylene glycol, continuing to react for 3 hours to prepare the cyclic phosphate ester flame retardant, and performing reduced pressure distillation at 110 ℃ for purification; wherein the molar ratio of phosphorus trichloride to 2-methyl-1, 3-propylene glycol is 1:1.1, the molar ratio of cyclic phosphate ester monoacyl chloride to ethylene glycol is 2:1, and the mass ratio of trichloromethane to phosphorus trichloride is 3: 1.
The structural formula of the finally prepared cyclic phosphate ester flame retardant is shown in the specification
Example 2
A preparation method of a cyclic phosphorus boron flame retardant comprises the following specific steps:
(1) uniformly mixing phosphorus trichloride, 2-methyl-1, 3-propylene glycol and chloroform, reacting at 20 ℃ for 4h to prepare cyclic phosphate ester monoacyl chloride, adding ethylene glycol, continuing to react for 2.5h to prepare cyclic phosphate ester alcohol, and distilling under reduced pressure at 110 ℃ for purification; wherein the molar ratio of phosphorus trichloride to 2-methyl-1, 3-propylene glycol is 1:1, the molar ratio of cyclic phosphate ester monoacyl chloride to ethylene glycol is 1:1, and the mass ratio of trichloromethane to phosphorus trichloride is 3: 1;
(2) boron trichloride, 2-methyl-1, 3-propylene glycol and chloroform are mixed uniformly and react for 4 hours at 25 ℃ to prepare cyclic boric acid ester monoacyl chloride, and the cyclic boric acid ester monoacyl chloride is purified by reduced pressure distillation at 70 ℃; wherein the molar ratio of boron trichloride to 2-methyl-1, 3-propanediol is 1:1.2, and the mass ratio of trichloromethane to boron trichloride is 3: 1;
(3) uniformly mixing cyclic phosphate alcohol, cyclic boric acid ester monoacyl chloride and trichloromethane, reacting at 30 ℃ for 3 hours to prepare a cyclic phosphorus-boron flame retardant, and carrying out reduced pressure distillation at 70 ℃ for purification; wherein the molar ratio of the cyclic boric acid ester monoacyl chloride to the cyclic phosphate ester alcohol is 1:1.2, and the mass ratio of the trichloromethane to the cyclic phosphate ester alcohol is 3: 1.
The structural formula of the finally prepared cyclic phosphorus boron flame retardant is shown in the specification
Example 3
A preparation method of a cyclic phosphorus boron flame retardant comprises the following specific steps:
(1) uniformly mixing phosphorus trichloride, 2-methyl-1, 3-propylene glycol and trichloromethane, reacting at 22 ℃ for 3 hours to obtain cyclic phosphate ester monoacyl chloride, adding glycerol, continuing to react at 25 ℃ for 3 hours to obtain cyclic phosphate ester alcohol, and distilling under reduced pressure at 70 ℃ for purification; wherein the molar ratio of phosphorus trichloride to 2-methyl-1, 3-propylene glycol is 1:1.1, the molar ratio of cyclic phosphate ester monoacyl chloride to glycerol is 1:1.1, and the mass ratio of trichloromethane to phosphorus trichloride is 3: 1;
(2) boron trichloride, 2-methyl-1, 3-propylene glycol and trichloromethane are uniformly mixed and react for 3 hours at 35 ℃ to prepare cyclic boric acid ester monoacyl chloride, and the cyclic boric acid ester monoacyl chloride is purified by reduced pressure distillation at 70 ℃; wherein the molar ratio of boron trichloride to 2-methyl-1, 3-propanediol is 1:1.25, and the mass ratio of trichloromethane to boron trichloride is 3: 1;
(3) uniformly mixing cyclic phosphate alcohol, cyclic boric acid ester monoacyl chloride and trichloromethane, reacting at 35 ℃ for 2 hours to prepare a cyclic phosphorus-boron flame retardant, and performing reduced pressure distillation at 70 ℃ for purification; wherein the molar ratio of the cyclic boric acid ester monoacyl chloride to the cyclic phosphate ester alcohol is 2:1.1, and the mass ratio of the trichloromethane to the cyclic phosphate ester alcohol is 3: 1.
