CN114644656B - Preparation method of annular phosphorus-boron flame retardant and flame-retardant smoke-suppressing polyester film - Google Patents
Preparation method of annular phosphorus-boron flame retardant and flame-retardant smoke-suppressing polyester film Download PDFInfo
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- CN114644656B CN114644656B CN202210179673.2A CN202210179673A CN114644656B CN 114644656 B CN114644656 B CN 114644656B CN 202210179673 A CN202210179673 A CN 202210179673A CN 114644656 B CN114644656 B CN 114644656B
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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
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229920006267 polyester film Polymers 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 79
- 229920000728 polyester Polymers 0.000 claims abstract description 70
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 57
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 49
- 239000010452 phosphate Substances 0.000 claims abstract description 49
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 43
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 36
- 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
- 239000000779 smoke Substances 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- -1 cyclic boric acid ester acyl chloride Chemical class 0.000 claims abstract description 21
- 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
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000004327 boric acid Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 14
- 238000009998 heat setting Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 3
- HITBOAGYESUOFH-UHFFFAOYSA-N boric acid hydrochloride Chemical compound Cl.OB(O)O HITBOAGYESUOFH-UHFFFAOYSA-N 0.000 claims 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 39
- 229960001701 chloroform Drugs 0.000 description 21
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052796 boron Inorganic materials 0.000 description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 230000001629 suppression Effects 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 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
- 238000002485 combustion reaction Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- SORDQUQOEUVZKD-UHFFFAOYSA-N (2-aminoacetyl)oxyboronic acid Chemical compound NCC(=O)OB(O)O SORDQUQOEUVZKD-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004821 distillation Methods 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
- 230000007246 mechanism Effects 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
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910003867 O—B—O Inorganic materials 0.000 description 1
- 229910003873 O—P—O Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 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
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
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 Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—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
Landscapes
- 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 application 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 as followsWherein n=1 to 2, m=1 to 2, and n+m=2 to 3; the preparation method comprises the following steps: the cyclic phosphate ester alcohol and cyclic boric acid ester acyl chloride are subjected to nucleophilic substitution reaction to prepare the cyclic phosphorus-boron flame retardant; the cyclic phosphate ester alcohol is prepared by reacting cyclic phosphate ester monoacyl chloride with ethylene glycol, and the cyclic phosphate ester monoacyl chloride is prepared by nucleophilic substitution reaction of phosphorus trichloride and 2-methyl-1, 3-propylene glycol; the cyclic borate monoacyl chloride is prepared by adopting boron trichloride and 2-methyl-1, 3-propanediol through nucleophilic substitution reaction; and (3) uniformly mixing the annular phosphorus-boron flame retardant and the polyester master batch, putting the mixture into a double-screw extruder, carrying out melt blending, and extruding to obtain the flame-retardant polyester master batch, thereby preparing the flame-retardant smoke-suppressing polyester film. The prepared annular phosphorus-boron flame retardant has good compatibility with polyester, and the flame-retardant polyester film prepared from the annular phosphorus-boron flame retardant has excellent flame retardant property and lower smoke release.
Description
Technical Field
The application 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 properties, excellent processability and the like, and is widely applied to the fields of textile clothing, decoration, packaging materials and the like. However, the polyester material is inflammable, the molten drop phenomenon in the combustion process is serious, and the smoke amount is large (especially regenerated polyester), so that the application of the polyester material is greatly limited. The cyclic phosphate 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 a high polymer material, and has good development prospect. The types of the currently reported cyclic phosphate flame retardants are more, wherein the flame retardant effect of an Antiblaze 19 product (also called Amgard CU) developed by the American Mobil company and a domestic FRC-1 product is better, and the melting and dripping phenomena of polyester can be effectively inhibited. However, the cyclic phosphate flame retardant has the defects of large smoke generation amount, large toxicity and the like, and still has large fire hazard, so that the application of the cyclic phosphate flame retardant is limited to a certain extent. In recent years, with the enhancement of environmental protection consciousness and safety consciousness of people, boron-containing flame retardants are receiving a great deal of attention because of their non-toxicity, smoke suppression and other advantages. Chinese patent No. 103046336A discloses a phosphorus-boron composite flame retardant, which is characterized in that phosphorus oxychloride and pentaerythritol are firstly adopted to react for 7 hours at 80 ℃ in acetonitrile to synthesize spiro phosphoric acid ester diacid chloride, boric acid and glycerin are reacted for 3 hours at 130 ℃ to synthesize boric acid glycyl ester, then the spiro phosphoric acid ester diacid chloride and the boric acid glycyl ester are reacted for 12-14 hours at 150-180 ℃ to synthesize a phosphorus-boron composite flame retardant which is a product of family-part, and the reported synthesis has harsh conditions, high reaction temperature, long reaction time and low reaction yield.
