CN110498914B - Modified liquid crystal high-molecular polymer, high-molecular film and corresponding preparation method - Google Patents
Modified liquid crystal high-molecular polymer, high-molecular film and corresponding preparation method Download PDFInfo
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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
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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Abstract
A modified liquid crystal high molecular polymer, the chemical structural formula of which is
Wherein R is1、R2And R3Are respectively selected from chain alkane groups, p and q are natural numbers larger than 1, and the melting point of the modified liquid crystal high molecular polymer is 220-300 ℃. In addition, the invention also provides a preparation method of the modified liquid crystal high molecular polymer, a high molecular film applying the modified liquid crystal high molecular polymer and a preparation method thereof.
Description
Technical Field
The invention relates to a modified liquid crystal high molecular polymer, a preparation method of the modified liquid crystal high molecular polymer, a high molecular film using the modified liquid crystal high molecular polymer and a preparation method of the high molecular film.
Background
In the big data age, information processing of electronic products is continuously developing towards high frequency and high speed digitization of signal transmission. If it is to be guaranteedThe electronic product has good signal transmission quality under the condition of high-frequency signal transmission, and the transmission line in the conductive copper foil of the flexible circuit board and the electronic element connected with the transmission line need to be in an impedance matching state, so that the phenomena of signal reflection, scattering, attenuation, delay and the like are avoided. The dielectric constant and dielectric dissipation factor of the material of the adhesive layer in contact with the conductive circuit in the flexible circuit board are important factors influencing the impedance matching of high-frequency transmission. In the prior art, the polymer film layer used in the flexible printed circuit board usually adopts a liquid crystal polymer film formed by liquid crystal polymer, and the polymer structure is arranged in order, so that the liquid crystal polymer film has a lower dielectric loss factor D fHowever, the liquid crystal polymer in the prior art has poor film forming processing characteristics when forming the liquid crystal polymer film.
Disclosure of Invention
In view of the above, there is a need for a modified liquid crystal polymer that is favorable for high frequency signal transmission and has good film forming properties.
In addition, it is also necessary to provide a method for preparing the modified liquid crystal high molecular polymer.
In addition, it is necessary to provide a polymer film prepared by applying the modified liquid crystal polymer and a preparation method thereof.
A modified liquid crystal high molecular polymer, the chemical structural formula of which is
Wherein R is1、R2And R3The modified liquid crystal high molecular polymer is respectively selected from chain alkane groups, p and q are natural numbers larger than 1, and the melting point of the modified liquid crystal high molecular polymer is 220-300 ℃.
A method for preparing a modified liquid crystal high molecular polymer, which comprises the following steps:
mixing 4-tosyl chloride, N-dimethylformamide and pyridine to form a first composition;
respectively adding pyridine into 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid to dissolve and disperse the 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid in the pyridine to obtain a first solution and a second solution, respectively 1Diol compound of-OH and structural formula
In a mixture of diacid compound(s) or of the structural formula
Adding pyridine to the hydroxy acid compound(s) of (a), and dissolving and dispersing the mixture or the hydroxy acid compound(s) in pyridine to produce a third solution, wherein R is1、R2And R3Are respectively selected from chain alkane groups;
adding the first solution into the first composition, uniformly mixing, and then heating for reaction to obtain a second composition;
adding the second solution into the second composition under the heating condition to react to obtain a third composition;
adding the third solution into the third composition under heating condition to react to obtain a fourth composition, wherein the fourth composition is dissolved with a chemical structural formula
The modified liquid crystal high molecular polymer of (1), wherein p and q are natural numbers greater than 1;
and separating out the modified liquid crystal high molecular polymer in the fourth composition to form a precipitate, and then separating and cleaning to obtain the modified liquid crystal high molecular polymer, wherein the melting point of the modified liquid crystal high molecular polymer is 220-300 ℃.
A polymer film is prepared by baking and curing the modified liquid crystal polymer, wherein the polymer film comprises a chemical crosslinking network structure formed by crosslinking reaction among the modified liquid crystal polymer.
A method for preparing a polymer film using the modified liquid crystal polymer as described above, comprising the steps of: baking and curing a resin composition, wherein the resin composition comprises the modified liquid crystal high molecular polymers and a solvent, and a chemical crosslinking network structure is formed by crosslinking reaction among the modified liquid crystal high molecular polymers.
