CN106543720B - A kind of Kapton of low thermal coefficient of expansion and preparation method thereof - Google Patents
A kind of Kapton of low thermal coefficient of expansion and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention belongs to polymeric material fields, are specifically related to a kind of Kapton and preparation method thereof of low thermal coefficient of expansion.The Kapton has the following structure formula:
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of low thermal coefficient of expansion Kapton and its
Preparation method.
Background technique
Polyimides is most important kind in the aromatic heterocyclic copolymer to grow up nearly half a century, and uses temperature
Highest a kind of high molecular material is spent, there is the very excellent synthesis such as high mechanical strength, high temperature resistant, chemical stabilization, creep resistant
Performance, Aeronautics and Astronautics, electrical, machinery, microelectronics, in terms of be widely used.
But polyimides has biggish thermal expansion coefficient (40-80 × 10-6/ K), this greatly limits it to apply model
It encloses, the application especially in microelectronic industry, such as in above-mentioned encapsulated circuit, polyimides and conductive material or substrate
Thermal expansion coefficient has very big difference, and (thermal expansion coefficient of such as Cu is 16-18 × 10-6/ K, SiO2Thermal expansion coefficient be 14
×10-6/ K, Si thermal expansion coefficient are 3-6 × 10-6/ K), serious thermal expansion coefficient mismatch will lead to encapsulating material and encapsulate
The heat treatment of process or layering or cracking in encapsulated circuit use process, even result in the failure of material or device.Therefore,
The thermal expansion coefficient for reducing polyimides is allowed to the conductive layer in encapsulated circuit with preferable thermally matched with important meaning
Justice.
Summary of the invention
The purpose of the present invention is overcoming the deficiencies in the prior art described above, a kind of polyimides of low thermal coefficient of expansion is provided
Film and preparation method thereof.
Overcome the deficiencies in the prior art of the present invention is the technical solution adopted is as follows: a kind of polyimides of low thermal coefficient of expansion
The structural formula of film, the polyimides is as follows:
Wherein, R1 and R3 is the residue of two different tetracarboxylic dianhydride's monomers, and R2 and R4 are two different binary primary
The residue of amine monomers, m and n are the integer greater than zero.
Specifically, the R4 is one or more of following three kinds of groups:
The R1 is one or both of the following two kinds group:
The R2 is one or more of following three kinds of groups:
The R3 is one or both of the following two kinds group:
Optimal, the R4 is preferably one or both of the following two kinds group:
Optimal, the R2 is preferably one or both of the following two kinds group:.
Optimal, the R3 is preferably following group:
The present invention also provides the preparation methods of the Kapton of the above-mentioned low thermal coefficient of expansion stated comprising as follows
Step:
S1. under nitrogen protection, the first tetracarboxylic dianhydride's monomer, the first binary primary amine monomer and organic solvent are added
It into consersion unit, is stirred at room temperature, prepares sticky polyamide solution A, it is spare；
S2. under nitrogen protection, second of tetracarboxylic dianhydride's monomer, second of binary primary amine monomer and organic solvent are added
It in consersion unit, is stirred at room temperature, prepares sticky polyamic acid solution B, it is spare；
S3. the polyamic acid solution B in the polyamide solution A and S2 in S1 is mixed, is stirred at room temperature, preparation is most
Whole polyamic acid solution；
S4., solution after dilution is coated uniformly on to the glass of cleaning by the polyamic acid solution dilution of S3 and with the tape casting
On plate, heat drying processing to get the low thermal coefficient of expansion Kapton.
Wherein, the first tetracarboxylic dianhydride's monomer, the first binary primary amine monomer, second of tetracarboxylic dianhydride's monomer and
The molar ratio of two kinds of binary primary amine monomers is (0.1-0.6): (0.1-0.6): (0.4-0.9): (0.4-0.9).
Preferably, the first described tetracarboxylic dianhydride's monomer uses pyromellitic acid anhydride and 3,3', 4,4'- biphenyl four
One or both of carboxylic acid dianhydride, the first binary primary amine monomer use 4,4'- diaminodiphenylsulfone, 4,4 '-diamino connection
One of benzene and p-phenylenediamine are a variety of, and second of tetracarboxylic dianhydride uses in benzene diester dianhydride and terephthalate amine dianhydride
One or two, second binary primary amine monomer use 2- (4- aminophenyl) -6- aminobenzimidazole, 2- (4- aminobenzene
Base) one of -6- amino benzoxazoles and 2- (5- aminophenyl) -6- amino benzoxazoles or a variety of.