Disclosure of Invention
The application 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. The application takes boron trichloride, phosphorus trichloride, 2-methyl-1, 3-propanediol and ethylene glycol as raw materials to prepare the annular phosphorus-boron flame retardant through reaction, and the annular phosphorus-boron flame retardant is used for preparing the flame-retardant smoke-suppressing polyester film, has good compatibility with polyester, can generate better combination, and has high flame retardant efficiency. The polyester film prepared by the method has the advantages of excellent flame retardant effect, no generation of molten drops, low smoke release, good washability and important practical application value.
In order to achieve the above purpose, the application adopts the following technical scheme:
a cyclic phosphorus-boron flame retardant having a chemical structure as shown below;
wherein n=1 to 2, m=1 to 2, and n+m=2 to 3.
Specifically, the cyclic phosphorus-boron flame retardant is one of the following chemical structures:
the annular structure in the annular phosphorus-boron flame retardant is a six-membered ring structure, the number of the six-membered ring structures in the annular phosphorus-boron flame retardant is 2-3, at least one of the six-membered ring containing phosphorus and the six-membered ring containing boron is connected with oxygen atoms to form O-B-O and O-P-O structures, and the molecular chain segment of the annular phosphorus-boron flame retardant has better linearity.
The application also provides a preparation method of the annular phosphorus-boron flame retardant, wherein the annular phosphorus-boron flame retardant is prepared by nucleophilic substitution reaction of the annular phosphate alcohol and the annular boric acid ester monoacyl chloride;
the cyclic phosphate ester alcohol is prepared by reacting cyclic phosphate ester monoacyl chloride with ethylene glycol, and the cyclic phosphate ester monoacyl chloride is prepared by nucleophilic substitution reaction of phosphorus trichloride and 2-methyl-1, 3-propylene glycol;
the cyclic borate monoacyl chloride is prepared by adopting boron trichloride and 2-methyl-1, 3-propanediol through nucleophilic substitution reaction.
As a preferable technical scheme:
the preparation method of the cyclic phosphorus-boron flame retardant comprises the steps that the nucleophilic substitution reaction temperature of cyclic phosphate ester alcohol and cyclic borate ester-acyl chloride is 30-35 ℃ and the time is 1-3 h;
the molar ratio of the cyclic borate mono-acyl chloride to the cyclic phosphate alcohol is 1:1-1.2.
The preparation method of the cyclic phosphorus-boron flame retardant comprises the steps that the reaction temperature of cyclic phosphate acyl chloride and ethylene glycol is 25-30 ℃ and the reaction time is 2-3 h;
the molar ratio of the cyclic phosphate acyl chloride to the glycol is 1:1-1.3, and the glycol is slightly excessive, so that the residual active chlorine is ensured to fully participate in the reaction.
The preparation method of the cyclic phosphorus-boron flame retardant has the advantages that the nucleophilic substitution reaction temperature of phosphorus trichloride and 2-methyl-1, 3-propanediol is 20-25 ℃, and the time is 2-4 hours;
the molar ratio of the phosphorus trichloride to the 2-methyl-1, 3-propanediol is 1:1-1.1,2-methyl-1, 3-propanediol is slightly excessive, so that two active chlorine in the phosphorus trichloride molecule react with two hydroxyl groups of the 2-methyl-1, 3-propanediol to generate a cyclic phosphate structure.
The preparation method of the cyclic phosphorus-boron flame retardant has the advantages that 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, and the nucleophilic substitution reaction temperature is not too high, otherwise, the boron trichloride is volatilized, which is unfavorable for the nucleophilic substitution reaction.
All the reactions adopt chloroform as a solvent, and the purification is carried out by reduced pressure distillation after the reaction is finished.
The application 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 with 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.