The polymer film made of the modified liquid crystal polymer of the present invention has a dielectric constant D equivalent to that of the polymer film made of the liquid crystal polymer of the prior artkAnd dielectric loss DfMeanwhile, the modified liquid crystal high molecular polymer is bonded with a long chain structure
Or is linked with a long chain structure
The modified liquid crystal high molecular polymer has a lower melting point, so that the modified liquid crystal high molecular polymer can be dissolved in a solvent when forming the high molecular film, and the film forming property of the modified liquid crystal high molecular polymer is better when forming the high molecular film.
Detailed Description
The modified liquid crystal high molecular polymer of the preferred embodiment of the invention can be used in a substrate, an adhesive layer or a covering film of a circuit board (such as a rigid-flex printed circuit board). The chemical structural formula of the modified liquid crystal high molecular polymer is shown in the specification
Wherein R is1、R2And R3Are respectively selected from chain alkane groups. Preferably, R1、R2And R3Are respectively selected from at least one of ethyl, n-propyl and n-butyl. In this embodiment, the ratio of x, y, z and w is (45-49), (1-5) and (1-5). The ratio of m to n to r is (45-49) to (2-10). Preferably, the ratio of x: y: z: w is selected from at least one of 49:1:1, 48:48:2:2, 47:47:3:3, 46:46:4:4 and 45:45:5:5, and the ratio of m: n: r is selected from at least one of 49:2, 48:48:4, 47:47:6, 46:46:8 and 45:45: 10. p and q are natural numbers greater than 1. The melting point of the modified liquid crystal high molecular polymer is 220-300 ℃.
The preferred embodiment of the present invention further provides a method for preparing the modified liquid crystal polymer, which comprises the following steps:
in step S1, 4-toluenesulfonyl chloride, N-dimethylformamide, and pyridine are mixed and left to stand to form a first composition.
In this embodiment, the content relationship among 4-toluenesulfonyl chloride, N-dimethylformamide, and pyridine is not particularly limited, and it is only necessary to ensure that the three substances are uniformly dispersed.
In the present embodiment, the time for the standing is 30 minutes or more. Preferably, the standing time is 30 minutes.
Step S2, adding pyridine to 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, respectively, and adding a solution of formula HO-R1Diol compound of-OH and structural formula
In a mixture of diacid compounds or of the formula
Pyridine is added into the hydroxy acid compound, so that 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid are respectively dissolved and dispersed in the pyridine to sequentially prepare a first solution and a second solution, and the mixture or the hydroxy acid compound is dissolved and dispersed in the pyridine to prepare a third solution. Wherein R is1、R2And R3Are respectively selected from chain alkanesA hydrocarbon group. Preferably, R1、R2And R3Are respectively selected from at least one of ethyl, n-propyl and n-butyl. In the mixture, the mass ratio of the diol compound to the diacid compound is 0.02: 10-10: 0.02. Preferably, the mass ratio of the diol compound to the diacid compound is 1: 1.
In this embodiment, the 4-hydroxybenzoic acid, the 6-hydroxy-2-naphthoic acid, the mixture, and the hydroxy acid compound are dissolved and dispersed in pyridine by ultrasonic oscillation. In other embodiments, the 4-hydroxybenzoic acid, the 6-hydroxy-2-naphthoic acid, the mixture, and the hydroxyacid compound can be dissolved and dispersed in pyridine by other means (e.g., stirring).
And step S3, adding the first solution dissolved with the 4-hydroxybenzoic acid into the first composition, uniformly mixing, and then stirring for 10 minutes or more in a nitrogen atmosphere at 60-100 ℃ to obtain a second composition.
In this embodiment, the mass ratio of 4-hydroxybenzoic acid to 4-toluenesulfonyl chloride is 49: 0.1.
And step S4, adding the second solution containing the 6-hydroxy-2-naphthoic acid into the second composition under the conditions of nitrogen atmosphere and 60-100 ℃, and pre-reacting for 30 minutes or more to obtain a third composition.
The mass ratio of the 4-hydroxybenzoic acid to the 6-hydroxy-2-naphthoic acid is 1: 1.
And step S5, adding the third solution in which the mixture or the hydroxy acid compound is dissolved into the third composition to react for 24 hours or more under the conditions of nitrogen atmosphere and 60-100 ℃, thus obtaining the fourth composition. Wherein the modified liquid crystal polymer is dissolved in the fourth composition.
In the present embodiment, the mass ratio of the 4-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid to the diacid compound or the diol compound in the mixture is 1:5 to 50:0.01, or the mass ratio of the 4-hydroxybenzoic acid or the 6-hydroxy-2-naphthoic acid to the hydroxy acid compound is 1:10 to 50: 0.01.
