CN110724287A - Preparation method of high-temperature-resistant red polyimide film - Google Patents
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- 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
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- 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
- 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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Abstract
The invention discloses a preparation method of a high-temperature-resistant red polyimide film, which comprises the following steps: 1) mixing a heat stabilizer, a coupling agent, a solvent and an organic red pigment, and carrying out ultrasonic stirring treatment to obtain a modified red solution; 2) adding aromatic diamine into a solvent for dissolving; 3) mixing the modified red solution prepared in the step 1) with the solution prepared in the step 2), and dispersing by a high-speed emulsification pump; 4) adding aromatic dianhydride into the solution emulsified in the step 3) in batches for reaction to obtain a polyamic acid composite solution; 5) casting and molding the polyamic acid composite solution obtained in the step 4) to obtain the high-temperature-resistant red polyimide film. According to the invention, the organic pigment is modified by using the coupling agent and the heat stabilizer in the solvent before being used, so that the problem of temperature difference resistance of the organic red pigment is solved, and the coloring effect of the film is ensured.
Description
Technical Field
The invention relates to the technical field of film preparation, in particular to a preparation method of a high-temperature-resistant red polyimide film.
Background
Since the Polyimide (PI) film was put into use in the last 60 th century, the Polyimide (PI) film has been widely used in the fields of electronic circuits, aerospace and aviation due to its outstanding properties such as high temperature resistance, high strength and low dielectric constant. With the rapid development of electronic technology, the requirements of various industries on the performance of polyimide films are higher and higher.
High temperature resistant insulating material need be used to high temperature label, wire and cable etc. high temperature, electrified environment, and traditional red PVC membrane or red polyester material can't satisfy high temperature. The polyimide film can meet the requirements of high temperature resistance and high insulation, but the traditional color of the polyimide film is yellow. Red polyimide films are a material desired in the industry.
The prior art method for preparing red polyimide films is to add red fillers to the polyimide. Red fillers can be divided into organic and inorganic reds: the organic red includes conventional azo (toluidine red, permanent red FR), quinacridone (phthalocyanine red), thioindigo (c.i. pigment red 168), pyrrolopyrroledione (DPP red), and the like; inorganic red includes iron oxide red, cadmium red, molybdenum-chromium red, etc. Most of the organic red is not resistant to high temperature, and the highest temperature resistance is 250 ℃; although the inorganic red can resist high temperature, the inorganic red is not environment-friendly, and simultaneously has poorer tinting strength in a polyimide system, and the prepared red polyimide film has not bright color.
Therefore, it is an urgent need to solve the problem of providing a red polyimide film with high temperature resistance and good tinting strength.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a high temperature resistant red polyimide film, which modifies an organic red pigment and combines the generated polyimide matrix, so that the prepared film can meet the requirement of high temperature resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a high-temperature-resistant red polyimide film comprises the following steps:
1) adding a heat stabilizer and a coupling agent into an ultrasonic dispersion kettle, then adding a solvent, uniformly stirring, adding an organic red pigment, and carrying out ultrasonic stirring treatment to obtain a modified red solution (the coupling agent and the heat stabilizer are modified in the solvent before the organic pigment is used, so that the prepared product has high temperature resistance and good coloring capacity);
2) adding aromatic diamine into a solvent for dissolving (reacting at normal temperature);
3) mixing the modified red solution prepared in the step 1) with the solution prepared in the step 2), and dispersing for 15-30 min by a high-speed emulsification pump (in the emulsification process, a reaction kettle needs to be cooled by cooling water to prevent the solution from overheating, and the temperature is kept at 35-40 ℃);
4) adding aromatic dianhydride into the solution emulsified in the step 3) in batches for reaction, stirring, controlling the temperature to be 60-65 ℃, and enabling the viscosity of the polyamic acid glue solution obtained by the reaction to be 50000-70000Pa & s to obtain a polyamic acid composite solution (in the step, the aromatic diamine and the aromatic dianhydride are subjected to polycondensation reaction to obtain a polyimide substrate);
5) and (3) casting the polyamic acid composite solution obtained in the step (4) to form a tape (the imidization temperature is 400 ℃), and obtaining the high-temperature-resistant red polyimide film.
Preferably, the stirring reaction speed of the heat stabilizer and the coupling agent in the ultrasonic dispersion kettle in the step 1) is 1000r/min to 3000r/min, and the reaction time is 5 to 10 min.
