CN111303410A - Liquid crystal polymer and preparation method thereof - Google Patents
Liquid crystal polymer and preparation method thereof Download PDFInfo
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- CN111303410A CN111303410A CN202010192139.6A CN202010192139A CN111303410A CN 111303410 A CN111303410 A CN 111303410A CN 202010192139 A CN202010192139 A CN 202010192139A CN 111303410 A CN111303410 A CN 111303410A
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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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/44—Polyester-amides
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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
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
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- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
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- 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 provides a liquid crystal polymer and a preparation method thereof. The monomer comprises a structural unit derived from aromatic hydroxycarboxylic acid, a structural unit derived from dicarboxylic acid, diether fluorene and N-acetyl-p-aminophenol, wherein the mole percentage ranges of the components are 60-80%, 10-20%, 1-7% and 3-19% in sequence. In the invention, diether fluorene and N-acetyl-p-aminophenol are introduced into the liquid crystal polymer to replace a derivative containing a hydroxyl structural unit, and the prepared liquid crystal polymer has good fluidity and shows excellent processing performance.
Description
The technical field is as follows:
the invention relates to a liquid crystal polymer and a preparation method thereof, belonging to the technical field of high molecular chemistry.
Background art:
the liquid crystal polymer is a high molecular compound which can exist in a liquid crystal phase under a certain condition, and is characterized in that the molecules have higher molecular weight and have orientation order, the most important application direction is to manufacture high-strength and high-modulus fibers, liquid crystal self-reinforced plastics and in-situ composite materials, and the liquid crystal polymer is widely applied to aviation, aerospace, sports goods, automobile industry, ocean engineering, petroleum industry and other departments. With the wider application of liquid crystal polymer materials, higher requirements are made on the subsequent processability of the liquid crystal polymer materials, and the existing liquid crystal polymer has the problems of high flowability and the like, so that the subsequent processability of the liquid crystal polymer materials is improved, and the application range of the liquid crystal polymer materials is expanded.
The invention content is as follows:
the present invention has been made in view of the above problems, and an object of the present invention is to provide a liquid crystal polymer having good fluidity and exhibiting excellent processability, and a method for preparing the same.
The above purpose is realized by the following technical scheme:
a liquid crystal polymer, the monomers of which comprise: the structural unit derived from aromatic hydroxycarboxylic acid, the structural unit derived from dicarboxylic acid, diether fluorene and N-acetyl-p-aminophenol, wherein the mole percentage ranges of the components are 60-80%, 10-20%, 1-7% and 3-19% in sequence.
The structural unit derived from the aromatic hydroxycarboxylic acid is one or any combination of 4' -hydroxybiphenyl-4-carboxylic acid, 2-hydroxy-1-naphthoic acid, 6-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid and 4-hydroxybenzoic acid.
The structural unit derived from the aromatic hydroxycarboxylic acid of the liquid crystal polymer is compounded by adopting the molar ratio of 4-hydroxybenzoic acid to 6-hydroxy-2-naphthoic acid of 1:3-5: 1.
The structural unit derived from dicarboxylic acid is one or any combination of terephthalic acid, isophthalic acid, phthalic acid, 1 '-biphenyl-3, 4' -dicarboxylic acid, 1 '-biphenyl-3, 3' -dicarboxylic acid, 1, 6-naphthalenedicarboxylic acid, 1, 7-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4-diphenyl ether dicarboxylic acid, 1, 3-propane dicarboxylic acid, 1, 4-butane dicarboxylic acid and 1, 5-pentane dicarboxylic acid.
The structural unit derived from dicarboxylic acid is terephthalic acid.
The preparation method of the liquid crystal polymer comprises the following steps:
(1) pre-polymerization: refluxing aromatic hydroxycarboxylic acid, dicarboxylic acid, N-acetyl-p-aminophenol, diether fluorene, acetic anhydride and a catalyst for 3-6h at the temperature of 130-;
(2) final polymerization: and (2) further reacting the prepolymer in the step (1) at the temperature of 230-350 ℃ for 2-8h to obtain a final polymer.
In the preparation method of the liquid crystal polymer, the molar ratio of the sum of the hydroxyl content in the structural units derived from the aromatic hydroxycarboxylic acid, the N-acetyl-p-aminophenol and the diether fluorene to the acetic anhydride in the step (1) is 1: 1.2.
In the preparation method of the liquid crystal polymer, the catalyst used in the step (1) is one or any combination of sodium acetate, magnesium acetate, antimony trioxide, zinc acetate, stannous acetate, lead acetate and potassium acetate.
