CN115162050A - Modified polyimide fiber paper for copper-clad plate and preparation method thereof - Google Patents
Modified polyimide fiber paper for copper-clad plate and preparation method thereof Download PDFInfo
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- CN115162050A CN115162050A CN202210810854.0A CN202210810854A CN115162050A CN 115162050 A CN115162050 A CN 115162050A CN 202210810854 A CN202210810854 A CN 202210810854A CN 115162050 A CN115162050 A CN 115162050A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
- D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses modified polyimide fiber paper for a copper-clad plate and a preparation method thereof, belonging to the field of paper-based composite materials. The PI chopped fiber is modified through high-temperature oxidation treatment of concentrated nitric acid or oxidative autopolymerization of dopamine, then paper is manufactured through a paper sheet former, resin adhesive is sprayed on the surface of the formed wet paper sheet, and the PI fiber paper is obtained after squeezing and drying. Compared with other reinforced base materials for copper-clad plates, the copper-clad plate made of the modified polyimide fiber paper has the advantages of small dielectric constant (Dk), small dielectric loss factor (Df), high thermal decomposition temperature (Td), small Coefficient of Thermal Expansion (CTE) and the like, and can well meet the requirements of high-frequency high-speed communication era on the performance of the copper-clad plate.
Description
Technical Field
The invention relates to modified polyimide fiber paper for a copper-clad plate and a preparation method thereof, belonging to the field of paper-based composite materials.
Background
The Printed Circuit Board (PCB) is made by using a reinforcing material to impregnate resin, drying the resin to prepare a prepreg, pressing the prepreg into different Copper Clad Laminates (CCLs) according to needs, and then manufacturing one or more layers of printed circuit boards by using the CCLs according to needs. As one of core materials of the PCB, the transmission loss of a conventional PCB substrate (CCL and related materials (such as bonding sheets, etc.)) is large, and the transmission quality requirement of high frequency signals cannot be satisfied. Therefore, it is most important for the 5G communication PCB substrate material to satisfy the requirements of high frequency and high speed, as well as the requirements of miniaturization, weight reduction, multifunctionality, high reliability, and the like. The primary task is to select a CCL material that must meet the substrate material with reduced high frequency signal transmission speed, i.e., low Dk, low Df, high Tg, high Td (5% loss), low CTE, etc.
At present, relatively few researches on paper base materials for high-frequency and high-speed copper-clad plates are carried out, most researches on preparation and modification of base resin for the copper-clad plates, change of the overall structure of the copper-clad plates and the like are carried out, and the researches on preparation of the paper base materials for the high-frequency and high-speed copper-clad plates are relatively few. For example: the invention patent of publication number CN 109082944A discloses a novel aramid paper-based copper-clad plate and a preparation method thereof, wherein the novel aramid paper-based copper-clad plate comprises a substrate formed by laminating a plurality of semi-solid sheets and a copper foil laminated on at least one surface of the substrate; the semi-solid piece comprises modified para-aramid paper and a resin composite layer laminated on at least one surface of the modified para-aramid paper; the copper foil is adhered and stacked on the surface of the resin composite layer through glue; the invention patent of publication No. CN 113061223A discloses a preparation method of epoxy soybean oil modified resin and a method for preparing a paper-based copper clad laminate, wherein an amine compound-containing material is added in the reaction of the epoxy soybean oil modified resin, and because the amine compound contains a specific nitrogen element, the epoxy soybean oil resin modified by the amine compound is nitrogen-containing epoxy soybean oil modified resin, so that the epoxy soybean oil modified resin has excellent flame retardance; the invention patent of publication No. CN 109575482A discloses a substrate material for a high-frequency copper-clad plate and a preparation method thereof, wherein the substrate material is prepared from (100-x) wt% of polytetrafluoroethylene and x wt% of modified Li 2 TiO 3 Wherein x is more than or equal to 30 and less than or equal to 70; the modified Li 2 TiO 3 Has a chemical formula of (0.92-a) Li 2 TiO 3 -aMgO-0.08LiF, wherein a is more than or equal to 0 and less than or equal to 0.175, and the prepared substrate material has excellent dielectric property and low thermal expansion coefficient; the invention patent of publication number CN 110154464A discloses an aramid paper-based flexible copper clad plate and a manufacturing method thereof, wherein a copper clad plate substrate part is a meta-aramid paper liquid crystal polymer composite layer, and the liquid crystal polymer is embedded and filled in gaps of the meta-aramid paper, so that the aramid paper-based flexible copper clad plate has good dielectric property and low moisture absorption rate. However, when the paper-based materials obtained by the methods are applied to the copper-clad plate, the dielectric properties of the copper-clad plate need to be improved.
