CN111764002B - Preparation method of low-dielectric polyimide fiber - Google Patents
Preparation method of low-dielectric polyimide fiber Download PDFInfo
- Publication number
- CN111764002B CN111764002B CN202010590732.6A CN202010590732A CN111764002B CN 111764002 B CN111764002 B CN 111764002B CN 202010590732 A CN202010590732 A CN 202010590732A CN 111764002 B CN111764002 B CN 111764002B
- Authority
- CN
- China
- Prior art keywords
- polyimide
- diamine
- fiber
- benzocyclobutene
- spinning
- 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.)
- Active
Links
Images
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
-
- 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
-
- 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
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- 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
-
- 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
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
Abstract
The invention relates to a preparation method of a low dielectric polyimide fiber, which comprises the following steps: mixing benzocyclobutene-containing diamine, heterocyclic diamine and a polar aprotic solvent, stirring, adding aromatic dianhydride, carrying out polymerization reaction, defoaming the obtained soluble polyimide solution, spinning, and carrying out hot drawing treatment. The low dielectric polyimide fiber obtained by the method has the characteristics of low dielectric constant, low water absorption, stable size and the like, can be used in the fields of wave-transparent composite materials, flexible electronic substrates, wearable equipment and the like, endows the fiber with certain functionality, and further expands the application range of the material.
Description
Technical Field
The invention belongs to the field of polyimide fiber preparation, and particularly relates to a preparation method of a low-dielectric polyimide fiber.
Background
The dielectric properties of the material directly affect the rapidity, accuracy and reliability of information transmission. Generally, a high dielectric constant material medium is easy to absorb electromagnetic waves and dissipate the electromagnetic waves in the form of heat, is not beneficial to information transmission and has a large potential safety hazard, so that the development of a low dielectric material has important application value in the fields of wave transmission, microelectronics, flexible display and the like.
Polyimide (PI) fibers, an important high-performance fiber, are imide ring structures containing polarity in molecular chains, have high temperature resistance, high specific strength, ultraviolet resistance and other properties, and are successfully applied to high and new fields such as high-temperature filtration, aerospace, marine equipment and the like at present. However, the imide structure has high polarity, which means that the material has high molecular polarizability, and usually the dielectric constant k of the polyimide material is greater than 3.0 (e.g. the dielectric constant k of Kapton film of dupont is approximately equal to 3.4), which is not favorable for obtaining high-performance low-dielectric composite material, so that it is of great significance to develop a low-dielectric polyimide fiber material with k < 3.0.
Polyimide has rich structure, and the molecular structure design and the hybridization of nano particles are effective strategies for reducing the dielectric constant of the material. For example, Zhang et al introduced trifluoromethyl, bulky pendant propeller groups into the polyimide molecular structure to produce an intrinsic low dielectric polyimide film with a dielectric constant of 1.52 (Chemistry of materials.2015; 27(19): 6543-. Huang et al introduced perfluoroaliphatic structures into polyimides to produce polyimide Materials having dielectric constants of about 2.43(ACS Applied Materials & interfaces.2016; 8(39): 26352-. In the early work, the hyperbranched siloxane nanoparticles are introduced into polyimide by the patent inventor group, the molecular polarizability is reduced by utilizing the intramolecular micro-crosslinking structure of the hyperbranched siloxane nanoparticles, and a high-performance polyimide fiber material with the dielectric constant of about 2.2 is prepared (Journal of Materials Chemistry C,2017,5(11): 2818-2825).
From the above studies, it is known that the molecular polarizability of polyimide can be effectively reduced by introducing bulky side groups and aliphatic groups to construct a cross-linked structure, thereby preparing a low dielectric material.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of low-dielectric polyimide fiber so as to fill the blank in the prior art.
The invention provides a preparation method of polyimide fibers, which comprises the following steps:
(1) mixing benzocyclobutene-containing diamine, heterocyclic diamine and a polar aprotic solvent, stirring, adding aromatic dianhydride, and carrying out polymerization reaction to obtain a soluble polyimide solution, wherein the molar ratio of benzocyclobutene-containing diamine to heterocyclic diamine is 1: 9-4: 6, and the ratio of the total molar amount of benzocyclobutene-containing diamine and heterocyclic diamine to the molar amount of aromatic dianhydride is 1: 0.99-1: 1;
(2) defoaming the soluble polyimide solution obtained in the step (1), and spinning to obtain polyimide nascent fiber;
(3) and (3) carrying out hot drawing treatment on the polyimide nascent fiber in the step (2) to enable benzocyclobutene to be crosslinked, so as to obtain the polyimide fiber.
