CN103898771B - The method of the nano-fiber composite material of preparation containing PMMA - Google Patents

The method of the nano-fiber composite material of preparation containing PMMA Download PDF

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CN103898771B
CN103898771B CN201410078191.3A CN201410078191A CN103898771B CN 103898771 B CN103898771 B CN 103898771B CN 201410078191 A CN201410078191 A CN 201410078191A CN 103898771 B CN103898771 B CN 103898771B
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CN103898771A (en
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符思敏
费辉
周建伟
刘创
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Abstract

The invention discloses a kind of method preparing nano-fiber composite material containing PMMA.1) under 70 ~ 90 DEG C of conditions, after nanometer PMMA is dried, join in solvent, uniform stirring under 60 DEG C of airtight conditions, dissolve, obtain PMMA solution; 2) add fluoro containing polymers polymer, stirring at normal temperature, dissolve, obtain nanometer PMMA/ fluoro containing polymers polymer solution; 3) get ethanolic solution, add nanometer oxide particle, ultrasonic oscillation; 4) scattered nano-oxide solution is joined in PMMA/ fluoro containing polymers polymer solution, obtain spinning solution; 5) spinning solution is evenly coated at least one side on structure sheaf fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.Raw material of the present invention is easy to get, the nano-fiber composite material mechanical strength of gained is high, heat endurance and have excellent weather resistance, porosity is high, light transmission ventilation, and possesses and intercepts the function of Nanoparticle, has application and industrialization value greatly.

Description

The method of the nano-fiber composite material of preparation containing PMMA
Technical field
The present invention relates to extraordinary nano-fiber material field, particularly relate to a kind of method preparing nano-fiber composite material containing PMMA.
Background technology
Polymethyl methacrylate (PMMA) is also known as lucite, it is one of transparent best polymeric material, there are good optical clarity, chemical stability, good processing characteristics and insulating properties etc., but it has the shortcoming that self cannot overcome, its Thermal Resistant Surface is poor, hardness is low, wear no resistance, and impact strength is low, modified poly complex process etc., this limits its range of application to a certain extent.Therefore, for meeting the simple requirement of special condition of work, using function and technique, be necessary on the basis keeping PMMA superperformance its further modification.
Fluoro containing polymers polymer, because fluorine atom polarizability is minimum in all elements, make C-F bond polarity stronger, the intermolecular forces of the polymer molecule containing C-F key is little, thus has excellent surface property (resistance to water, oil resistivity, stain resistance, self-cleaning property), optical property (low-refraction), electric property (high insulation, low-k).Again because fluorine atom distributes more symmetrical in the molecular structure, perfluorinated side chains orientation, forms " shielding protection " to main polymer chain and from the direct effect of extraneous factor outwardly.Therefore, fluoro containing polymers polymer has much special performance, as the heat endurance of excellence, chemical stability and weatherability, UV resistant and high-energy radiation.
Nano-meter SiO_2 2be the inorganic nano-particle of a kind of excellent performance, wide material sources, the hardness of organic polymer can be strengthened, improve its ABRASION RESISTANCE, scratch resistance, ultravioletlight screening performance etc.Nano-TiO 2, also known as nanometer titanium dioxide, shielding ultraviolet rays effect is strong, has good dispersiveness and weatherability, has anti-line, antibacterial, self-cleaning, ageing resistace, be usually used in the fields such as cosmetics, functional fibre, plastics, ink, coating, paint, fine ceramics.
How this Molecularly Imprinted Polymer fluorine-containing, nanometer oxide particle are incorporated in PMMA modifying process by simple, effective technique, obtain that mechanical strength is high, heat endurance and have excellent weather resistance, porosity is high, light transmission ventilation, and the target that the nano-fiber material possessing the function intercepting Nanoparticle is material supplier author always to be laid siege to and direction, but there is no successful story at present.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method preparing nano-fiber composite material containing PMMA is provided.
Prepare a method for the nano-fiber composite material containing PMMA, step is as follows:
1) under 70 ~ 90 DEG C of conditions, after nanometer PMMA is dried, join in solvent, in confined conditions uniform stirring 4 ~ 6h, make it fully dissolve, obtain the PMMA solution that concentration is 10 ~ 24wt%;
2) add fluoro containing polymers polymer, stirring at normal temperature, make it fully dissolve, obtain nanometer PMMA: fluoro containing polymers polymer quality is than the solution of 2.33-19;
3) get 10mL ethanolic solution, add 0.0075-0.03g nanometer oxide particle, ultrasonic oscillation 1 ~ 2h;
4) scattered nano-oxide solution is joined step 2) in the PMMA/ fluoro containing polymers polymer solution that obtains, obtain the spinning solution that concentration is 15 ~ 25wt%;
5) spinning solution is evenly coated at least one side on structure sheaf fabric by electrostatic spinning technique, obtains the nano-fiber composite material containing PMMA.
Solvent selected from acetone described in step 1), at least one in 1-METHYLPYRROLIDONE (NMP), dimethylacetylamide (DMAc), DMF (DMF).
Step 2) described in fluoro containing polymers polymer be Kynoar (PVDF), polyvinyl fluoride (PVF), Kynoar-hexafluoropropylene copolymer (PVDF-co-HFP), polytetrafluoroethylene (PTFE), Kynoar-acrylonitrile copolymer (PVDF-co-AN).
Nanometer oxide particle described in step 3) is silica (SiO 2), alundum (Al2O3) (Al 2o 3), titanium dioxide (TiO 2), magnesia (MgO), barium titanate (BaTiO 3) at least one.
Surface treatment is carried out through coupling agent or surfactant in nanometer oxide particle surface described in step 3).
Structure sheaf fabric described in step 5) is nonwoven fabric, glass fabric, spandex fibre fabric.
Structure sheaf fabric surface described in step 5) is through modification.
Described modification, silane resin acceptor kh-550, KH-560 and titanate coupling agent NDZ-201 to be dissolved in ethanol obtained surface modifier solution respectively, and coupling agent mass fraction is 1%, carries out surface treatment to structure sheaf fabric, after through drying and processing.
Beneficial effect of the present invention: raw material is easy to get, the nano-fiber composite material mechanical strength of gained is high, heat endurance and have excellent weather resistance, porosity is high, light transmission ventilation, and possesses and intercepts the function of Nanoparticle, has application and industrialization value greatly.
Accompanying drawing explanation
Fig. 1 is the ESEM spectrogram of the nano-fiber composite material containing PMMA of embodiment 1;
Fig. 2 is the ESEM spectrogram of the nano-fiber composite material containing PMMA of embodiment 4;
Fig. 3 is the ESEM spectrogram of the nano-fiber composite material containing PMMA of embodiment 11;
Fig. 4 is the ESEM spectrogram of the nano-fiber composite material containing PMMA of embodiment 18.
Detailed description of the invention
The step of the method for the nano-fiber composite material of preparation containing PMMA is as follows:
1) under 70 ~ 90 DEG C of conditions, after nanometer PMMA is dried 1 ~ 2h, join in a certain amount of solvent, uniform stirring 4 ~ 6h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10 ~ 24wt%;
2) add a certain amount of fluoro containing polymers polymer, stirring at normal temperature 0.5 ~ 1h, make it fully dissolve, obtain the nanometer PMMA/ fluoro containing polymers polymer solution of mass ratio 7:3 ~ 19:1;
3) get 10mL ethanolic solution, add 0.0075 ~ 0.03g nanometer oxide particle, ultrasonic oscillation 1 ~ 2h;
4) scattered nano-oxide solution is joined in PMMA/ fluoro containing polymers polymer solution, obtain the spinning solution that concentration is 15 ~ 25wt%;
5) spinning solution is evenly coated at least one side on structure sheaf fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
Described fluoro containing polymers polymer is Kynoar (PVDF), polyvinyl fluoride (PVF), Kynoar-hexafluoropropylene copolymer (PVDF-co-HFP), polytetrafluoroethylene (PTFE), Kynoar-acrylonitrile copolymer (PVDF-co-AN).Described solvent is at least one in acetone, 1-METHYLPYRROLIDONE (NMP), dimethylacetylamide (DMAc), DMF (DMF).Described nanometer oxide particle is silica (SiO 2), alundum (Al2O3) (Al 2o 3), titanium dioxide (TiO 2), magnesia (MgO), barium titanate (BaTiO 3) at least one.Surface treatment is carried out through coupling agent or surfactant in described nanometer oxide particle surface.Described structure sheaf fabric is nonwoven fabric, glass fabric, spandex fibre fabric.Through certain process, (silane resin acceptor kh-550, KH-560 and titanate coupling agent NDZ-201 are dissolved in obtained surface modifier solution in ethanol to described structure sheaf fabric surface respectively, coupling agent mass fraction is 1%, surface treatment is carried out to fabric, after through drying and processing).
embodiment 1
1) under 70 DEG C of conditions, after 7g nanometer PMMA is dried 2h, join in the DMAc solvent of 70g, uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVDF, stirring at normal temperature 0.5h, make it fully dissolve, obtain the nanometer PMMA/PVDF solution of mass ratio 7:3;
3) get 10mL ethanolic solution, add 0.0075g Nano-meter SiO_2 2particle, ultrasonic oscillation 1h;
4) by scattered Nano-meter SiO_2 2solution joins in PMMA/PVDF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.Fig. 1 is the ESEM spectrogram of the nano-fiber composite material containing PMMA of embodiment 1.
embodiment 2
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, joining 70g mass ratio is in the solvent of DMAc/ acetone=7:3, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add the PVF of 3g, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVF solution of mass ratio 7:3;
3) get 10mL ethanolic solution, add 0.0075g Nano-meter SiO_2 2particle, ultrasonic oscillation 1h;
4) by scattered Nano-meter SiO_2 2solution joins in PMMA/PVF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf nonwoven fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 3
1) under 90 DEG C of conditions, after 9.5g nanometer PMMA is dried 1h, joining 40g mass ratio is in the solvent of DMAc/ acetone=7:3, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 0.5gPVDF, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF solution of mass ratio 19:1;
3) get 10mL ethanolic solution, add 0.0075g nanometer Al 2o 3particle, ultrasonic oscillation 2h;
4) by scattered nanometer Al 2o 3solution joins in PMMA/PVDF solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 4
1) under 90 DEG C of conditions, after 9.5g nanometer PMMA is dried 1h, joining 40g mass ratio is in the solvent of DMF/ acetone=8:2, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 0.5gPVDF-co-HFP, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF solution of mass ratio 19:1;
3) get 10mL ethanolic solution, add 0.0075g nano-TiO 2particle, ultrasonic oscillation 2h;
4) by scattered nano-TiO 2solution joins in PMMA/PVDF-co-HFP solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated at least one side on structure sheaf glass fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.Fig. 2 is the ESEM spectrogram of the nano-fiber composite material containing PMMA of embodiment 4.
embodiment 5
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, joining 70g mass ratio is in the solvent of NMP/ acetone=9:1, and uniform stirring 6h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPTFE, stirring at normal temperature 0.5h, make it fully dissolve, obtain the nanometer PMMA/PTFE solution of mass ratio 7:3;
3) get 10mL ethanolic solution, add 0.03g nano-MgO particle, ultrasonic oscillation 2h;
4) scattered nano-MgO solution is joined in PMMA/PTFE solution, obtain the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf glass fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 6
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, join in the DMAc solvent of 70g, uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVDF-co-AN, stirring at normal temperature 0.5h, make it fully dissolve, obtain the nanometer PMMA/PVDF-co-AN solution of mass ratio 7:3;
3) get 10mL ethanolic solution, add 0.0075g nanometer BaTiO 3particle, ultrasonic oscillation 1h;
4) by scattered nanometer BaTiO 3solution joins in PMMA/PVDF-co-AN solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf nonwoven fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 7
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, join in the DMAc solvent of 70g, uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVDF, stirring at normal temperature 0.5h, make it fully dissolve, obtain the nanometer PMMA/PVDF solution of mass ratio 7:3;
3) get 10mL ethanolic solution, add 0.0075g nanometer BaTiO 3particle, ultrasonic oscillation 1h;
4) by scattered nanometer BaTiO 3solution joins in PMMA/PVDF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 8
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, join in the DMAc solvent of 70g, uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVF, stirring at normal temperature 0.5h, make it fully dissolve, obtain the nanometer PMMA/PVF solution of mass ratio 7:3;
3) get 10mL ethanolic solution, add 0.0075g nanometer BaTiO 3particle, ultrasonic oscillation 1h;
4) by scattered nanometer BaTiO 3solution joins in PMMA/PVF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 9
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, join in the DMAc solvent of 70g, uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPTFE, stirring at normal temperature 0.5h, make it fully dissolve, obtain the nanometer PMMA/PTFE solution of mass ratio 7:3;
3) get 10mL ethanolic solution, add 0.0075g nanometer BaTiO 3particle, ultrasonic oscillation 1h;
4) by scattered nanometer BaTiO 3solution joins in PMMA/PTFE solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 10
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, joining 70g mass ratio is in the solvent of DMAc/ acetone=7:3, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVDF, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF solution of mass ratio 7:3;
3) get 10mL ethanolic solution, adding 0.0075g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVDF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 11
1) under 90 DEG C of conditions, after 9.5g nanometer PMMA is dried 1h, joining 40g mass ratio is in the solvent of DMAc/ acetone=7:3, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 24wt%;
2) add 0.5gPVDF, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF solution of mass ratio 19:1;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVDF solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.Fig. 3 is the ESEM spectrogram of the nano-fiber composite material containing PMMA of embodiment 11.
embodiment 12
1) under 90 DEG C of conditions, after 9.5g nanometer PMMA is dried 1h, joining 40g mass ratio is in the solvent of DMF/ acetone=8:2, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 24wt%;
2) add 0.5gPVF, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVF solution of mass ratio 19:1;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVF solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 13
1) under 90 DEG C of conditions, after 9.5g nanometer PMMA is dried 1h, joining 40g mass ratio is in the solvent of DMF/ acetone=8:2, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 24wt%;
2) add 0.5gPVDF-co-HFP, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF-co-HFP solution of mass ratio 19:1;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVDF-co-HFP solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 14
1) under 90 DEG C of conditions, after 9.5g nanometer PMMA is dried 1h, joining 40g mass ratio is in the solvent of DMF/ acetone=8:2, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 24wt%;
2) add 0.5gPTFE, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PTFE solution of mass ratio 19:1;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PTFE solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated at least one side on structure sheaf glass fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 15
1) under 90 DEG C of conditions, after 9.5g nanometer PMMA is dried 1h, joining 40g mass ratio is in the solvent of DMF/ acetone=8:2, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 24wt%;
2) add 0.5gPVDF-co-AN, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF-co-AN solution of mass ratio 19:1;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVDF-co-AN solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 16
1) under 90 DEG C of conditions, after 9.5g nanometer PMMA is dried 1h, joining 40g mass ratio is in the solvent of DMF/ acetone=8:2, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 24wt%;
2) add 0.5gPVDF-co-AN, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF-co-AN solution of mass ratio 19:1;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVDF-co-AN solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 17
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, joining 70g mass ratio is in the solvent of DMF/ acetone=8:2, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVDF, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF solution of mass ratio 7:3;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVDF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 18
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, joining 70g mass ratio is in the solvent of DMF/ acetone=8:2, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVF, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVF solution of mass ratio 7:3;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.Fig. 4 is the ESEM spectrogram of the nano-fiber composite material containing PMMA of embodiment 18.