In the preparation method of the liquid crystal polymer, zinc acetate is used as the catalyst in the step (1).
In the preparation method of the liquid crystal polymer, the dosage of the catalyst used in the step (1) accounts for 0.008-0.012 percent of the total mass of the monomer charge.
Has the advantages that:
in the invention, diether fluorene and N-acetyl-p-aminophenol are introduced into the liquid crystal polymer to replace a derivative containing a hydroxyl structural unit, and the prepared liquid crystal polymer has good fluidity and shows excellent processing performance.
The specific implementation mode is as follows:
the liquid crystal polymer in the present embodiment includes, as monomers: the structural unit derived from aromatic hydroxycarboxylic acid, the structural unit derived from dicarboxylic acid, diether fluorene and N-acetyl-p-aminophenol, wherein the mole percentage ranges of the components are 60-80%, 10-20%, 1-7% and 3-19% in sequence.
The structural unit derived from the aromatic hydroxycarboxylic acid is one or any combination of 4' -hydroxybiphenyl-4-carboxylic acid, 2-hydroxy-1-naphthoic acid, 6-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid and 4-hydroxybenzoic acid.
The structural unit derived from the aromatic hydroxycarboxylic acid of the liquid crystal polymer is compounded by adopting the molar ratio of 4-hydroxybenzoic acid to 6-hydroxy-2-naphthoic acid of 1:3-5: 1.
The structural unit derived from dicarboxylic acid is one or any combination of terephthalic acid, isophthalic acid, phthalic acid, 1 '-biphenyl-3, 4' -dicarboxylic acid, 1 '-biphenyl-3, 3' -dicarboxylic acid, 1, 6-naphthalenedicarboxylic acid, 1, 7-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4-diphenyl ether dicarboxylic acid, 1, 3-propane dicarboxylic acid, 1, 4-butane dicarboxylic acid and 1, 5-pentane dicarboxylic acid.
The structural unit derived from dicarboxylic acid is terephthalic acid.
The preparation method of the liquid crystal polymer comprises the following steps:
(1) pre-polymerization: refluxing aromatic hydroxycarboxylic acid, dicarboxylic acid, N-acetyl-p-aminophenol, diether fluorene, acetic anhydride and a catalyst for 3-6h at the temperature of 130-;
(2) final polymerization: and (2) further reacting the prepolymer in the step (1) at the temperature of 230-350 ℃ for 2-8h to obtain a final polymer.
In the preparation method of the liquid crystal polymer, the molar ratio of the sum of the hydroxyl content in the structural units derived from the aromatic hydroxycarboxylic acid, the N-acetyl-p-aminophenol and the diether fluorene to the acetic anhydride in the step (1) is 1: 1.2.
In the preparation method of the liquid crystal polymer, the catalyst used in the step (1) is one or any combination of sodium acetate, magnesium acetate, antimony trioxide, zinc acetate, stannous acetate, lead acetate and potassium acetate.
In the preparation method of the liquid crystal polymer, zinc acetate is used as the catalyst in the step (1).
In the preparation method of the liquid crystal polymer, the dosage of the catalyst used in the step (1) accounts for 0.008-0.012 percent of the total mass of the monomer charge.
The specific embodiment is as follows:
comparative example 1
Taking 15 moles of 4-hydroxybenzoic acid, 45 moles of 6-hydroxy-2-naphthoic acid, 20 moles of terephthalic acid and 20 moles of hydroquinone, refluxing for 6 hours at 130 ℃ under the action of acetic anhydride and zinc acetate, then heating to 330 ℃, and reacting for 5 hours to obtain a prepolymer; the prepolymer was further reacted at 300 ℃ for 4 hours to give a final polymer.
Comparative example 2
Taking 15 moles of 4-hydroxybenzoic acid, 45 moles of 6-hydroxy-2-naphthoic acid, 20 moles of terephthalic acid and 20 moles of p-phenylenediamine to reflux for 5 hours at 140 ℃ under the action of acetic anhydride and zinc acetate, then heating to 340 ℃, and reacting for 4 hours to obtain a prepolymer; the prepolymer was further reacted at 320 ℃ for 3h to give the final polymer.
Example 1
Taking 15 moles of 4-hydroxybenzoic acid, 45 moles of 6-hydroxy-2-naphthoic acid, 20 moles of terephthalic acid, 7 moles of diether fluorene and 13 moles of N-acetyl-p-aminophenol, refluxing for 5 hours at 140 ℃ under the action of acetic anhydride and zinc acetate, then heating to 350 ℃, and reacting for 2 hours to obtain a prepolymer; the prepolymer was further reacted at 320 ℃ for 3h to give the final polymer.