Preferably, the reaction time is 24 hours.
Step S6, adding the fourth composition into methanol or ethanol to separate out the modified liquid crystal high molecular polymer to form a precipitate, and then separating and cleaning to obtain the modified liquid crystal high molecular polymer.
In this embodiment, the precipitate is separated by air-suction filtration to obtain the modified liquid crystal polymer, and the precipitate is washed with methanol or ethanol to remove residual 4-tosyl chloride, N-dimethylformamide, and pyridine.
The reaction mechanism of the modified liquid crystal high molecular polymer formed by the method is as follows:
a polymer film is prepared by baking and curing a resin containing the modified liquid crystal polymer. Wherein, the polymer film comprises a chemical crosslinking network structure formed by crosslinking reaction among the modified liquid crystal polymer.
In this embodiment, the temperature of the baking and curing is 130 to 150 ℃, and the time of the baking and curing is 20 to 40 minutes.
A preparation method of a polymer film comprises the following steps:
step one, a resin composition is provided, wherein the resin composition comprises the modified liquid crystal high molecular polymer and a solvent. Wherein the solvent dissolves the liquid crystal high molecular polymer. In the present embodiment, the viscosity of the resin composition is 1000cps to 2000 cps.
In this embodiment, the solvent is N, N-dimethylformamide. In other embodiments, the solvent may also be other organic solvents commonly used in the art to dissolve liquid crystalline high molecular polymers.
And step two, baking and curing the resin composition to obtain the polymer film. Wherein, the polymer film comprises a chemical crosslinking network structure formed by crosslinking reaction among the modified liquid crystal polymer.
In the embodiment, the temperature of the baking and curing is 130-150 ℃, and the time of the baking and curing is 20-40 minutes.
The modified liquid crystal high molecular polymer is bonded with a long chain structure
Or is linked with a long chain structure
The modified liquid crystal high molecular polymer is made to have a lower melting point, so that the modified liquid crystal high molecular polymer in the resin composition can be dissolved in a solvent, and the film forming property of the resin composition is better when the high molecular film is formed.
The present invention will be specifically described below with reference to examples and comparative examples.
Example 1
A first composition was prepared by mixing 0.1g of 4-toluenesulfonyl chloride, 50mL of N, N-dimethylformamide, and 3mL of pyridine and allowing to stand for 30 minutes.
0.2g of pyridine was added to 49g of 4-hydroxybenzoic acid and the 4-hydroxybenzoic acid was dissolved and dispersed in the pyridine by ultrasonic oscillation to prepare a first solution, 0.2g of pyridine was added to 49g of 6-hydroxy-2-naphthoic acid to disperse the 6-hydroxy-2-naphthoic acid in the pyridine to prepare a second solution, and 0.2g of pyridine was added to a mixture consisting of 1g of ethylene glycol and 1g of succinic acid to dissolve and disperse the mixture in the pyridine to prepare a third solution.
And adding the first solution into the first composition, stirring for 10 minutes at room temperature, and then stirring for 10 minutes under the conditions of nitrogen atmosphere and 80 ℃ to obtain a second composition.
And adding the suspension into the second composition under the nitrogen atmosphere and at the temperature of 80 ℃, and continuing to react for 30 minutes after the 6-hydroxy-2-naphthoic acid is dissolved to obtain a third composition.
And adding the second solution into the third composition to react for 24 hours under the conditions of nitrogen atmosphere and 80 ℃ to obtain a fourth composition.
And adding the fourth composition into methanol to separate out the modified liquid crystal high molecular polymer to form a precipitate, separating by air suction filtration to obtain the precipitate, and simultaneously washing with methanol to obtain the modified liquid crystal high molecular polymer.
Dissolving the modified liquid crystal high molecular polymer in N, N-dimethylformamide to prepare the resin composition, wherein the viscosity of the resin composition is 1345cps, and the solid content of the resin composition is 25%.
Example 2
The difference compared to example 1 is that: 48g of 4-hydroxybenzoic acid, 48g of 6-hydroxy-2-naphthoic acid and 2g of ethylene glycol and succinic acid respectively. The viscosity of the resin composition was 1521cps, and the solids of the resin composition were 25%.
Example 3
The difference compared to example 1 is that: 47g of 4-hydroxybenzoic acid, 47g of 6-hydroxy-2-naphthoic acid and 3g of ethylene glycol and succinic acid respectively. The viscosity of the resin composition was 1578cps, and the solids of the resin composition were 25%.
