CN110498914A - Modified polymeric liquid crystal copolymer, polymeric membrane and corresponding preparation method - Google Patents
Modified polymeric liquid crystal copolymer, polymeric membrane and corresponding preparation method Download PDFInfo
- Publication number
- CN110498914A CN110498914A CN201810472113.XA CN201810472113A CN110498914A CN 110498914 A CN110498914 A CN 110498914A CN 201810472113 A CN201810472113 A CN 201810472113A CN 110498914 A CN110498914 A CN 110498914A
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- polymeric liquid
- crystal copolymer
- modification
- polymeric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyamides (AREA)
Abstract
A kind of polymeric liquid crystal copolymer of modification, the chemical structural formula of the polymeric liquid crystal copolymer of the modification areWherein, R1、R2And R3It is respectively selected from chain alkane group, p, q are the natural number greater than 1, and the fusing point of the polymeric liquid crystal copolymer of the modification is 220 degrees Celsius~300 degrees Celsius.In addition, the present invention also provides a kind of preparation methods of the polymeric liquid crystal copolymer of above-mentioned modification, a kind of polymeric membrane of polymeric liquid crystal copolymer of the application modification and preparation method thereof.
Description
Technical field
The present invention relates to the preparation sides of a kind of polymeric liquid crystal copolymer of modification, the polymeric liquid crystal copolymer of the modification
Method, using the modification polymeric liquid crystal copolymer polymeric membrane and the polymeric membrane preparation method.
Background technique
In big data era, the information processing of electronic product is constantly towards the side of signal transmission high frequency and high-speed digitization
To development.To guarantee that electronic product has good signal transmission quality simultaneously under conditions of high frequency signal transmission, need
It is in impedance matching condition between transmission line and its electronic component connected in the copper-foil conducting electricity of flexible circuit board, avoids making
Phenomena such as at signal reflex, scattering, decaying and delay.Jie of the material for the glue-line being in contact in flexible circuit board with conducting wire
Electric constant and dielectric loss factor are to influence a key factor of high-frequency transmission impedance matching.It is used for flexible printing in the prior art
The liquid crystal polymer membrane that macromolecule membranous layer in circuit board usually uses polymeric liquid crystal copolymer to be formed, because polymer architecture is arranged
Column are neat, so that liquid crystal polymer membrane has lower dielectric loss factor Df, however, liquid crystal high score in the prior art
Film forming processing characteristics of the sub- polymer when forming the liquid crystal polymer membrane are poor.
Summary of the invention
In view of this, it is necessary to provide a kind of liquid crystal polymers of modification conducive to signal high-frequency transmission and good film-forming property to gather
Close object.
In addition, there is a need to provide a kind of preparation method of polymeric liquid crystal copolymer for preparing above-mentioned modification.
In addition, there is a need to provide polymeric membrane and its system made from a kind of polymeric liquid crystal copolymer using the modification
Preparation Method.
A kind of polymeric liquid crystal copolymer of modification, the chemical structural formula of the polymeric liquid crystal copolymer of the modification are
Wherein, R1、R2And R3It is respectively selected from chain alkane group, p, q are the natural number greater than 1, and the liquid crystal of the modification is high
The fusing point of Molecularly Imprinted Polymer is 220 degrees Celsius~300 degrees Celsius.
A kind of preparation method of the polymeric liquid crystal copolymer of modification comprising following steps:
4- toluene sulfochloride, N,N-dimethylformamide and pyridine are mixed to form a first chamber；
It is separately added into pyridine toward 4-HBA, 6-Hydroxy-2-naphthoic acid, so that 4-HBA, 6- hydroxyl -2-
Naphthoic acid dissolves in pyridine respectively and disperses that the first solution and the second solution is successively made, toward by structural formula be HO-R1- OH's
Glycol compound and structural formula areTwo acid compounds constitute mixture
In or structural formula beHydroxyl acid compounds in pyridine is added so that the mixture
Or the hydroxyl acid compounds dissolve in pyridine and disperse that third solution is made, wherein R1、R2And R3It is respectively selected from chain
Shape alkane group；
Above-mentioned first solution is added in the first chamber, the second combination is made in middle heating reaction after mixing
Object；
In a heated condition, second solution is added to react in the second chamber and third composition is made；
In a heated condition, the third solution is added to react in the third composition and the 4th composition is made,
In, it is dissolved with chemical structural formula in the 4th composition
Modification polymeric liquid crystal copolymer, wherein p, q are natural number greater than 1；
It is precipitated the polymeric liquid crystal copolymer of the modification in the 4th composition to form precipitating, then separation cleaning
Obtaining the polymeric liquid crystal copolymer of the modification, the fusing point of the polymeric liquid crystal copolymer of the modification is 220 degrees Celsius~
300 degrees Celsius.
