CN111501200B - Preparation method of polysiloxane imide micro-nano porous fiber non-woven fabric - Google Patents
Preparation method of polysiloxane imide micro-nano porous fiber non-woven fabric Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
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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
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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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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- 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
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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Abstract
本发明涉及一种聚硅氧烷酰亚胺微纳多孔纤维无纺布的制备方法，所述聚硅氧烷酰亚胺微纳孔纤维无纺布由芳香二胺、芳香二酐、硅封端剂、改性剂聚硅氧烷前驱体、酰亚胺化催化剂、微纳孔稳定剂、颜料和溶剂为原材料，以及采用静电纺丝装置、石墨履带动态模具和远红外辐射加热隧道一体化工艺制得，该无纺布幅宽为10mm～5000mm、纤维直径为100nm～1000nm、纤维内微纳孔直径为50nm～800nm，该聚硅氧烷酰亚胺微纳孔纤维无纺布的玻璃化转变温度为260℃～350℃。本发明是利用酰亚胺化过程中溶剂、缩聚反应中产生的小分子挥发分为微纳多孔形成机制；在聚酰亚胺中引入聚硅氧烷前驱体和硅封端剂，提高了组分间相互分散与反应程度；微纳多孔的形成与酰亚胺化同步，操作简单，成本低。The invention relates to a preparation method of a polysiloxane imide micro-nano porous fiber non-woven fabric. The polysiloxane imide micro-nano porous fiber non-woven fabric is made of aromatic diamine, aromatic dianhydride and silicon Terminal agent, modifier polysiloxane precursor, imidization catalyst, micro-nano pore stabilizer, pigment and solvent are used as raw materials, and the integration of electrospinning device, graphite crawler dynamic mold and far-infrared radiation heating tunnel The non-woven fabric has a width of 10 mm to 5000 mm, a fiber diameter of 100 nm to 1000 nm, and a diameter of micro-nano pores in the fiber of 50 nm to 800 nm. The transition temperature is 260°C to 350°C. The invention uses the solvent in the imidization process and the small molecule volatilization generated in the polycondensation reaction to divide into micro-nano porous formation mechanism; the polysiloxane precursor and the silicon end capping agent are introduced into the polyimide, which improves the composition. The degree of mutual dispersion and reaction between the parts; the formation of micro-nano porosity is synchronized with the imidization, the operation is simple, and the cost is low.
Description
Technical Field
The invention relates to a preparation method of a polysiloxane imide micro-nano porous fiber non-woven fabric. The invention particularly relates to a polysiloxane imide micro-nano porous fiber non-woven fabric which takes aromatic dianhydride, aromatic diamine, a silicon end capping agent, a polysiloxane precursor and a micro-nano pore stabilizer as main raw materials and takes electrostatic spinning as a preparation means.
Background
Polyimide is a special high polymer material with high heat resistance and excellent comprehensive performance, and is used as polyimide fiber in the fields of advanced thermal underwear, bedding and clothing, fire-fighting clothing, bag-type dust collectors, separation membranes and the like, and is used as polyimide film, composite material, adhesive and the like in the fields of aviation, aerospace, national defense, high-speed rail, smart phones and microelectronics, and the like, and is in a rapidly increasing trend. To further accommodate this development, it is necessary to innovate a lightweight polyimide fiber nonwoven fabric.
Chinese patent CN101473080B (japan tokyo textile co., ltd.) describes a polyimide nonwoven fabric and a method for producing the same: a polyimide nonwoven fabric having a fiber diameter of 0.001 to 1 μm and a linear expansion coefficient of-6 ppm/DEG C to-14 ppm/DEG C was prepared by electrospinning using an aromatic tetracarboxylic acid and an aromatic diamine as main raw materials.
Japanese patent laid-open No. 2004-308031 (Diperson corporation) describes a polyamide nonwoven fabric and a polyimide nonwoven fabric thereof and a preparation method: a thermosetting polyimide nonwoven fabric having an average fiber diameter of 0.001 to 1 μm, which is formed from an aromatic tetracarboxylic acid and an aromatic diamine, is proposed.