The structural formula of the benzocyclobutene-containing diamine in the step (1) is as follows:
The structural formula of the heterocyclic diamine in the step (1) is as follows:
In the step (1), the polar aprotic solvent is N, N-dimethylacetamide (DMAc) or N-methylpyrrolidone (NMP).
The structural formula of the aromatic dianhydride in the step (1) is as follows:
In the step (1), the total mass of the benzocyclobutene diamine, the heterocyclic diamine and the aromatic dianhydride accounts for 12-15% of the total mass of the benzocyclobutene diamine, the heterocyclic diamine, the aromatic dianhydride and the polar aprotic solvent.
And (2) stirring time in the step (1) is 1-2 h.
The polymerization reaction in the step (1) is as follows: stirring and reacting for 8-12 h at 10-30 ℃, then heating to 160-190 ℃ in a gradient manner, and reacting for 6-12 h at constant temperature.
The gradient temperature is increased to 160-190 ℃, and the constant-temperature reaction is carried out for 6-12 h as follows: staying at 130 ℃, 145 ℃ and 155 ℃ for 1 hour respectively, and finally heating to 160-190 ℃ to react for 6-12 hours at constant temperature.
The steps (1) and (3) are carried out under the protection of nitrogen.
And (3) spinning in the step (2) is wet spinning, dry spinning or dry-jet wet spinning.
The temperature of the hot drawing treatment in the step (3) is 400-460 ℃.
In the step (3), the retention time of the polyimide nascent fiber in the hot drawing channel is 0.5-2 min.
And (4) in the step (3), the thermal drafting multiplying power of the polyimide nascent fiber is 2-6 times.
The invention provides a polyimide fiber prepared by the method.
The invention also provides an application of the polyimide fiber prepared by the method.
According to the invention, a benzocyclobutene and aromatic heterocyclic structure is introduced into a polyimide structure, on one hand, the steric effect of the side group and the asymmetry of the aromatic heterocyclic structure are utilized to prepare soluble polyimide, and the problems of difficult dissolution and difficult processing of the polyimide are solved; on the other hand, the introduced benzocyclobutene side group has thermal crosslinking reactivity, and a micro-crosslinking network can be formed after thermal drafting, so that the polyimide molecule polarizability is greatly reduced, and the low-dielectric polyimide fiber is obtained.
According to the invention, large-volume aliphatic benzocyclobutene is introduced into a polyimide molecular structure, and the molecules are crosslinked through high-temperature drawing, so that the low-dielectric fiber material is obtained.
Advantageous effects
The low dielectric polyimide fiber prepared by the invention has the characteristics of low dielectric constant, low water absorption, stable size and the like, can be used in the fields of wave-transparent composite materials, flexible electronic substrates, wearable equipment and the like, endows the fiber with certain functionality, and further expands the application range of the material.
Drawings
FIG. 1(A) is a cross-sectional SEM of a polyimide fiber in example 2; (B) the dielectric constants of the polyimide fibers of example 2 are compared with those of the Kapton structure polyimide fibers.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The main chemical reagents and sources in the invention are as follows:
2 (4-aminophenyl) -5-aminobenzimidazole, 2 (4-aminophenyl) -5-aminobenzoxazole, hexafluorodianhydride, and 3,3',4,4' -benzophenone tetracarboxylic dianhydride were purchased from Changzhou sunshine pharmaceutical Co., Ltd; the aprotic polar solvent N-methyl-pyrrolidone (NMP) was purchased from the national pharmaceutical group; the diamine containing benzocyclobutene is synthesized by self.
Fiber performance test conditions:
the mechanical property of the fiber is tested according to GB/T35441-2017; testing the water absorption of the fiber: taking quantity (w)1) Placing the fiber sample in deionized water, soaking for 24h at room temperature, taking out, removing water adsorbed on the surface of the fiber by using absorbent paper, and weighing the weight of the fiber sample as w2Water absorption rate ═ w2-w1)/w1X is 100%; the thermal expansion coefficient test is carried out by a static thermal mechanical analysis method, the temperature range is 25-400 ℃, the heating rate is 5 ℃/min, and the load (2-4) kPa is applied; dielectric property testing was performed on a Novocontrol Concept 80 apparatus at a frequency of 3 muHz-3 GHz at room temperature.