A kind of polymeric membrane, by after will including polymeric liquid crystal copolymer baking-curing modified as described above
It is made, the chemical crosslinking that reaction is formed is crosslinked between the polymeric liquid crystal copolymer in the polymeric membrane including the modification
Network structure.
A kind of preparation method using polymeric membrane made from polymeric liquid crystal copolymer modified as described above, packet
It includes following steps: a resin combination baking-curing is made, the resin combination includes the liquid crystal polymer of the modification
Polymer and solvent crosslink the chemical crosslinking network structure that reaction is formed between the polymeric liquid crystal copolymer of the modification.
Polymeric membrane made from the polymeric liquid crystal copolymer of modification of the invention has and liquid crystal in the prior art
The comparable dielectric constant D of polymeric membrane made from high molecular polymerkAnd dielectric loss Df, simultaneously as the liquid crystal of the modification
Bonded backbone in high molecular polymerOr
The bonded backbone of personSo that the polymeric liquid crystal copolymer of the modification is with lower
Fusing point so that the polymeric liquid crystal copolymer of the modification in a solvent can when film forming forms the polymeric membrane
Dissolution, so that film forming of the polymeric liquid crystal copolymer of the modification when forming the polymeric membrane is more preferable.
Specific embodiment
The polymeric liquid crystal copolymer of the modification of better embodiment of the present invention can be used for circuit board (such as rigid-flexible knot
Plywood) substrate, in glue-line or cover film.The chemical structural formula of the polymeric liquid crystal copolymer of the modification is
Wherein, R1、R2And R3It is respectively selected from chain alkane group.Preferably, R1、R2And R3It is respectively selected from ethyl, n-propyl
And at least one of normal-butyl.In present embodiment, the ratio range of x:y:z:w is (45~49): (45~49): (1~
5): (1~5).The ratio range of m:n:r is (45~49): (45~49): (2~10).Preferably, the ratio of x:y:z:w is selected from
At least one of 49:49:1:1,48:48:2:2,47:47:3:3,46:46:4:4 and 45:45:5:5, the ratio choosing of m:n:r
From at least one of 49:49:2,48:48:4,47:47:6,46:46:8 and 45:45:10.P and q is respectively the nature for being greater than 1
Number.The fusing point of the polymeric liquid crystal copolymer of the modification is 220 degrees Celsius~300 degrees Celsius.
Better embodiment of the present invention also provides a kind of preparation method of the polymeric liquid crystal copolymer of above-mentioned modification, packet
Include following steps:
4- toluene sulfochloride, n,N-Dimethylformamide and pyridine are mixed and stand to form one first combination by step S1
Object.
In present embodiment, the relation with contents between 4- toluene sulfochloride, n,N-Dimethylformamide and pyridine is not made to have
Body limits, and only need to guarantee that three kinds of substances are evenly dispersed.
In present embodiment, time of the standing be 30 minutes and its more than.Preferably, the time of the standing is 30
Minute.
Step S2 is separately added into pyridine toward 4-HBA, 6-Hydroxy-2-naphthoic acid, and toward being HO- by structural formula
R1The glycol compound and structural formula of-OH beTwo acid compounds constitute
Mixture in or structural formula beHydroxyl acid compounds in pyridine is added so that 4-
Hydroxybenzoic acid, 6-Hydroxy-2-naphthoic acid dissolve in pyridine respectively and disperse that the first solution and the second solution, institute is successively made
It states mixture or the hydroxyl acid compounds dissolves in pyridine and disperse that third solution is made.Wherein, R1、R2And R3Point
It Xuan Zi not chain alkane group.Preferably, R1、R2And R3It is respectively selected from least one of ethyl, n-propyl and normal-butyl.In
In the mixture, the mass ratio of the glycol compound and two acid compounds is 0.02:10~10:0.02.
Preferably, the mass ratio of the glycol compound and two acid compounds is 1:1.
In present embodiment, 4-HBA, 6-Hydroxy-2-naphthoic acid, institute are made in the way of ultrasonic oscillation
It states mixture and the hydroxyl acid compounds dissolves and disperse in pyridine respectively.In other embodiments, also available
Other modes (as stirred) make the 4-HBA, 6-Hydroxy-2-naphthoic acid, the mixture and the hydroxyl acids
Compound dissolves and disperses in pyridine respectively.