Disclosure of Invention
The technical problem is as follows:
in order to meet the development of the current high-frequency high-speed communication, the invention provides PI fiber paper which is prepared by taking PI chopped fibers with the length of 6mm as a raw material, has excellent dielectric property and heat resistance and meets the development requirement of a copper-clad plate, and a corresponding prepreg. On one hand, the defects of high dielectric constant, poor machining performance, large abrasion to a drill bit, high cost and the like of a glass fiber cloth substrate which is a commonly used reinforcing material of a copper-clad plate are overcome, and on the other hand, the application range of the polyimide fiber paper-based composite material is widened.
Aiming at the demand of the development of the copper-clad plate base material in the current high-frequency and high-speed communication era, the PI fiber paper prepared by taking the modified PI chopped fibers as the raw material has the advantages of high strength, high temperature resistance and excellent insulating property. When the PI fiber paper is used as a reinforced base material of a copper-clad plate, the prepreg is formed and needs to be soaked with a certain amount of resin glue solution. Therefore, the copper foil, the reinforced material composition and the resin type have direct influence on various performance indexes of the copper-clad plate.
The technical scheme is as follows:
the first purpose of the invention is to provide a modified PI fiber paper for a copper-clad plate, which takes modified PI chopped fibers as raw materials to prepare PI fiber paper, the PI fiber paper is made of pure PI fibers, but because the surface of unmodified PI chopped fibers does not have active groups and hydrophilic groups, no physical and chemical connection is generated in the paper sheet drying process, so that the paper strength is improved, certain modification treatment needs to be carried out on the fibers, on one hand, through concentrated nitric acid high-temperature oxidation treatment, the number of surface acid functional groups of the PI chopped fibers after concentrated nitric acid treatment is increased, the bonding force between the fibers is enhanced, the integral strength of the paper is improved, and the later-stage resin infiltration is facilitated. On the other hand, the PI chopped fibers are modified through oxidation self-polymerization reaction of dopamine, a polydopamine layer is deposited on the surfaces of the fibers, a large number of active phenolic hydroxyl groups and amino groups are introduced into the surfaces of the PI chopped fibers after dopamine treatment, modified PI chopped fibers which are high in surface activity and rich in active groups are successfully obtained, the bonding force among the fibers can be improved, and paper forming is facilitated.
A preparation method of modified PI fiber paper for a copper-clad plate comprises the following steps:
(1) Pretreatment: soaking PI fiber in sodium dodecyl benzene sulfonate (LAS) solution for cleaning, and drying after cleaning; then dispersing in water to prepare slurry, pulping and drying to obtain uniformly dispersed PI fibers;
(2) Modification treatment: soaking the pretreated PI fiber in the step (1) in a modified solution, adjusting and maintaining the pH of the solution to be 8-10, performing ultrasonic treatment, standing, taking out, washing and drying to obtain a modified PI fiber; the modified solution comprises concentrated nitric acid or dopamine solution;
(3) Presetting the quantitative amount of PI fiber paper, preparing the modified PI fiber obtained in the step (2) into slurry, uniformly dispersing, making paper by a paper sheet former, spraying resin adhesive on the surface of the wet paper sheet, squeezing and drying to obtain the modified polyimide fiber paper.
In an embodiment of the present invention, the method specifically includes:
(1) Cleaning and dispersing PI fibers, soaking the fibers in an LAS solution, cleaning, drying for later use, and pulping the cleaned PI fibers by using a pulping machine so as to disperse uniformly;
(2) Modification treatment: carrying out high-temperature oxidation treatment on the PI fiber by using concentrated nitric acid, soaking the PI fiber in concentrated nitric acid at the temperature of 60 ℃ for treatment for 2h, washing the PI fiber by using a large amount of deionized water to make the PI fiber neutral, and carrying out vacuum drying at the temperature of 80 ℃ for 48h and then taking out the PI fiber to obtain an acid modified PI fiber;
or carrying out dopamine oxidation autopolymerization treatment on the PI fiber, soaking the fiber in a dopamine solution with the concentration of 2.0g/L, adjusting and maintaining the pH value of the solution at about 8.5, continuing carrying out ultrasonic treatment for 2h, standing for 24h, taking out the fiber, repeatedly washing the fiber with deionized water, carrying out vacuum drying at 30 ℃ for 48h, and taking out the fiber to obtain the dopamine modified PI fiber;
(3) Presetting the quantification of PI fiber paper, weighing the modified PI fiber, preparing into slurry, stirring and dispersing uniformly, then manufacturing paper by a paper sheet former, spraying a certain resin adhesive on the surface of the wet paper sheet, squeezing and drying to obtain the modified polyimide fiber paper.
