CN101974148A - High-molecular weight phosphorous flame retardant random copolyester and preparation method thereof - Google Patents
High-molecular weight phosphorous flame retardant random copolyester and preparation method thereof Download PDFInfo
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- CN101974148A CN101974148A CN 201010284925 CN201010284925A CN101974148A CN 101974148 A CN101974148 A CN 101974148A CN 201010284925 CN201010284925 CN 201010284925 CN 201010284925 A CN201010284925 A CN 201010284925A CN 101974148 A CN101974148 A CN 101974148A
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Abstract
The invention discloses high-molecular weight phosphorous flame retardant random copolyester. The structural general formula of the random copolyester is shown in the specification. In the formula, A is the repetition structure unit of a phosphorous flame retardant monomer, and m and n are positive integers; moreover, the intrinsic viscosity of the random copolyester is 1.2-2.2dL/g, and the content of the repetition structure unit of the phosphorous flame retardant monomer is 0.5-25 percent of the total mass of the repetition structure unit of the copolyester. The invention also discloses a preparation method of the copolyester. Due to the adoption of a solid-phase polymerization mode with mild reaction condition and simple and convenient operation in the invention, the molecular weight of the obtained phosphorous flame retardant random copolyester is high, and the mechanical property and the flame retardant property are good. The invention can be widely used for manufacturing films, bottles, fireproofing clothes, tents and even flame retardant high-strength industrial yarns and also avoids the abuses that the conventional polycondensation mode is high in the energy consumption, relatively harsh in the control condition and high in the requirement on production equipment , and is not beneficial to the industrial production.
Description
Technical field
The invention belongs to the technical field of phosphor-containing flame-proof atactic polyester.Specifically, the present invention relates to a kind of high molecular phosphor-containing flame-proof atactic polyester and preparation method thereof.
Background technology
Along with the development of society, the progress of science and technology, human demand to material enlarges day by day, and the production of macromolecule polymeric material and application have also obtained development at full speed.Polyethylene terephthalate (PET) is widely used in fields such as packing, building, automobile, electronic apparatus, health care because of having advantages such as high-modulus, high strength, snappiness, good model keeping character and thermotolerance.
Yet, because PET belongs to combustible material, it is when burning, not only heat release rate is big, calorific value is high, flame propagation speed, also might discharge toxic gas, in case thereby presence of fire, PET is ignited, hazardness is very big, brings huge threat even loss also can for people's life and property safety.This characteristic of PET has limited it greatly in the application that much needs flame retardant area, and therefore, the flame-retardant modified of PET just seems very necessary.
In general, it is flame-retardant modified that macromolecule polymeric material flame-retardant modified is divided into copolymerization usually, blending fire retardant modification or flame-retardant after-finishing three major types.For PET, copolymerization is flame-retardant modified to be its fire-retardant important way.It can not only give the polyester material excellent flame-retardant, and because the fire retardant monomer is to be connected with polymer phase with the chemical bond form, so after overcoming blending fire retardant modification and flame-retardant after-finishing, contained fire retardant easily moves in the material, the unabiding shortcoming of flame retardant effect.But, the flame-retardant modified shortcoming that exists equally of the copolymerization of PET.Behind the 3rd monomer introducing polyester molecule chain, the molecular weight of the copolyesters that is obtained can descend to some extent, and this can directly influence the mechanical property of copolyesters undoubtedly, and then influences its result of use.Especially can not satisfy high-intensity fiber, Application Areass such as engineering plastics need the requirement of high-molecular weight polyester.Though can improve the molecular weight of material to a certain extent by the prolongation melt phase polycondensation time, promptly obtain the flame-proof copolyester of higher intrinsic viscosity, but because conventional polycondensation is carried out under high-temperature and high-pressure conditions, if thereby adopt the prolongation melt phase polycondensation time to improve the molecular weight of material, it is big to make it power consumption, control condition is comparatively harsh in addition, and production unit is required height, is unfavorable for suitability for industrialized production.
Summary of the invention
The objective of the invention is at the prior art defective, propose a kind of high molecular phosphor-containing flame-proof atactic polyester, to satisfy high-intensity fiber, Application Areass such as engineering plastics need the requirement of high molecular weight polyesters.
Second purpose of the present invention provides a kind of method for preparing above-mentioned high molecular phosphor-containing flame-proof atactic polyester.