Preferably, the ultrasonic frequency during the ultrasonic stirring treatment in the step 1) is 20kHz-100kHz, the power is 2000W-4000W, and the treatment time is 30min-60 min.
Preferably, the aromatic diamine monomer is dissolved in the solvent in the step 2) with a stirring speed of 80r/min to 200r/min until the crystals of the diamine monomer are completely dissolved.
Preferably, the aromatic diamine and the aromatic dianhydride are added according to an equal molar ratio and undergo a polycondensation reaction to prepare a polyimide matrix; the organic red pigment in the step 1) accounts for 0.6-4% of the mass of the polyimide matrix.
Preferably, the heat stabilizer accounts for 2% -10% of the mass of the organic red pigment; the coupling agent accounts for 0.5-5% of the mass of the organic red pigment.
Preferably, the aromatic diamine is one or a mixture of any more of 4,4' -diaminodiphenyl ether (ODA), p-phenylenediamine (p-PD), m-phenylenediamine (m-PDA), 4' -diaminodiphenylmethane (MDA), diaminobenzophenone, 4' -bis (4-aminophenoxy) diphenyl sulfone (BAPS), and diaminodiphenyl sulfone; the aromatic dianhydride is one or more of pyromellitic dianhydride (PMDA), 3',4,4' -biphenyl tetracarboxylic dianhydride (s-BPDA), 3',4,4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 4,4' -diphenyl ether dianhydride (ODPA); the solvent may be one or more of N-methylpyrrolidone (NMP), Dimethylformamide (DMF), dimethylacetamide (DMAc).
Preferably, the heat stabilizer is one or a mixture of more of sodium stearate, calcium stearate, phosphite ester, para-polyphenol and beta-diketone compounds.
Preferably, the coupling agent is one or a mixture of any more of gamma-aminopropyltriethoxysilane, vinyltrimethoxysilane, tetra-n-butyl titanate and isopropyl stearate.
Preferably, the solvent is one or more of N, N-dimethylformamide, dimethylacetamide or N-methylpyrrolidone.
According to the technical scheme, compared with the prior art, the invention has the following beneficial effects:
according to the invention, through reasonable raw material proportion, the organic pigment is modified in a solvent by using a coupling agent and a heat stabilizer before being used, and the modified organic pigment is combined with the prepared polyimide substrate, so that the problem of temperature difference resistance of the organic red pigment is solved, the thermal decomposition rate of the polyimide film is reduced under the high-temperature condition of 400 ℃ of imidization temperature, the polyimide film has good heat resistance, and the coloring effect of the film is ensured.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
the preparation method of the red polyimide film comprises the steps of adopting pyrrolo-pyrrole-dione organic red pigment DPP red, using para-phenol as a heat stabilizer, using gamma-aminopropyl triethoxysilane as a coupling agent, using 4,4' -diaminodiphenyl ether as an aromatic diamine monomer, using pyromellitic dianhydride as an aromatic dianhydride, wherein the organic red pigment accounts for 0.6% of the polyamic acid by weight, the para-phenol accounts for 5% of the organic red pigment, and the gamma-aminopropyl triethoxysilane accounts for 1% of the organic red pigment.
The p-phenol and the gamma-aminopropyl triethoxysilane are treated by ultrasonic stirring in N-methyl pyrrolidone for 5min at normal temperature, and then the organic red pigment is added and ultrasonically stirred for 60min, so that the red pigment is uniformly dispersed in the N-methyl pyrrolidone solvent. Adding 4,4' -diaminodiphenyl ether into the residual dimethylformamide, stirring to dissolve, adding the treated red pigment solution into the dissolved amine solution, emulsifying for 30min, adding 98% of pyromellitic dianhydride with equal molar quantity into a reaction kettle in batches, adding the rest 2% into the reaction kettle to adjust the viscosity to reach 58000cP, and defoaming and casting to form a film.
Example two:
the preparation method of the red polyimide film comprises the steps of adopting an organic red pigment DPP red, using para-phenol as a heat stabilizer, using gamma-aminopropyl triethoxysilane as a coupling agent, using 4,4' -diaminodiphenyl ether as an aromatic diamine monomer, using pyromellitic dianhydride as an aromatic dianhydride, wherein the organic red pigment accounts for 4% of the weight of the polyamic acid, the para-phenol accounts for 10% of the organic red pigment, and the gamma-aminopropyl triethoxysilane accounts for 5% of the organic red pigment.