Example 4
The difference compared to example 1 is that: 46g of 4-hydroxybenzoic acid, 46g of 6-hydroxy-2-naphthoic acid and 4g of ethylene glycol and 4g of succinic acid respectively. The viscosity of the resin composition was 1741cps, and the solids of the resin composition were 25%.
Example 5
The difference compared to example 1 is that: 45g of 4-hydroxybenzoic acid, 45g of 6-hydroxy-2-naphthoic acid and 5g of ethylene glycol and succinic acid respectively. The viscosity of the resin composition was 1842cps, and the solid content of the resin composition was 25%.
Example 6
The difference compared to example 1 is that: the ethylene glycol and the succinic acid are replaced by 3-hydroxypropionic acid, and the 3-hydroxypropionic acid is 2 g. The viscosity of the resin composition was 1436cps, and the solid content of the resin composition was 25%.
Example 7
The difference compared to example 2 is that: the ethylene glycol and the succinic acid were replaced with 3-hydroxypropionic acid, and the 3-hydroxypropionic acid was 4 g. The viscosity of the resin composition was 1589cps, and the solid content of the resin composition was 25%.
Example 8
The difference compared to example 3 is that: the ethylene glycol and the succinic acid are replaced by 3-hydroxypropionic acid, and the 3-hydroxypropionic acid is 6 g. The viscosity of the resin composition was 1642cps, and the solid content of the resin composition was 25%.
Example 9
The difference compared to example 4 is that: the ethylene glycol and the succinic acid are replaced by 3-hydroxypropionic acid, and the 3-hydroxypropionic acid is 8 g. The viscosity of the resin composition was 1895cps, and the solids of the resin composition were 25%.
Example 10
The difference compared to example 5 is that: the ethylene glycol and the succinic acid are replaced by 3-hydroxypropionic acid, and the 3-hydroxypropionic acid accounts for 10 g. The viscosity of the resin composition was 1821cps, and the solids of the resin composition were 25%.
Comparative example 1
A first composition was prepared by mixing 0.1g of 4-toluenesulfonyl chloride, 50mL of N, N-dimethylformamide, and 3mL of pyridine and allowing to stand for 30 minutes.
0.2g of pyridine was added to 49g of 4-hydroxybenzoic acid and the 4-hydroxybenzoic acid was dissolved and dispersed in pyridine by ultrasonic oscillation to prepare a first solution, and 0.2g of pyridine was added to 49g of 6-hydroxy-2-naphthoic acid to disperse the 6-hydroxy-2-naphthoic acid in pyridine to prepare a suspension.
And adding the first solution into the first composition, stirring for 10 minutes at room temperature, and then stirring for 10 minutes under the conditions of nitrogen atmosphere and 80 ℃ to obtain a second composition.
And adding the suspension into the second composition under the conditions of nitrogen atmosphere and 80 ℃, pre-reacting for 30 minutes after the 6-hydroxy-2-naphthoic acid is dissolved, and then continuously reacting for 24 hours to obtain the composition containing the liquid crystal high polymer.
Adding a composition containing a liquid crystal high molecular polymer into methanol to separate out the liquid crystal high molecular polymer to form a precipitate, separating by air suction filtration to obtain the precipitate, and simultaneously washing with methanol to obtain the liquid crystal high molecular polymer.
Respectively coating the resin compositions prepared in the embodiments 1 to 10 on one surface of 10 copper foils to form experiment samples 1 to 10 in sequence, and baking the experiment samples 1 to 10 at 140 ℃ for 30 minutes to enable the modified liquid crystal high polymer on the surface of the copper foil to generate a crosslinking reaction and solidify to prepare 10 polymer films with the same thickness; the liquid crystal polymer prepared in comparative example 1 was coated on one surface of a copper foil to form an experimental sample 11, and the experimental sample 11 was baked at 140 ℃ for 10 minutes to cause the liquid crystal polymer on the surface of the copper foil to undergo a crosslinking reaction and to be cured, thereby preparing a liquid crystal polymer film having the same thickness as the polymer film formed in example 1.