JP 2013-217008A discloses an electrostatic spinning Fluorinated Polyimide (FPI) fiber non-woven fabric, the fiber diameter of which is 10nm-50 μm, and the non-woven fabric is used as an oleophobic membrane material. The voltage used by the electrostatic spinning device is 8-20kv, the solid content of the FPI solution concentration is 5 wt% -20 wt%, the flow rate is 0.7mL/h-1.4mL/h, the distance between the needle and the collector is 10cm-20cm, the needle size is 0.5 μm-1 μm, the thickness of the uniform non-woven fabric is 20 μm-about 120 μm, and the non-woven fabric is porous.
JP-A-5, 2016/056480 (application No. 2015-553944) (Toray corporation) describes a method for preparing a polyimide solution and a heat-resistant polyimide electrospun nonwoven fabric, wherein the fiber diameter is 1-6 μm, the glass transition temperature is 170-220 ℃, the dielectric constant is 2.3-3.5, and the water absorption is 0.8-4.3%.
JP 2008-002011 (Toyo Boseki Co., Ltd.) discloses a method for producing an electrospun polyimide nonwoven fabric, the nonwoven fabric having a fiber diameter of 0.001 μm to 1 μm and a linear expansion coefficient of-6 ppm/. degree.C. -14 ppm/. degree.C..
JP-A-2004-308031 (Diman corporation) discloses an electrospun polyamide acid nonwoven fabric and a polyimide nonwoven fabric thereof, wherein the polyimide nonwoven fabric has an average fiber diameter of 0.001 μm to 1 μm.
JP-A2011-132611 (Nissan Co., Ltd.) describes a polyimide fiber and a method for producing an electrospun nonwoven fabric thereof, wherein the diameter of the nonwoven fabric is 0.001 μm to 1 μm.
Japanese patent laid-open No. 2011-132611: disclosed are a polyimide composition and an electro-spun (ESP) nonwoven fabric of a filter for high temperature use thereof.
Japanese laid-open patent publication No. 2003-183966(Unitika strain)Kokko) describes a process for preparing a polyimide nonwoven fabric having a nonwoven fabric density of less than 10g/m from a dispersion of ordinary PI staple fibers2(ii) a Japanese laid-open patent publication No. 2012-251287 (Mitsukawa chemical industries, Ltd.) describes a method for producing a polyimide fiber, a polyimide nonwoven fabric, a heat insulating material, an electromagnetic shielding film and a battery separator by a common spinning method, wherein the nonwoven fabric has a fiber average diameter of 0.1 to 10 μm, a glass transition temperature of 310 to 338 ℃, a linear expansion coefficient of 0 to 20 ppm/DEG C, a thermal conductivity of 0.08W/m.K or less, a loss tangent of 0.0045 to 0.010, and a dielectric constant of 1.26 to 3.27.
The most significant feature of the nonwoven fabric patents described above is that the porous structure of the fibers is not involved.
In addition, Chinese patent CN 104752665B (Bohai university) introduces a preparation method of a polyimide porous nanofiber electrode diaphragm, and a polyamide acid solution is obtained by condensation reaction of binary organic amine and binary organic acid anhydride in an organic solvent; then adding soluble metal salt to prepare a spinning precursor, preparing a polyamic acid-metal salt electrostatic spinning fiber membrane through high-voltage electrostatic spinning, performing sub-thermal amination treatment to obtain a polyimide-metal oxide fiber composite membrane, dissolving the polyimide-metal oxide fiber composite membrane in an inorganic acid aqueous solution to perform acid treatment, and converting metal oxide nanoparticles into soluble metal salt to be dissolved in the inorganic acid aqueous solution to obtain the polyimide nano-micron porous fiber membrane. The porous nanoparticles described in this patent are pores that have been previously mixed with metal oxide nanoparticles and left after a solvation treatment.
The preparation method of the polysiloxane imide micro-nano porous fiber non-woven fabric provided by the invention is a micro-nano porous fiber non-woven fabric which takes components of polymerized polysiloxane polyimide as raw materials, takes electrostatic spinning as an important means, and takes small molecule volatile generated in a solvent and a polycondensation reaction as a micro-nano porous formation mechanism, and has remarkable novelty.