The solvent used when specifically, being diluted in S4 to the polyamic acid solution of S3 for N-Methyl pyrrolidone or N,
N- dimethyl acetamide.
Specifically, the particular content that heat drying is handled in S4 are as follows: glass plate is placed in 0.5- in 80 DEG C of drying box
1h is warming up to 150 DEG C, dry 0.5-1h, is warming up to 200 DEG C, dry 0.5-1h, is warming up to 250 DEG C, dry 0.5-1h, heating
To 300 DEG C, dry 0.5-1h takes out glass plate after temperature is down to 25 DEG C, places it in demoulding in water, be then placed in film
Dry water removal, obtains Kapton, then by the Kapton under the conditions of 300-400 DEG C in 100 DEG C of drying boxes
It is heat-treated 0.5-1h.
Compared with prior art, the Kapton of low thermal coefficient of expansion provided by the invention is in Molecular Design
The structural units such as ester bond/amide, imidazoles/oxazole are introduced simultaneously, intermolecular interaction force is improved, improves the orderly of strand
Arrangement, using the method for multistep copolymerization in the preparation process of Kapton resin, realizing reduces Kapton
Thermal expansion coefficient.Use different formulas simultaneously, can thermal expansion coefficient to Kapton between 0-15ppm/K into
Row regulation, to solve the matching problem of different base materials.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail, and example is served only for explaining this hair
It is bright, it is not intended to limit the scope of the present invention.
Embodiment 1:
In the present embodiment, polyimide resin material has the following structure formula:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by the 3,3' of 4.0mmol, 4,4'- biphenyltetracarboxylic dianhydrides, 4, the 4 '-diaminos of 4.0mmol
Base biphenyl, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, it is molten to prepare sticky polyamic acid
Liquid A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 4.0mmol, 2- (4- aminophenyl) -6- ammonia of 4.0mmol
Base benzimidazole, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), by the polyamic acid solution of preparation with N-Methyl pyrrolidone be configured to concentration expressed in percentage by weight be 10% it is molten
Solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating is with a thickness of 0.5 millimeter.Wherein film drying
It handles as follows: glass plate being placed in 80 DEG C of drying box 1 hour, be warming up to 150 DEG C, drying 0.5-1 hours is warming up to
It is 200 DEG C, 0.5-1 hours dry, 250 DEG C are warming up to, drying 0.5-1 hours is warming up to 300 DEG C, drying 0.5-1 hours, to temperature
Degree takes out glass plate after being down to 25 DEG C, places it in demoulding in water, and film is then placed in 100 DEG C of drying boxes dry water removal,
Kapton is obtained, the Kapton is heat-treated 0.5-1 hours under the conditions of 300-400 DEG C then, is obtained low
The Kapton of thermal expansion coefficient.
Hot for film can be carried out test and obtain, and glass transition temperature is 383 DEG C, and 5% thermal decomposition temperature is 530
DEG C, thermal expansion coefficient CTE is 7ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.02% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 160MPa, stretch modulus 5GPa,
Elongation at break is 45%.Mechanical performance is excellent.
Embodiment 2:
In the present embodiment, polyimide resin material has the following structure formula:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by the 3,3' of 2.0mmol, 4,4'- biphenyltetracarboxylic dianhydrides, 4, the 4 '-diaminos of 4.0mmol
Base biphenyl, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, it is molten to prepare sticky polyamic acid
Liquid A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 6.0mmol, 2- (4- aminophenyl) -6- ammonia of 4.0mmol
Base benzimidazole, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), Kapton is obtained according to film drying processing method in embodiment 1.
Hot for film can be carried out test and obtain, and glass transition temperature is 375 DEG C, and 5% thermal decomposition temperature is 530
DEG C, thermal expansion coefficient CTE is 8ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.02% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 151MPa, stretch modulus are
4.6GPa, elongation at break 52%.Mechanical performance is excellent.
Embodiment 3:
In the present embodiment, polyimide resin material has the following structure formula:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by the 3,3' of 1.0mmol, 4,4'- biphenyltetracarboxylic dianhydrides, 4, the 4 '-diaminos of 3.0mmol
Base biphenyl, 10 milliliters of n,N-dimethylacetamide are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 7.0mmol, 2- (4- aminophenyl) -6- ammonia of 5.0mmol
Base benzimidazole, 20 milliliters of n,N-dimethylacetamide are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamides
Amino acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), by the polyamic acid solution of preparation with N-Methyl pyrrolidone be configured to concentration expressed in percentage by weight be 10% it is molten
Solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating is with a thickness of 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Hot for film can be carried out test and obtain, and glass transition temperature is 380 DEG C, and 5% thermal decomposition temperature is 540
DEG C, thermal expansion coefficient CTE is 8ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.03% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 153MPa, stretch modulus 4GPa,
Elongation at break is 64%.Mechanical performance is excellent.