Example 2
Taking 50 moles of 4-hydroxybenzoic acid, 10 moles of 6-hydroxy-2-naphthoic acid, 20 moles of terephthalic acid, 5 moles of diether fluorene and 15 moles of N-acetyl-p-aminophenol, refluxing for 4 hours at 150 ℃ under the action of acetic anhydride and zinc acetate, then heating to 340 ℃, and reacting for 4 hours to obtain a prepolymer; the prepolymer was further reacted at 330 ℃ for 4 hours to give a final polymer.
Example 3
Taking 28 moles of 4-hydroxybenzoic acid, 42 moles of 6-hydroxy-2-naphthoic acid, 15 moles of 1,1 '-biphenyl-3, 4' -dicarboxylic acid, 5 moles of diether fluorene and 10 moles of N-acetyl-p-aminophenol, refluxing for 5 hours at 140 ℃ under the action of acetic anhydride and stannous acetate, then heating to 330 ℃, and reacting for 5 hours to obtain a prepolymer; the prepolymer was further reacted at 240 ℃ for 7 hours to give a final polymer.
Example 4
Taking 10 moles of 4-hydroxybenzoic acid, 60 moles of 6-hydroxy-2-naphthoic acid, 15 moles of 1, 4-butanedicarboxylic acid, 3 moles of diether fluorene and 12 moles of N-acetyl-p-aminophenol, refluxing for 4 hours at 150 ℃ under the action of acetic anhydride and zinc acetate, then heating to 300 ℃, and reacting for 7 hours to obtain a prepolymer; the prepolymer was further reacted at 320 ℃ for 3h to give the final polymer.
Example 5
60 moles of 1-hydroxy-2-naphthoic acid, 20 moles of 6-hydroxy-2-naphthoic acid, 10 moles of terephthalic acid, 7 moles of diether fluorene and 3 moles of N-acetyl-p-aminophenol are taken, refluxed for 3 hours at 160 ℃ under the action of acetic anhydride and zinc acetate, and then heated to 350 ℃ to react for 2 hours to obtain a prepolymer; the prepolymer was further reacted at 270 ℃ for 6h to give the final polymer.
Example 6
Taking 45 moles of 4-hydroxybenzoic acid, 15 moles of 3-hydroxy-2-naphthoic acid, 20 moles of terephthalic acid, 5 moles of diether fluorene and 15 moles of N-acetyl-p-aminophenol, refluxing for 4 hours at 150 ℃ under the action of acetic anhydride and zinc acetate, then heating to 330 ℃, and reacting for 5 hours to obtain a prepolymer; the prepolymer was further reacted at 330 ℃ for 4 hours to give a final polymer.
Performance testing
(1) And (3) molten finger test: the test was carried out at a temperature of 300 ℃ under a load of 2.16 kg.
| Name (R) | Finger melt (g/10 min) |
| Comparative example 1 | 34.24 |
| Comparative example 2 | 32.78 |
| Example 1 | 47.57 |
| Example 2 | 48.34 |
| Example 3 | 45.73 |
| Example 4 | 46.37 |
| Example 5 | 47.32 |
| Example 6 | 46.28 |
As can be seen from the above comparative examples and examples, in the case of examples 1 to 6 in which diether fluorene and N-acetyl-p-aminophenol were introduced into the liquid crystal polymer instead of hydroquinone and hydroquinone in comparative examples 1 and 2, the melt index of the prepared liquid crystal polymer was significantly improved, i.e., the product had good fluidity and exhibited excellent processability.
The above are only the best embodiments of the present invention, and the method of the present invention includes but is not limited to the above embodiments, and the present invention is not limited to the matters described above, which belong to the common general knowledge of those skilled in the art.
Claims (10)
1. A liquid crystal polymer, the monomers of which comprise: the structural unit derived from aromatic hydroxycarboxylic acid, the structural unit derived from dicarboxylic acid, diether fluorene and N-acetyl-p-aminophenol, wherein the mole percentage ranges of the components are 60-80%, 10-20%, 1-7% and 3-19% in sequence.
2. The liquid crystal polymer according to claim 1, wherein the structural unit derived from aromatic hydroxycarboxylic acid is one or more of 4' -hydroxybiphenyl-4-carboxylic acid, 2-hydroxy-1-naphthoic acid, 6-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 1-hydroxy-2-naphthoic acid, and 4-hydroxybenzoic acid.
