CN113929884A - Environment-friendly liquid crystal copolyester material and preparation method thereof - Google Patents
Environment-friendly liquid crystal copolyester material and preparation method thereof Download PDFInfo
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- CN113929884A CN113929884A CN202111243197.8A CN202111243197A CN113929884A CN 113929884 A CN113929884 A CN 113929884A CN 202111243197 A CN202111243197 A CN 202111243197A CN 113929884 A CN113929884 A CN 113929884A
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- liquid crystal
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- crystal copolyester
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/065—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids the hydroxy and carboxylic ester groups being bound to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
- C09K19/3804—Polymers with mesogenic groups in the main chain
- C09K19/3809—Polyesters; Polyester derivatives, e.g. polyamides
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Abstract
The invention discloses an environment-friendly liquid crystal copolyester material and a preparation method thereof, wherein the preparation method comprises the following steps: 1) carrying out melt polycondensation on 4, 4-biphenol, p-hydroxybenzoic acid and a blocking agent to obtain a prepolymer; 2) carrying out ester exchange reaction on 2-hydroxy-6-naphthoic acid and the prepolymer to obtain copolyester; 3) and carrying out negative pressure polycondensation on the copolyester to obtain the environment-friendly liquid crystal copolyester material. The preparation method disclosed by the invention is simple in process, does not need to use a solvent, synthesizes the liquid crystal copolyester material, reduces the pollution to the environment, accords with the development concept of green chemistry, and the prepared environment-friendly liquid crystal copolyester material has good dielectric property.
Description
Technical Field
The invention relates to the technical field of liquid crystal polymers, in particular to an environment-friendly liquid crystal copolyester material and a preparation method thereof.
Background
The Liquid Crystal Polymer (LCP) is a high-performance polymer material, which loses the fluidity of the material after being heated and melted or dissolved by a solvent, but still can keep partial ordered arrangement to form a polymer material with the properties of crystals and liquid. Liquid crystal polymers can be further classified into thermotropic liquid crystal polymers and lyotropic liquid crystal polymers according to the different ways of exhibiting a liquid crystal state. The thermotropic liquid crystal is that the material is in a liquid crystal state along with the temperature change in a certain temperature range, and the lyotropic liquid crystal is that the material is in a liquid crystal state in a certain concentration range. Liquid crystalline polymeric materials are generally known for their high strength, high modulus, excellent melt processing characteristics, flame retardancy, low water absorption, chemical resistance and radiation resistance.
The existing LCP material is usually required to be carried out in organic solution in the preparation process, a large amount of organic solvent is used, the damage is caused to the environment and human body, and the requirement of green production is not met.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide an environment-friendly liquid crystal copolyester material and a preparation method thereof, and aims to prepare the environment-friendly liquid crystal copolyester material without a solvent.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of an environment-friendly liquid crystal copolyester material comprises the following steps:
1) carrying out melt polycondensation on 4, 4-biphenol, p-hydroxybenzoic acid and a blocking agent to obtain a prepolymer;
2) carrying out ester exchange reaction on 2-hydroxy-6-naphthoic acid and the prepolymer to obtain copolyester;
3) and carrying out negative pressure polycondensation on the copolyester to obtain the environment-friendly liquid crystal copolyester material.
The preparation method of the environment-friendly liquid crystal copolyester material comprises the following step of enabling the molar ratio of 4, 4-biphenol to p-hydroxybenzoic acid to 2-hydroxy-6-naphthoic acid to be 1-5:5-10: 2-6.
The preparation method of the environment-friendly liquid crystal copolyester material comprises the step of preparing a metal salt by using a solution of a solvent.
The preparation method of the environment-friendly liquid crystal copolyester material comprises the step of preparing an end-capping reagent, wherein the end-capping reagent is at least one of sodium phenolate, potassium phenolate, calcium phenolate and magnesium phenolate.
The preparation method of the environment-friendly liquid crystal copolyester material comprises the step of preparing the environment-friendly liquid crystal copolyester material, wherein the mass ratio of the end-capping reagent to the p-hydroxybenzoic acid is 1-10: 100.
