CN112646153A - Flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof - Google Patents
Flame-retardant anti-dripping aromatic liquid crystal copolyester and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a flame-retardant anti-dripping aromatic liquid crystal copolyester and a preparation method thereof, wherein the flame-retardant anti-dripping aromatic liquid crystal copolyester comprises a main chain which is formed by copolymerizing rigid mesomorphic elements and polyester granules, and an end sealing group is a phenylacetylene group or a norbornene acetylene group; mesogenic units are selected from 4, 4' -dihydroxybiphenyl; terephthalic acid and 2, 7-naphthalenedicarboxylic acid; and p-hydroxybenzoic acid containing both terminal carboxyl group A and terminal hydroxyl group B. The flame-retardant anti-dripping aromatic liquid crystal copolyester has lower melting processing temperature and flame-retardant anti-dripping performance, and can effectively reduce life and property losses caused by fire, so the flame-retardant anti-dripping aromatic liquid crystal copolyester has wide application prospects in the fields of civil textiles and high-temperature protective materials, and in addition, the molecular weight is controllable in the polymerization process, the preparation process is simpler, more convenient, efficient and environment-friendly, and harmful gas cannot be generated during combustion.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to 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 invention aims to solve the problems and provides a flame-retardant anti-dripping aromatic liquid crystal copolyester and a preparation method thereof, wherein the flame-retardant anti-dripping aromatic liquid crystal copolyester has the characteristics of low melting point, anti-dripping property and no harmful gas generation during combustion.
The purpose of the invention is realized as follows:
the flame-retardant anti-dripping aromatic liquid crystal copolyester comprises a main chain, an end sealing group and a main chain, 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' -dihydroxybiphenyl;
wholly aromatic diacid monomers are terephthalic acid and 2, 7-naphthalenedicarboxylic acid;
meanwhile, the AB type wholly aromatic monomer containing the terminal carboxyl group A and the terminal hydroxyl group B is p-hydroxybenzoic acid.
The polyester particles in the flame-retardant anti-dripping aromatic liquid crystal copolyester are one or more of polyethylene terephthalate, polytrimethylene terephthalate and polybutylene terephthalate.
The phenylacetylene or norbornene acetylene group in the 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 flame-retardant anti-dripping aromatic liquid crystal copolyester are polytrimethylene terephthalate;
the end capping group is
The structural formula of the flame-retardant anti-dripping aromatic liquid crystal copolyester in the 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 flame-retardant anti-dripping aromatic liquid crystal copolyester in the flame-retardant anti-dripping aromatic liquid crystal copolyester is 1000-10000 g/mol.
The preparation method of the flame-retardant anti-dripping aromatic liquid crystal copolyester comprises the following steps:
(1) adding 4, 4' -dihydroxybiphenyl, terephthalic acid, 2, 7-naphthalenedicarboxylic acid, p-hydroxybenzoic acid, polyester particles, compounds 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 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, and/or the mass of the catalyst is 0.1-0.5% of the total mass of all the raw materials;
in the preparation method of the 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 flame-retardant anti-dripping aromatic liquid crystal copolyester comprises the following steps:
(1) 4, 4' -dihydroxybiphenyl, terephthalic acid, 2, 7-naphthalenedicarboxylic acid, p-hydroxybenzoic acid, PET particles, N- (3-carboxyphenyl) -4-phenylethynylphthalimide, N- (3-hydroxyphenyl) -4-phenylethynylphthalimide and 140 ml of acetic anhydride were added in a molar ratio of 30:20:10:40:400:7:7, 0.1 wt% of titanium sesquioxide was used as a catalyst, and the flask was equipped with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing a nitrogen flow, and acetylating the reaction mixture in a flowing sand bath at 140 ℃ for 40 min;
(2) heating to 310 ℃ at the heating rate of 1 ℃/min to perform ester exchange reaction for 3 h;
(3) slowly vacuumizing the reaction system, and keeping the vacuum degree at 3mbar and the temperature at 310 ℃ for 20 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 24 hours at the temperature of 240 ℃ and under the vacuum degree of 2 mbar.
Naphthalene monomers are introduced into a molecular chain of the flame-retardant anti-dripping aromatic liquid crystal copolyester material to destroy the linearity of a main chain, the molecular chain is of a semi-aromatic structure, and compared with a straight-chain wholly aromatic liquid crystal material, the flame-retardant anti-dripping aromatic liquid crystal copolyester material has lower melting processing temperature, 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 be subjected to 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 macromolecular chain of the 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 thermosetting reaction has excellent flame-retardant anti-dripping performance and can effectively reduce life and property losses caused by fire, so the 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 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 flame-retardant anti-dripping aromatic liquid crystal copolyester prepared by the invention does not contain any solvent, no small molecule is generated in the curing process, thermotropic liquid crystal polyarylate plates and fibers can be prepared by hot pressing or melt spinning, and no solvent is required in the process, so that the preparation process is simpler, more efficient and more environment-friendly;
(4) the 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 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 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;
4, 4' -dihydroxybiphenyl, terephthalic acid, 2, 7-naphthalenedicarboxylic acid, p-hydroxybenzoic acid, PET particles, N- (3-carboxyphenyl) -4-phenylethynylphthalimide, N- (3-hydroxyphenyl) -4-phenylethynylphthalimide and 140 ml of acetic anhydride were added in a 250 ml three-necked round-bottomed flask in a molar ratio of 30:20:10:40:400:7:7, with 0.1% by weight of titanium trioxide 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 140 ℃ for 40min in a sand bath with a nitrogen flow and then transesterified at 310 ℃ with a temperature increase of 1 ℃/min for 3 h. At this time, the reaction system was slowly evacuated to a vacuum of 3mbar 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. And carrying out solid state polycondensation reaction at 240 ℃ under the vacuum degree of 2mbar for 24 hours 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
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. 1.