Above-mentioned the first solution dissolved with the 4-HBA is added in the first chamber, mixes by step S3
Close uniformly after be placed under nitrogen atmosphere and 60 degrees Celsius~100 degrees Celsius again stir 10 minutes and its it is produced above second combine
Object.
In present embodiment, the mass ratio of 4-HBA and 4- toluene sulfochloride is 49:0.1.
Step S4 contains the 6- hydroxyl-for above-mentioned under conditions of nitrogen atmosphere and 60 degrees Celsius~100 degrees Celsius
Second solution of 2- naphthoic acid is added in the second chamber, and pre-reaction 30 minutes and third produced above combination
Object.
The mass ratio of the 4-HBA and 6-Hydroxy-2-naphthoic acid is 1:1.
Step S5 is dissolved with the mixture for above-mentioned under conditions of nitrogen atmosphere and 60 degrees Celsius~100 degrees Celsius
Or the third solution of the hydroxyl acid compounds is added in the third composition and reacts 24 hours and its produced above the
Four compositions.Wherein, the polymeric liquid crystal copolymer of the modification is dissolved in the 4th composition.
Two acids chemical combination in present embodiment, in 4-HBA or 6-Hydroxy-2-naphthoic acid and the mixture
The mass ratio of object or glycol compound is 1:5~50:0.01 or 4-HBA or 6-Hydroxy-2-naphthoic acid and institute
The mass ratio for stating hydroxyl acid compounds is 1:10~50:0.01.
Preferably, the time of the reaction is 24 hours.
Step S6 the 4th composition is added in methanol or ethyl alcohol, so that the liquid crystal polymer of the modification polymerize
Object is precipitated to form precipitating, then separation cleaning obtains the polymeric liquid crystal copolymer of the modification.
In present embodiment, separated by way of pumping filtering it is described precipitate obtain the modification liquid crystal polymer it is poly-
Close object, and by methanol or ethyl alcohol clean it is described precipitating with remove remnants 4- toluene sulfochloride, n,N-Dimethylformamide and
Pyridine.
Wherein, the above method forms the polymeric liquid crystal copolymer of the modification the reaction mechanism is as follows:
A kind of polymeric membrane, by will include above-mentioned modification the resin baking-curing of polymeric liquid crystal copolymer after
It is made.Wherein, the change that reaction is formed is crosslinked between the polymeric liquid crystal copolymer in the polymeric membrane including the modification
Learn cross-linked network structure.
In present embodiment, the temperature of the baking-curing is 130 degrees Celsius~150 degrees Celsius, the baking-curing
Time is 20 minutes~40 minutes.
A kind of preparation method of polymeric membrane comprising following steps:
Step 1, provides a resin combination, and the resin combination includes the polymeric liquid crystal copolymer of above-mentioned modification
And solvent.Wherein, the solvent dissolves the polymeric liquid crystal copolymer.In present embodiment, the resin combination
The viscosity of object is 1000cps~2000cps.
In present embodiment, the solvent is n,N-Dimethylformamide.In other embodiments, the solvent may be used also
For the organic solvent of other dissolution polymeric liquid crystal copolymers commonly used in the art.
The polymeric membrane is made in step 2, resin combination described in baking-curing.Wherein, include in the polymeric membrane
The chemical crosslinking network structure that reaction is formed is crosslinked between the polymeric liquid crystal copolymer of the modification.
In present embodiment, the temperature of the baking-curing is 130 degrees Celsius~150 degrees Celsius, the baking-curing
Time is 20 minutes~40 minutes.
Due to backbone bonded in the polymeric liquid crystal copolymer of the modificationOr bonded backboneSo that the polymeric liquid crystal copolymer of the modification has lower fusing point, so that
The polymeric liquid crystal copolymer of modification in the resin combination can dissolve in a solvent, so that the resin combination
Film forming of the object when forming the polymeric membrane is more preferable.
Invention is specifically described below by Examples and Comparative Examples.
Embodiment 1
By the 4- toluene sulfochloride of 0.1g, the n,N-Dimethylformamide of 50mL and the pyridine of 3mL, mixes and stand 30 points
A first chamber is made in clock.