Example 1
(1) Under the protection of nitrogen, 250mL of NMP, 11.34g (0.05mol) of 2- (4-aminophenyl) -5-aminobenzimidazole (BIA) and 4.42g (0.017mol) of 3, 5-diaminobenzoyl-4-amine-benzocyclobutene (a synthetic method such as U.S. patent 6,534,250[ P ] 2003-3-18.) are sequentially added into a three-neck flask, stirred for 1h, then 21.74g (0.067mol) of 3,3',4,4' -benzophenone tetracarboxylic dianhydride is added, and stirred for reaction for 10h at 15 ℃; then respectively heating to 130 ℃, 145 ℃ and 155 ℃ and staying for 1h, finally heating to 190 ℃ and reacting at constant temperature for 12h to obtain the high-viscosity polyimide solution with the solid content of 13%.
(2) And (2) taking the polyimide solution prepared in the step (1) as a spinning solution, standing for defoaming, taking NMP (N-methyl pyrrolidone) and deionized water which are solidified in a volume ratio of 1:1 as a coagulating bath and deionized water as a water system bath, preparing the polyimide nascent fiber by adopting a wet spinning technology, and drying for later use.
(3) And (3) carrying out hot drawing treatment on the polyimide fiber obtained in the step (2) in a nitrogen atmosphere, wherein the hot drawing temperature is 420 ℃, the residence time of the fiber in a hot box is 45 seconds, the drawing ratio is 3, and the low-dielectric polyimide fiber is obtained, the tensile strength of the low-dielectric polyimide fiber is 1.2GPa, the modulus of the low-dielectric polyimide fiber is 85GPa, the dielectric constant of the low-dielectric polyimide fiber is 2.4, the water absorption rate of the obtained fiber is 0.5 wt%, and the thermal expansion coefficient of the low-dielectric polyimide fiber is 7 ppm/K.
Example 2
(1) 300mL of DMAc, 13.04g (0.058mol) of 2- (4-aminophenyl) -5-aminobenzoxazole (BOA) and 3.66g (0.014mol) of 3, 5-diaminobenzoyl-4-amine-benzocyclobutene (synthetic method such as U.S. patent 6,534,250[ P ].2003-3-18.) are added in sequence in a three-necked flask under the protection of nitrogen, and after stirring for 1h, 32.14g (0.072mol) of hexafluorodianhydride (6-FDA) is added and the reaction is stirred at 15 ℃ for 10 h; then respectively heating to 130 ℃, 145 ℃ and 155 ℃ and staying for 1h, finally heating to 165 ℃ and reacting at constant temperature for 12h to obtain the high-viscosity polyimide solution with the solid content of 14%.
(2) Taking the polyimide solution prepared in the step (1) as a spinning solution, standing for defoaming, and preparing polyimide nascent fiber by adopting a dry spinning technology, wherein the channel temperature is 230 ℃, the channel length is 10m, and the spinning speed is 300 m/min.
(3) And (3) carrying out hot drawing treatment on the polyimide fiber obtained in the step (2) in a nitrogen atmosphere, wherein the hot drawing temperature is 400 ℃, the residence time of the fiber in a hot box is 40 seconds, the drawing ratio is 5, and the low-dielectric polyimide fiber is obtained, the tensile strength of the low-dielectric polyimide fiber is 1.32GPa, the modulus of the low-dielectric polyimide fiber is 102GPa, the dielectric constant of the low-dielectric polyimide fiber is 2.1, the water absorption rate of the obtained fiber is 0.2%, and the thermal expansion coefficient of the low-dielectric polyimide fiber is 19 ppm/K.
FIG. 1 shows that: the polyimide fiber prepared by dry spinning has a regular round and dense microstructure (A), and has a dielectric constant of about 2.1 and excellent stability in a test frequency range.
Example 3
(1) 300mL of NMP, 13.92g (0.062mol) of 2- (4-aminophenyl) -5-aminobenzimidazole (BIA), 3.92g (0.016mol) of 3, 5-diaminobenzoyl-3-amine-benzocyclobutene (a synthetic method such as U.S. patent 6,534,250[ P ].2003-3-18.) are added in sequence in a three-necked flask under nitrogen protection, 25.0g (0.0776mol) of 3,3',4,4' -benzophenone tetracarboxylic dianhydride is added after stirring for 1h, and the mixture is stirred and reacted at 20 ℃ for 10 h; then respectively heating to 130 ℃, 145 ℃ and 155 ℃ and staying for 1h, finally heating to 185 ℃ and reacting for 10h at constant temperature to obtain the high-viscosity polyimide solution with the solid content of 12.5%.
(2) And (2) taking the polyimide solution prepared in the step (1) as a spinning solution, standing for defoaming, taking NMP (N-methyl pyrrolidone) and deionized water which are solidified into a volume ratio of 6:4 as a coagulating bath and deionized water as a water system bath, preparing the polyimide nascent fiber by adopting a dry jet-wet spinning technology, and drying for later use.
(3) And (3) carrying out hot drawing treatment on the polyimide fiber obtained in the step (2) in a nitrogen atmosphere, wherein the hot drawing temperature is 430 ℃, the residence time of the fiber in a hot box is 50 seconds, the drawing ratio is 4, and the low-dielectric polyimide fiber is obtained, the tensile strength of the low-dielectric polyimide fiber is 1.85GPa, the modulus of the low-dielectric polyimide fiber is 93GPa, the dielectric constant of the low-dielectric polyimide fiber is 2.5, the water absorption rate of the obtained fiber is 0.45%, and the thermal expansion coefficient of the low-dielectric polyimide fiber is 12 ppm/K.
Comparative example 1
In the early reported literature, hyperbranched siloxane nanoparticles are introduced into polyimide, the molecular polarizability is reduced by using the intramolecular micro-crosslinked structure, and polyimide fibers with a dielectric constant of about 2.2 are prepared (Journal of Materials Chemistry C,2017,5(11): 2818-2825). However, the nano particles are easy to agglomerate, and negative influence is brought to the spinning forming and the final mechanical property of the fiber. According to the preparation method, the benzocyclobutene unit capable of forming the crosslinking structure is introduced through copolymerization, so that the problems can be effectively solved, and the prepared fiber is lower in dielectric constant (2.1) and has a good industrial application prospect.
Claims (8)
1. A method for preparing a polyimide fiber, comprising:
(1) mixing benzocyclobutene diamine, heterocyclic diamine and polar aprotic solvent, stirring, adding aromatic dianhydride, and carrying out polymerization reaction to obtain soluble polyimide solution, wherein the mole ratio of the benzocyclobutene diamine and the heterocyclic diamineThe molar ratio is 1: 9-4: 6, the ratio of the total molar amount of the benzocyclobutene diamine and the heterocyclic diamine to the molar amount of the aromatic dianhydride is 1: 0.99-1: 1, and the structural formula of the benzocyclobutene diamine is shown in the specification,One or two of them, the structural formula of the heterocyclic diamine is shown in the specification,One or two of the following, the polymerization reaction is: stirring and reacting for 8-12 h at 10-30 ℃, then heating to 160-190 ℃ in a gradient manner, and reacting for 6-12 h at constant temperature;
the gradient temperature is increased to 160-190 ℃, and the constant-temperature reaction is carried out for 6-12 h as follows: standing at 130 ℃, 145 ℃ and 155 ℃ for 1h respectively, and finally heating to 160-190 ℃ to react for 6-12 h at constant temperature;
(2) defoaming the soluble polyimide solution obtained in the step (1), and spinning to obtain polyimide nascent fiber;
(3) and (3) carrying out hot drawing treatment on the polyimide nascent fiber in the step (2) to enable benzocyclobutene to be crosslinked, so as to obtain the polyimide fiber.
3. The method according to claim 1, wherein the total mass of the benzocyclobutene diamine, the heterocyclic diamine and the aromatic dianhydride in the step (1) is 12-15% of the total mass of the benzocyclobutene diamine, the heterocyclic diamine, the aromatic dianhydride and the polar aprotic solvent.
4. The method according to claim 1, wherein the stirring time in the step (1) is 1-2 h.
5. The method of claim 1, wherein the spinning in the step (2) is wet spinning, dry spinning or dry-jet wet spinning.
6. The method according to claim 1, wherein the temperature of the hot drawing treatment in the step (3) is 400 to 460 ℃; the residence time of the polyimide nascent fiber in the hot drawing channel is 0.5-2 min; the heat drafting multiplying power of the polyimide nascent fiber is 2-6 times.
7. A polyimide fiber prepared according to the method of claim 1.
8. Use of the polyimide fiber prepared by the method of claim 1 in a wave-transparent composite, a flexible electronic substrate or a wearable device.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010590732.6A CN111764002B (en) | 2020-06-24 | 2020-06-24 | Preparation method of low-dielectric polyimide fiber |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010590732.6A CN111764002B (en) | 2020-06-24 | 2020-06-24 | Preparation method of low-dielectric polyimide fiber |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111764002A CN111764002A (en) | 2020-10-13 |
CN111764002B true CN111764002B (en) | 2021-07-20 |
Family
ID=72721828
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010590732.6A Active CN111764002B (en) | 2020-06-24 | 2020-06-24 | Preparation method of low-dielectric polyimide fiber |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111764002B (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114634619B (en) * | 2022-03-16 | 2023-04-28 | 中国科学院过程工程研究所 | Polyimide, preparation method thereof and gas separation membrane |
CN115583889B (en) * | 2022-10-26 | 2023-09-19 | 波米科技有限公司 | Diamine, liquid crystal aligning agent, and preparation method and application thereof |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5239049A (en) * | 1991-12-16 | 1993-08-24 | Olin Corporation | Selected poly(dianhydrides) compounds, selected poly(amic acid) compounds, and selected poly(imide) compounds |
US5464925A (en) * | 1994-05-25 | 1995-11-07 | The Dow Chemical Company | Benzocyclobutene-terminated polymides |
CN103483240A (en) * | 2013-09-25 | 2014-01-01 | 复旦大学 | Soluble benzocyclobutene-terminated imide monomer as well as preparation method and curing method thereof |
CN106947251B (en) * | 2017-04-13 | 2019-08-13 | 江苏先诺新材料科技有限公司 | A kind of low dielectric polymer base wave-penetrating composite material and its preparation method and application |
CN107200845B (en) * | 2017-06-14 | 2019-10-22 | 中国科学院上海有机化学研究所 | A kind of high glass-transition temperature and low thermal expansion coefficient polyimide and its preparation method and application |
CN110655472B (en) * | 2019-10-10 | 2022-09-27 | 中国科学院深圳先进技术研究院 | Diamine monomer with bulky side group and preparation method and application thereof |
CN110791833B (en) * | 2019-11-26 | 2021-02-05 | 中国科学院长春应用化学研究所 | Polyimide fiber and preparation method thereof |
-
2020
- 2020-06-24 CN CN202010590732.6A patent/CN111764002B/en active Active
Also Published As
Publication number | Publication date |
---|---|
CN111764002A (en) | 2020-10-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN105461923B (en) | A kind of Kapton and preparation method thereof | |
CN111764002B (en) | Preparation method of low-dielectric polyimide fiber | |
CN102030989B (en) | Transparent polyimide film with improved solvent resistance | |
CN105315665A (en) | Polyimide precursor composition, method for preparing polyimide precursor, polyimide molded article, and method for preparing polyimide molded article | |
CN101787129A (en) | Soluble and high-temperature resistant aromatic polyimide and preparation method thereof | |
CN113667120B (en) | Polyimide and preparation method thereof | |
CN114891209B (en) | Low-dielectric-constant organic silicon modified polyimide film and preparation method thereof | |
CN109776791B (en) | Amino modified polyphenyl ether, preparation method thereof, copper-clad plate using amino modified polyphenyl ether and application | |
CN109796590A (en) | A kind of polyimide resin and transparent polyimide film | |
CN111253614A (en) | Ultra-light polyimide aerogel and preparation method thereof | |
CN111286195A (en) | Polyimide film containing bisbenzoxazole unit and preparation method and application thereof | |
CN102911595B (en) | Benzimidazole-type humidity-sensitive high-molecular coating material and preparation method and application thereof | |
CN113527683B (en) | Polyimide and polyimide film using the same | |
Li et al. | Fluorinated polyimide with triphenyl pyridine structure for 5G communications: Low dielectric, highly hydrophobic, and highly transparent | |
Zheng et al. | Soluble polyimides containing bulky rigid terphenyl groups with low dielectric constant and high thermal stability | |
CN112961349B (en) | High-performance transparent polyimide, polyimide film and preparation method thereof | |
CN111825867B (en) | Low-dielectric modified polyimide film and preparation method thereof | |
CN112300388B (en) | Polyimide precursor solution and preparation method thereof, polyimide film and preparation method thereof | |
CN109456482A (en) | Fluorinated polyimide polymer, preparation method and polyimide composite film | |
Qu et al. | Preparation and dielectric properties research of a novel kind of intrinsic silane-containing polyimide | |
CN105295374A (en) | Polyimide precursor composition, method for preparing polyimide precursor, polyimide molded article, and method for preparing polyimide molded article | |
CN109912618B (en) | Multifunctional organic acid anhydride and low-dielectric-constant hyperbranched polyimide film | |
CN112585198B (en) | Polyimide film containing crystalline polyimide resin and thermally conductive filler, and method for producing same | |
Wei et al. | Effects of triethylamine on the imidization temperature and properties of PI adhesive | |
CN115322371B (en) | Silicon-containing polyester imide and preparation method and application 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 |