For reaching the high molecular phosphor-containing flame-proof atactic polyester that first goal of the invention provides, this atactic polyester general structure is as follows:
A is the monomeric repeated structural unit of phosphor-containing flame-proof in the formula, m and n are positive integer, and the limiting viscosity number of this atactic polyester is 1.2-2.2dL/g, preferred 1.4-2.2dL/g, and the content of the monomeric repeated structural unit of phosphor-containing flame-proof is the 1-30% of this copolyesters repeated structural unit total mass.
The monomeric repeated structural unit A of phosphor-containing flame-proof is at least a in the following structure in this atactic polyester:
In the formula, R
1For containing C
1-C
8Alkyl or phenyl or benzyl, R
2And R
3Be C
1～C
8Alkylidene group or aryl, the two can be identical also can be inequality; X, Y and Z are O atom or S atom.
For reaching the method for the above-mentioned high molecular phosphor-containing flame-proof of the preparation atactic polyester that second goal of the invention provide, the processing step and the condition of this method are as follows:
1) with terephthalic acid, ethylene glycol, phosphor-containing flame-proof monomer and catalyzer add in the reaction unit, stir, vacuumize successively then, be forced into 0.1MPa behind the logical nitrogen replacement four times, be warming up to and carry out esterification under 200～280 ℃, pressure maintains 0.30～0.40MPa simultaneously, when the water that esterification generates substantially no longer changes near theoretical amount and system pressure, slowly be depressurized to normal pressure, the mol ratio of wherein added terephthalic acid and ethylene glycol is 1: 1.2～1: 2, added phosphor-containing flame-proof monomer accounts for 1～30% of flame-proof copolyester total mass, and added catalyzer is the 0.01-0.1% of copolyesters total mass, or
Dimethyl terephthalate (DMT), ethylene glycol, phosphor-containing flame-proof monomer and catalyzer are added in the reaction unit, stir, under 160～220 ℃ of temperature, carried out transesterification reaction 0.5～6 hour then, wherein the mol ratio of dimethyl terephthalate (DMT) and ethylene glycol is 1: 2～1: 3, added phosphor-containing flame-proof monomer accounts for 1～30% of flame-proof copolyester total mass, and added catalyzer is 0.01～0.1% of a copolyesters total mass;
2) with the product after esterification or the transesterification reaction, after system pressure 150～400Pa, 220～280 ℃ of following prepolymerization reactions of temperature 1～3 hour, continuation is 280 ℃ of following polycondensations discharging in 0.5～5 hour in system pressure 10～100Pa, temperature, and the intrinsic viscosity of gained copolyesters prepolymer is 0.3～0.8dL/g;
3) elder generation is a granulated into the copolyesters prepolymer of gained the particle of 10～10000/g size, then under 100～160 ℃ of temperature, crystallization pre-treatment 0.5～4h, again with its vacuum state or inert gas flow 0.5～5L/[min (kg PET) at 10～200Pa] state under, under 160～218 ℃ of temperature, carry out solid state polycondensation and got final product in 4～36 hours.
Used phosphor-containing flame-proof monomer is at least a in the following structure monomer in the above method:
In the formula, R
1For containing C
1-C
8Alkyl or phenyl or benzyl, R
2And R
3Be C
1～C
8Alkylidene group or aryl, the two can be identical also can be inequality; X, Y and Z are O atom or S atom.
The used catalyzer of direct esterification is at least a in antimonous oxide, antimony glycol, titanium ethylene glycolate, earth silicon/titanic oxide mixture or the titanic acid ester in the aforesaid method; The used catalyzer of transesterify is at least a in zinc acetate, manganese acetate or the titanic acid ester, and the used catalyzer of polycondensation is at least a in antimonous oxide, antimony glycol, titanium ethylene glycolate or the earth silicon/titanic oxide mixture.
In addition, the present invention also can add auxiliary agents such as oxidation inhibitor, stablizer, matting agent as required in the process of preparation high molecular phosphor-containing flame-proof atactic polyester, and these all are the common practise of this area.
The high molecular phosphor-containing flame-proof atactic polyester that the present invention is prepared can be used for fields such as fiber, film, polyester bottles, engineering plastics.
The present invention compared with prior art has the following advantages:
1, because phosphor-containing flame-proof atactic polyester limiting viscosity number height provided by the invention, promptly directly reflect this copolyesters molecular weight height, thereby make this copolyesters on basis with excellent flame retardancy energy, also improved its relevant mechanical properties, thereby can be widely used in manufacturing film, bottle class, protective clothing, tent, even fire-retardant high-strength industry silk, expanded the range of application of polyester greatly.