In one embodiment of the present invention, the concentration of the LAS solution in step (1) is 1.2X 10 -3 mol/L。
In one embodiment of the invention, the cleaning condition in step (1) is 60 ℃ constant temperature water bath stirring for 30min.
In one embodiment of the invention, the beating condition of the beating machine in the step (1) is that the frequency is 20Hz, the weight is 3kg, and the beating time is 1h.
In one embodiment of the present invention, the concentration of the dopamine solution in step (2) is 2.0g/L.
In one embodiment of the present invention, the PI fiber paper in the step (3) has a basis weight of 75g/m 2 The raw material is 100% of PI chopped fiber with the length of 6 mm.
In an embodiment of the present invention, the resin adhesive in step (3) may be selected from a polyimide resin glue solution.
The invention provides modified PI fiber paper for a copper-clad plate based on the preparation method.
Has the beneficial effects that:
1) The invention provides a preparation method of a modified PI fiber paper base material for a high-frequency high-speed copper-clad plate, which adopts modified PI fibers to enhance the surface roughness of the fibers and greatly increase the surface groups of the fibers, thereby improving the bonding force among the fibers and obviously enhancing the strength of the whole piece of paper.
2) The modified PI fiber paper base material prepared using the PI fiber with excellent dielectric properties and high temperature resistance of the present invention has Dk at 1MHz not more than 1.5, df less than 0.01, CTE less than 4 μm/(m DEG C) in the range of 50 ℃ to 260 ℃, td (5% loss) more than 500 ℃. The requirements of high-frequency high-speed communication on the copper-clad plate base material are well met, and the application range of the PI fiber paper-based composite material is further expanded.
3) The modified PI paper-based composite material for the high-frequency and high-speed copper-clad plate has the following advantages: the organic reinforced material is more suitable for laser drilling; the weight ratio is light, which is beneficial to the light weight of electronic products; the low dielectric constant and dielectric loss are beneficial to improving the high-frequency characteristic of the plate, and the plate is suitable for high-speed operation of electronic products; the plane thermal shrinkage performance is good, the plane thermal expansion rate of the plate can be effectively reduced, and the densification of electronic products is facilitated.
Drawings
Fig. 1 is a scanning electron micrograph of the dopamine modified PI fiber of example 1.
FIG. 2 is a scanning electron micrograph of concentrated nitric acid modified PI fibers of example 2.
FIG. 3 is a scanning electron micrograph of PI fibers after the cleaning pretreatment of comparative example 1.
Detailed Description
Exemplified according to what is contained in the claims.
Example 1: preparation of modified PI fiber paper
(1) Cleaning and dispersing PI fiber, soaking PI fiber at concentration of 1.2 × 10 -3 Adding mol/L sodium dodecyl benzene sulfonate (LAS) solution, stirring in a constant temperature water bath at 60 deg.C for 30min, repeatedly washing with deionized water, and drying at 105 deg.C; then dispersing the cleaned PI fiber in water to prepare 2wt% slurry, pulping for 30min by using a tile power beater under the conditions that the frequency is 20Hz and the weight is 3kg, and obtaining uniformly dispersed PI fiber after vacuum drying for 24h at 105 ℃;
(2) Carrying out dopamine oxidation self-polymerization treatment on the PI fiber, soaking the fiber in a dopamine solution with the concentration of 2.0g/L, adjusting and maintaining the pH of the solution at about 8.5, continuing ultrasonic treatment for 2 hours, standing for 24 hours, taking out the fiber, repeatedly washing with deionized water, and carrying out vacuum drying at 30 ℃ for 48 hours to obtain a dopamine modified PI fiber;
(3) Preparation of polyimide fiber paper, presetting the quantitative of the polyimide fiber paper to be 75g/m 2 The preparation method comprises the steps of weighing dopamine modified PI fibers, dispersing the dopamine modified PI fibers in water to prepare slurry with the slurry concentration of 1wt%, uniformly dispersing the slurry, making paper by a paper sheet former, spraying 1mL of resin adhesive (polyimide resin adhesive, purchased from Hangzhou plastic union technology Co., ltd.) with the concentration of 1wt% on the surface of formed wet paper sheets, squeezing and drying to obtain the modified polyimide fiber paper.
The physical and mechanical properties of the resulting modified PI fiber paper were measured, and the results are shown in table 1.