According to the invention, aromatic diamine and aromatic dianhydride react in a solvent, and polysiloxane is introduced into a polyimide molecular chain to improve the high temperature resistance of the polysiloxane imide micro-nano porous fiber non-woven fabric.
According to the invention, a silicon end-capping agent is used for end-capping polyimide acid, a modifier polysiloxane precursor, an imidization catalyst, a micro-nano pore stabilizer and a pigment are added, polysiloxane is introduced into a polyimide molecular chain to prepare a polysiloxane imide precursor paste, an electrostatic spinning process is adopted to prepare a polysiloxane imide micro-nano porous fiber non-woven fabric preform, a solvent and micromolecule volatilization generated in a polycondensation reaction are used as a micro-nano porous forming mechanism, and the high heat-resistant polysiloxane imide micro-nano porous fiber non-woven fabric is prepared through drying, porous micro-nano forming and imidization.
The invention relates to a preparation method of polysiloxane imide micro-nano porous fiber non-woven fabric, which mainly aims to develop materials such as thermal underwear, bedding and clothing, fire-fighting clothes, filters, separation membranes, aerospace sound absorption and heat insulation, low dielectric constant and the like which can be used in high and low temperature environments, wherein the filters comprise bag-type dust collectors, dustproof filters, precision instrument filters, cabin filters of automobiles, trains, buildings and the like, engine filters and the like, and can also be used as materials such as electronic circuit insulating substrates or battery diaphragms and the like.
Disclosure of Invention
The invention relates to a preparation method of a polysiloxane imide micro-nano porous fiber non-woven fabric, which comprises the following raw materials in parts by weight: 1-100 parts of aromatic diamine, 1-300 parts of aromatic dianhydride, 0.1-15 parts of silicon end-capping agent, 0-30 parts of modifier polysiloxane precursor but not 0 part, 0-10 parts of imidization catalyst but not 0 part, 0.01-50 parts of micro-nano pore stabilizer, 0-5 parts of pigment and 10-500 parts of solvent, wherein the aromatic diamine is selected from 3,4 '-diaminodiphenyl ether, 4' -diaminobenzophenone, 3 '-diaminobenzophenone, bisphenol A diphenyl ether diamine, m-diphenylamine, p-phenylenediamine, 4' -diaminodiphenylmethane, 4 '-diaminodiphenylsulfone, 3' -diaminodiphenylsulfone and 4,4 '-diamino-2, 2' -bistrifluoromethylbiphenyl, the aromatic dianhydride is selected from 3, 3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3, 3',4,4' -benzophenone tetracarboxylic dianhydride, bisphenol A type diether dianhydride, 3, 3',4,4' -biphenyl tetracarboxylic dianhydride, 3, 3',4,4' -biphenyl sulfone tetracarboxylic dianhydride, 1,2,4, 5-pyromellitic dianhydride, 2,3',4,4' -biphenyl tetracarboxylic dianhydride, 2,3, 3', 4' -benzophenone tetracarboxylic dianhydride and 2,3, 3', 4' -diphenyl ether tetracarboxylic dianhydride, the silicon end-capping agent is selected from N- (beta-aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane, the silicon end-capping agent is selected from N- (beta-aminoethyl) -gamma-aminopropyl-triethoxysilane, the silicon end-capping agent is selected from the group consisting of N, 3', 4' -diphenyl, More than one of N- (beta-aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane or gamma-aminopropylmethyldimethoxysilane, more than one of polysiloxane precursor as modifier selected from methyl orthosilicate, ethyl orthosilicate, propyl silicate, methyltrimethoxysilane, methyltriethoxysilane and phenyltriethoxysilane, more than one of imidization catalyst selected from 1, 2-dimethylimidazole, 2-ethyl-4-methylimidazole, benzimidazole, isoquinoline, 2-methylpyridine, 3-hydroxypyridine, 4-hydroxypyridine or 4, 6-dimethylpyridine, pyridine/acetic anhydride, triethylamine/acetic anhydride and sodium acetate/acetic anhydride, the micro-nano hole stabilizer is selected from more than one of polymethylsiloxane, polydimethylsiloxane, polyether modified polysiloxane or vinyl polysiloxane, organic silicon glycol copolymer, vinyl polysiloxane, cationic fluorocarbon surfactant and polyoxyethylene ether nonionic fluorocarbon surfactant, the pigment is selected from one of phthalocyanine blue, red lead powder, permanent yellow, benzidine yellow, scarlet powder, iron oxide black, carbon black and copper chromium black, the solvent is selected from more than one of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, 2-methyl-butanol, 3-methyl-butanol, 2-dimethylpropanol, tetrahydrofuran, polyethylene glycol dimethyl ether, diethylene glycol dimethyl ether and dioxane, dimethylformamide, dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone;