2, because the molecular weight height of phosphor-containing flame-proof atactic polyester provided by the invention, its melt viscosity is bigger, thereby on the basis of existing flame retardant effect, and also can be fire-retardantly provides certain refractory to drip effect.
3, since preparation method provided by the invention after polycondensation, adopted the solid state polymerization mode of reaction conditions gentleness synthesize direct condensation the high molecular phosphorous copolyester that can not make, thereby not only reached the set goal, and also avoided conventional polycondensation mode to consume energy greatly, control condition is comparatively harsh, production unit is required height, be unfavorable for the disadvantage of suitability for industrialized production.
4, the method for preparing high molecular phosphor-containing flame-proof atactic polyester provided by the invention is simple and convenient, is easy to control and realizes suitability for industrialized production.
Embodiment
Provide embodiment below so that the invention will be further described.Be necessary to be pointed out that at this following examples can not be interpreted as limiting the scope of the invention; if the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to protection domain of the present invention.
In addition, intrinsic viscosity [η] that what deserves to be explained is following each embodiment gained prepolymer and product all be with phenol/sym.-tetrachloroethane (1: 1, v: be solvent v), be mixed with the solution that concentration is 0.5g/dL, record at 25 ℃ with dark type viscometer; Tensile property records according to ASTM D638-03 standard, and shock strength records according to ASTM D256-05 standard; Limiting oxygen index(LOI) then is to be made into 120 * 6.5 * 3.2mm
3The standard oxygen exponential spline, measure on the HC-2C oxygen index instrument according to the ASTMD2863-97 standard; Vertical combustion then is to be made into 125 * 12.7 * 3.2mm
3The standard batten, adopt CZF-2 type vertical combustion instrument to measure according to UL-94.The performance that records is seen each embodiment and subordinate list respectively.
Embodiment 1
In reactor, add terephthalic acid 817g, ethylene glycol 481g, phosphor-containing flame-proof monomer 2-contract ethylphenyl phospho acid (CEPP) 55g, The catalytic antimony trioxide 0.350g, stir, vacuumize successively then, be forced into 0.1MPa behind the logical nitrogen replacement gas reactor four times, slowly be warming up to and carry out esterification under 260 ℃, pressure maintains 0.32～0.36MPa simultaneously, the water that esterification generates is told by fractional column, when the water that generates substantially no longer changes near theoretical amount and system pressure, slowly be depressurized to normal pressure and the water of system remnants is taken out of; With the product after the esterification, under the rough vacuum 200Pa in 260～280 ℃ of polycondensations after 1 hour, continue under high vacuum 20Pa in 280 ℃ of polycondensations discharging in 3.5 hours, the intrinsic viscosity of gained copolyesters performed polymer is 0.63dL/g; The copolyesters prepolymer of gained is a granulated into the particle of 800/g size, gets 500g then at 100 ℃ of pre-crystallization 2h down, reheat to 190 ℃ carries out solid state polycondensation 6h and gets final product under vacuum tightness 20Pa.
Embodiment 2
Adding contract ethyl-methyl phospho acid (CEMPP) 132g, mol ratio of dimethyl terephthalate (DMT) 884g, ethylene glycol 722g, phosphor-containing flame-proof monomer 2-in reactor is 1: 1 zinc acetate and the common 1.052g of antimonous oxide catalyzer, stir, under normal pressure, slowly be warming up to then and carried out transesterification reaction under 240 ℃ 4 hours; With the product after the transesterification reaction, under the rough vacuum 150Pa in 260～280 ℃ of polycondensations after 1 hour, continue under high vacuum 25Pa in 280 ℃ of polycondensations discharging in 4 hours, the intrinsic viscosity of gained copolyesters performed polymer is 0.72dL/g; The copolyesters prepolymer of gained is a granulated into the particle of 1000/g size, gets 500g then at 120 ℃ of pre-crystallization 2h down, reheat to 200 ℃ carries out solid state polycondensation 8h and gets final product under vacuum tightness 40Pa.
Embodiment 3
In reactor, add terephthalic acid 774g, ethylene glycol 541g, phosphor-containing flame-proof monomer 9, the 10-dihydro-9-oxy is mixed-10-phosphinylidyne assorted phenanthrene-Succinic Acid (DDP) 179g, catalyst glycol antimony 0.583g, stir, carry out esterification according to embodiment 1 described step, condition then; With the product after the esterification, under the rough vacuum 150Pa in 260～280 ℃ of polycondensations after 1 hour, continue under high vacuum 70Pa in 280 ℃ of polycondensations discharging in 2.5 hours, the intrinsic viscosity of gained copolyesters performed polymer is 0.53dL/g; The copolyesters prepolymer of gained is a granulated into the particle of 300/g size, gets 500g then at 100 ℃ of pre-crystallization 1h down, reheat to 190 ℃ is 2L/[min (kgPET) at nitrogen flow] condition under carry out solid state polycondensation 12h and get final product.
Embodiment 4
In reactor, add terephthalic acid 645g, ethylene glycol 541g, phosphor-containing flame-proof monomer 9, the 10-dihydro-9-oxy is mixed-10-phosphinylidyne assorted phenanthrene-arboxylic acid (DOPO/maleic acid) 448g, The catalytic antimony trioxide 0.145g, stir, carry out esterification according to embodiment 1 described step, condition then; With the product after the esterification, under the rough vacuum 250Pa in 260～280 ℃ of polycondensations after 1 hour, continue under high vacuum 33Pa in 280 ℃ of polycondensations discharging in 2 hours, the intrinsic viscosity of gained copolyesters performed polymer is 0.30dL/g; The copolyesters prepolymer of gained is a granulated into the particle of 2000/g size, gets 500g then at 150 ℃ of pre-crystallization 0.5h down, reheat to 210 ℃ is to carry out solid state polycondensation 4h under the condition of 50Pa to get final product in vacuum tightness.
Embodiment 5
Adding dimethyl terephthalate (DMT) 994g, ethylene glycol 793g, two (to carboxyphenyl) phenyl phosphine oxide (BCPPO) 14g of phosphor-containing flame-proof monomer, mol ratio are that 1: 1 the manganese acetate and the catalyzer of antimonous oxide are total to 0.637g in reactor, stir, carry out transesterification reaction according to embodiment 2 described conditions then; With the product after the transesterification reaction, under the rough vacuum 250Pa in 260～280 ℃ of polycondensations after 1 hour, continue under high vacuum 40Pa in 280 ℃ of polycondensations discharging in 4.5 hours, the intrinsic viscosity of gained copolyesters performed polymer is 0.75dL/g; The copolyesters prepolymer of gained is a granulated into the particle of 10/g size, gets 500g then at 150 ℃ of pre-crystallization 2h down, reheat to 160 ℃ is 0.5L/[min (kg PET) at nitrogen flow] condition under carry out solid state polycondensation 24h and get final product.
Embodiment 6
Adding dimethyl terephthalate (DMT) 804g, ethylene glycol 902g, two (to carboxyphenyl) phenyl phosphine oxide 326g of phosphor-containing flame-proof monomer, mol ratio are 1: 1 zinc acetate and the common 0.902g of antimonous oxide catalyzer in reactor, stir, carry out transesterification reaction according to embodiment 2 described conditions then; With the product after the transesterification reaction, under the rough vacuum 400Pa in 260～280 ℃ of polycondensations after 1 hour, continue under high vacuum 10Pa in 280 ℃ of polycondensations discharging in 4.5 hours, the intrinsic viscosity of gained copolyesters performed polymer is 0.80dL/g; The copolyesters prepolymer of gained is a granulated into the particle of 10000/g size, gets 500g then at 150 ℃ of pre-crystallization 4h down, reheat to 218 ℃ is to carry out solid state polycondensation 10h under the condition of 10Pa to get final product in vacuum tightness.
Embodiment 7
Adding terephthalic acid 774g, ethylene glycol 722g, mol ratio are 1: 1 fire-retardant monomer 9 in reactor, the 10-dihydro-9-oxy is assorted-the assorted phenanthrene of 10-phosphinylidyne-Succinic Acid 89g and 2-contract ethylphenyl phospho acid 55g, catalyst glycol antimony 0.687g, stir, carry out esterification according to embodiment 1 described step, condition then; With the product after the esterification, under the rough vacuum 320Pa in 260～280 ℃ of polycondensations after 1 hour, continue under high vacuum 60Pa in 280 ℃ of polycondensations discharging in 8 hours, the intrinsic viscosity of gained copolyesters performed polymer is 0.66dL/g; The copolyesters prepolymer of gained is a granulated into the particle of 3000/g size, gets 500g then at 130 ℃ of pre-crystallization 1h down, reheat to 210 ℃ is to carry out solid state polycondensation 12h under the condition of 200Pa to get final product in vacuum tightness.
Embodiment 8
The fire-retardant monomer 2-that in reactor, added terephthalic acid 774g, ethylene glycol 481g, mol ratio and be 1: 1 contract ethylphenyl phospho acid 55g and two (to carboxyphenyl) phenyl phosphine oxide 81g, The catalytic antimony trioxide 1.27g, stir, carry out esterification according to embodiment 1 described step, condition then; With the product after the esterification, under the rough vacuum 200Pa in 260～280 ℃ of polycondensations after 1 hour, continue under high vacuum 100Pa in 280 ℃ of polycondensations discharging in 2 hours, the intrinsic viscosity of gained copolyesters performed polymer is 0.42dL/g; The copolyesters prepolymer of gained is a granulated into the particle of 5000/g size, gets 500g then at 150 ℃ of pre-crystallization 2h down, reheat to 210 ℃ is 5L/[min (kg PET) at nitrogen flow] condition under carry out solid state polycondensation 36h and get final product.
Embodiment 9
Adding dimethyl terephthalate (DMT) 791g, ethylene glycol 469g, mol ratio are 1: 1 fire-retardant monomer 9 in reactor, the 10-dihydro-9-oxy is assorted-and the assorted phenanthrene of 10-phosphinylidyne-Succinic Acid 72g and two (to carboxyphenyl) phenyl phosphine oxide 66g, mol ratio are 1: 1 zinc acetate and glycol antimony catalyst 0.902g altogether, stir, carry out transesterification reaction according to embodiment 2 described conditions then; With the product after the transesterification reaction, under the rough vacuum 180Pa in 260～280 ℃ of polycondensations after 1 hour, continue under high vacuum 85Pa in 280 ℃ of polycondensations discharging in 2.5 hours, the intrinsic viscosity of gained copolyesters performed polymer is 0.57dL/g; The copolyesters prepolymer of gained is a granulated into the particle of 1000/g size, gets 500g then at 160 ℃ of pre-crystallization 3h down, reheat to 215 ℃ is to carry out solid state polycondensation 12h under the condition of 20Pa to get final product in vacuum tightness.
Comparative Examples
In reactor, add terephthalic acid 817g, ethylene glycol 481g, phosphor-containing flame-proof monomer 2-contract ethylphenyl phospho acid (CEPP) 55g, The catalytic antimony trioxide 0.350g, stir, carry out esterification according to embodiment 1 described step, condition then; With the product after the esterification, under the rough vacuum 200Pa in 260～280 ℃ of polycondensations after 1 hour, continue under high vacuum 20Pa in 280 ℃ of polycondensations discharging in 4 hours, the intrinsic viscosity of gained copolyesters performed polymer is that 0.70dL/g gets final product.
Subordinate list:
Claims (5)
1. high molecular phosphor-containing flame-proof atactic polyester, this atactic polyester general structure is as follows:
A is the monomeric repeated structural unit of phosphor-containing flame-proof in the formula, and m and n are positive integer, and the limiting viscosity number of this atactic polyester is 1.2-2.2dL/g, and the content of the monomeric repeated structural unit of phosphor-containing flame-proof is the 1-30% of this copolyesters repeated structural unit total mass.
2. high molecular phosphor-containing flame-proof atactic polyester according to claim 1, the monomeric repeated structural unit A of phosphor-containing flame-proof is at least a in the following structure in this atactic polyester:
In the formula, R
1For containing C
1-C
8Alkyl or phenyl or benzyl, R
2And R
3Be C
1～C
8Alkylidene group or aryl, the two can be identical also can be inequality; X, Y and Z are O atom or S atom.
3. high molecular phosphor-containing flame-proof atactic polyester according to claim 1 and 2, the limiting viscosity number of this atactic polyester is 1.4-2.2dL/g.
4. method for preparing each described high molecular phosphor-containing flame-proof atactic polyester in the claim 1～3, the processing step and the condition of this method are as follows:
1) with terephthalic acid, ethylene glycol, phosphor-containing flame-proof monomer and catalyzer add in the reaction unit, stir, vacuumize successively then, be forced into 0.1MPa behind the logical nitrogen replacement four times, be warming up to and carry out esterification under 200～280 ℃, pressure maintains 0.30～0.40MPa simultaneously, when the water that esterification generates substantially no longer changes near theoretical amount and system pressure, slowly be depressurized to normal pressure, the mol ratio of wherein added terephthalic acid and ethylene glycol is 1: 1.2～1: 2, added phosphor-containing flame-proof monomer accounts for 1～30% of flame-proof copolyester total mass, and added catalyzer is the 0.01-0.1% of flame-proof copolyester total mass, or
Dimethyl terephthalate (DMT), ethylene glycol, phosphor-containing flame-proof monomer and catalyzer are added in the reaction unit, stir, under 160～220 ℃ of temperature, carried out transesterification reaction 0.5～6 hour then, wherein the mol ratio of dimethyl terephthalate (DMT) and ethylene glycol is 1: 2～1: 3, added phosphor-containing flame-proof monomer accounts for 1～30% of flame-proof copolyester total mass, and added catalyzer is 0.01～0.1% of a flame-proof copolyester total mass;
2) with the product after esterification or the transesterification reaction, after system pressure 100～600Pa, 220～280 ℃ of following prepolymerization reactions of temperature 1～3 hour, continuation is 280 ℃ of following polycondensations discharging in 0.5～5 hour in system pressure 10～200Pa, temperature, and the intrinsic viscosity of gained copolyesters prepolymer is 0.3～0.8dL/g;
3) elder generation is a granulated into the copolyesters prepolymer of gained the particle of 10～10000/g size, then under 100～160 ℃ of temperature, crystallization pre-treatment 0.5～4h, again with its vacuum state or inert gas flow 0.5～5L/[min (kg PET) at 10～200Pa] state under, under 160～218 ℃ of temperature, carry out solid state polycondensation and got final product in 4～36 hours.
5. the method for preparing high molecular phosphor-containing flame-proof atactic polyester according to claim 4, used phosphor-containing flame-proof monomer is at least a in the following structure monomer in this method:
In the formula, R
1For containing C
1-C
8Alkyl or phenyl or benzyl, R
2And R
3Be C
1～C
8Alkylidene group or aryl, the two can be identical also can be inequality; X, Y and Z are O atom or S atom.
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| CN102174183A (en) * | 2011-02-23 | 2011-09-07 | 四川大学 | High-temperature self-crosslinking flame-retardant anti-dripping copolyester and preparation method thereof |
| CN102199807A (en) * | 2011-03-29 | 2011-09-28 | 浙江古纤道新材料股份有限公司 | Method for producing phosphorus copolymerized flame-retarding terylene high-strength industrial yarns |
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| CN106977706A (en) * | 2016-01-18 | 2017-07-25 | 中国石油化工股份有限公司 | Atactic polyester composition and preparation method thereof and flame retardant polyester composition and preparation method thereof |
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| CN108164689A (en) * | 2017-11-30 | 2018-06-15 | 中国科学院长春应用化学研究所 | A kind of response type is copolymerized fire-retardant furyl polyester and preparation method thereof |
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| CN106977706A (en) * | 2016-01-18 | 2017-07-25 | 中国石油化工股份有限公司 | Atactic polyester composition and preparation method thereof and flame retardant polyester composition and preparation method thereof |
| CN106977706B (en) * | 2016-01-18 | 2019-07-19 | 中国石油化工股份有限公司 | Atactic polyester composition and preparation method thereof and flame retardant polyester composition and preparation method thereof |
| CN106977884B (en) * | 2016-01-18 | 2019-07-19 | 中国石油化工股份有限公司 | Atactic polyester composition and preparation method thereof and flame retardant polyester composition and preparation method thereof |
| CN107326458A (en) * | 2017-06-22 | 2017-11-07 | 江苏飞翔化工股份有限公司 | A kind of flame-retardant polyester fiber and preparation method thereof |
| CN108164689A (en) * | 2017-11-30 | 2018-06-15 | 中国科学院长春应用化学研究所 | A kind of response type is copolymerized fire-retardant furyl polyester and preparation method thereof |
| CN114957636A (en) * | 2022-06-14 | 2022-08-30 | 四川轻化工大学 | Phosphorus-containing flame-retardant copolymerized PBS and preparation method thereof |
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