Embodiment 4:
In the present embodiment, polyimide resin material has the following structure formula:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by equal benzene tertacarbonic acid's dianhydride of 2.0mmol, 4, the 4 '-benzidines of 3.0mmol, 10
Milliliter N-Methyl pyrrolidone is added in reaction flask, is stirred at room temperature 8 hours, is prepared sticky polyamic acid solution A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 6.0mmol, 2- (4- aminophenyl) -6- ammonia of 5.0mmol
Base benzoxazoles, 20 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), by the polyamic acid solution of preparation with N-Methyl pyrrolidone be configured to concentration expressed in percentage by weight be 10% it is molten
Solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating is with a thickness of 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Hot for film can be carried out test and obtain, and glass transition temperature is 400 DEG C, and 5% thermal decomposition temperature is 560
DEG C, thermal expansion coefficient CTE is 7ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.01% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 200MPa, stretch modulus are
5.3GPa, elongation at break 38%.Mechanical performance is excellent.
Embodiment 5:
In the present embodiment, polyimide resin material has the following structure formula:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by equal benzene tertacarbonic acid's dianhydride of 2.0mmol, 4, the 4 '-benzidines of 3.0mmol, 10
Milliliter n,N-dimethylacetamide is added in reaction flask, is stirred at room temperature 8 hours, is prepared sticky polyamic acid solution A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 6.0mmol, 2- (4- aminophenyl) -6- ammonia of 5.0mmol
Base benzimidazole, 20 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), the polyamic acid solution of preparation is configured to concentration expressed in percentage by weight with DMAC N,N' dimethyl acetamide is 10%
Solution is coated uniformly on clean glass plate by solution with the tape casting, and solution coating is with a thickness of 0.5 millimeter.According to embodiment 1
Middle film drying processing method obtains Kapton.Obtain the Kapton of low thermal coefficient of expansion.
Hot for film can be carried out test and obtain, and glass transition temperature is 408 DEG C, and 5% thermal decomposition temperature is 556
DEG C, thermal expansion coefficient CTE is 9ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.02% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 203MPa, stretch modulus are
5.6GPa, elongation at break 40%.Mechanical performance is excellent.
Embodiment 6:
In the present embodiment, polyimide resin material has the following structure formula:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by equal benzene tertacarbonic acid's dianhydride of 2.0mmol, 4, the 4 '-benzidines of 3.0mmol, 10
Milliliter N-Methyl pyrrolidone is added in reaction flask, is stirred at room temperature 8 hours, is prepared sticky polyamic acid solution A；
(2), under nitrogen protection, by 2- (4- aminophenyl) -6- amino to benzene diester dianhydride, 5.0mmol of 6.0mmol
Benzimidazole, 20 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), by the polyamic acid solution of preparation with N-Methyl pyrrolidone be configured to concentration expressed in percentage by weight be 10% it is molten
Solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating is with a thickness of 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Hot for film can be carried out test and obtain, and glass transition temperature is 363 DEG C, and 5% thermal decomposition temperature is 552
DEG C, thermal expansion coefficient CTE is 10ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.04% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 160MPa, stretch modulus are
4.6GPa, elongation at break 80%.Mechanical performance is excellent.
Embodiment 7:
In the present embodiment, polyimide resin material has the following structure formula:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by equal benzene tertacarbonic acid's dianhydride of 2.0mmol, 4, the 4 '-benzidines of 3.0mmol, 10
Milliliter N-Methyl pyrrolidone is added in reaction flask, is stirred at room temperature 8 hours, is prepared sticky polyamic acid solution A；
(2), under nitrogen protection, by 2- (4- aminophenyl) -6- amino to benzene diester dianhydride, 5.0mmol of 6.0mmol
Benzoxazoles, 20 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), by the polyamic acid solution of preparation with N-Methyl pyrrolidone be configured to concentration expressed in percentage by weight be 10% it is molten
Solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating is with a thickness of 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Hot for film can be carried out test and obtain, and glass transition temperature is 368 DEG C, and 5% thermal decomposition temperature is 540
DEG C, thermal expansion coefficient CTE is 6ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.04% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 158MPa, stretch modulus are
4.8GPa, elongation at break 75%.Mechanical performance is excellent.