The p-phenol and the gamma-aminopropyl triethoxysilane are treated by ultrasonic stirring in N-methyl pyrrolidone for 5min at normal temperature, and then the organic red pigment is added and ultrasonically stirred for 60min, so that the red pigment is uniformly dispersed in the N-methyl pyrrolidone solvent. Adding 4,4' -diaminodiphenyl ether into the residual dimethylformamide, stirring to dissolve, adding the treated red pigment solution into the dissolved amine solution, emulsifying for 30min, adding 98% of pyromellitic dianhydride with equal molar quantity into a reaction kettle in batches, adding the remaining 2% into the reaction kettle to adjust the viscosity to 57000cP, and defoaming, casting and forming a film.
Example three:
the preparation method of the red polyimide film comprises the steps of adopting azo organic red pigment to fix red FR, using para-phenol as a heat stabilizer, using gamma-aminopropyl triethoxysilane as a coupling agent, using 4,4' -diaminodiphenyl ether as an aromatic diamine monomer, using pyromellitic dianhydride as an aromatic dianhydride, wherein the organic red pigment accounts for 3% of the weight of polyamic acid, the para-phenol accounts for 5% of the organic red pigment, and the gamma-aminopropyl triethoxysilane accounts for 1% of the organic red pigment.
The p-phenol and the gamma-aminopropyl triethoxysilane are treated by ultrasonic stirring in the dimethyl acetamide at normal temperature for 5min, and then the organic red pigment is added and ultrasonically stirred for 60min, so that the red pigment is uniformly dispersed in the N-methyl pyrrolidone solvent. Adding 4,4' -diaminodiphenyl ether into the residual dimethylformamide, stirring and dissolving, then adding the treated red pigment solution into the dissolved amine solution, emulsifying for 30min, then adding 98% of pyromellitic dianhydride with equal molar quantity into a reaction kettle in batches, finally adding the rest 2% into the reaction kettle to adjust the viscosity to 62000cP, and then defoaming and tape-casting to form the film.
Example four:
the preparation method of the red polyimide film comprises the steps of adopting pyrrolo-pyrrole-dione DPP red, using beta-diketone as a heat stabilizer, using vinyl trimethoxy silane as a coupling agent, using 4,4' -diaminodiphenyl ether as an aromatic diamine monomer, using pyromellitic dianhydride as an aromatic dianhydride, wherein the organic red pigment accounts for 3% of the weight of polyamic acid, and the beta-diketone accounts for 1% of the vinyl trimethoxy silane in 5% of the organic red pigment.
The beta-diketone and the vinyl trimethoxy silane are treated by ultrasonic stirring in dimethyl acetamide at normal temperature for 5min, and then the organic red pigment is added for ultrasonic stirring for 60min, so that the red pigment is uniformly dispersed in the N-methyl pyrrolidone solvent. Adding 4,4' -diaminodiphenyl ether into the residual dimethylformamide, stirring and dissolving, then adding the treated red pigment solution into the dissolved amine solution, emulsifying for 30min, then adding 98% of pyromellitic dianhydride with equal molar quantity into a reaction kettle in batches, finally adding the rest 2% into the reaction kettle to adjust the viscosity to 53000cP, and then defoaming and casting to form a film.
Example five:
the preparation method of the red polyimide film comprises the steps of adopting iron oxide red, using p-beta-diketone as a heat stabilizer, using vinyl trimethoxy silane as a coupling agent, using 4,4' -diaminodiphenyl ether as an aromatic diamine monomer, using pyromellitic dianhydride as an aromatic dianhydride, wherein the organic red pigment accounts for 3% of the weight of polyamic acid, and the beta-diketone accounts for 1% of the vinyl trimethoxy silane in 5% of the organic red pigment.
The beta-diketone and the vinyl trimethoxy silane are treated by ultrasonic stirring in dimethyl acetamide at normal temperature for 5min, and then the organic red pigment is added for ultrasonic stirring for 60min, so that the red pigment is uniformly dispersed in the N-methyl pyrrolidone solvent. Adding 4,4' -diaminodiphenyl ether into the rest dimethylacetamide, stirring to dissolve, adding the treated red pigment solution into the dissolved amine solution, emulsifying for 30min, adding 98% of pyromellitic dianhydride with equal molar quantity into a reaction kettle in batches, adding the rest 2% into the reaction kettle to adjust the viscosity to reach 55000cP, and defoaming, casting and forming a film.