3. The liquid crystalline polymer of claim 1, said structural units derived from an aromatic hydroxycarboxylic acid being compounded with a molar ratio of 4-hydroxybenzoic acid to 6-hydroxy-2-naphthoic acid of 1:3 to 5: 1.
4. The liquid-crystalline polymer of claim 1, wherein the structural unit derived from dicarboxylic acid is one or more of terephthalic acid, isophthalic acid, phthalic acid, 1 '-biphenyl-3, 4' -dicarboxylic acid, 1 '-biphenyl-3, 3' -dicarboxylic acid, 1, 6-naphthalenedicarboxylic acid, 1, 7-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, 4-diphenyl ether dicarboxylic acid, 1, 3-propanedicarboxylic acid, 1, 4-butanedicarboxylic acid, and 1, 5-pentanedicarboxylic acid.
5. The liquid crystalline polymer of claim 1, said structural units derived from a dicarboxylic acid being terephthalic acid.
6. A process for the preparation of a liquid crystalline polymer as claimed in any one of claims 1 to 5, which process comprises the steps of:
(1) pre-polymerization: refluxing aromatic hydroxycarboxylic acid, dicarboxylic acid, N-acetyl-p-aminophenol, diether fluorene, acetic anhydride and a catalyst for 3-6h at the temperature of 130-;
(2) final polymerization: and (2) further reacting the prepolymer in the step (1) at the temperature of 230-350 ℃ for 2-8h to obtain a final polymer.
7. The method for producing a liquid-crystalline polymer according to claim 1, wherein the molar ratio of the sum of the hydroxyl group contents in the structural units derived from an aromatic hydroxycarboxylic acid, N-acetyl-p-aminophenol, diethofefluorene and acetic anhydride in step (1) is 1: 1.2.
8. The method for preparing a liquid crystal polymer according to claim 1, wherein the catalyst used in the step (1) is one or a mixture of any more of sodium acetate, magnesium acetate, antimony trioxide, zinc acetate, stannous acetate, lead acetate and potassium acetate.
9. The method for preparing a liquid crystalline polymer according to claim 1, wherein the catalyst used in step (1) is zinc acetate.
10. The method for preparing a liquid crystalline polymer according to claim 1, wherein the amount of the catalyst used in the step (1) is 0.008-0.012% of the total mass of the monomer charge.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010192139.6A CN111303410A (en) | 2020-03-18 | 2020-03-18 | Liquid crystal polymer and preparation method thereof |
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| CN202010192139.6A CN111303410A (en) | 2020-03-18 | 2020-03-18 | Liquid crystal polymer and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012759A (en) * | 2011-09-23 | 2013-04-03 | 金发科技股份有限公司 | Liquid crystal polyester and its preparation method and use |
| JP2013075990A (en) * | 2011-09-30 | 2013-04-25 | Sumitomo Chemical Co Ltd | Liquid crystalline polymer, molded product, and methods for manufacturing liquid crystalline polymer |
| CN103764741A (en) * | 2011-08-29 | 2014-04-30 | 提克纳有限责任公司 | Melt polymerization of low melt viscosity liquid crystalline polymers |
| CN104662087A (en) * | 2012-09-27 | 2015-05-27 | 宝理塑料株式会社 | Composite resin composition and flat connector molded from same |
| CN105358657A (en) * | 2013-06-07 | 2016-02-24 | 提克纳有限责任公司 | High strength thermotropic liquid crystalline polymer |
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2020
- 2020-03-18 CN CN202010192139.6A patent/CN111303410A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103764741A (en) * | 2011-08-29 | 2014-04-30 | 提克纳有限责任公司 | Melt polymerization of low melt viscosity liquid crystalline polymers |
| CN103012759A (en) * | 2011-09-23 | 2013-04-03 | 金发科技股份有限公司 | Liquid crystal polyester and its preparation method and use |
| JP2013075990A (en) * | 2011-09-30 | 2013-04-25 | Sumitomo Chemical Co Ltd | Liquid crystalline polymer, molded product, and methods for manufacturing liquid crystalline polymer |
| CN104662087A (en) * | 2012-09-27 | 2015-05-27 | 宝理塑料株式会社 | Composite resin composition and flat connector molded from same |
| CN105358657A (en) * | 2013-06-07 | 2016-02-24 | 提克纳有限责任公司 | High strength thermotropic liquid crystalline polymer |
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