Embodiment 8:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by the 3,3' of 2.0mmol, 4,4'- biphenyltetracarboxylic dianhydrides, 4, the 4 '-diaminos of 4.0mmol
Base biphenyl, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, it is molten to prepare sticky polyamic acid
Liquid A；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 6.0mmol, 2- (4- aminophenyl) -6- ammonia of 4.0mmol
Base benzoxazoles, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), by the polyamic acid solution of preparation with N-Methyl pyrrolidone be configured to concentration expressed in percentage by weight be 10% it is molten
Solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating is with a thickness of 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Hot for film can be carried out test and obtain, and glass transition temperature is 420 DEG C, and 5% thermal decomposition temperature is 575
DEG C, thermal expansion coefficient CTE is 5ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.02% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 202MPa, stretch modulus 6GPa,
Elongation at break is 70%.Mechanical performance is excellent.
Embodiment 9:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by the 3,3' of 2.0mmol, 4,4'- biphenyltetracarboxylic dianhydrides, 4, the 4 '-diaminos of 4.0mmol
Base biphenyl, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, it is molten to prepare sticky polyamic acid
Liquid A；
(2), under nitrogen protection, by 2- (4- aminophenyl) -6- amino to benzene diester dianhydride, 4.0mmol of 6.0mmol
Benzimidazole, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), by the polyamic acid solution of preparation with N-Methyl pyrrolidone be configured to concentration expressed in percentage by weight be 10% it is molten
Solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating is with a thickness of 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Hot for film can be carried out test and obtain, and glass transition temperature is 390 DEG C, and 5% thermal decomposition temperature is 563
DEG C, thermal expansion coefficient CTE is 6ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.01% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 156MPa, stretch modulus 4GPa,
Elongation at break is 67%.Mechanical performance is excellent.
Embodiment 10:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by the 3,3' of 2.0mmol, 4,4'- biphenyltetracarboxylic dianhydrides, 4, the 4 '-diaminos of 4.0mmol
Base biphenyl, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, it is molten to prepare sticky polyamic acid
Liquid A；
(2), under nitrogen protection, by 2- (4- aminophenyl) -6- amino to benzene diester dianhydride, 4.0mmol of 6.0mmol
Benzoxazoles, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), by the polyamic acid solution of preparation with N-Methyl pyrrolidone be configured to concentration expressed in percentage by weight be 10% it is molten
Solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating is with a thickness of 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Hot for film can be carried out test and obtain, and glass transition temperature is 386 DEG C, and 5% thermal decomposition temperature is 552
DEG C, thermal expansion coefficient CTE is 5ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.04% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 157MPa, stretch modulus are
4.8GPa, elongation at break 58%.Mechanical performance is excellent.
Embodiment 11:
In the present embodiment, polyimide resin material has the following structure formula:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by the 3,3' of 4.0mmol, 4,4'- biphenyltetracarboxylic dianhydrides, 4.0mmol p-phenylenediamine,
15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, and sticky polyamic acid solution A is prepared；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 4.0mmol, 2- (4- aminophenyl) -6- ammonia of 4.0mmol
Base benzimidazole, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), by the polyamic acid solution of preparation with N-Methyl pyrrolidone be configured to concentration expressed in percentage by weight be 10% it is molten
Solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating is with a thickness of 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Hot for film can be carried out test and obtain, and glass transition temperature is 420 DEG C, and 5% thermal decomposition temperature is 580
DEG C, thermal expansion coefficient CTE is 6ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.01% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 220MPa, stretch modulus 8GPa,
Elongation at break is 58%.Mechanical performance is excellent.
Embodiment 12:
In the present embodiment, polyimide resin material has the following structure formula:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by the 3,3' of 4.0mmol, 4,4'- biphenyltetracarboxylic dianhydrides, 4.0mmol p-phenylenediamine,
15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, and sticky polyamic acid solution A is prepared；
(2), under nitrogen protection, by the terephthalate amine dianhydride of 4.0mmol, 2- (4- aminophenyl) -6- ammonia of 4.0mmol
Base benzoxazoles, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamide
Acid solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), by the polyamic acid solution of preparation with N-Methyl pyrrolidone be configured to concentration expressed in percentage by weight be 10% it is molten
Solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating is with a thickness of 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Hot for film can be carried out test and obtain, and glass transition temperature is 412 DEG C, and 5% thermal decomposition temperature is 578
DEG C, thermal expansion coefficient CTE is 4ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.03% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 210MPa, stretch modulus 7GPa,
Elongation at break is 60%.Mechanical performance is excellent.