The pyridine of 0.2g is added in the 4-HBA of 49g and the 4-HBA is made by ultrasonic oscillation
It is dissolved in pyridine and disperses that the first solution is made, the 6-Hydroxy-2-naphthoic acid that 49g is added in the pyridine of 0.2g is made into the 6-
Hydroxy-2-naphthoic acid disperses that the second solution is made in pyridine, and the pyridine of 0.2g is added by the ethylene glycol of 1g and the fourth two of 1g
Make the mixture in the mixture of acid composition in the dissolution of pyridine and disperses that third solution is made.
Above-mentioned first solution is added in the first chamber, and is stirred at room temperature 10 minutes, nitrogen is then placed at
Atmosphere enclose and 80 degrees celsius under stir 10 minutes obtained second chambers.
Under nitrogen atmosphere and 80 degrees celsius, the suspension is added in the second chamber, to 6- hydroxyl-
The reaction was continued 30 minutes obtained third compositions after the dissolution of 2- naphthoic acid.
Under nitrogen atmosphere and 80 degrees celsius, it is small that reaction 24 in the third composition is added in second solution
When be made the 4th composition.
By the 4th composition be added methanol in so that the polymeric liquid crystal copolymer of the modification be precipitated to be formed it is heavy
It forms sediment, is simultaneously cleaned simultaneously with methanol by the isolated precipitating of pumping filtering, so that the liquid crystal polymer for obtaining the modification is poly-
Close object.
The polymeric liquid crystal copolymer of the modification is dissolved in n,N-Dimethylformamide, resin combination is made,
In, the viscosity of the resin combination is 1345cps, and the solid of the resin combination is divided into 25%.
Embodiment 2
Compared to embodiment 1, the difference is that: the 4-HBA is 48g, the 6-Hydroxy-2-naphthoic acid
For 48g, the ethylene glycol and the succinic acid are respectively 2g.The viscosity of the resin combination is 1521cps, and the resin
The solid of composition is divided into 25%.
Embodiment 3
Compared to embodiment 1, the difference is that: the 4-HBA is 47g, the 6-Hydroxy-2-naphthoic acid
For 47g, the ethylene glycol and the succinic acid are respectively 3g.The viscosity of the resin combination is 1578cps, and the resin
The solid of composition is divided into 25%.
Embodiment 4
Compared to embodiment 1, the difference is that: the 4-HBA is 46g, the 6-Hydroxy-2-naphthoic acid
For 46g, the ethylene glycol and the succinic acid are respectively 4g.The viscosity of the resin combination is 1741cps, and the resin
The solid of composition is divided into 25%.
Embodiment 5
Compared to embodiment 1, the difference is that: the 4-HBA is 45g, the 6-Hydroxy-2-naphthoic acid
For 45g, the ethylene glycol and the succinic acid are respectively 5g.The viscosity of the resin combination is 1842cps, and the resin
The solid of composition is divided into 25%.
Embodiment 6
Compared to embodiment 1, the difference is that: the ethylene glycol and the succinic acid are replaced by 3- hydracrylic acid, institute
Stating 3- hydracrylic acid is 2g.The viscosity of the resin combination is 1436cps, and the solid of the resin combination is divided into
25%.
Embodiment 7
Compared to embodiment 2, the difference is that: the ethylene glycol and the succinic acid are replaced by 3- hydracrylic acid, institute
Stating 3- hydracrylic acid is 4g.The viscosity of the resin combination is 1589cps, and the solid of the resin combination is divided into
25%.
Embodiment 8
Compared to embodiment 3, the difference is that: the ethylene glycol and the succinic acid are replaced by 3- hydracrylic acid, institute
Stating 3- hydracrylic acid is 6g.The viscosity of the resin combination is 1642cps, and the solid of the resin combination is divided into
25%.
Embodiment 9
Compared to embodiment 4, the difference is that: the ethylene glycol and the succinic acid are replaced by 3- hydracrylic acid, institute
Stating 3- hydracrylic acid is 8g.The viscosity of the resin combination is 1895cps, and the solid of the resin combination is divided into
25%.
Embodiment 10
Compared to embodiment 5, the difference is that: the ethylene glycol and the succinic acid are replaced by 3- hydracrylic acid, institute
Stating 3- hydracrylic acid is 10g.The viscosity of the resin combination is 1821cps, and the solid of the resin combination is divided into
25%.
Comparative example 1
By the 4- toluene sulfochloride of 0.1g, the n,N-Dimethylformamide of 50mL and the pyridine of 3mL, mixes and stand 30 points
A first chamber is made in clock.