TABLE 1 physical and mechanical Properties of PI fiber papers
| Item | Unit of | Test results |
| Quantification of | g/m 2 | 73.87 |
| Thickness of | mm | 0.29 |
| Tightness degree | g/m 3 | 0.25 |
| Tensile index | N*m/g | 10.24 |
| Elongation percentage | ％ | 2.54 |
Example 2: preparation of modified PI fiber paper
(1) Cleaning and dispersing PI fiber, soaking PI fiber at concentration of 1.2 × 10 -3 Adding mol/L sodium dodecyl benzene sulfonate (LAS) solution, stirring in a constant temperature water bath at 60 deg.C for 30min, repeatedly washing with deionized water, and drying at 105 deg.C; then, dispersing the cleaned PI fibers in water to prepare 2wt% slurry, pulping for 30min by using a tile power beater under the conditions that the frequency is 20Hz and the weight is 3kg, and performing vacuum drying for 24h at 105 ℃ to obtain uniformly dispersed PI fibers;
(2) Carrying out concentrated nitric acid oxidation treatment on the PI chopped fibers, soaking the fibers in concentrated nitric acid at the temperature of 60 ℃ for treatment for 2h, washing the fibers with a large amount of deionized water to make the fibers neutral, and carrying out vacuum drying at the temperature of 80 ℃ for 48h and then taking out the fibers to obtain oxidized modified PI fibers;
(3) Preparing PI fiber paper, and presetting the quantitative ratio of the PI fiber paper to be 75g/m 2 Weighing oxidized modified PI fiber, dispersing in water to prepare slurry with the slurry concentration of 1wt%, uniformly dispersing, making paper by a paper sheet former, spraying 1mL of resin adhesive (polyimide resin adhesive, purchased from Hangzhou plastic union Tech Co., ltd.) with the concentration of 1wt% on the surface of the formed wet paper sheet, squeezing, and drying to obtain the modified PI fiber paper.
The physical and mechanical properties of the resulting modified PI fiber papers were measured, and the results are shown in table 2.
TABLE 2 physical and mechanical Properties of PI fiber paper
| Item | Unit of | Test results |
| Quantification of | g/m 2 | 74.60 |
| Thickness of | mm | 0.28 |
| Tightness degree | g/m 3 | 0.27 |
| Tensile index | N*m/g | 8.86 |
| Elongation percentage | ％ | 2.14 |
Comparative example 1: preparation of modified PI fiber paper
(1) Pretreatment of PI fibers: soaking PI fiber at a concentration of 1.2 × 10 -3 Adding sodium dodecyl benzene sulfonate (LAS) solution in mol/L, stirring in a constant temperature water bath at 60 deg.C for 30min, and adding deionized waterRepeatedly washing, and drying at 105 deg.C; then dispersing the cleaned PI fiber in water to prepare 2wt% slurry, pulping for 30min by using a tile power beater under the conditions that the frequency is 20Hz and the weight is 3kg, and obtaining uniformly dispersed PI fiber after vacuum drying for 24h at 105 ℃;
(2) Preparing PI fiber paper: the quantitative ratio of the preset PI fiber paper is 75g/m 2 The method comprises the steps of weighing PI fibers which are pretreated before modification, dispersing the PI fibers in water to prepare slurry with the slurry concentration of 1wt%, uniformly dispersing the slurry, manufacturing paper by a paper sheet former, spraying 1mL of resin adhesive (polyimide resin adhesive, purchased from Hangzhou plastic union special technology Co., ltd.) with the concentration of 1wt% on the surface of the formed wet paper sheet, squeezing and drying to obtain the modified PI fiber paper.
The physical and mechanical properties of the resulting modified PI fiber papers were measured, and the results are shown in table 3.
TABLE 3 physico-mechanical properties of PI fiber paper
| Item | Unit | Test results |
| Quantification of | g/m 2 | 68.13 |
| Thickness of | mm | 0.41 |
| Tightness degree | g/m 3 | 0.17 |
| Tensile index | N*m/g | 1.21 |
| Elongation percentage of the polymer | ％ | 0.56 |
Dielectric properties and heat resistance of the modified PI fiber papers obtained in examples 1 to 2 and comparative example 1 were measured:
preparing a prepreg and a copper-clad plate: the modified PI fiber paper prepared in the above examples 1-2 and comparative example 1 is used for preparing a prepreg and a copper-clad plate: drying the PI fiber paper impregnating resin glue solution (generally polyimide resin, polytetrafluoroethylene resin and polyphenyl ether resin) to prepare a prepreg; and superposing one or more layers of prepregs according to the required thickness, heating and pressurizing the prepregs and compositely pressing the prepregs with copper foils to prepare the copper-clad plate.
The preparation process comprises the following steps:
preparing a PI fiber paper impregnating resin glue solution: polyimide resin and N, N-dimethylacetamide the following ratio of 3:97 to obtain 3 percent of resin glue solution.
Impregnating PI fiber paper with polyimide resin, wherein the impregnation process is that the PI fiber paper is impregnated in resin glue solution with the concentration of 3% for 3min at normal temperature, then the PI fiber paper is taken out, and the PI fiber paper is dried at 70 ℃ to be prepared into a prepreg;
and (3) overlapping 8 layers of prepregs together, covering a sizing electrolytic copper foil with the thickness of 18 mu m on the lower surface, putting the prepregs into a flat vulcanizing machine, setting the pressure to be 5MPa within the range from normal temperature to 140 ℃, increasing the pressure to 15MPa when the resin is basically gelled (the edge glue and the corner glue are solidified), continuously hot-pressing for 2h, closing the heating, naturally cooling to room temperature, continuously pressing for 30min, and taking out the prepregs to obtain the paper-based copper clad plate with the thickness condition of (1 +/-0.25) mm.
The performance results of the obtained paper-based copper-clad plate are shown in table 4.
TABLE 4 dielectric and heat resistance results of copper clad laminates made from modified PI fiber papers obtained in examples 1-2 and comparative example 1
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. A preparation method of modified PI fiber paper is characterized by comprising the following steps:
(1) Pretreatment: soaking the PI fiber in a sodium dodecyl benzene sulfonate solution for cleaning, and drying for later use after the cleaning is finished; then dispersing in water to prepare slurry, pulping and drying to obtain uniformly dispersed PI fibers;
(2) Modification treatment: soaking the pretreated PI fiber in the step (1) in a modified solution, adjusting and maintaining the pH of the solution to be 8-10, performing ultrasonic treatment, standing, taking out, washing and drying to obtain a modified PI fiber; the modified solution comprises concentrated nitric acid or dopamine solution;
(3) Presetting the quantification of PI fiber paper, preparing the dopamine modified PI fiber obtained in the step (2) into slurry, uniformly dispersing, making paper by a paper sheet former, spraying a resin adhesive on the surface of the wet paper sheet, squeezing and drying to obtain the modified PI fiber paper.
2. The method according to claim 1, wherein the concentration of the sodium dodecylbenzenesulfonate solution in step (1) is 1.2 x 10 -3 mol/L。
3. The method according to claim 1, wherein the cleaning condition in step (1) is 60 ℃ constant temperature water bath stirring for 30-60min.
4. The method according to claim 1, wherein the PI fibers of step (1) are selected from PI chopped fibers having a length of 6 mm.
5. The method according to claim 1, wherein the beating condition in the step (1) is a frequency of 20Hz and a weight of 3kg.
6. The method as claimed in claim 1, wherein the beating time in step (1) is 0.5-1.5h.
7. The method according to claim 1, wherein the concentration of the dopamine solution in step (2) is 2.0g/L.
8. The method according to claim 1, wherein the resin adhesive in the step (3) is a polyimide resin glue solution.
9. The method according to any one of claims 1 to 8, wherein the PI fiber paper in step (3) has a basis weight of 75g/m 2 。
10. A modified PI fiber paper prepared by the method of any one of claims 1-9.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011005258A1 (en) * | 2009-07-09 | 2011-01-13 | Board Of Regents, The University Of Texas System | Polymer deposition and modification of membranes for fouling resistance |
| CN105818398A (en) * | 2016-03-13 | 2016-08-03 | 北京化工大学 | Chopped fiber dispersion and preparation method thereof |
| CN106436441A (en) * | 2016-12-05 | 2017-02-22 | 江南大学 | Preparation method of polyimide fiber paper |
| CN108486888A (en) * | 2018-04-08 | 2018-09-04 | 北京化工大学 | A kind of surface biomimetic method of modifying of High performance polyimide fibres and application |
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- 2022-07-11 CN CN202210810854.0A patent/CN115162050A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011005258A1 (en) * | 2009-07-09 | 2011-01-13 | Board Of Regents, The University Of Texas System | Polymer deposition and modification of membranes for fouling resistance |
| CN105818398A (en) * | 2016-03-13 | 2016-08-03 | 北京化工大学 | Chopped fiber dispersion and preparation method thereof |
| CN106436441A (en) * | 2016-12-05 | 2017-02-22 | 江南大学 | Preparation method of polyimide fiber paper |
| CN108486888A (en) * | 2018-04-08 | 2018-09-04 | 北京化工大学 | A kind of surface biomimetic method of modifying of High performance polyimide fibres and application |
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