As a preferable technical scheme:
the method for preparing the flame-retardant smoke-suppressing polyester film by using the annular phosphorus-boron flame retardant comprises the following specific steps of:
(1) Respectively drying and dewatering the annular phosphorus-boron flame retardant and the polyester master batch, mixing the annular 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 blending, and then granulating to obtain flame-retardant polyester master batch;
(3) And introducing the flame-retardant polyester master batch into a die for casting, and stretching, heat setting and cooling to obtain the flame-retardant smoke-suppressing polyester film.
The polyester master batch is virgin polyester master batch or recycled polyester master batch according to the method.
The method has the advantages that the drying temperature of the polyester master batch is 140-160 ℃ and the time is 2-4 h; the drying temperature of the annular phosphorus-boron flame retardant is 70-90 ℃ and the drying time is 5-7 h, so that the final moisture of the polyester master batch and the annular phosphorus-boron flame retardant is ensured to be lower than 250ppm.
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 mixed uniformly, granulation is not facilitated, energy waste can be caused due to too high temperature, and the uniform flame retardant polyester master batch can be smoothly prepared in the temperature range provided by the application.
The stretching temperature is 100-140 deg.c and the heat setting temperature is 200-250 deg.c.
According to the method, the using amount of the annular phosphorus-boron flame retardant is 5-10% based on the total mass of the annular phosphorus-boron flame retardant and the polyester master batch.
The thickness of the flame-retardant smoke-suppressing polyester film is 10-200 mu m by the method.
The flame retardant rating measured according to the UL94 standard is V-0, as described above; maximum smoke release D measured according to ISO 5659.2 standard smax Less than or equal to 68; the damage length of the flame-retardant smoke-suppressing polyester film is 10.2-13.9 cm when the film is not washed with water, and the damage length after washing for 30 times is 10.5-14.2 cm.
The mechanism of the application is as follows:
the active chlorine atoms in the boron trichloride and phosphorus trichloride molecules can carry out nucleophilic substitution reaction with the hydroxyl groups of the polyalcohol, and the reaction conditions are controlled to prepare the cyclic phosphorus-boron flame retardant. The six-membered ring structure of the annular phosphorus-boron flame retardant molecule is similar to that of polyester, so that the two have good compatibility, the negative influence in the flame retardant adding process is small, the flame retardant cannot be separated out, the adverse effect on the mechanical property of the polyester film is avoided, and the annular phosphorus-boron ester flame retardant can be combined with the polyester through a similar compatibility principle, so that the flame retardant polyester film has good water washing resistance; in the thermal decomposition process, the phosphorus-containing flame retardant groups are decomposed into phosphorus-containing volatile substances, hydrogen radicals are eliminated, the decomposition of the boron-containing groups is performed in a gas phase to form a boron-rich carbon residue layer, the decomposition of the boron-containing groups is performed in a solid phase, and the boron-rich carbon residue layer 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 annular phosphorus-boron flame retardant are relatively close, and only a relatively short C-C chain segment is arranged in the middle of the annular phosphorus-boron flame retardant, so that the structure is easy to thermally decompose, and in the combustion process, the structure of the flame retardant is decomposed to easily form complex carbon residue containing the P-O-B. Therefore, the phosphorus-containing group and the boron-containing group have 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 application, the thermal stability of the P-O-B complex carbon residue is better than that of the P-O and B-O carbon residue, the heat insulation and the oxygen supply can be more effectively prevented, and a better flame-retardant effect is achieved, so that the prepared flame-retardant polyester film has good flame-retardant effect and no molten drop; 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.
The beneficial effects are that:
(1) The raw materials of boron trichloride, phosphorus trichloride, 2-methyl-1, 3-propanediol and ethylene glycol used in the application 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 prepared annular phosphorus-boron flame retardant has high phosphorus content and boron content, the phosphorus content and the boron content are synergistic to improve the flame retardant property of the polyester film through a flame retardant mechanism, and the prepared polyester film has excellent flame retardant property, has lower smoke release and obviously reduces fire hazard;
(3) The annular phosphorus-boron flame retardant prepared by the application has a similar structure to polyester, has good compatibility with the polyester, has no obvious influence on the mechanical properties of the prepared flame-retardant polyester film, has excellent flame-retardant durability, and has wide application prospect.