Embodiment 13:
In the present embodiment, polyimide resin material has the following structure formula:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by the 3,3' of 4.0mmol, 4,4'- biphenyltetracarboxylic dianhydrides, 4.0mmol p-phenylenediamine,
15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, and sticky polyamic acid solution A is prepared；
(2), under nitrogen protection, by 2- (4- aminophenyl) -6- amino to benzene diester dianhydride, 4.0mmol of 4.0mmol
Benzoxazoles, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), by the polyamic acid solution of preparation with N-Methyl pyrrolidone be configured to concentration expressed in percentage by weight be 10% it is molten
Solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating is with a thickness of 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Hot for film can be carried out test and obtain, and glass transition temperature is 391 DEG C, and 5% thermal decomposition temperature is 550
DEG C, thermal expansion coefficient CTE is 4ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.04% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 155MPa, stretch modulus are
4.8GPa, elongation at break 60%.Mechanical performance is excellent.
Embodiment 14:
In the present embodiment, polyimide resin material has the following structure formula:
It is specific the preparation method comprises the following steps:
(1), under nitrogen protection, by the 3,3' of 4.0mmol, 4,4'- biphenyltetracarboxylic dianhydrides, 4.0mmol p-phenylenediamine,
15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, and sticky polyamic acid solution A is prepared；
(2), under nitrogen protection, by 2- (4- aminophenyl) -6- amino to benzene diester dianhydride, 4.0mmol of 4.0mmol
Benzimidazole, 15 milliliters of N-Methyl pyrrolidones are added in reaction flask, are stirred at room temperature 8 hours, are prepared sticky polyamic acid
Solution B；
(3), polyamic acid solution A and polyamic acid solution B are mixed, is stirred at room temperature 8 hours, prepares final
Polyamic acid solution；
(4), by the polyamic acid solution of preparation with N-Methyl pyrrolidone be configured to concentration expressed in percentage by weight be 10% it is molten
Solution is coated uniformly on clean glass plate by liquid with the tape casting, and solution coating is with a thickness of 0.5 millimeter.According in embodiment 1
Film drying processing method obtains Kapton.
Hot for film can be carried out test and obtain, and glass transition temperature is 382 DEG C, and 5% thermal decomposition temperature is 546
DEG C, thermal expansion coefficient CTE is 5ppm/K (100 DEG C -200 DEG C), and percent thermal shrinkage is 0.06% (200 DEG C, 2 hours).Have hot steady
Qualitative and low-expansion coefficient feature.The measuring mechanical property result of film: tensile strength 180MPa, stretch modulus are
5.3GPa, elongation at break 45%.Mechanical performance is excellent.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of Kapton of low thermal coefficient of expansion, which is characterized in that the structural formula of the polyimides is as follows:
Wherein, R1 and R3 is the residue of two different tetracarboxylic dianhydride's monomers, and R2 and R4 are two different binary primary amine lists
The residue of body, m and n are the integer greater than zero；
Wherein, the R4 is one or more of following three kinds of groups:
The R1 is one or both of the following two kinds group:
The R2 is one or more of following three kinds of groups:
The R3 is following group:
2. a kind of Kapton of low thermal coefficient of expansion according to claim 1, which is characterized in that the R4 is
One or both of the following two kinds group:
3. according to right want 2 described in a kind of Kapton of low thermal coefficient of expansion, which is characterized in that the R2 be such as
One or both of lower two kinds of groups:
The R3 is following group:
4. a kind of preparation method of the Kapton of low thermal coefficient of expansion as described in any one of claims 1 to 3, special
Sign is, includes the following steps:
S1. under nitrogen protection, the first tetracarboxylic dianhydride's monomer, the first binary primary amine monomer and organic solvent are added to instead
It answers in equipment, is stirred at room temperature, prepare sticky polyamide solution A, it is spare；
S2. under nitrogen protection, second of tetracarboxylic dianhydride's monomer, second of binary primary amine monomer and organic solvent is added and reacted
It in equipment, is stirred at room temperature, prepares sticky polyamic acid solution B, it is spare；
S3. the polyamic acid solution B in the polyamide solution A and S2 in S1 is mixed, is stirred at room temperature, prepares final
Polyamic acid solution；
S4., solution after dilution is coated uniformly on to the glass plate of cleaning by the polyamic acid solution dilution of S3 and with the tape casting
On, heat drying processing to get the low thermal coefficient of expansion Kapton.