embodiment 19
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, joining 70g mass ratio is in the solvent of DMF/ acetone=8:2, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPTFE, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PTFE solution of mass ratio 7:3;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PTFE solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 20
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, joining 70g mass ratio is in the solvent of DMF/ acetone=8:2, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVDF-co-HFP, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF-co-HFP solution of mass ratio 7:3;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVDF-co-HFP solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 21
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, joining 70g mass ratio is in the solvent of DMF/ acetone=8:2, and uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVDF-co-AN, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF-co-AN solution of mass ratio 7:3;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVDF-co-AN solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 22
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, join in the solvent of 70gDMAc, uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVDF, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF solution of mass ratio 7:3;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVDF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 23
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, join in 70gDMAc solvent, uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVF, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVF solution of mass ratio 7:3;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 24
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, join in 70gDMAc solvent, uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPTFE, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PTFE solution of mass ratio 7:3;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PTFE solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 25
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, join in 70gDMAc solvent, uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVDF-co-HFP, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF-co-HFP solution of mass ratio 7:3;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVDF-co-HFP solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.
embodiment 26
1) under 90 DEG C of conditions, after 7g nanometer PMMA is dried 1h, join in 70gDMAc solvent, uniform stirring 4h under 60 DEG C of airtight conditions, makes it fully dissolve, and obtains the PMMA solution that concentration is 10wt%;
2) add 3gPVDF-co-AN, stirring at normal temperature 1h, make it fully dissolve, obtain the nanometer PMMA/PVDF-co-AN solution of mass ratio 7:3;
3) get 10mL ethanolic solution, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered Nano-meter SiO_2 2/ TiO 2solution joins in PMMA/PVDF-co-AN solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material containing PMMA.

Claims (5)

1. prepare a method for the nano-fiber composite material containing PMMA, it is characterized in that its step is as follows:
1) under 70 ~ 90 DEG C of conditions, after nanometer PMMA is dried, join in solvent, in confined conditions uniform stirring 4 ~ 6h, make it fully dissolve, obtain the PMMA solution that concentration is 10 ~ 24wt%;
2) add fluoro containing polymers polymer, stirring at normal temperature, make it fully dissolve, obtain nanometer PMMA: fluoro containing polymers polymer quality is than the solution of 2.33-19;
3) get 10mL ethanolic solution, add 0.0075-0.03g nanometer oxide particle, ultrasonic oscillation 1 ~ 2h;
4) scattered nano-oxide solution is joined step 2) in the PMMA/ fluoro containing polymers polymer solution that obtains, obtain the spinning solution that concentration is 15 ~ 25wt%;
5) spinning solution is evenly coated at least one side on structure sheaf fabric by electrostatic spinning technique, obtains the nano-fiber composite material containing PMMA;
At least one in solvent selected from acetone described in step 1), 1-METHYLPYRROLIDONE (NMP), dimethylacetylamide (DMAc), DMF (DMF);
Step 2) described in fluoro containing polymers polymer be Kynoar (PVDF), polyvinyl fluoride (PVF), Kynoar-hexafluoropropylene copolymer (PVDF-co-HFP), polytetrafluoroethylene (PTFE), Kynoar-acrylonitrile copolymer (PVDF-co-AN);
Nanometer oxide particle described in step 3) is silica (SiO 2), alundum (Al2O3) (Al 2o 3), titanium dioxide (TiO 2), magnesia (MgO), barium titanate (BaTiO 3) at least one.
2. method according to claim 1, is characterized in that, surface treatment is carried out through coupling agent or surfactant in the nanometer oxide particle surface described in step 3).
3. method according to claim 1, is characterized in that, the structure sheaf fabric described in step 5) is nonwoven fabric, glass fabric, spandex fibre fabric.
4. method according to claim 1, is characterized in that, the structure sheaf fabric surface described in step 5) is through modification.
5. according to claim 4described method, it is characterized in that, described modification, silane resin acceptor kh-550, KH-560 and titanate coupling agent NDZ-201 are dissolved in obtained surface modifier solution in ethanol respectively, coupling agent mass fraction is 1%, surface treatment is carried out to structure sheaf fabric, after through drying and processing.
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