Drawings
FIG. 1 is a synthetic route for the cyclic phosphorus boron flame retardant of example 1.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The test method of the polyester film performance in the application comprises the following steps:
the tensile properties of the polyester film were tested with reference to GB/T13022-1991 standard;
the flame retardant property of the polyester film is tested according to the UL94 standard;
the fuming performance of the polyester film was tested with reference to ISO 5659.2 using an NBS smoke density box with maximum smoke release D smax Characterizing;
the water 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 the annular phosphorus-boron flame retardant is shown in figure 1, and comprises the following specific steps:
(1) Uniformly mixing phosphorus trichloride, 2-methyl-1, 3-propanediol and chloroform, reacting at 25 ℃ for 3 hours to obtain cyclic phosphate monoacyl chloride, adding ethylene glycol for continuous reaction for 3 hours to obtain cyclic phosphate alcohol, and distilling under reduced pressure at 110 ℃ for purification; wherein, the mol ratio of the phosphorus trichloride to the 2-methyl-1, 3-propanediol is 1:1.1, the mol ratio of the cyclic phosphate acyl chloride to the glycol is 1:1.3, and the mass ratio of the phosphorus trichloride to the chloroform is 3:1;
(2) Uniformly mixing boron trichloride, 2-methyl-1, 3-propanediol and chloroform, reacting at 30 ℃ for 4 hours to obtain cyclic borate monoacyl chloride, and distilling at 70 ℃ under reduced pressure for purification; wherein, the mol ratio of the boron trichloride to the 2-methyl-1, 3-propanediol is 1:1, and the mass ratio of the chloroform to the boron trichloride is 3:1;
(3) The cyclic phosphate alcohol, the cyclic borate monoacyl chloride and the chloroform are uniformly mixed and then react for 2 hours at 35 ℃ to prepare the cyclic phosphorus-boron flame retardant, and the cyclic phosphorus-boron flame retardant is distilled under reduced pressure at 70 ℃ for purification; wherein, the mol ratio of the cyclic borate acyl 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 annular phosphorus-boron flame retardant is
Comparative example 1
The preparation method of the cyclic phosphate flame retardant comprises the steps of uniformly mixing phosphorus trichloride, 2-methyl-1, 3-propanediol and chloroform, reacting at 25 ℃ for 3 hours to obtain cyclic phosphate monoacyl chloride, adding ethylene glycol for continuous reaction for 3 hours to obtain the cyclic phosphate flame retardant, and purifying by reduced pressure distillation at 110 ℃; wherein, the mol ratio of the phosphorus trichloride to the 2-methyl-1, 3-propanediol is 1:1.1, the mol ratio of the cyclic phosphate acyl chloride to the glycol is 2:1, and the mass ratio of the phosphorus trichloride to the chloroform is 3:1.
The structural formula of the finally prepared cyclic phosphate flame retardant is
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-propanediol and chloroform, reacting at 20 ℃ for 4 hours to obtain cyclic phosphate monoacyl chloride, adding ethylene glycol, continuously reacting for 2.5 hours to obtain cyclic phosphate alcohol, and distilling at 110 ℃ under reduced pressure to purify; wherein, the mol ratio of the phosphorus trichloride to the 2-methyl-1, 3-propanediol is 1:1, the mol ratio of the cyclic phosphate acyl chloride to the glycol is 1:1, and the mass ratio of the phosphorus trichloride to the chloroform is 3:1;
(2) Uniformly mixing boron trichloride, 2-methyl-1, 3-propanediol and chloroform, reacting at 25 ℃ for 4 hours to obtain cyclic borate monoacyl chloride, and distilling at 70 ℃ under reduced pressure for purification; wherein, the mol ratio of the boron trichloride to the 2-methyl-1, 3-propanediol is 1:1.2, and the mass ratio of the chloroform to the boron trichloride is 3:1;
(3) The cyclic phosphate alcohol, the cyclic borate monoacyl chloride and the chloroform are uniformly mixed and then react for 3 hours at 30 ℃ to prepare the cyclic phosphorus-boron flame retardant, and the cyclic phosphorus-boron flame retardant is distilled under reduced pressure at 70 ℃ for purification; wherein, the molar ratio of the cyclic borate acyl 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 annular phosphorus-boron flame retardant is
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-propanediol and chloroform, reacting at 22 ℃ for 3 hours to obtain cyclic phosphate monoacyl chloride, adding glycerol, continuously reacting at 25 ℃ for 3 hours to obtain cyclic phosphate alcohol, and distilling at 70 ℃ under reduced pressure to purify; wherein, the mol ratio of the phosphorus trichloride to the 2-methyl-1, 3-propanediol is 1:1.1, the mol ratio of the cyclic phosphate acyl chloride to the glycerol is 1:1.1, and the mass ratio of the phosphorus trichloride to the chloroform is 3:1;
(2) Uniformly mixing boron trichloride, 2-methyl-1, 3-propanediol and chloroform, reacting at 35 ℃ for 3 hours to obtain cyclic borate monoacyl chloride, and distilling at 70 ℃ under reduced pressure for purification; wherein, the mol ratio of the boron trichloride to the 2-methyl-1, 3-propanediol is 1:1.25, and the mass ratio of the chloroform to the boron trichloride is 3:1;
(3) The cyclic phosphate alcohol, the cyclic borate monoacyl chloride and the chloroform are uniformly mixed and then react for 2 hours at 35 ℃ to prepare the cyclic phosphorus-boron flame retardant, and the cyclic phosphorus-boron flame retardant is distilled under reduced pressure at 70 ℃ for purification; wherein the molar ratio of the cyclic borate mono-acyl chloride to the cyclic phosphate alcohol is 2:1.1, and the mass ratio of the trichloromethane to the cyclic phosphate alcohol is 3:1.