The pyridine of 0.2g is added in the 4-HBA of 49g and the 4-HBA is made by ultrasonic oscillation
It is dissolved in pyridine and disperses that the first solution is made, the 6-Hydroxy-2-naphthoic acid that 49g is added in the pyridine of 0.2g is made into the 6-
Hydroxy-2-naphthoic acid disperses that suspension is made in pyridine.
Above-mentioned first solution is added in the first chamber, and is stirred at room temperature 10 minutes, nitrogen is then placed at
Atmosphere enclose and 80 degrees celsius under stir 10 minutes obtained second chambers.
Under nitrogen atmosphere and 80 degrees celsius, the suspension is added in the second chamber, to 6- hydroxyl-
Pre-reaction 30 minutes after the dissolution of 2- naphthoic acid, then the reaction was continued 24 hours, and the combination containing polymeric liquid crystal copolymer is made
Object.
Composition containing polymeric liquid crystal copolymer is added in methanol, so that the polymeric liquid crystal copolymer is precipitated
Precipitating is formed, is simultaneously cleaned simultaneously with methanol by the isolated precipitating of pumping filtering, so that it is poly- to obtain the liquid crystal polymer
Close object.
The surface that resin combination prepared by Examples 1 to 10 is respectively coated on 10 copper foils is sequentially formed into experiment sample
Product 1~10, and the laboratory sample 1~10 is toasted to the liquid crystal for making the modification of copper foil surface for 30 minutes under 140 degrees Celsius
High molecular polymer, which crosslinks reaction and solidifies, is made the identical polymeric membrane of 10 kinds of thickness；Liquid crystal prepared by comparative example 1
The surface that high molecular polymer is coated on a copper foil forms laboratory sample 11, and by the laboratory sample 11 at 140 degrees Celsius
Lower baking makes the polymeric liquid crystal copolymer of copper foil surface crosslink reaction for 10 minutes and solidifies that be made one right with embodiment 1
The identical liquid crystal polymer membrane of polymeric membrane thickness that should be formed.
The liquid crystal polymer that the 10 kinds of polymeric membranes and comparative example 1 be correspondingly formed to above-described embodiment 1~10 are correspondingly formed
The dielectric constant D of filmkWith dielectric absorption DfTested respectively, and to above-mentioned 11 kinds of laboratory samples carry out copper-stripping strength test,
The test of tin heat resistance is floated, liquid crystal prepared by the polymeric liquid crystal copolymer and comparative example 1 to the modification of Examples 1 to 10 preparation is high
11 kinds of polymer such as Molecularly Imprinted Polymer carry out the dissolubility test in n,N-Dimethylformamide, and to Examples 1 to 10
11 kinds of polymer such as polymeric liquid crystal copolymer that the polymeric liquid crystal copolymer of the modification of preparation is prepared with comparative example 1 are melted
The test of point.Testing result please refers to the performance detection data of table 1.Wherein, if drift tin heat resistance test condition is more than or equal to 320
DEG C, 10sec when, glue-line do not generate blistering, removing phenomena such as, then float tin heat resistance test result be " passing through ", show circuit board
Reach the requirement of heat resistance.
Measured value of the table 1 about the related data of polymeric membrane and polymer in above-mentioned each laboratory sample
As can be seen from table 1, compared to the liquid crystal polymer membrane of comparative example 1, the polymeric membrane of Examples 1 to 10 is same
With lower dielectric constant DkAnd lower dielectric loss Df, similarly have good heat resistance, and its copper-stripping intensity with
The liquid crystal polymer membrane copper-stripping intensity of comparative example 1 is suitable.In addition, not dissolving in n,N-Dimethylformamide compared to comparative example 1
In polymeric liquid crystal copolymer, the polymeric liquid crystal copolymer of the modification in Examples 1 to 10 dissolves in N, N- dimethyl methyl
In amide, i.e., the polymeric liquid crystal copolymer of the described modification has more preferable compared to the polymeric liquid crystal copolymer in comparative example 1
Film forming.
The above is only better embodiment of the invention, not the limitation to the present invention in any form, though
The right present invention has been that better embodiment is disclosed above, is not intended to limit the invention, any person skilled in the art,
Without departing from the scope of the present invention, when the technology contents using the disclosure above are modified or are modified to
With the equivalent implementations of variation, but without departing from the technical solutions of the present invention, according to the technical essence of the invention to
Any simple modification, equivalent change and modification that upper embodiment is done, all of which are still within the scope of the technical scheme of the invention.