The structural formula of the finally prepared cyclic phosphorus boron flame retardant is shown in the specification
Example 4
A preparation method of a flame-retardant smoke-suppressing polyester film comprises the following specific steps:
(1) respectively drying and dewatering the primary polyester master batch (namely, an characterized chemical fiber FG650 film grade slice) and the cyclic phosphorus-boron flame retardant prepared in the embodiment 1, wherein the drying temperature of the primary polyester master batch is 150 ℃, and the drying time is 3 hours; the drying temperature of the cyclic phosphorus boron flame retardant is 80 ℃, and the drying time is 6 hours;
(2) mixing the dried annular phosphorus-boron flame retardant with the primary polyester master batch, and putting the mixture into a double-screw extruder for melt blending; wherein the total mass of the cyclic phosphorus-boron flame retardant and the primary polyester master batch is taken as a reference, and the dosage of the cyclic phosphorus-boron flame retardant is 8 percent; the processing temperature of the double-screw extruder is 270 ℃;
(3) extruding and cooling the melt after melt blending, and then carrying out grain cutting to obtain flame-retardant polyester master batches;
(4) and introducing the flame-retardant polyester master batch into a mold for casting, stretching by 3 times at 130 ℃, heat setting at 230 ℃, and cooling to obtain the flame-retardant smoke-suppressing polyester film with the thickness of 20 mu m.
The prepared flame-retardant smoke-suppressing polyester film is subjected to performance test, and the tensile strength is 201 MPa; the flame-retardant grade of the flame-retardant smoke-suppressing polyester film measured according to the UL94 standard is V-0; the maximum smoke release D of the flame-retardant smoke-inhibiting polyester film is measured according to the ISO 5659.2 standardsmaxIs 48; the damage length of the flame-retardant smoke-suppressing polyester film is 11.3cm, and the damage length after washing for 30 times is 11.5 cm.
Comparative example 2
The preparation method of the polyester film comprises the steps of putting the dried primary polyester master batch in the embodiment 4 into a double-screw extruder, extruding at 270 ℃, introducing the extruded and cooled polyester master batch into a die for casting, stretching by 3 times at 130 ℃, performing heat setting at 230 ℃, and cooling to obtain the flame-retardant smoke-suppression polyester film with the thickness of 20 mu m.
The prepared polyester film is subjected to performance test, and the tensile strength is 215 MPa; the flame retardant grade of the flame retardant smoke suppression polyester film measured according to the UL94 standard is V-2; the maximum smoke release D of the flame-retardant smoke-inhibiting polyester film is measured according to the ISO 5659.2 standardsmaxIs 70; the damage length of the flame-retardant smoke-suppressing polyester film is 30cm, and the damage length after washing for 30 times is 30 cm.
Comparative example 3
A method for preparing a flame-retardant smoke-suppressing polyester film is substantially the same as that in example 4, except that a cyclic phosphorus-boron flame retardant is replaced with the cyclic phosphate ester flame retardant prepared in comparative example 1. The prepared flame-retardant smoke-suppressing polyester film is subjected to performance test, and the tensile strength is 203 MPa; the flame-retardant grade of the flame-retardant smoke-suppressing polyester film measured according to the UL94 standard is V-0; the maximum smoke release D of the flame-retardant smoke-inhibiting polyester film is measured according to the ISO 5659.2 standardsmaxIs 80; the damage length of the flame-retardant smoke-suppressing polyester film is 10.8cm, and the damage length after washing for 30 times is 10.9 cm.
When the example 4 is compared with the comparative examples 2 and 3, the tensile strength of the polyester film after the flame retardant addition of the example 4 is not obviously changed, which shows that the mechanical property of the polyester film is not obviously influenced. The polyester film which is not subjected to flame-retardant modification is completely combusted in the vertical combustion process, the damage length is 30cm, the molten drop is serious, and is V-2 grade, so that the flame retardant property is poor, and the smoke release amount of the polyester film is large; although the polyester film modified by the cyclic phosphate ester flame retardant has better flame retardant property, the smoke generation amount of the polyester film is increased compared with that of the polyester film which is not flame retardant, which shows that the smoke generation amount of the cyclic phosphate ester modified polyester is larger and the fire hazard is large; the damage length of the polyester film modified by the cyclic phosphorus boron flame retardant is obviously reduced, no molten drop is generated, the flame retardant conforms to the V-0 flame retardant level, and the smoke generation amount is reduced, which shows that the polyester film modified by the cyclic phosphorus boron flame retardant has excellent flame retardant property and smaller fire hazard. In addition, the flame-retardant polyester film of example 4 still has good flame retardant property after being washed for 30 times, which shows that the water-washing resistance is excellent.
Example 5
A preparation method of a flame-retardant smoke-suppressing polyester film comprises the following specific steps:
(1) respectively drying and dewatering the primary polyester master batch (characterized chemical fiber FG650 film grade slice) and the cyclic phosphorus boron flame retardant prepared in the embodiment 1, wherein the drying temperature of the primary polyester master batch is 150 ℃, and the drying time is 3 h; the drying temperature of the cyclic phosphorus boron flame retardant is 80 ℃, and the drying time is 6 hours;
(2) mixing the dried annular phosphorus-boron flame retardant with the primary polyester master batch, and putting the mixture into a double-screw extruder for melt blending; wherein, the total mass of the cyclic phosphorus-boron flame retardant and the primary polyester master batch is taken as a reference, and the dosage of the cyclic phosphorus-boron flame retardant is 5 percent; the processing temperature of the double-screw extruder is 270 ℃;
(3) extruding and cooling the melt after melt blending, and then carrying out grain cutting to obtain flame-retardant polyester master batches;
(4) and introducing the flame-retardant polyester master batch into a mold for casting, stretching by 3 times at 130 ℃, heat setting at 230 ℃, and cooling to obtain the flame-retardant smoke-suppressing polyester film with the thickness of 20 mu m.
The prepared flame-retardant smoke-suppressing polyester film is subjected to performance test, and the tensile strength is 206 MPa; the flame-retardant grade of the flame-retardant smoke-suppressing polyester film measured according to the UL94 standard is V-0; the maximum smoke release D of the flame-retardant smoke-inhibiting polyester film is measured according to the ISO 5659.2 standardsmaxIs 57; the damage length of the flame-retardant smoke-suppressing polyester film is 13.9cm, and the damage length after washing for 30 times is 14.2 cm.
Example 6
A preparation method of a flame-retardant smoke-suppressing polyester film comprises the following specific steps:
(1) respectively drying and dehydrating the regenerated polyester master batch (characterization chemical fiber HS500) and the cyclic phosphorus-boron flame retardant prepared in the embodiment 2, wherein the drying temperature of the regenerated polyester master batch is 160 ℃, and the drying time is 2.5 hours; the drying temperature of the cyclic phosphorus boron flame retardant is 90 ℃, and the drying time is 5 hours;
(2) mixing the dried annular phosphorus-boron flame retardant with the regenerated polyester master batch, and putting the mixture into a double-screw extruder for melt blending; wherein the total mass of the cyclic phosphorus-boron flame retardant and the regenerated polyester master batch is taken as a reference, and the dosage of the cyclic phosphorus-boron flame retardant is 10 percent; the processing temperature of the double-screw extruder is 280 ℃;
(3) extruding and cooling the melt after melt blending, and then carrying out grain cutting to obtain flame-retardant polyester master batches;
(4) and introducing the flame-retardant polyester master batch into a mold for casting, stretching by 3 times at 140 ℃, heat setting at 250 ℃, and cooling to obtain the flame-retardant smoke-suppressing polyester film with the thickness of 100 mu m.
The prepared flame-retardant smoke-suppressing polyester film is subjected to performance test, and the tensile strength is 210 MPa; the flame-retardant grade of the flame-retardant smoke-suppressing polyester film measured according to the UL94 standard is V-0; the maximum smoke release D of the flame-retardant smoke-inhibiting polyester film is measured according to the ISO 5659.2 standardsmaxIs 54; the damage length of the flame-retardant smoke-suppressing polyester film is 10.2cm, and the damage length after 30 times of water washing is 10.5 cm.
Comparative example 4
A preparation method of a polyester film comprises the steps of putting the dried regenerated polyester master batch obtained in the embodiment 6 into a double-screw extruder, extruding at the temperature of 280 ℃, introducing the extruded and cooled polyester master batch into a die for casting, stretching for 3 times at the temperature of 140 ℃, performing heat setting at the temperature of 250 ℃, and cooling to obtain the flame-retardant smoke-suppressing polyester film with the thickness of 100 mu m.
The prepared polyester film is subjected to performance test, and the tensile strength is 196 MPa; the flame retardant grade of the flame retardant smoke suppression polyester film measured according to the UL94 standard is V-2; the maximum smoke release D of the flame-retardant smoke-inhibiting polyester film is measured according to the ISO 5659.2 standardsmaxIs 105; the damage length of the flame-retardant smoke-suppressing polyester film is 30cm, and the damage length after washing for 30 times is 30 cm.
Example 7
A preparation method of a flame-retardant smoke-suppressing polyester film comprises the following specific steps:
(1) respectively drying and dewatering the regenerated polyester master batch (characterization chemical fiber HS500) and the cyclic phosphorus-boron flame retardant prepared in the embodiment 2, wherein the drying temperature of the regenerated polyester master batch is 140 ℃ and the drying time is 4 hours; the drying temperature of the cyclic phosphorus boron flame retardant is 70 ℃, and the drying time is 7 hours;
(2) mixing the dried annular phosphorus-boron flame retardant with the regenerated polyester master batch, and putting the mixture into a double-screw extruder for melt blending; wherein the total mass of the cyclic phosphorus-boron flame retardant and the regenerated polyester master batch is taken as a reference, and the dosage of the cyclic phosphorus-boron flame retardant is 6.5 percent; the processing temperature of the double-screw extruder is 240 ℃;
(3) extruding and cooling the melt after melt blending, and then carrying out grain cutting to obtain flame-retardant polyester master batches;
(4) and introducing the flame-retardant polyester master batch into a mold for casting, stretching by 3 times at 110 ℃, heat setting at 210 ℃, and cooling to obtain the flame-retardant smoke-suppressing polyester film with the thickness of 150 mu m.
The prepared flame-retardant smoke-suppressing polyester film is subjected to performance test, and the tensile strength is 202 MPa; the flame-retardant grade of the flame-retardant smoke-suppressing polyester film measured according to the UL94 standard is V-0; the maximum smoke release D of the flame-retardant smoke-inhibiting polyester film is measured according to the ISO 5659.2 standardsmaxIs 68; destroyed length of flame-retardant smoke-inhibiting polyester film13.1cm, and the length of the damage after washing with water 30 times was 13.4 cm.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (15)
1. A cyclic phosphorus boron flame retardant is characterized in that: has the chemical structure shown as follows;
wherein n is 1 to 2, m is 1 to 2, and n + m is 2 to 3.
2. A preparation method of a cyclic phosphorus boron flame retardant is characterized by comprising the following steps: preparing a cyclic phosphorus-boron flame retardant by nucleophilic substitution reaction of cyclic phosphate alcohol and cyclic boric acid ester monoacyl chloride;
the cyclic phosphate alcohol is prepared by reacting cyclic phosphate monoacyl chloride with ethylene glycol, and the cyclic phosphate monoacyl chloride is prepared by performing nucleophilic substitution reaction on phosphorus trichloride and 2-methyl-1, 3-propylene glycol;
the cyclic borate ester monoacyl chloride is prepared by adopting boron trichloride and 2-methyl-1, 3-propanediol through nucleophilic substitution reaction.