The structural formula of the finally prepared annular phosphorus-boron flame retardant is
Example 4
A preparation method of a flame-retardant smoke-suppressing polyester film comprises the following specific steps:
(1) Drying and dewatering the primary polyester master batch (instrumentation chemical fiber FG650 film grade slice) and the annular phosphorus-boron flame retardant prepared in the example 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 annular phosphorus-boron flame retardant is 80 ℃ and the drying time is 6 hours;
(2) Mixing the dried annular phosphorus-boron flame retardant with primary polyester master batch, and putting the mixture into a double-screw extruder for melt blending; wherein, the consumption of the annular phosphorus-boron flame retardant is 8 percent based on the total mass of the annular phosphorus-boron flame retardant and the primary polyester master batch; the processing temperature of the twin-screw extruder is 270 ℃;
(3) Extruding and cooling the melt blending, and then granulating to obtain flame-retardant polyester master batch;
(4) And introducing the flame-retardant polyester master batch into a die for casting, stretching at 130 ℃ for 3 times, and performing heat setting at 230 ℃ and cooling to obtain the flame-retardant smoke-suppressing polyester film with the thickness of 20 mu m.
Performing performance test on the prepared flame-retardant smoke-suppressing polyester film, wherein the tensile strength is 201MPa; the flame retardant rating of the flame retardant smoke suppression polyester film measured according to UL94 standard is V-0; maximum smoke release D of flame-retardant smoke-suppressing polyester film measured according to ISO 5659.2 standard smax 48; the damage length of the flame-retardant smoke-suppressing polyester film is 11.The damage length after washing for 30 times is 11.5cm and 3 cm.
Comparative example 2
A preparation method of a polyester film comprises the steps of putting the raw polyester master batch dried in the embodiment 4 into a double-screw extruder, extruding at 270 ℃, introducing the extruded and cooled polyester master batch into a casting sheet in a die, stretching at 130 ℃ for 3 times, heat setting at 230 ℃, and cooling to obtain the flame-retardant smoke-suppressing polyester film with the thickness of 20 mu m.
Performing performance test on the prepared polyester film, wherein the tensile strength is 215MPa; the flame retardant rating of the flame retardant and smoke suppressing polyester film measured according to UL94 standard is V-2; maximum smoke release D of flame-retardant smoke-suppressing polyester film measured according to ISO 5659.2 standard smax 70; the damage length of the flame-retardant smoke-suppressing polyester film is 30cm, and the damage length after 30 times of water washing is 30cm.
Comparative example 3
A method for preparing a flame-retardant smoke-suppressing polyester film is basically the same as in example 4, except that the cyclic phosphorus-boron flame retardant is replaced with the cyclic phosphate flame retardant prepared in comparative example 1. Performing performance test on the prepared flame-retardant smoke-suppressing polyester film, wherein the tensile strength is 203MPa; the flame retardant rating of the flame retardant smoke suppression polyester film measured according to UL94 standard is V-0; maximum smoke release D of flame-retardant smoke-suppressing polyester film measured according to ISO 5659.2 standard smax 80; the damage length of the flame-retardant smoke-suppressing polyester film is 10.8cm, and the damage length after 30 times of water washing is 10.9cm.
As can be seen by comparing example 4 with comparative example 2 and comparative example 3, the tensile strength of the polyester film after flame retardant addition of example 4 is not significantly changed, which indicates that the mechanical properties are not significantly affected. 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, the V-2 level shows that the flame retardant performance is poor, and the smoke release amount of the polyester film is large; although the polyester film modified by the cyclic phosphate flame retardant has better flame retardant property, the smoke amount of the polyester film is increased compared with that of the polyester film not flame retardant, which shows that the smoke amount of the polyester modified by the cyclic phosphate is larger and the fire hazard is large; the damage length of the polyester film modified by the annular phosphorus-boron flame retardant is obviously reduced, no molten drop is generated, the flame retardant V-0 grade is met, and the smoke quantity is reduced, so that the polyester film modified by the annular phosphorus-boron flame retardant has excellent flame retardant property and less fire hazard. In addition, the flame-retardant polyester film of the example 4 still has better flame-retardant performance after 30 times of water washing, which shows that the flame-retardant polyester film has excellent water washing resistance.
Example 5
A preparation method of a flame-retardant smoke-suppressing polyester film comprises the following specific steps:
(1) Drying and dewatering the primary polyester master batch (instrumentation chemical fiber FG650 film grade slice) and the annular phosphorus-boron flame retardant prepared in the example 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 annular phosphorus-boron flame retardant is 80 ℃ and the drying time is 6 hours;
(2) Mixing the dried annular phosphorus-boron flame retardant with primary polyester master batch, and putting the mixture into a double-screw extruder for melt blending; wherein, the consumption of the annular phosphorus-boron flame retardant is 5 percent based on the total mass of the annular phosphorus-boron flame retardant and the primary polyester master batch; the processing temperature of the twin-screw extruder is 270 ℃;
(3) Extruding and cooling the melt blending, and then granulating to obtain flame-retardant polyester master batch;
(4) And introducing the flame-retardant polyester master batch into a die for casting, stretching at 130 ℃ for 3 times, and performing heat setting at 230 ℃ and cooling to obtain the flame-retardant smoke-suppressing polyester film with the thickness of 20 mu m.
Performing performance test on the prepared flame-retardant smoke-suppressing polyester film, wherein the tensile strength is 206MPa; the flame retardant rating of the flame retardant smoke suppression polyester film measured according to UL94 standard is V-0; maximum smoke release D of flame-retardant smoke-suppressing polyester film measured according to ISO 5659.2 standard smax 57; the damage length of the flame-retardant smoke-suppressing polyester film is 13.9cm, and the damage length after 30 times of water washing is 14.2cm.
Example 6
A preparation method of a flame-retardant smoke-suppressing polyester film comprises the following specific steps:
(1) Drying and dewatering the regenerated polyester master batch (ceremonious chemical fiber HS 500) and the annular 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 2.5h; the drying temperature of the annular 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 consumption of the annular phosphorus-boron flame retardant is 10 percent based on the total mass of the annular phosphorus-boron flame retardant and the regenerated polyester master batch; the processing temperature of the twin-screw extruder is 280 ℃;
(3) Extruding and cooling the melt blending, and then granulating to obtain flame-retardant polyester master batch;
(4) And introducing the flame-retardant polyester master batch into a die for casting, stretching at 140 ℃ for 3 times, performing heat setting at 250 ℃, and cooling to obtain the flame-retardant smoke-suppressing polyester film with the thickness of 100 mu m.
Performing performance test on the prepared flame-retardant smoke-suppressing polyester film, wherein the tensile strength is 210MPa; the flame retardant rating of the flame retardant smoke suppression polyester film measured according to UL94 standard is V-0; maximum smoke release D of flame-retardant smoke-suppressing polyester film measured according to ISO 5659.2 standard smax 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 10.5cm.
Comparative example 4
A preparation method of a polyester film comprises the steps of putting the dried regenerated polyester master batch in example 6 into a double-screw extruder, extruding at 280 ℃, introducing the extruded and cooled polyester master batch into a casting sheet in a die, stretching at 140 ℃ for 3 times, heat setting at 250 ℃, and cooling to obtain the flame-retardant smoke-suppressing polyester film with the thickness of 100 mu m.