Claims (13)
1. a kind of polymeric liquid crystal copolymer of modification, the chemical structural formula of the polymeric liquid crystal copolymer of the modification are
Wherein, R1、R2And R3It is respectively selected from chain alkane group, p, q are the natural number greater than 1, the liquid crystal polymer of the modification
The fusing point of polymer is 220 degrees Celsius~300 degrees Celsius.
2. the polymeric liquid crystal copolymer being modified as described in claim 1, which is characterized in that R1、R2And R3It is respectively selected from second
At least one of base, n-propyl and normal-butyl.
3. the polymeric liquid crystal copolymer being modified as described in claim 1, which is characterized in that the ratio range of x:y:z:w is
(45~49): (45~49): (1~5): the ratio range of (1~5) or m:n:r are (45~49): (45~49): (2~
10)。
4. a kind of preparation method of the polymeric liquid crystal copolymer of modification comprising following steps:
4- toluene sulfochloride, N,N-dimethylformamide and pyridine are mixed to form a first chamber；
It is separately added into pyridine toward 4-HBA, 6-Hydroxy-2-naphthoic acid, so that 4-HBA, 6- hydroxyl -2- naphthalene first
Acid dissolved in pyridine respectively and disperse that the first solution and the second solution is successively made, toward by structural formula be HO-R1The glycol of-OH
Class compound and structural formula areTwo acid compounds constitute mixture in or
Person's structural formula isHydroxyl acid compounds in pyridine is added so that the mixture or
The hydroxyl acid compounds dissolve in pyridine and disperse that third solution is made, wherein R1、R2And R3It is respectively selected from chain alkane
Hydrocarbyl group；
Above-mentioned first solution is added in the first chamber, reheats react obtained second chamber after mixing；
In a heated condition, second solution is added to react in the second chamber and third composition is made；
In a heated condition, the third solution is added to react in the third composition and the 4th composition is made, wherein institute
It states in the 4th composition and is dissolved with chemical structural formula
Modification polymeric liquid crystal copolymer, wherein p, q are natural number greater than 1；
It is precipitated the polymeric liquid crystal copolymer of the modification in the 4th composition to form precipitating, then separation cleaning obtains
The fusing point of the polymeric liquid crystal copolymer of the modification, the polymeric liquid crystal copolymer of the modification is taken the photograph for 220 degrees Celsius~300
Family name's degree.
5. the preparation method for the polymeric liquid crystal copolymer being modified as claimed in claim 4, which is characterized in that R1、R2And R3Point
It Xuan Zi not at least one of ethyl, n-propyl and normal-butyl.
6. the preparation method for the polymeric liquid crystal copolymer being modified as claimed in claim 4, which is characterized in that in the mixing
In object, the mass ratio of the glycol compound and two acid compounds is 1:1.
7. the preparation method for the polymeric liquid crystal copolymer being modified as claimed in claim 4, which is characterized in that 4- hydroxy benzenes first
The mass ratio of acid and 4- toluene sulfochloride is 49:0.1.
8. the preparation method for the polymeric liquid crystal copolymer being modified as claimed in claim 4, which is characterized in that 4- hydroxy benzenes first
The mass ratio of acid and 6-Hydroxy-2-naphthoic acid is 1:1.
9. the preparation method for the polymeric liquid crystal copolymer being modified as claimed in claim 4, which is characterized in that 4- hydroxy benzenes first
The mass ratio of two acid compounds or glycol compound in acid or 6-Hydroxy-2-naphthoic acid and the mixture be 1:5~
The mass ratio of 50:0.01 or 4-HBA or 6-Hydroxy-2-naphthoic acid and the hydroxyl acid compounds be 1:10~
50:0.01。
10. the preparation method for the polymeric liquid crystal copolymer being modified as claimed in claim 4, which is characterized in that x:y:z:w's
Ratio range is (45~49): (45~49): (1~5): the ratio range of (1~5) or m:n:r are (45~49): (45~
49): (2~10).
11. a kind of polymeric membrane, by the way that the liquid crystal high score just like modification described in claims 1 to 3 any one will be included
It is made after sub- polymer baking-curing, is crosslinked between the polymeric liquid crystal copolymer in the polymeric membrane including the modification
React the chemical crosslinking network structure formed.