As can be seen from the combination of FIG. 1 and Table 1, the melting points of the pure thermotropic liquid crystal high polymers of comparative examples 1 and 2 are 267 ℃ and 270 ℃, respectively, while the melting point of the copolymer of example 1 is lower than that of comparative examples 1-2 and PET (Tm is 250-260 ℃), which can reduce the molding production cost of the copolyester material to a certain extent; meanwhile, the thermal decomposition temperature Td 5% of the liquid crystal copolyester is above 370 ℃, and the 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 flame-retardant anti-dripping aromatic liquid crystal copolyester is characterized by comprising a main chain, an end sealing group and a main chain, 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 A and a terminal hydroxyl B;
the wholly aromatic diphenol monomer is 4, 4' -dihydroxybiphenyl;
the wholly aromatic diacid monomers are terephthalic acid and 2, 7-naphthalene dicarboxylic acid;
the AB type wholly aromatic monomer containing both a terminal carboxyl group A and a terminal hydroxyl group B is p-hydroxybenzoic acid.
2. The flame retardant anti-drip aromatic liquid crystal copolyester of claim 1, wherein the polyester particles are one or more of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate.
3. The flame retardant, drip resistant aromatic liquid crystal copolyester of claim 1 or 2 wherein said phenylacetylene or norbornene acetylene groups are one or more of the following compounds:
wherein Y is amino or imino; z is hydroxyl, carboxyl, ester group or carbonyl.
4. The flame retardant anti-drip aromatic liquid crystalline copolyester of claim 3, wherein the polyester particles are polytrimethylene terephthalate;
the end capping group is
5. The flame retardant anti-dripping aromatic liquid crystal copolyester as claimed in claim 4, wherein the structural formula of the flame retardant anti-dripping aromatic liquid crystal copolyester is as follows:
wherein m is 90-100, and n is 2-20.
6. The flame retardant anti-dripping aromatic liquid crystal copolyester as claimed in any one of claims 1 to 5, wherein the molecular weight of the flame retardant anti-dripping aromatic liquid crystal copolyester is 1000 to 10000 g/mol.
7. The method for preparing flame-retardant anti-dripping aromatic liquid crystal copolyester according to claim 1, which comprises the following steps:
(1) adding 4, 4' -dihydroxybiphenyl, terephthalic acid, 2, 7-naphthalenedicarboxylic acid, p-hydroxybenzoic acid, polyester particles, compounds 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 preparation method of the 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 flame-retardant anti-dripping aromatic liquid crystal copolyester according to claim 7, which comprises the following steps:
(1) 4, 4' -dihydroxybiphenyl, terephthalic acid, 2, 7-naphthalenedicarboxylic acid, p-hydroxybenzoic acid, PET particles, N- (3-carboxyphenyl) -4-phenylethynylphthalimide, N- (3-hydroxyphenyl) -4-phenylethynylphthalimide and 140 ml of acetic anhydride were added in a molar ratio of 30:20:10:40:400:7:7, 0.1 wt% of titanium sesquioxide was used as a catalyst, and the flask was equipped with a sealed glass paddle stirrer, a nitrogen inlet and an insulated distillation head. Introducing a nitrogen flow, and acetylating the reaction mixture in a flowing sand bath at 140 ℃ for 40 min;
(2) heating to 310 ℃ at the heating rate of 1 ℃/min to perform ester exchange reaction for 3 h;
(3) slowly vacuumizing the reaction system, and keeping the vacuum degree at 3mbar and the temperature at 310 ℃ for 20 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 24 hours at the temperature of 240 ℃ and under the vacuum degree of 2 mbar.
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Cited By (2)
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| WO2024025814A1 (en) * | 2022-07-28 | 2024-02-01 | Iowa State University Research Foundation, Inc. | Biobased copolymers of poly(ethylene terephthalate) with superior thermomechanical properties |
| US11976169B2 (en) | 2015-11-10 | 2024-05-07 | Iowa State University Research Foundation, Inc. | Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine |
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| CN102153738A (en) * | 2010-12-29 | 2011-08-17 | 浙江超维新材料有限公司 | Preparation method of polyester liquid crystal polymer and product thereby |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11976169B2 (en) | 2015-11-10 | 2024-05-07 | Iowa State University Research Foundation, Inc. | Bioadvantaged nylon: polycondensation of 3-hexenedioic acid with hexamethylenediamine |
| WO2024025814A1 (en) * | 2022-07-28 | 2024-02-01 | Iowa State University Research Foundation, Inc. | Biobased copolymers of poly(ethylene terephthalate) with superior thermomechanical properties |
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