5. a kind of preparation method of the Kapton of low thermal coefficient of expansion according to claim 4, which is characterized in that
The first tetracarboxylic dianhydride's monomer, the first binary primary amine monomer, second of tetracarboxylic dianhydride's monomer and second of binary primary amine
The molar ratio of monomer is (0.1-0.6): (0.1-0.6): (0.4-0.9): (0.4-0.9).
6. a kind of preparation method of the Kapton of low thermal coefficient of expansion according to claim 4, which is characterized in that
The first described tetracarboxylic dianhydride's monomer uses pyromellitic acid anhydride and 3,3', and one in 4,4'- biphenyltetracarboxylic dianhydride
Kind or two kinds, the first binary primary amine monomer uses 4,4'- diaminodiphenylsulfone, 4, in 4 '-benzidines and p-phenylenediamine
It is one or more, second tetracarboxylic dianhydride uses to one or both of benzene diester dianhydride and terephthalate amine dianhydride,
Second of binary primary amine monomer uses 2- (4- aminophenyl) -6- aminobenzimidazole, 2- (4- aminophenyl) -6- amino benzo
One of oxazole and 2- (5- aminophenyl) -6- amino benzoxazoles are a variety of.
7. special according to a kind of preparation method of the Kapton of any low thermal coefficient of expansion of claim 4 to 6
Sign is that the solvent used when being diluted in S4 to the polyamic acid solution of S3 is N-Methyl pyrrolidone or N, N- dimethyl
Acetamide.
8. special according to a kind of any one of claim 4 to 6 preparation method of the Kapton of low thermal coefficient of expansion
Sign is, the particular content that heat drying is handled in S4 are as follows: glass plate is placed in 0.5-1h in 80 DEG C of drying box, is warming up to
150 DEG C, dry 0.5-1h, 200 DEG C, dry 0.5-1h are warming up to, is warming up to 250 DEG C, dry 0.5-1h is warming up to 300 DEG C, does
Dry 0.5-1h takes out glass plate after temperature is down to 25 DEG C, places it in demoulding in water, and film is then placed in 100 DEG C of dryings
Dry water removal, obtains Kapton, the Kapton is then heat-treated 0.5- under the conditions of 300-400 DEG C in case
1h。
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| CN106928481A (en) * | 2017-04-06 | 2017-07-07 | 上海交通大学 | The optimization preparation method of Kapton |
| CN107556501A (en) * | 2017-08-23 | 2018-01-09 | 中国科学院理化技术研究所 | A kind of polyimide film and its preparation method and application |
| KR102430152B1 (en) * | 2017-12-08 | 2022-08-08 | 주식회사 두산 | Polyamic acid solution, transparent polyimide film and transparent substrate using the same |
| CN109721749A (en) * | 2018-12-14 | 2019-05-07 | 上海市合成树脂研究所有限公司 | A kind of thermostable type Kapton and preparation method containing heteroaromatic |
| CN109817852A (en) * | 2018-12-29 | 2019-05-28 | 武汉依麦德新材料科技有限责任公司 | A kind of lithium ion battery outer cover material and preparation method thereof |
| CN110372896A (en) * | 2019-06-20 | 2019-10-25 | 重庆文理学院 | A kind of heat treatment process of low thermal expansion coefficient polyimide |
| CN111484615A (en) * | 2020-05-11 | 2020-08-04 | 浙江中科玖源新材料有限公司 | Transparent polyimide film with low thermal expansion coefficient and water absorption and preparation method thereof |
| CN112457493A (en) * | 2020-11-30 | 2021-03-09 | 山东华夏神舟新材料有限公司 | High-transparency low-expansion polyimide film and preparation method thereof |
| CN112876680B (en) * | 2021-02-04 | 2022-09-23 | 武汉柔显科技股份有限公司 | Polyamide acid slurry, preparation method thereof and polyimide film |
| JP7183377B1 (en) | 2021-11-26 | 2022-12-05 | 住友化学株式会社 | polyimide resin |
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| CN102558860A (en) * | 2011-12-22 | 2012-07-11 | 桂林电器科学研究院 | Dimensionally-stable polyimide film and preparation method thereof |
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| CN102558860A (en) * | 2011-12-22 | 2012-07-11 | 桂林电器科学研究院 | Dimensionally-stable polyimide film and preparation method thereof |
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