Performing performance test on the prepared polyester film, wherein the tensile strength is 196MPa; the flame retardant rating of the flame retardant and smoke suppressing polyester film measured according to UL94 standard is V-2; maximum smoke release D of flame-retardant smoke-suppressing polyester film measured according to ISO 5659.2 standard smax 105; the damage length of the flame-retardant smoke-suppressing polyester film is 30cm, and the damage length after 30 times of water washing is 30cm.
Example 7
A preparation method of a flame-retardant smoke-suppressing polyester film comprises the following specific steps:
(1) Drying and dewatering the regenerated polyester master batch (instrumentation chemical fiber HS 500) and the annular 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 annular 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 consumption of the annular phosphorus-boron flame retardant is 6.5 percent based on the total mass of the annular phosphorus-boron flame retardant and the regenerated polyester master batch; the processing temperature of the twin-screw extruder is 240 ℃;
(3) Extruding and cooling the melt blending, and then granulating to obtain flame-retardant polyester master batch;
(4) And introducing the flame-retardant polyester master batch into a die for casting, stretching at 110 ℃ for 3 times, and performing heat setting at 210 ℃ and cooling to obtain the flame-retardant smoke-suppressing polyester film with the thickness of 150 mu m.
Performing performance test on the prepared flame-retardant smoke-suppressing polyester film, wherein the tensile strength is 202MPa; the flame retardant rating of the flame retardant smoke suppression polyester film measured according to UL94 standard is V-0; maximum smoke release D of flame-retardant smoke-suppressing polyester film measured according to ISO 5659.2 standard smax 68; the damage length of the flame-retardant smoke-suppressing polyester film is 13.1cm, and the damage length after 30 times of water washing is 13.4cm.
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, and it should be noted that it is possible for those skilled in the art to make several improvements and modifications without departing from the technical principle of the present application, and these improvements and modifications should also be regarded as the protection scope of the present application.
Claims (14)
1. A preparation method of a cyclic phosphorus-boron flame retardant is characterized by comprising the following steps: the cyclic phosphate ester alcohol and cyclic boric acid ester acyl chloride are subjected to nucleophilic substitution reaction to prepare the cyclic phosphorus-boron flame retardant; the molar ratio of the cyclic borate mono-acyl chloride to the cyclic phosphate alcohol is 1:1-1.2;
the cyclic phosphate ester alcohol is prepared by reacting cyclic phosphate ester monoacyl chloride with ethylene glycol, and the cyclic phosphate ester monoacyl chloride is prepared by nucleophilic substitution reaction of phosphorus trichloride and 2-methyl-1, 3-propylene glycol; the molar ratio of the cyclic phosphate acyl chloride to the ethylene glycol is 1:1-1.3; the molar ratio of the boron trichloride to the 2-methyl-1, 3-propanediol is 1:1-1.25;
the cyclic borate monoacyl chloride is prepared by adopting boron trichloride and 2-methyl-1, 3-propanediol through nucleophilic substitution reaction; the mol ratio of the phosphorus trichloride to the 2-methyl-1, 3-propanediol is 1:1-1.1;
the prepared annular phosphorus-boron flame retardant has the chemical structure shown as follows;
；
wherein n=1 to 2, m=1 to 2, and n+m=2 to 3.
2. The method for preparing the cyclic phosphorus-boron flame retardant according to claim 1, wherein the nucleophilic substitution reaction temperature of the cyclic phosphate alcohol and the cyclic borate monochloride is 30-35 ℃ and the time is 1-3 h.
3. The method for preparing the cyclic phosphorus-boron flame retardant according to claim 1, wherein the reaction temperature of the cyclic phosphoric acid ester monochloride and the ethylene glycol is 25-30 ℃ and the reaction time is 2-3 h.
4. The preparation method of the annular phosphorus-boron flame retardant according to claim 1, 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.
5. The preparation method of the annular phosphorus-boron flame retardant according to claim 1, 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.
6. A method for preparing a flame-retardant smoke-suppressing polyester film by adopting the cyclic phosphorus-boron flame retardant as defined in claim 1, which is characterized in that: 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, extruding to obtain flame-retardant polyester master batch, putting the flame-retardant master batch into a die for casting, and stretching, heat setting and cooling to obtain the flame-retardant smoke-suppressing polyester film.
7. The method for preparing the flame-retardant smoke-suppressing polyester film by using the annular phosphorus-boron flame retardant as claimed in claim 6, which is characterized by comprising the following specific steps:
(1) Respectively drying and dewatering the annular phosphorus-boron flame retardant and the polyester master batch, mixing the annular 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 blending, and then granulating to obtain flame-retardant polyester master batch;
(3) And introducing the flame-retardant polyester master batch into a die for casting, and stretching, heat setting and cooling to obtain the flame-retardant smoke-suppressing polyester film.
8. The method of claim 7, wherein the polyester master batch is a virgin polyester master batch or a recycled polyester master batch.
9. The method of claim 7, wherein the polyester master batch is dried at 140-160 ℃ for 2-4 hours; the drying temperature of the annular phosphorus-boron flame retardant is 70-90 ℃ and the drying time is 5-7 h.
10. The method of claim 7, wherein the twin screw extruder is operated at a temperature of 240 ℃ to 280 ℃.
11. The method of claim 7, wherein the stretching temperature is 100-140 ℃ and the heat setting temperature is 200-250 ℃.
12. The method according to claim 7, 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.
13. The method of claim 12, wherein the flame retardant smoke suppressant polyester film has a thickness of 10 to 200 μm.
14. The method of claim 13, wherein the flame retardant smoke suppressant polyester film has a flame retardant rating of V-0 as measured according to UL94 standard; maximum smoke release D of flame-retardant smoke-suppressing polyester film measured according to ISO 5659.2 standard smax Less than or equal to 68; the damage length of the flame-retardant smoke-suppressing 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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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5156775A (en) * | 1991-10-17 | 1992-10-20 | Blount David H | Flame retardant compositions |
| US5523448A (en) * | 1993-07-22 | 1996-06-04 | General Electric Company | Diphosphites |
| US5539141A (en) * | 1992-06-16 | 1996-07-23 | Chemische Fabrik Budenheim Rudolf A. Oetker | Mixed boric acid/phosphoric acid esters of polyols, their preparation and use |
| JPH10152496A (en) * | 1996-08-27 | 1998-06-09 | Sumitomo Chem Co Ltd | Phosphorous esters, their production and their use |
| EP0940407A1 (en) * | 1998-03-06 | 1999-09-08 | General Electric Company | Cyclic bis-phosphites |
| JP2005200326A (en) * | 2004-01-14 | 2005-07-28 | Sumitomo Chemical Co Ltd | Method for producing phosphite compounds |
| CN103046336A (en) * | 2012-11-06 | 2013-04-17 | 青岛文创科技有限公司 | Phosphor-boron composite flame retardant |
| JP2020083932A (en) * | 2018-11-16 | 2020-06-04 | 帝人株式会社 | Flame-retardant polyester resin composition and molded article therefrom |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1148090A1 (en) * | 2000-04-17 | 2001-10-24 | Clariant Finance (BVI) Limited | Flame retardant polymers |
| DE10360771A1 (en) * | 2003-12-23 | 2005-07-28 | Oxeno Olefinchemie Gmbh | Process for the preparation of trivalent organophosphorus compounds |
| KR101286484B1 (en) * | 2005-09-14 | 2013-07-16 | 다이하치 카가쿠 고교 가부시키가이샤 | Phosphorus compound, use thereof and flame-retardant polyester fiber |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5156775A (en) * | 1991-10-17 | 1992-10-20 | Blount David H | Flame retardant compositions |
| US5539141A (en) * | 1992-06-16 | 1996-07-23 | Chemische Fabrik Budenheim Rudolf A. Oetker | Mixed boric acid/phosphoric acid esters of polyols, their preparation and use |
| US5523448A (en) * | 1993-07-22 | 1996-06-04 | General Electric Company | Diphosphites |
| JPH10152496A (en) * | 1996-08-27 | 1998-06-09 | Sumitomo Chem Co Ltd | Phosphorous esters, their production and their use |
| EP0940407A1 (en) * | 1998-03-06 | 1999-09-08 | General Electric Company | Cyclic bis-phosphites |
| JP2005200326A (en) * | 2004-01-14 | 2005-07-28 | Sumitomo Chemical Co Ltd | Method for producing phosphite compounds |
| CN103046336A (en) * | 2012-11-06 | 2013-04-17 | 青岛文创科技有限公司 | Phosphor-boron composite flame retardant |
| JP2020083932A (en) * | 2018-11-16 | 2020-06-04 | 帝人株式会社 | Flame-retardant polyester resin composition and molded article therefrom |
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