The preparation method of the environment-friendly liquid crystal copolyester material comprises the following steps of: heating to 180-230 ℃ under an inert atmosphere for refluxing for 2-4h, then heating to 240-260 ℃ at the speed of 0.5-1 ℃/min, and refluxing and stirring for 0.5-2 h.
The preparation method of the environment-friendly liquid crystal copolyester material comprises the following steps of enabling the inert atmosphere to be nitrogen or argon, and enabling the gas flow to be 20-50 mL/min.
The preparation method of the environment-friendly liquid crystal copolyester material comprises the following steps: heating to 300-320 ℃ at the speed of 0.5-2 ℃/min, and reacting for 1-3 h.
The preparation method of the environment-friendly liquid crystal copolyester material comprises the following steps of: reacting for 20-30min at the temperature of 270 ℃ and 300 ℃ and under the vacuum degree of 3-6 mbar.
Meanwhile, the invention also provides an environment-friendly liquid crystal copolyester material, which is prepared by the method; the tensile strength of the environment-friendly liquid crystal copolyester material is more than 90MPa, and the relative dielectric constant of 10GHz is 2.8-3.
Has the advantages that: the invention discloses an environment-friendly liquid crystal copolyester material and a preparation method thereof, which can synthesize the liquid crystal copolyester material without using a solvent, reduce the pollution to the environment and accord with the development concept of green chemistry. The preparation method has simple process, strong processability and good dielectric property.
Detailed Description
The invention provides an environment-friendly liquid crystal copolyester material and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and more clear and definite. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Specifically, the invention provides a preparation method of an environment-friendly liquid crystal copolyester material, which comprises the following steps:
1) heating 4, 4-biphenol, p-hydroxybenzoic acid and an end-capping reagent in an inert atmosphere to 180-230 ℃ for refluxing for 2-4h, then heating to 240-260 ℃ at the speed of 0.5-1 ℃/min, refluxing and stirring for 0.5-2h, and carrying out melt polycondensation to obtain a prepolymer;
wherein the inert atmosphere is nitrogen or argon, and the gas flow is 20-50 mL/min;
the end capping agent is metal phenolate and is at least one of sodium phenolate, potassium phenolate, calcium phenolate and magnesium phenolate;
the mass ratio of the blocking agent to the p-hydroxybenzoic acid is 1-10: 100.
2) Heating the 2-hydroxy-6-naphthoic acid and the prepolymer to 300-320 ℃ at the speed of 0.5-2 ℃/min, and reacting for 1-3h to perform an ester exchange reaction to obtain copolyester;
wherein the molar ratio of the 4, 4-biphenol to the p-hydroxybenzoic acid to the 2-hydroxy-6-naphthoic acid is 1-5:5-10: 2-6.
3) And (3) reacting the copolyester for 20-30min at the temperature of 270-300 ℃ and the vacuum degree of 3-6mbar, and performing negative pressure polycondensation to obtain the environment-friendly liquid crystal copolyester material.
Meanwhile, the invention also provides an environment-friendly liquid crystal copolyester material, which is prepared by the method; the tensile strength of the environment-friendly liquid crystal copolyester material is more than 90MPa, and the relative dielectric constant of 10GHz is 2.8-3.
The environment-friendly liquid crystal copolyester material and the preparation method thereof are further explained by the following specific examples:
example 1
One embodiment of the invention provides a preparation method of an environment-friendly liquid crystal copolyester material, which comprises the following steps:
1) heating 0.1mol of 4, 4-biphenol, 1mol of p-hydroxybenzoic acid and 0.1g of sodium phenolate to 180 ℃ in a nitrogen atmosphere of 20mL/min for refluxing for 4h, then heating to 260 ℃ at 0.5 ℃/min for refluxing and stirring for 0.5h, and carrying out melt polycondensation to obtain a prepolymer;
2) heating 0.2mol of 2-hydroxy-6-naphthoic acid and the prepolymer to 300 ℃ at the temperature of 0.5 ℃/min, reacting for 3 hours, and carrying out ester exchange reaction to obtain copolyester;
3) and (3) reacting the copolyester for 30min at 270 ℃ and under the vacuum degree of 3mbar, and carrying out negative pressure polycondensation to obtain the environment-friendly liquid crystal copolyester material.
The invention also provides an environment-friendly liquid crystal copolyester material, which is prepared by the method of the embodiment 1; the tensile strength of the environment-friendly liquid crystal copolyester material is 92MPa, and the relative dielectric constant of 10GHz is 2.83.
Example 2
One embodiment of the invention provides a preparation method of an environment-friendly liquid crystal copolyester material, which comprises the following steps:
1) heating 0.5mol of 4, 4-biphenol, 1mol of p-hydroxybenzoic acid and 1g of sodium phenolate to 230 ℃ in an argon atmosphere of 50mL/min, refluxing for 2h, heating to 240 ℃ at 1 ℃/min, refluxing and stirring for 2h, and carrying out melt polycondensation to obtain a prepolymer;
2) heating 0.6mol of 2-hydroxy-6-naphthoic acid and the prepolymer to 320 ℃ at the speed of 2 ℃/min, reacting for 1h, and carrying out ester exchange reaction to obtain copolyester;
3) and (3) reacting the copolyester for 20min at the temperature of 300 ℃ and the vacuum degree of 6mbar, and carrying out negative pressure polycondensation to obtain the environment-friendly liquid crystal copolyester material.
The invention also provides an environment-friendly liquid crystal copolyester material, which is prepared by the method of the embodiment 2; the tensile strength of the environment-friendly liquid crystal copolyester material is 95MPa, and the relative dielectric constant of 10GHz is 2.89.
Example 3
One embodiment of the invention provides a preparation method of an environment-friendly liquid crystal copolyester material, which comprises the following steps:
1) heating 0.1mol of 4, 4-biphenol, 0.5mol of p-hydroxybenzoic acid and 0.1g of potassium phenoxide to 200 ℃ in a nitrogen atmosphere of 40mL/min for refluxing for 3h, then heating to 250 ℃ at the speed of 0.5 ℃/min, refluxing and stirring for 1h, and carrying out melt polycondensation to obtain a prepolymer;
2) heating 0.2mol of 2-hydroxy-6-naphthoic acid and the prepolymer to 310 ℃ at the temperature of 1 ℃/min, reacting for 2h, and carrying out ester exchange reaction to obtain copolyester;
3) and (3) reacting the copolyester for 30min at 290 ℃ and under the condition that the vacuum degree is 4mbar, and carrying out negative pressure polycondensation to obtain the environment-friendly liquid crystal copolyester material.
The invention also provides an environment-friendly liquid crystal copolyester material, which is prepared by the method of the embodiment 3; the tensile strength of the environment-friendly liquid crystal copolyester material is 101MPa, and the relative dielectric constant of 10GHz is 2.92.
Example 4
One embodiment of the invention provides a preparation method of an environment-friendly liquid crystal copolyester material, which comprises the following steps:
1) heating 0.3mol of 4, 4-biphenol, 0.5mol of p-hydroxybenzoic acid and 0.1g of calcium phenate to 210 ℃ in 30mL/min nitrogen atmosphere, refluxing for 4h, heating to 260 ℃ at 1 ℃/min, refluxing and stirring for 1h, and carrying out melt polycondensation to obtain a prepolymer;
2) heating 0.4mol of 2-hydroxy-6-naphthoic acid and the prepolymer to 300 ℃ at the temperature of 0.5 ℃/min, reacting for 3 hours, and carrying out ester exchange reaction to obtain copolyester;
3) and (3) reacting the copolyester for 30min at 290 ℃ and under the condition that the vacuum degree is 5mbar, and carrying out negative pressure polycondensation to obtain the environment-friendly liquid crystal copolyester material.
The invention also provides an environment-friendly liquid crystal copolyester material, which is prepared by the method of the embodiment 4; the tensile strength of the environment-friendly liquid crystal copolyester material is 98MPa, and the relative dielectric constant of 10GHz is 2.94.