12. macromolecule made from a kind of polymeric liquid crystal copolymer using the modification as described in claims 1 to 3 any one
The preparation method of film comprising following steps: a resin combination baking-curing is made, and the resin combination includes described
Modified polymeric liquid crystal copolymer and solvent crosslinks the change that reaction is formed between the polymeric liquid crystal copolymer of the modification
Learn cross-linked network structure.
13. the preparation method of polymeric membrane as claimed in claim 12, which is characterized in that the temperature of the baking-curing is
130 degrees Celsius~150 degrees Celsius, the time of the baking-curing is 20 minutes~40 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810472113.XA CN110498914B (en) | 2018-05-17 | 2018-05-17 | Modified liquid crystal high-molecular polymer, high-molecular film and corresponding preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810472113.XA CN110498914B (en) | 2018-05-17 | 2018-05-17 | Modified liquid crystal high-molecular polymer, high-molecular film and corresponding preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110498914A true CN110498914A (en) | 2019-11-26 |
| CN110498914B CN110498914B (en) | 2022-06-03 |
Family
ID=68583908
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810472113.XA Active CN110498914B (en) | 2018-05-17 | 2018-05-17 | Modified liquid crystal high-molecular polymer, high-molecular film and corresponding preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110498914B (en) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368929A (en) * | 1999-08-12 | 2002-09-11 | 纳幕尔杜邦公司 | Method and composition for improving gas barrier properties of polymeric containers and films |
| CN1470887A (en) * | 2002-07-08 | 2004-01-28 | �ն��繤��ʽ���� | Surface protective film for optical film |
| CN1616598A (en) * | 2003-08-28 | 2005-05-18 | 住友化学工业株式会社 | Aromatic liquid crystalline polyester film |
| CN1616526A (en) * | 2003-09-30 | 2005-05-18 | 可乐丽股份有限公司 | Method of making liquid crystal polymer films |
| CN1817939A (en) * | 2006-03-22 | 2006-08-16 | 南昌大学 | Synthesis of degradable aromatic/fatty copolymer ester by in-situ ester |
| CN1835988A (en) * | 2003-08-12 | 2006-09-20 | 三井化学株式会社 | Polyester resin and polyester resin laminate container |
| CN101218311A (en) * | 2005-06-20 | 2008-07-09 | 陶氏环球技术公司 | Protective coating for window glass |
| US20100155120A1 (en) * | 2008-12-23 | 2010-06-24 | Samsung Electronics Co. Ltd. | Thermosetting oligomer or polymer, thermosetting resin composition including the oligomer or polymer, and printed circuit board using the composition |
| CN101875762A (en) * | 2008-12-25 | 2010-11-03 | 住友化学株式会社 | Liquid crystal polyester resin compositions and utilize its junctor |
| CN102827362A (en) * | 2011-05-12 | 2012-12-19 | 中国科学院宁波材料技术与工程研究所 | Polylactic acid block copolymer |
| CN102898630A (en) * | 2011-07-27 | 2013-01-30 | 上海杰事杰新材料(集团)股份有限公司 | Copolyarylate and its preparation method |
| 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 |
| CN104349571A (en) * | 2013-07-29 | 2015-02-11 | 富葵精密组件(深圳)有限公司 | Flexible circuit board and manufacturing method thereof |
| CN104356375A (en) * | 2014-10-09 | 2015-02-18 | 东北大学 | Biodegradable liquid crystal copolymer for side chain sterides comprising primitive and preparation method for copolymer |
-
2018
- 2018-05-17 CN CN201810472113.XA patent/CN110498914B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1368929A (en) * | 1999-08-12 | 2002-09-11 | 纳幕尔杜邦公司 | Method and composition for improving gas barrier properties of polymeric containers and films |
| CN1470887A (en) * | 2002-07-08 | 2004-01-28 | �ն��繤��ʽ���� | Surface protective film for optical film |
| CN1835988A (en) * | 2003-08-12 | 2006-09-20 | 三井化学株式会社 | Polyester resin and polyester resin laminate container |
| CN1616598A (en) * | 2003-08-28 | 2005-05-18 | 住友化学工业株式会社 | Aromatic liquid crystalline polyester film |
| CN1616526A (en) * | 2003-09-30 | 2005-05-18 | 可乐丽股份有限公司 | Method of making liquid crystal polymer films |
| CN101218311A (en) * | 2005-06-20 | 2008-07-09 | 陶氏环球技术公司 | Protective coating for window glass |
| CN1817939A (en) * | 2006-03-22 | 2006-08-16 | 南昌大学 | Synthesis of degradable aromatic/fatty copolymer ester by in-situ ester |