Further, the films prepared in examples 1 to 5 were tested for their properties according to the present invention, and the test results are shown in Table 1:
TABLE 1
As can be seen from Table 1, the film prepared by the invention has the effects of high temperature resistance and good coloring performance, and overcomes the defects in the prior art.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the high-temperature-resistant red polyimide film is characterized by comprising the following steps of:
1) adding a heat stabilizer and a coupling agent into an ultrasonic dispersion kettle, then adding a solvent, uniformly stirring, adding an organic red pigment, and performing ultrasonic stirring treatment to obtain a modified red solution;
2) adding aromatic diamine into a solvent for dissolving;
3) mixing the modified red solution prepared in the step 1) with the solution prepared in the step 2), and dispersing for 15-30 min by a high-speed emulsification pump;
4) adding aromatic dianhydride into the solution emulsified in the step 3) in batches for reaction, and stirring to obtain a polyamic acid composite solution;
5) casting and molding the polyamic acid composite solution obtained in the step 4) to obtain the high-temperature-resistant red polyimide film.
2. The method for preparing the high-temperature-resistant red polyimide film according to claim 1, wherein the heat stabilizer and the coupling agent in the step 1) are stirred in an ultrasonic dispersion kettle for reaction at a rotating speed of 1000r/min-3000r/min for 5-10 min.
3. The preparation method of the high-temperature-resistant red polyimide film according to claim 1, wherein the ultrasonic frequency during the ultrasonic stirring treatment in the step 1) is 20kHz-100kHz, the power is 2000W-4000W, and the treatment time is 30min-60 min.
4. The method as claimed in claim 1, wherein the aromatic diamine monomer is dissolved in the solvent in step 2) at a stirring speed of 80r/min to 200r/min until the diamine monomer crystals are completely dissolved.
5. The method for preparing the high-temperature resistant red polyimide film according to claim 1, wherein the aromatic diamine and the aromatic dianhydride are added in an equimolar ratio and undergo a polycondensation reaction to prepare a polyimide substrate; the organic red pigment in the step 1) accounts for 0.6-4% of the mass of the polyimide matrix.
6. The preparation method of the high-temperature-resistant red polyimide film according to claim 5, wherein the heat stabilizer accounts for 2% -10% of the mass of the organic red pigment; the coupling agent accounts for 0.5-5% of the mass of the organic red pigment.
7. The method of claim 1, wherein the aromatic diamine is one or a mixture of any more of 4,4' -diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, 4' -diaminodiphenylmethane, diaminobenzophenone, 4' -bis (4-aminophenoxy) diphenyl sulfone, and diaminodiphenyl sulfone; the aromatic dianhydride is one or a mixture of more of pyromellitic dianhydride, 3',4,4' -biphenyl tetracarboxylic dianhydride, 3',4,4' -benzophenone tetracarboxylic dianhydride and 4,4' -biphenyl ether dianhydride; the solvent may be one or more of N-methyl pyrrolidone, dimethylformamide and dimethylacetamide.
8. The method as claimed in claim 1, wherein the heat stabilizer is one or more selected from sodium stearate, calcium stearate, phosphite, para-polyphenol, and β -diketone compounds.
9. The method for preparing a high temperature resistant red polyimide film according to claim 1, wherein the coupling agent is one or a mixture of any more of gamma-aminopropyltriethoxysilane, vinyltrimethoxysilane, tetra-n-butyl titanate and isopropyl trisstearate.
10. The method as claimed in claim 1, wherein the solvent is one or more of N, N-dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112251024A (en) * | 2020-08-21 | 2021-01-22 | 湖南国柔科技有限公司 | Small-radius bending temperature-resistant quick CPI film and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311851A (en) * | 2014-10-24 | 2015-01-28 | 宁波今山电子材料有限公司 | Preparation method of red polyimide film |
| CN106832367A (en) * | 2017-03-17 | 2017-06-13 | 桂林电器科学研究院有限公司 | Coloured Kapton of high temperature resistant and preparation method thereof |
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- 2019-11-13 CN CN201911107621.9A patent/CN110724287A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104311851A (en) * | 2014-10-24 | 2015-01-28 | 宁波今山电子材料有限公司 | Preparation method of red polyimide film |
| CN106832367A (en) * | 2017-03-17 | 2017-06-13 | 桂林电器科学研究院有限公司 | Coloured Kapton of high temperature resistant and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112251024A (en) * | 2020-08-21 | 2021-01-22 | 湖南国柔科技有限公司 | Small-radius bending temperature-resistant quick CPI film and preparation method thereof |
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