3. The preparation method of the cyclic phosphorus boron flame retardant according to claim 2, wherein the nucleophilic substitution reaction temperature of the cyclic phosphate alcohol and the cyclic borate monoacyl chloride is 30-35 ℃ and the time is 1-3 h;
the molar ratio of the cyclic boric acid ester monoacyl chloride to the cyclic phosphoric acid ester alcohol is 1: 1-1.2.
4. The method for preparing the cyclic phosphorus boron flame retardant according to claim 2, wherein the reaction temperature of the cyclic phosphate ester monoacyl chloride and the glycol is 25-30 ℃ and the reaction time is 2-3 h;
the molar ratio of the cyclic phosphate ester monoacyl chloride to the ethylene glycol is 1: 1-1.3.
5. The preparation method of the cyclic phosphorus boron flame retardant according to claim 2, wherein the nucleophilic substitution reaction temperature of phosphorus trichloride and 2-methyl-1, 3-propanediol is 20-25 ℃ and the time is 2-4 h;
the molar ratio of the phosphorus trichloride to the 2-methyl-1, 3-propylene glycol is 1: 1-1.1.
6. The preparation method of the cyclic phosphorus boron flame retardant according to claim 2, wherein the nucleophilic substitution reaction temperature of boron trichloride and 2-methyl-1, 3-propanediol is 25-35 ℃ and the time is 3-4 h;
the molar ratio of the boron trichloride to the 2-methyl-1, 3-propanediol is 1: 1-1.25.
7. The method for preparing the flame-retardant smoke-suppressing polyester film by adopting the cyclic phosphorus-boron flame retardant as claimed in claim 1, which is characterized in that: the method comprises the following steps of uniformly mixing the annular phosphorus-boron flame retardant and the polyester master batch, putting the mixture into a double-screw extruder for melt blending, extruding the mixture to obtain the flame-retardant polyester master batch, putting the flame-retardant master batch into a die for casting, and stretching, heat setting and cooling the die to obtain the flame-retardant smoke-suppressing polyester film.
8. The method for preparing the flame-retardant smoke-suppressing polyester film by using the cyclic phosphorus boron flame retardant according to claim 7 is characterized by comprising the following specific steps of:
(1) respectively drying the cyclic phosphorus-boron flame retardant and the polyester master batch to remove water, mixing the cyclic phosphorus-boron flame retardant and the polyester master batch, and putting the mixture into a double-screw extruder for melt blending;
(2) extruding and cooling the melt after melt blending, and then carrying out grain cutting to obtain flame-retardant polyester master batches;
(3) and introducing the flame-retardant polyester master batch into a mold for casting, and stretching, heat setting and cooling to obtain the flame-retardant smoke-suppressing polyester film.
9. The method of claim 8, wherein the polyester masterbatch is a virgin polyester masterbatch or a recycled polyester masterbatch.
10. The method according to claim 8, wherein the drying temperature of the polyester masterbatch is 140-160 ℃ and the drying time is 2-4 h; the drying temperature of the cyclic phosphorus boron flame retardant is 70-90 ℃, and the drying time is 5-7 h.
11. The method according to claim 8, wherein the processing temperature of the twin-screw extruder is 240 to 280 ℃.
12. The method according to claim 8, wherein the stretching temperature is 100 to 140 ℃ and the heat setting temperature is 200 to 250 ℃.
13. The method according to claim 8, wherein the amount of the cyclic phosphorus boron flame retardant is 5-10% based on the total mass of the cyclic phosphorus boron flame retardant and the polyester master batch.
14. The method of claim 13, wherein the flame retardant and smoke suppressant polyester film has a thickness of 10 to 200 μm.
15. The method of claim 14, wherein the flame retardant smoke-suppressing polyester film has a flame retardant rating of V-0 as measured according to UL 94; the maximum smoke release D of the flame-retardant smoke-inhibiting polyester film is measured according to the ISO 5659.2 standardsmaxLess than or equal to 68; the damage length of the flame-retardant smoke-suppression polyester film is 10.2-13.9 cm, and the damage length after 30 times of water washing is 10.5-14.2 cm.
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