the preparation process of the polysiloxane imide micro-nano porous fiber non-woven fabric comprises the following steps:
1) reacting more than one aromatic dianhydride with more than one aromatic diamine in a solvent for 2 to 20 hours, then adding a silicon end capping agent, reacting for 2 to 10 hours, then adding a modifier polysiloxane precursor, an imidization catalyst, a micro-nano pore stabilizer and a pigment, and reacting for 2 to 10 hours to form a polysiloxane imide acid solution with the solid content of 8 to 45 weight percent;
2) heating to remove small molecule volatile matters to prepare polysiloxane imide precursor paste;
3) performing electrostatic spinning on the polysiloxane imide precursor paste by adopting an electrostatic spinning device, a graphite caterpillar dynamic die and a far infrared radiation heating tunnel integrated continuous preparation process to prepare a polysiloxane imide fiber non-woven fabric preform, wherein the heating temperature in the electrostatic spinning process is 40-100 ℃, the applied voltage is 1kV/cm-100kV/cm, the diameter of a needle hole of a needle is 0.5-2 mu m, the distance between the needle and a collector is 1-50 cm, and the flow rate from the needle hole is 0.5-10 mL/h;
4) conveying the above electrospun polysiloxane imide fiber nonwoven fabric preform into a far infrared radiation heating tunnel equipped with a graphite caterpillar dynamic mold, and:
(1) drying the polysiloxane imide fiber non-woven fabric pre-forming body for 1min to 60min at the temperature of 100 ℃ to 150 ℃ in a first heating zone of the tunnel to prepare a dried polysiloxane imide fiber non-woven fabric pre-forming body;
(2) pre-imidizing the non-woven fabric pre-forming body in the step (1) for 5-60 min at a second heating zone of a tunnel at 150-250 ℃, and simultaneously preparing a polysiloxane imide pre-imidized micro-nano porous fiber non-woven fabric pre-forming body through a solvent and micromolecule volatile components generated by a polycondensation reaction;
(3) performing imidization on the micro-nano porous non-woven fabric preform in the step (2) at 250-500 ℃ in a third heating zone of the tunnel for 5-120 min, and further preparing the polysiloxane imide micro-nano porous fiber non-woven fabric with a stable micro-nano porous structure through a solvent and micromolecule volatile components generated by polycondensation reaction;
(4) in a fourth heat treatment area of the tunnel, performing air cooling treatment on the polysiloxane imide micro-nano porous fiber non-woven fabric in the step (3) to room temperature, and then performing edge cutting to obtain the polysiloxane imide micro-nano porous fiber non-woven fabric, wherein the width of the non-woven fabric is 10-5000 mm, the fiber diameter of the non-woven fabric is 100-1000 nm, the diameter of the micro-nano porous fiber in the fiber is 50-800 nm, and the glass transition temperature of the non-woven fabric is 260-350 ℃.
The preparation process of the polysiloxane imide micro-nano porous fiber non-woven fabric comprises the following steps: firstly, preparing a polysiloxane imide micro-nano porous fiber non-woven fabric by using a polysiloxane imide acid solution; secondly, preparing polysiloxane imide precursor paste; thirdly, preparing a polysiloxane imide fiber non-woven fabric pre-forming body by electrostatic spinning; fourthly, drying the polysiloxane imide fiber non-woven fabric preformed body; fifthly, pre-imidizing the polysiloxane imide into a micro-nano porous fiber non-woven fabric preform; sixthly, stabilizing the polysiloxane imide micro-nano porous fiber non-woven fabric with the micro-nano porous structure; and seventhly, trimming, rolling and packaging.
The invention has the advantages that:
1) according to the invention, porous fibers are not formed through solvation treatment, but a micro-nano porous forming mechanism is adopted by utilizing a solvent in the imidization process and micromolecule volatile matter generated in the polycondensation reaction;
2) polysiloxane precursors and silicon end capping agents are introduced into polyimide, so that the mutual dispersion and reaction degree of the components are improved;
3) the formation of micro-nano pores and imidization are synchronous, the operation is simple, the stability of the structure and the performance of the product is good, and the cost is low.
Detailed Description
The present invention is described below by way of examples, which are intended to be illustrative only and not to be construed as limiting the scope of the invention, which is to be given the full breadth of the appended claims and any and all insubstantial modifications and variations thereof which are within the scope of the appended claims.
Example 1:
(1) preparation of polysiloxane imide acid solution: dissolving 36 parts of 4,4 '-diaminodiphenyl ether (4, 4' -ODA) in 220 parts of tetrahydrofuran and 73 parts of methanol mixed solvent, stirring to completely dissolve and uniformly mix solids, then adding 57 parts of 3, 3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA) into the solution, stirring for 10 to 12 hours at the temperature lower than 30 ℃, then adding 1.7 parts of gamma-aminopropyltriethoxysilane silicon end-capping agent, continuously stirring for 3 to 5 hours till complete reaction, then adding 2.8 parts of polysiloxane precursor ethyl orthosilicate modifier for reaction for 3 to 4 hours, finally adding 2.8 parts of polymethylsiloxane micropore stabilizer, 5 parts of 2-ethyl-4-methylimidazolidinization catalyst and 0.05 part of phthalocyanine blue pigment, stirring for 1 to 2 hours to form a uniform solution, preparing polysiloxane imide acid solution;
(2) preparation of polysiloxane imide precursor paste: discharging small molecule volatile matters in the polysiloxane imide acid solution in the temperature environment below 40 ℃ to prepare polysiloxane imide precursor paste;
(3) preparing an electrostatic spinning polysiloxane imide fiber non-woven fabric preformed body: and (2) carrying out electrostatic spinning on the polysiloxane imide precursor paste to obtain a polysiloxane imide fiber non-woven fabric pre-forming body, wherein the heating temperature in the electrostatic spinning process is 50 ℃, the applied voltage is 15kV/cm, the diameter of a needle hole of the needle is 1 mu m, the distance between the needle and a collector is 20cm, and the flow rate from the needle hole is about 3 mL/h.
(4) Preparing polysiloxane imide micro-nano porous fiber non-woven fabric: feeding the above (3) electrospun polysiloxane imide fiber nonwoven fabric preform into a far infrared radiation heating tunnel equipped with a graphite caterpillar dynamic mold, and:
a. drying the polysiloxane imide fiber non-woven fabric pre-forming body for 10min at 120 ℃ of a first heating area of the tunnel to obtain a dried polysiloxane imide fiber non-woven fabric pre-forming body;
b. pre-imidizing the non-woven fabric pre-forming body a for 5-60 min at 200 ℃ in a second heating zone of a tunnel, and simultaneously preparing a polysiloxane imide pre-imidized micro-nano porous fiber non-woven fabric pre-forming body through a solvent and micromolecule volatile components generated by polycondensation reaction;
c. performing imidization on the micro-nano porous non-woven fabric preform in the step b for 5-120 min at 400 ℃ in a third heating zone of the tunnel, and further preparing the polysiloxane imide micro-nano porous fiber non-woven fabric with a stable micro-nano porous structure through a solvent and micromolecule volatile components generated by polycondensation reaction;
d. in a fourth heat treatment area of the tunnel, carrying out air cooling treatment on the polysiloxane imide micro-nano porous fiber non-woven fabric c to room temperature, and carrying out subsequent trimming, rolling and packaging to obtain the polysiloxane imide micro-nano porous fiber non-woven fabric, wherein the breadth of the non-woven fabric is 500mm, the average fiber diameter of the non-woven fabric is 405nm, the average micro-nano porous diameter in the fiber is 265nm, and the glass transition temperature of the non-woven fabric is 290 ℃.
Example 2:
(1) preparation of polysiloxane imide acid solution: dissolving 34 parts of 4,4 '-diaminodiphenyl ether (4, 4' -ODA) in 278 parts of mixed solvent of tetrahydrofuran and 70 parts of methanol, stirring to completely dissolve and uniformly mix solids, then adding 53 parts of 3, 3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA) into the solution, stirring for 10 to 12 hours at the temperature lower than 30 ℃, then adding 1.6 parts of gamma-aminopropyltriethoxysilane silicon end-capping agent, continuously stirring for 3 to 5 hours till complete reaction, then adding 7.8 parts of polysiloxane precursor ethyl orthosilicate modifier for reaction for 3 to 4 hours, finally adding 2.6 parts of polymethylsiloxane micropore stabilizer, 5 parts of 2-ethyl-4-methylimidazoliminate imidization catalyst and 0.05 part of phthalocyanine blue pigment, stirring for 1 to 2 hours to form a uniform solution, preparing polysiloxane imide acid solution;
(2) preparation of a polysiloxane imide precursor paste as in (2) of example 1;
(3) the preparation of the electrospun silicone imide fiber nonwoven preform was the same as in (3) of example 1;
(4) the preparation of the polysiloxane imide micro-nano porous fiber non-woven fabric is the same as that of the (4) of the example 1;
the breadth of the polysiloxane imide micro-nano porous fiber non-woven fabric is 500mm, the average fiber diameter of the non-woven fabric is 455nm, the average micro-nano porous diameter in the fiber is 245nm, and the glass transition temperature of the non-woven fabric is 295 ℃.
Example 3:
(1) preparation of polysiloxane imide acid solution: dissolving 30 parts of 4,4 '-diaminodiphenyl ether (4, 4' -ODA) in 255 parts of tetrahydrofuran and 64 parts of methanol mixed solvent, stirring to completely dissolve and uniformly mix solids, then adding 50 parts of 3, 3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA) into the solution, stirring for 10 to 12 hours at the temperature lower than 30 ℃, then adding 3.5 parts of gamma-aminopropyltriethoxysilane silicon end-capping agent, continuously stirring for 3 to 5 hours till the reaction is complete, then adding 14.5 parts of polysiloxane precursor ethyl orthosilicate modifier for reacting for 3 to 4 hours, finally adding 2.4 parts of polymethylsiloxane micropore stabilizer, 5 parts of 2-ethyl-4-methylimidazole imidization catalyst and 0.05 part of phthalocyanine blue pigment, stirring for 1 to 2 hours to form a uniform solution, preparing polysiloxane imide acid solution;
(2) preparation of a polysiloxane imide precursor paste as in (2) of example 1;
(3) the preparation of the electrospun silicone imide fiber nonwoven preform was the same as in (3) of example 1;
(4) the preparation of the polysiloxane imide micro-nano porous fiber non-woven fabric is the same as that of the (4) of the example 1;
the breadth of the polysiloxane imide micro-nano porous fiber non-woven fabric is 500mm, the average fiber diameter of the non-woven fabric is 445nm, the average micro-nano porous diameter in the fiber is 255nm, and the glass transition temperature of the non-woven fabric is 299 ℃.
Example 4:
(1) preparation of polysiloxane imide acid solution: dissolving 36 parts of 3,4 '-diaminodiphenyl ether (4, 4' -ODA) in 294 parts of tetrahydrofuran and 73 parts of methanol mixed solvent, stirring to completely dissolve and mix solids, then adding 57 parts of 3, 3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA) into the solution, stirring for 10 to 12 hours at the temperature lower than 30 ℃, then adding 1.7 parts of gamma-aminopropyltriethoxysilane silicon agent, continuously stirring for 3 to 5 hours till complete reaction, then adding 2.75 parts of polysiloxane precursor terminated tetraethoxysilane modifier, reacting for 3 to 4 hours, finally adding 2.75 parts of polymethylsiloxane micropore stabilizer, 5 parts of 2-ethyl-4-methylimidazolidine imidization catalyst and 0.05 part of phthalocyanine blue pigment, stirring for 1 to 2 hours to form a uniform solution, preparing polysiloxane imide acid solution;
(2) preparation of a polysiloxane imide precursor paste as in (2) of example 1;
(3) the preparation of the electrospun silicone imide fiber nonwoven preform was the same as in (3) of example 1;
(4) the preparation of the polysiloxane imide micro-nano porous fiber non-woven fabric is the same as that of the (4) of the example 1;
the breadth of the polysiloxane imide micro-nano porous fiber non-woven fabric is 500mm, the average fiber diameter of the non-woven fabric is 505nm, the average micro-nano porous diameter in the fiber is 275nm, and the glass transition temperature of the non-woven fabric is 260 ℃.
Example 5:
(1) preparation of polysiloxane imide acid solution: dissolving 35 parts of 3,4 '-diaminodiphenyl ether (4, 4' -ODA) in 287 parts of tetrahydrofuran and 72 parts of methanol mixed solvent, stirring to completely dissolve and mix the solid, then adding 58 parts of 3, 3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) into the solution, stirring for 10-12 hours at the temperature lower than 30 ℃, adding 1.7 parts of gamma-aminopropyltriethoxysilane silicon end-capping agent, continuously stirring for 3-5 hours till the reaction is complete, adding 2.7 parts of polysiloxane precursor ethyl orthosilicate modifier for reaction for 3-4 hours, finally adding 2.7 parts of polymethylsiloxane micropore stabilizer, 5 parts of 2-ethyl-4-methylimidazoliminate imidization catalyst and 0.05 part of phthalocyanine blue pigment, stirring for 1-2 hours to form a uniform solution, preparing polysiloxane imide acid solution;
(2) preparation of a polysiloxane imide precursor paste as in (2) of example 1;
(3) the preparation of the electrospun silicone imide fiber nonwoven preform was the same as in (3) of example 1;
(4) the preparation of the polysiloxane imide micro-nano porous fiber non-woven fabric is the same as that of the (4) of the example 1;
the breadth of the polysiloxane imide micro-nano porous fiber non-woven fabric is 500mm, the average fiber diameter of the non-woven fabric is 581nm, the average micro-nano porous diameter in the fiber is 282nm, and the glass transition temperature of the non-woven fabric is 270 ℃.
Example 6:
(1) preparation of polysiloxane imide acid solution: dissolving 35 parts of 4,4 '-diaminodiphenyl ether (4, 4' -ODA) in 287 parts of tetrahydrofuran and 72 parts of methanol mixed solvent, stirring to completely dissolve and mix the solid, then adding 58 parts of 3, 3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA) into the solution, stirring for 10-12 hours at the temperature lower than 30 ℃, adding 1.7 parts of gamma-aminopropyltriethoxysilane silicon end-capping agent, continuously stirring for 3-5 hours till the reaction is complete, adding 2.7 parts of polysiloxane precursor ethyl orthosilicate modifier for reaction for 3-4 hours, finally adding 2.7 parts of polymethylsiloxane micropore stabilizer, 5 parts of 2-ethyl-4-methylimidazoliminate imidization catalyst and 0.05 part of phthalocyanine blue pigment, stirring for 1-2 hours to form a uniform solution, preparing polysiloxane imide acid solution;
(2) preparation of a polysiloxane imide precursor paste as in (2) of example 1;
(3) the preparation of the electrospun silicone imide fiber nonwoven preform was the same as in (3) of example 1;
(4) the preparation of the polysiloxane imide micro-nano porous fiber non-woven fabric is the same as that of the (4) of the example 1;
the breadth of the polysiloxane imide micro-nano porous fiber non-woven fabric is 500mm, the average fiber diameter of the non-woven fabric is 598nm, the average micro-nano porous diameter in the fiber is 278nm, and the glass transition temperature of the non-woven fabric is 315 ℃.
Example 7:
(1) preparation of polysiloxane imide acid solution: dissolving 36 parts of 4,4 '-diaminodiphenyl ether (4, 4' -ODA) in 293 parts of tetrahydrofuran and 73 parts of methanol mixed solvent, stirring to completely dissolve and uniformly mix solids, adding 53 parts of 3, 3',4,4' -diphenyl ether tetracarboxylic dianhydride (BTDA) and 4 parts of 1,2,4, 5-pyromellitic dianhydride (PMDA) into the solution, stirring for 10-12 hours at the temperature of lower than 30 ℃, adding 1.7 parts of gamma-aminopropyltriethoxysilane silicon end-capping agent, continuously stirring for 3-5 hours until the reaction is complete, adding 2.8 parts of polysiloxane precursor ethyl orthosilicate modifier for reacting for 3-4 hours, and finally adding 2.8 parts of polymethylsiloxane micropore stabilizer and 5 parts of 2-ethyl-4-methylimidazoliminate catalyst, 0.05 part of phthalocyanine blue pigment is stirred for 1 hour to 2 hours to form a uniform solution, and polysiloxane imide acid solution is prepared;
(2) preparation of a polysiloxane imide precursor paste as in (2) of example 1;
(3) the preparation of the electrospun silicone imide fiber nonwoven preform was the same as in (3) of example 1;
(4) the preparation of the polysiloxane imide micro-nano porous fiber non-woven fabric is the same as that of the (4) of the example 1;
the breadth of the polysiloxane imide micro-nano porous fiber non-woven fabric is 500mm, the average fiber diameter of the non-woven fabric is 578nm, the average micro-nano porous diameter in the fiber is 268nm, and the glass transition temperature of the non-woven fabric is 313 ℃.
Example 8:
(1) preparation of polysiloxane imide acid solution: dissolving 18 parts of 4,4 '-diaminodiphenyl ether (4, 4' -ODA) and 19 parts of 4,4 '-diaminobenzophenone (4, 4' -DABP) in 290 parts of tetrahydrofuran and 73 parts of methanol mixed solvent in a reaction kettle, stirring to completely dissolve and uniformly mix solids, then adding 56 parts of 3, 3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA) into the solution, stirring for 10-12 hours at the temperature lower than 30 ℃, then adding 1.6 parts of gamma-aminopropyltriethoxysilane silicon end-capping agent, continuously stirring for 3-5 hours till the reaction is complete, then adding 2.8 parts of polysiloxane precursor ethyl orthosilicate modifier for reaction for 3-4 hours, finally adding 2.8 parts of polymethylsiloxane micropore stabilizer and 5 parts of 2-ethyl-4-methylimidazoliminate catalyst, 0.05 part of phthalocyanine blue pigment is stirred for 1 hour to 2 hours to form a uniform solution, and polysiloxane imide acid solution is prepared;
(2) preparation of a polysiloxane imide precursor paste as in (2) of example 1;
(3) the preparation of the electrospun silicone imide fiber nonwoven preform was the same as in (3) of example 1;
(4) the preparation of the polysiloxane imide micro-nano porous fiber non-woven fabric is the same as that of the (4) of the example 1;
the breadth of the polysiloxane imide micro-nano porous fiber non-woven fabric is 500mm, the average fiber diameter of the non-woven fabric is 682nm, the average micro-nano porous diameter in the fiber is 335nm, and the glass transition temperature of the non-woven fabric is 310 ℃.
Preferred embodiments of the present invention are described by the above-mentioned examples 1 to 8, the average density and glass transition temperature density of the silicone imide micro/nano porous fiber nonwoven fabric are closely related to the electrospinning process, the nonwoven fabric fiber micro/nano porous structure, the upper and lower spacing and conveying speed of the graphite caterpillar dynamic mold, the imidization temperature, etc., and the thickness of the silicone imide micro/nano porous fiber nonwoven fabric of the present invention is mainly related to the conveying speed of the graphite caterpillar dynamic mold, and therefore, as described above, it should be understood that the present invention is not limited to the form disclosed herein, and should not be construed as excluding other embodiments, but can be used in various other combinations and modifications, and can be modified within the scope of the inventive concept described herein by the above or knowledge in the related art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
The electrostatic spinning polysiloxane imide micro-nano porous fiber non-woven fabric has excellent high temperature resistance, low temperature resistance, flame retardance, heat insulation and low dielectric constant performance, can be used as materials of clothing, fire-fighting clothing, filters, insulating substrates of electronic circuits, electromagnetic diaphragms and the like in high and low temperature environments, and has important significance in industry.
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