| US20100155120A1 (en) * | 2008-12-23 | 2010-06-24 | Samsung Electronics Co. Ltd. | Thermosetting oligomer or polymer, thermosetting resin composition including the oligomer or polymer, and printed circuit board using the composition |
| CN101875762A (en) * | 2008-12-25 | 2010-11-03 | 住友化学株式会社 | Liquid crystal polyester resin compositions and utilize its junctor |
| CN102827362A (en) * | 2011-05-12 | 2012-12-19 | 中国科学院宁波材料技术与工程研究所 | Polylactic acid block copolymer |
| CN102898630A (en) * | 2011-07-27 | 2013-01-30 | 上海杰事杰新材料(集团)股份有限公司 | Copolyarylate and its preparation method |
| CN104349571A (en) * | 2013-07-29 | 2015-02-11 | 富葵精密组件(深圳)有限公司 | Flexible circuit board and manufacturing method thereof |
| 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 |
| CN104356375A (en) * | 2014-10-09 | 2015-02-18 | 东北大学 | Biodegradable liquid crystal copolymer for side chain sterides comprising primitive and preparation method for copolymer |
Non-Patent Citations (3)
| Title |
|---|
| XIAOMING JIN，等: "synthesis，characterization，and in vitro degradation of novel thermotropic ternary copolyester based p-hydroxybenzoic acid，glycolic acid，and p-hydroxycinnamic acid", 《MACROMOLECULES》 * |
| 田宗全: "含萘环结构液晶聚合物的合成及性质研究", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技I辑》 * |
| 钟晓慧: "生物基液晶共聚酯的合成及性能研究", 《中国优秀硕士学位论文全文数据库（电子期刊）工程科技I辑》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110498914B (en) | 2022-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110498913A (en) | Modified polymeric liquid crystal copolymer, polymeric membrane and corresponding preparation method | |
| JP4947989B2 (en) | Polyimide precursor solution, polyimide porous film, and production method thereof | |
| JP2012077144A (en) | Polyamideimide resin, manufacturing method therefor, polyamideimide resin solution, polyamideimide film, and use thereof | |
| CN111133055B (en) | Polyimide powder, polyimide varnish, and polyimide film | |
| JP5985977B2 (en) | Polyimide resin solution | |
| JP3414479B2 (en) | Film forming solution and porous film obtained therefrom or coating of porous film | |
| WO2002066546A1 (en) | Polyimide film and process for producing the same | |
| CN112300388B (en) | Polyimide precursor solution and preparation method thereof, polyimide film and preparation method thereof | |
| CN110498914A (en) | Modified polymeric liquid crystal copolymer, polymeric membrane and corresponding preparation method | |
| CN103765304B (en) | Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal display cells comprising poly amic acid ester | |
| JP6336194B2 (en) | Method for producing polyimide laminate and use thereof | |
| TW201831599A (en) | Resin composition, film, method for making the same and circuit board using the same | |
| Kim et al. | Biodegradable hot melt adhesive based on partially saponified polyvinyl acetate/cellulose diacetate blend | |
| CN109265674B (en) | Modified polyphenyl ether high-molecular polymer, high-molecular film and corresponding preparation method | |
| CN114479458B (en) | All-organic low-dielectric polyimide composite film and preparation method and application thereof | |
| JP4974068B2 (en) | Polyimide film, method for producing the same, and flexible circuit board | |
| CN111662662B (en) | Antistatic hot melt adhesive and preparation method thereof | |
| TWI688587B (en) | Modified liquid crystal polymer, polymeric layer, and method for making the same | |
| Liu et al. | Preparation and Characterization of Temperature‐Sensitive Poly (Styrene‐Butadiene‐Styrene)/Poly (N‐Isopropylacrylamide) Hydrogel Elastomer with Interpenetrating Polymeric Networks | |
| TWI668299B (en) | Modified liquid crystal polymer, polymeric layer, and method for making the same | |
| CN110857332B (en) | Polymer resin, polymer resin composition and copper-clad plate | |
| JP4826134B2 (en) | Polyimide resin, paint, seamless tubular body and heat resistant paint | |
| CN114276541A (en) | Polyimide and polyimide film with low CTE (coefficient of thermal expansion) value and high optical performance prepared from same | |
| CN110499014A (en) | Macromolecule resin composition, macromolecule resin and polymeric membrane | |
| CN112625278A (en) | Low-dielectric polyimide film and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |