CN112608461A - Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof - Google Patents
Thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and a preparation method thereof, wherein the aromatic liquid crystal copolyester comprises a main chain which is copolymerized by rigid mesomorphic elements and polyester granules, an end sealing group is a phenylacetylene group or a norbornene acetylene group, and the mesomorphic elements are composed of a full aromatic diphenol monomer, a full aromatic diacid monomer and an AB type full aromatic monomer containing a terminal carboxyl A and a terminal hydroxyl B. The aromatic liquid crystal copolyester has lower melting processing temperature and flame-retardant anti-dripping performance, can effectively reduce life and property loss caused by fire, has wide application prospect in the fields of civil textiles and high-temperature protective materials, has controllable molecular weight in the polymerization process, is simpler, more efficient and environment-friendly in preparation process, and does not generate harmful gas during combustion.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester and a preparation method thereof.
Background
The semi-aromatic polyester is used as a high polymer material with wide application, and has wide application in civil and industrial aspects due to the characteristics of high strength, high modulus and low water absorption. Polyester fiber, also known as terylene, occupies most of the share of chemical fiber industry. The class of polyesters that are marketed includes PET, PBT, PTT, and the like. As the polymer can be oxidized and degraded at high temperature, once the polymer is burnt, fire is easily formed, and the life and property safety of people can be seriously influenced. Therefore, the flame retardant property of the polyester material is improved, and the flame retardant property has great significance.
The patent CN107938014A discloses a preparation method of a flame-retardant thermotropic polyarylate liquid crystal fiber, wherein a thermotropic liquid crystal polyarylate slice is obtained by introducing a phosphorus-containing aromatic unit into a main chain, the slice is spun into filaments by melt extrusion, and finally the flame-retardant thermotropic polyarylate liquid crystal fiber is prepared by post-treatment. The process flow is simple, the fiber has good flame retardant effect, but white smoke and molten drops can be generated during combustion due to the phosphorus flame retardant. Therefore, in order to reduce the dripping of the flame-retardant polyester fiber and the harm to human body, research on a novel phosphorus-free flame-retardant polyester material is urgently needed. On the other hand, if the main chain of the liquid crystalline polyarylate is a rigid linear structure, it needs to be melted at a high temperature (300 ℃ or higher) to be molded, and the liquid crystalline polyarylate monomer is relatively expensive, which further increases the production cost.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester having characteristics of low melting point, anti-dripping property, and no harmful gas generation during combustion, and a method for preparing the same.
The purpose of the invention is realized as follows:
the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester comprises a main chain, a main chain and an end sealing group, wherein the main chain is formed by copolymerizing rigid mesomorphic elements and polyester granules, and the end sealing group is a phenylacetylene group or a norbornene acetylene group;
the mesogen element is composed of a full aromatic diphenol monomer, a full aromatic diacid monomer and an AB type full aromatic monomer containing a terminal carboxyl group A and a terminal hydroxyl group B;
the wholly aromatic diphenol monomer is 4, 4' -biphenol;
wholly aromatic diacid monomers are 1, 4-terephthalic acid and 1, 7-naphthalene dicarboxylic acid;
meanwhile, the AB type wholly aromatic monomer containing the terminal carboxyl A and the terminal hydroxyl B is 4-hydroxybenzoic acid.
The polyester particles in the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester are one or more of polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate.
The phenylacetylene or norbornenyl acetylene group in the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester is one or more of the following compounds:
wherein Y is amino or imino; z is hydroxyl, carboxyl, ester group or carbonyl.
The polyester particles in the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester are polyethylene glycol terephthalate;
the end capping group is
Z is a carboxyl group.
The structural formula of the aromatic liquid crystal copolyester in the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester is as follows:
wherein m is 90-100, and n is 2-20.
The molecular weight of the aromatic liquid crystal copolyester in the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester is 1000-10000 g/mol.
The invention provides a preparation method of thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester, which comprises the following steps:
(1) adding a fully aromatic diphenol monomer, a fully aromatic diacid monomer, an AB type fully aromatic monomer containing a terminal carboxyl group A and a terminal hydroxyl group B, polyester particles, a compound containing phenylacetylene or norbornene acetylene groups, acetic anhydride and a catalyst in a molar ratio of 10-40: 80-20: 100-500: 2-8 into a reactor; performing acetylation reaction for 30-60 min under the protection of inert gas at the temperature of 120-150 ℃;
(2) heating to 300-340 ℃ at a heating rate of 0.5-1.5 ℃/min, and carrying out ester exchange reaction for 1-3 h;
(3) reacting for 10-30 min at 300-320 ℃ and under the condition that the vacuum degree is 1-3 mbar;
(4) and (3) cooling to room temperature in an inert gas atmosphere, grinding the product obtained in the step (3) into powder, and performing post-polycondensation reaction for 18-36 h under the conditions that the temperature is 200-260 ℃ and the vacuum degree is 1-3 mbar.
In the preparation method of the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester, the catalyst is one or more of sodium acetate, potassium acetate, zinc acetate, antimony trioxide, tetrabutyl titanate and germanium dioxide.
In the preparation method of the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester, the mass of the catalyst is 0.1-0.5% of the total mass of all raw materials;
in the preparation method of the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester, the molar amount of acetic anhydride is more than the total molar amount of hydroxyl in a full aromatic diphenol monomer, a full aromatic diacid monomer, an AB type full aromatic monomer containing a terminal carboxyl group A and a terminal hydroxyl group B, polyester particles and a compound containing phenylacetylene or norbornene acetylene groups.
The preparation method of the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester comprises the following steps:
(1) adding 4, 4' -dihydroxybiphenyl, terephthalic acid, 2, 6-naphthalenedicarboxylic acid, p-hydroxybenzoic acid, PET particles, N- (3-carboxyphenyl) -4-phenylethynylphthalimide and N- (3-hydroxyphenyl) -4-phenylethynylphthalimide in a molar ratio of 10:8:2:80:100:8:8 to 150 ml of acetic anhydride, using 0.1 wt% potassium acetate as a catalyst, placing the flask in a sealed glass paddle stirrer, introducing a nitrogen inlet tube and a thermal distillation head, introducing a nitrogen stream, and acetylating the reaction mixture in a sand bath at 120 ℃ for 30 min;
(2) heating to 340 ℃ at the heating rate of 1.5 ℃/min to perform ester exchange reaction for 1 h;
(3) slowly vacuumizing the reaction system, and keeping the vacuum degree at 1mbar and the temperature at 300 ℃ for 10 min;
(4) and (4) cooling the opaque melt obtained in the step (3) to room temperature, removing the product from the flask, grinding the product into fine powder, and carrying out solid-state polycondensation reaction for 36 hours at 260 ℃ under the vacuum degree of 3 mbar.
Naphthalene monomers are introduced into a molecular chain of the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester material to destroy the linearity of the main chain, the molecular chain is in a semi-aromatic structure and has a lower melting processing temperature compared with a straight-chain wholly aromatic liquid crystal material, on the other hand, two ends of the molecular chain are blocked by active groups which can be thermally cured, such as phenylacetylene or norbornene acetylene, and the like, and can generate cycloaddition reaction to form a solidified cross-linked network structure under a high-temperature environment (350-.
Compared with the prior art, the invention has the following technical effects:
(1) the high molecular chain of the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester material is in a semi-aromatic structure and has lower melting processing temperature, and a cross-linked network structure formed after the active end group is introduced for thermocuring reaction has excellent flame-retardant anti-dripping performance and can effectively reduce life and property losses caused by fire, so the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester material has wide application prospect in the fields of civil textiles and high-temperature protective materials.
(2) The thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester has controllable molecular weight in the polymerization process, and can be obtained into materials with different molecular weights according to requirements.
(3) The prepared thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester does not contain any solvent, does not generate any small molecules in the curing process, can be used for preparing thermotropic liquid crystal polyarylate plates and fibers by hot pressing or melt spinning, does not need to remove the solvent in the process, and has simpler, more convenient, efficient and environment-friendly preparation process;
(4) the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester prepared by the invention does not contain a phosphorus flame retardant, so that harmful gas is not generated during combustion.
Drawings
FIG. 1 is a hot stage polarization microscope photograph of the aromatic liquid crystalline copolyester of example 1;
FIG. 2 is a DSC chart of example 1 and comparative examples 1-2.
Detailed Description
The invention will be further explained with reference to the drawings.
The starting materials used in example 1 and comparative examples 1-2 below were purchased from Shanghai Bailingwei chemical technology, Inc., 100 g/bottle, and had a purity of > 98%.
Example 1
The thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester of the embodiment has the following chemical structural formula:
wherein n is 2-20, and m is 90-100;
adding 4, 4' -dihydroxybiphenyl, terephthalic acid, 2, 6-naphthalenedicarboxylic acid, p-hydroxybenzoic acid, PET particles, N- (3-carboxyphenyl) -4-phenylethynylphthalimide and N- (3-hydroxyphenyl) -4-phenylethynylphthalimide in a molar ratio of 10:8:2:80:100:8:8 in a 250 ml three-necked round-bottomed flask; 150 ml of acetic anhydride was added, and 0.1% by weight of potassium acetate was used as a catalyst; the flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. The reaction mixture was acetylated at 120 ℃ for 30min in a sand bath with a nitrogen flow and then raised to 340 ℃ at a heating rate of 1.5 ℃/min for 1h of transesterification. At this time, the reaction system was slowly evacuated to a vacuum of 1mbar and a temperature of 300 ℃ for 10 min. The opaque melt was cooled to room temperature and the product was removed from the flask and ground to a fine powder. And carrying out solid state polycondensation reaction for 36h at 260 ℃ and under the vacuum degree of 3mbar to obtain the sample of the embodiment.
Comparative example 1
4, 4' -dihydroxybiphenyl, terephthalic acid, 2, 6-naphthalenedicarboxylic acid, p-hydroxybenzoic acid, N- (3-carboxyphenyl) -4-phenylethynylphthalimide, N- (3-hydroxyphenyl) -4-phenylethynylphthalimide, as well as 150 ml of acetic anhydride and 0.1 wt% potassium acetate were added in a 250 ml three-necked round bottom flask in a molar ratio of 10:8:2:80:8: 8. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. The reaction mixture was acetylated at 140 ℃ for 40min in a fluid sand bath with a moderate nitrogen flow and then raised to 300 ℃ at a heating rate of 0.5 ℃/min for 2h transesterification. At this time, the reaction system was slowly evacuated to a vacuum of 2mbar and a temperature of 310 ℃ for 20 min. The opaque melt was cooled to room temperature and the product was removed from the flask and ground to a fine powder. Performing solid state polycondensation reaction for 24 hours at 230 ℃ and under the vacuum degree of 2mbar to obtain a target product with the chemical formula as follows:
comparative example 2
4, 4' -dihydroxybiphenyl, bis (p-carboxyphenyl) phenylphosphinate, 2, 6-naphthalenedicarboxylic acid, p-hydroxybenzoic acid, 150 ml acetic anhydride and 0.1% by weight potassium acetate were added in a 250 ml three-necked round bottom flask in a molar ratio of 10:8:2: 80. The flask was fitted with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. The reaction mixture was acetylated at 140 ℃ for 40min in a fluid sand bath with a moderate nitrogen flow and then raised to 300 ℃ at a heating rate of 0.5 ℃/min for 2h transesterification. At this time, the reaction system was slowly evacuated to a vacuum of 2mbar and a temperature of 310 ℃ for 20 min. The opaque melt was cooled to room temperature and the product was removed from the flask and ground to a fine powder. Performing solid state polycondensation reaction for 24 hours at 230 ℃ and under the vacuum degree of 2mbar to obtain a target product with the chemical formula as follows:
performance testing
Referring to fig. 1, the liquid crystallinity of example 1 was measured using a hot stage polarization microscope.
The thermal properties of the product were tested by Differential Scanning Calorimetry (DSC) and thermogravimetric analysis (TGA), and its flame retardant properties were determined by testing the vertical burning of the product while the intrinsic viscosity, thermal properties and flame retardant properties and the results of the intrinsic viscosity tests are shown in tables 1 and 2, respectively:
TABLE 1 results of the differential scanning calorimetry
TABLE 2 thermogravimetric analysis test results
The DSC curves of comparative examples 1-2 and example 1 are shown in FIG. 2.
The apparent banding texture can be seen in FIG. 1, indicating that the product of example 1 has a nematic liquid crystal texture and belongs to a liquid crystal copolyester. As can be seen from fig. 2 and table 1, the melting point of the pure thermotropic liquid crystal high polymer in comparative example 1 is 267 ℃, the melting point of the pure thermotropic liquid crystal high polymer in comparative example 2 is 270 ℃, and the melting point of the copolymer in example 1 is lower than that of comparative examples 1 and 2 and PET (Tm is 250-260 ℃), so that the molding production cost of the copolyester material can be reduced to a certain extent; meanwhile, the thermal decomposition temperature Td 5% of the aromatic liquid crystal copolyester is above 370 ℃, and the aromatic liquid crystal copolyester has high thermal stability.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.
Claims (10)
1. The thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester is characterized by comprising a main chain, a main chain and a tail end sealing group, wherein the main chain is formed by copolymerizing rigid mesogenic elements and polyester granules, and the tail end sealing group is a phenylacetylene group or a norbornene acetylene group; the mesogen element is composed of a full aromatic diphenol monomer, a full aromatic diacid monomer and an AB type full aromatic monomer containing a terminal carboxyl A and a terminal hydroxyl B;
the wholly aromatic diphenol monomer is 4, 4' -biphenol; the wholly aromatic diacid monomers are 1, 4-terephthalic acid and 1, 7-naphthalene dicarboxylic acid; the AB type wholly aromatic monomer containing both a terminal carboxyl group A and a terminal hydroxyl group B is 4-hydroxybenzoic acid.
2. The thermotropic flame retardant and droplet-resistant aromatic liquid crystalline copolyester of claim 1, wherein the polyester particles are one or more of polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate.
3. The thermotropic flame retardant anti-drip aromatic liquid crystalline copolyester of claim 1 or 2, wherein the phenylacetylene or norbornenyl acetylene group is one or more of the following compounds:
wherein Y is amino or imino; z is hydroxyl, carboxyl, ester group or carbonyl.
4. The thermotropic flame retardant anti-drip aromatic liquid crystalline copolyester of claim 1, wherein the polyester particles are polyethylene terephthalate;
the end capping group is
Z is a carboxyl group.
5. The thermotropic flame retardant anti-dripping aromatic liquid crystalline copolyester of claim 4, having the following structural formula:
wherein m is 90-100, and n is 2-20.
6. The thermotropic flame retardant and droplet-resistant aromatic liquid crystal copolyester according to any one of claims 1 to 5, wherein the molecular weight of the aromatic liquid crystal copolyester is 1000 to 10000 g/mol.
7. The method for preparing the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester according to claim 1, comprising the following steps of:
(1) adding a fully aromatic diphenol monomer, a fully aromatic diacid monomer, an AB type fully aromatic monomer containing a terminal carboxyl group A and a terminal hydroxyl group B, polyester particles, a compound containing phenylacetylene or norbornene acetylene groups, acetic anhydride and a catalyst in a molar ratio of 10-40: 80-20: 100-500: 2-8 into a reactor; performing acetylation reaction for 30-60 min under the protection of inert gas at the temperature of 120-150 ℃;
(2) heating to 300-340 ℃ at a heating rate of 0.5-1.5 ℃/min, and carrying out ester exchange reaction for 1-3 h;
(3) reacting for 10-30 min at 300-320 ℃ and under the condition that the vacuum degree is 1-3 mbar;
(4) and (3) cooling to room temperature in an inert gas atmosphere, grinding the product obtained in the step (3) into powder, and performing post-polycondensation reaction for 18-36 h under the conditions that the temperature is 200-260 ℃ and the vacuum degree is 1-3 mbar.
8. The method for preparing the thermotropic flame-retardant anti-dripping aromatic liquid crystal copolyester as claimed in claim 7, wherein the catalyst is one or more of sodium acetate, potassium acetate, zinc acetate, antimony trioxide, tetrabutyl titanate and germanium dioxide, and/or the mass of the catalyst is 0.1-0.5% of the total mass of all raw materials.
9. The method of claim 7, wherein the molar amount of acetic anhydride is greater than the total molar amount of hydroxyl groups in the wholly aromatic diphenol monomer, the wholly aromatic diacid monomer, the AB-type wholly aromatic monomer containing both terminal carboxyl groups A and terminal hydroxyl groups B, the polyester particles, the compound containing phenylacetylene or norbornene acetylene groups.
10. The method for preparing the thermotropic flame retardant and droplet-resistant aromatic liquid crystal copolyester according to claim 7, comprising the following steps of:
(1) adding 4, 4' -dihydroxybiphenyl, terephthalic acid, 2, 6-naphthalenedicarboxylic acid, p-hydroxybenzoic acid, PET particles, N- (3-carboxyphenyl) -4-phenylethynylphthalimide and N- (3-hydroxyphenyl) -4-phenylethynylphthalimide in a molar ratio of 10:8:2:80:100:8:8 to 150 ml of acetic anhydride, using 0.1 wt% potassium acetate as a catalyst, placing the flask in a sealed glass paddle stirrer, introducing a nitrogen inlet tube and a thermal distillation head, introducing a nitrogen stream, and acetylating the reaction mixture in a sand bath at 120 ℃ for 30 min;
(2) heating to 340 ℃ at the heating rate of 1.5 ℃/min to perform ester exchange reaction for 1 h;
(3) slowly vacuumizing the reaction system, and keeping the vacuum degree at 1mbar and the temperature at 300 ℃ for 10 min;
(4) and (4) cooling the opaque melt obtained in the step (3) to room temperature, removing the product from the flask, grinding the product into fine powder, and carrying out solid-state polycondensation reaction for 36 hours at 260 ℃ under the vacuum degree of 3 mbar.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6291526A (en) * | 1985-10-18 | 1987-04-27 | Nippon Ester Co Ltd | Liquid crystal polyester |
| CN1436811A (en) * | 2002-02-04 | 2003-08-20 | 四川大学 | Prepn process of in-situ compound thermal liquid crystal polyester material with both fireproof and reinforcing performance |
| CN1727439A (en) * | 2004-07-14 | 2006-02-01 | 株式会社上野制药应用研究所 | Liquid-crystalline polyester resin and method for producing it |
| 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 |
| CN102181958A (en) * | 2011-03-23 | 2011-09-14 | 东华大学 | Method for preparing flame-retardant anti-dripping copolyester fibers |
| CN102277653A (en) * | 2011-07-05 | 2011-12-14 | 东华大学 | Preparation method of inflame-retardant anti-dripping polyester composite fibers |
| CN103923306A (en) * | 2014-04-08 | 2014-07-16 | 金发科技股份有限公司 | Liquid crystal polyester and liquid crystal polyester composition consisting of liquid crystal polyester and application of liquid crystal polyester composition |
| CN104004170A (en) * | 2014-02-23 | 2014-08-27 | 华东理工大学 | Industrial preparation method for high-performance thermotropic liquid crystal polyester with homogeneous segmer structure |
| CN104592094A (en) * | 2015-02-10 | 2015-05-06 | 四川大学 | Monomer containing benzimide phenylacetylene structure, high temperature self-crosslinked copolyester and preparation method thereof |
| CN107793585A (en) * | 2017-10-30 | 2018-03-13 | 苏州大学 | A kind of liquid crystal flame-retardant foam material and preparation method thereof |
| CN108383987A (en) * | 2018-01-17 | 2018-08-10 | 四川大学 | Height based on arone structure is at charcoal low-smoke and flame retardant anti-dropping copolyesters and preparation method thereof |
| CN109517152A (en) * | 2017-09-20 | 2019-03-26 | 四川大学 | High-temperature self-crosslinking flame-retardant smoke inhibition anti-dropping copolyesters based on benzoyl amine structure and its preparation method and application |
| CN111886294A (en) * | 2018-03-20 | 2020-11-03 | 住友化学株式会社 | Liquid crystalline polyester liquid composition, method for producing liquid crystalline polyester film, and liquid crystalline polyester film |
-
2020
- 2020-12-17 CN CN202011496352.2A patent/CN112608461B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6291526A (en) * | 1985-10-18 | 1987-04-27 | Nippon Ester Co Ltd | Liquid crystal polyester |
| CN1436811A (en) * | 2002-02-04 | 2003-08-20 | 四川大学 | Prepn process of in-situ compound thermal liquid crystal polyester material with both fireproof and reinforcing performance |
| CN1727439A (en) * | 2004-07-14 | 2006-02-01 | 株式会社上野制药应用研究所 | Liquid-crystalline polyester resin and method for producing it |
| 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 |
| CN102181958A (en) * | 2011-03-23 | 2011-09-14 | 东华大学 | Method for preparing flame-retardant anti-dripping copolyester fibers |
| CN102277653A (en) * | 2011-07-05 | 2011-12-14 | 东华大学 | Preparation method of inflame-retardant anti-dripping polyester composite fibers |
| CN104004170A (en) * | 2014-02-23 | 2014-08-27 | 华东理工大学 | Industrial preparation method for high-performance thermotropic liquid crystal polyester with homogeneous segmer structure |
| CN103923306A (en) * | 2014-04-08 | 2014-07-16 | 金发科技股份有限公司 | Liquid crystal polyester and liquid crystal polyester composition consisting of liquid crystal polyester and application of liquid crystal polyester composition |
| CN104592094A (en) * | 2015-02-10 | 2015-05-06 | 四川大学 | Monomer containing benzimide phenylacetylene structure, high temperature self-crosslinked copolyester and preparation method thereof |
| CN109517152A (en) * | 2017-09-20 | 2019-03-26 | 四川大学 | High-temperature self-crosslinking flame-retardant smoke inhibition anti-dropping copolyesters based on benzoyl amine structure and its preparation method and application |
| CN107793585A (en) * | 2017-10-30 | 2018-03-13 | 苏州大学 | A kind of liquid crystal flame-retardant foam material and preparation method thereof |
| CN108383987A (en) * | 2018-01-17 | 2018-08-10 | 四川大学 | Height based on arone structure is at charcoal low-smoke and flame retardant anti-dropping copolyesters and preparation method thereof |
| CN111886294A (en) * | 2018-03-20 | 2020-11-03 | 住友化学株式会社 | Liquid crystalline polyester liquid composition, method for producing liquid crystalline polyester film, and liquid crystalline polyester film |
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