Example 5
One embodiment of the invention provides a preparation method of an environment-friendly liquid crystal copolyester material, which comprises the following steps:
1) heating 0.4mol of 4, 4-biphenol, 0.8mol of p-hydroxybenzoic acid and 0.1g of magnesium phenate to 210 ℃ in a nitrogen atmosphere of 50mL/min for refluxing for 4h, then heating to 260 ℃ at the speed of 1 ℃/min for refluxing and stirring for 1h, and carrying out melt polycondensation to obtain a prepolymer;
2) heating 0.5mol of 2-hydroxy-6-naphthoic acid and the prepolymer to 320 ℃ at the speed of 1 ℃/min, reacting for 3h, and carrying out ester exchange reaction to obtain copolyester;
3) and (3) reacting the copolyester for 20min at 280 ℃ and under the condition that the vacuum degree is 5mbar, and carrying out negative pressure polycondensation to obtain the environment-friendly liquid crystal copolyester material.
The invention also provides an environment-friendly liquid crystal copolyester material, which is prepared by the method of the embodiment 5; the tensile strength of the environment-friendly liquid crystal copolyester material is 92MPa, and the relative dielectric constant of 10GHz is 2.87.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the environment-friendly liquid crystal copolyester material is characterized by comprising the following steps of:
1) carrying out melt polycondensation on 4, 4-biphenol, p-hydroxybenzoic acid and a blocking agent to obtain a prepolymer;
2) carrying out ester exchange reaction on 2-hydroxy-6-naphthoic acid and the prepolymer to obtain copolyester;
3) and carrying out negative pressure polycondensation on the copolyester to obtain the environment-friendly liquid crystal copolyester material.
2. The method for preparing environment-friendly liquid crystal copolyester material according to claim 1, wherein the molar ratio of 4, 4-biphenol to p-hydroxybenzoic acid to 2-hydroxy-6-naphthoic acid is 1-5:5-10: 2-6.
3. The process of claim 1, wherein the end-capping reagent is a metal phenolate.
4. The method for preparing environment-friendly liquid crystal copolyester material according to claim 3, wherein the end-capping agent is at least one of sodium phenolate, potassium phenolate, calcium phenolate and magnesium phenolate.
5. The preparation method of the environment-friendly liquid crystal copolyester material according to claim 1, wherein the mass ratio of the end-capping agent to the p-hydroxybenzoic acid is 1-10: 100.
6. The method for preparing environment-friendly liquid crystal copolyester material according to claim 1, wherein the melt polycondensation conditions comprise: heating to 180-230 ℃ under an inert atmosphere for refluxing for 2-4h, then heating to 240-260 ℃ at the speed of 0.5-1 ℃/min, and refluxing and stirring for 0.5-2 h.
7. The method for preparing environment-friendly liquid crystal copolyester material according to claim 6, wherein the inert atmosphere is nitrogen or argon, and the gas flow is 20-50 mL/min.
8. The method for preparing environment-friendly liquid crystal copolyester material according to claim 1, wherein the ester exchange reaction conditions are as follows: heating to 300-320 ℃ at the speed of 0.5-2 ℃/min, and reacting for 1-3 h.
9. The method for preparing environment-friendly liquid crystal copolyester material according to claim 1, wherein the conditions of negative pressure polycondensation comprise: reacting for 20-30min at the temperature of 270 ℃ and 300 ℃ and under the vacuum degree of 3-6 mbar.
10. An environment-friendly liquid crystal copolyester material, which is prepared by the method of any one of claims 1 to 9; the tensile strength of the environment-friendly liquid crystal copolyester material is more than 90MPa, and the relative dielectric constant of 10GHz is 2.8-3.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117510814A (en) * | 2024-01-04 | 2024-02-06 | 宁波聚嘉新材料科技有限公司 | Liquid crystal polymer, fiber, preparation method of liquid crystal polymer and fiber, and conductive fiber |
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Cited By (2)
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| CN117510814A (en) * | 2024-01-04 | 2024-02-06 | 宁波聚嘉新材料科技有限公司 | Liquid crystal polymer, fiber, preparation method of liquid crystal polymer and fiber, and conductive fiber |
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Application publication date: 20220114 |