Dielectric constant D of 10 kinds of polymer films formed in accordance with examples 1 to 10 and the liquid crystal polymer film formed in accordance with comparative example 1kAnd dielectric loss DfThe test was conducted on the respective 11 kinds of test specimens, and the modified liquid crystal polymers prepared in examples 1 to 10 and the liquid crystal polymer prepared in comparative example 1 were subjected to a copper peel strength test and a tin-floating heat resistance test, respectivelyThe polymers were tested for solubility in N, N-dimethylformamide and for melting points of 11 polymers, such as the modified liquid crystalline high molecular polymers prepared in examples 1 to 10 and the liquid crystalline high molecular polymer prepared in comparative example 1. The test results refer to the performance test data in table 1. And if the adhesive layer does not generate phenomena such as foaming, peeling and the like under the test conditions of the tin-floating heat resistance of more than or equal to 320 ℃ and 10sec, the test result of the tin-floating heat resistance is 'pass', which indicates that the circuit board meets the requirement of heat resistance.
TABLE 1 measured values of data relating to polymer films and polymers in the above experimental samples
As can be seen from the Table I, the polymer films of examples 1 to 10 also had a lower dielectric constant D than the liquid crystal polymer film of comparative example 1kAnd lower dielectric loss DfIt also has good heat resistance and the copper peel strength thereof is comparable to that of the liquid crystal polymer film of comparative example 1. In addition, the modified liquid crystal polymer polymers of examples 1 to 10 were soluble in N, N-dimethylformamide as compared with the liquid crystal polymer of comparative example 1 which is insoluble in N, N-dimethylformamide, i.e., the modified liquid crystal polymer polymers had better film-forming properties than the liquid crystal polymer of comparative example 1.
Although the present invention has been described with reference to the above preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (5)
1. A method for preparing a modified liquid crystal high molecular polymer, which comprises the following steps:
mixing 4-tosyl chloride, N-dimethylformamide and pyridine to form a first composition;
respectively adding pyridine into 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid to dissolve and disperse the 4-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid in the pyridine to obtain a first solution and a second solution, respectively1Diol compound of-OH and structural formula
In a mixture of diacid compounds or of the formula
Adding pyridine to the hydroxy acid compound(s) of (a), and dissolving and dispersing the mixture or the hydroxy acid compound(s) in pyridine to produce a third solution, wherein R is1、R2And R3Are respectively selected from chain alkane groups; in the mixture, the mass ratio of the diol compound to the diacid compound is 1: 1; the mass ratio of the 4-hydroxybenzoic acid to the 4-toluenesulfonyl chloride is 49: 0.1; the mass ratio of the 4-hydroxybenzoic acid to the 6-hydroxy-2-naphthoic acid is 1: 1; the mass ratio of the 4-hydroxybenzoic acid or the 6-hydroxy-2-naphthoic acid to the diacid compound or the diol compound in the mixture is (1: 5) - (50): 0.01, or the mass ratio of 4-hydroxybenzoic acid or 6-hydroxy-2-naphthoic acid to the hydroxy acid compound is 1: 10-50: 0.01;
Adding the first solution into the first composition, uniformly mixing, and then heating for reaction to prepare a second composition;
adding the second solution into the second composition under the heating condition to react to obtain a third composition;
adding the third solution into the third composition under the heating condition to react to obtain a fourth composition;
and precipitating the modified liquid crystal high molecular polymer in the fourth composition to form a precipitate, and separating and cleaning to obtain the modified liquid crystal high molecular polymer, wherein the melting point of the modified liquid crystal high molecular polymer is 220-300 ℃, and the modified liquid crystal high molecular polymer can be dissolved in N, N-dimethylformamide.
2. A modified liquid crystalline polymer prepared by the method for preparing a modified liquid crystalline polymer according to claim 1;
the melting point of the modified liquid crystal high molecular polymer is 220-300 ℃, and the modified liquid crystal high molecular polymer can be dissolved in N, N-dimethylformamide.
3. A polymer film obtained by baking and curing a liquid crystal polymer composition comprising a modified liquid crystal polymer according to claim 2, wherein the polymer film comprises a chemically crosslinked network structure formed by a crosslinking reaction between the modified liquid crystal polymer compositions.
4. A method for producing a polymer film using the modified liquid crystal polymer of claim 2, which comprises the steps of: baking and curing a resin composition, wherein the resin composition comprises the modified liquid crystal high molecular polymers and a solvent, and a chemical crosslinking network structure is formed by crosslinking reaction among the modified liquid crystal high molecular polymers.
5. The method for preparing the polymer film according to claim 4, wherein the temperature of the baking and curing is 130 to 150 ℃, and the time of the baking and curing is 20 to 40 minutes.
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