CN103898771A - Method for preparing nano fiber composite material containing PMMA (Polymethyl Methacrylate) - Google Patents

Method for preparing nano fiber composite material containing PMMA (Polymethyl Methacrylate) Download PDF

Info

Publication number
CN103898771A
CN103898771A CN201410078191.3A CN201410078191A CN103898771A CN 103898771 A CN103898771 A CN 103898771A CN 201410078191 A CN201410078191 A CN 201410078191A CN 103898771 A CN103898771 A CN 103898771A
Authority
CN
China
Prior art keywords
pmma
solution
nano
nanometer
composite material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410078191.3A
Other languages
Chinese (zh)
Other versions
CN103898771B (en
Inventor
符思敏
费辉
周建伟
刘创
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201410078191.3A priority Critical patent/CN103898771B/en
Publication of CN103898771A publication Critical patent/CN103898771A/en
Application granted granted Critical
Publication of CN103898771B publication Critical patent/CN103898771B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Nonwoven Fabrics (AREA)
  • Multicomponent Fibers (AREA)

Abstract

The invention discloses a method for preparing a nano fiber composite material containing PMMA (Polymethyl Methacrylate). The method comprises the following steps: (1) after drying nano PMMA at 70-90 DEG C and adding the nano PMMA into a solvent; and uniformly agitating under a sealed condition at 60 DEG C and dissolving to obtain a PMMA solution; (2) adding a fluorine-containing high-molecular polymer and agitating at a room temperature for dissolving to obtain a nano PMMA/fluorine-containing high-molecular polymer solution; (3) adding an ethanol solution into nano oxide particles and carrying out ultrasonic vibration; (4) adding a dispersed nano oxide solution into the PMMA/fluorine-containing high-molecular polymer solution to obtain a spinning solution; and (5) uniformly coating at least one face of a structural layer fiber fabric with the spinning solution by an electrostatic spinning technology to form the nano fiber composite material containing the PMMA. According to the method, raw materials are easily available; the obtained nano fiber composite material has high mechanical strength, excellent heat stability, excellent weather resistance, high porosity and good light transmission and ventilation performances, has a function of blocking superfine particles and has very great application and industrialization values.

Description

The method of the nano-fiber composite material that preparation contains PMMA
Technical field
The present invention relates to extraordinary nano-fiber material field, relate in particular to a kind of method of preparing the nano-fiber composite material that contains PMMA.
Background technology
Polymethyl methacrylate (PMMA) claim again lucite, it is one of best polymeric material of the transparency, there are good optical lens photosensitiveness, 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 has limited its range of application to a certain extent.Therefore,, for meeting special condition of work, using function and the simple requirement of technique, be necessary on the basis that keeps PMMA superperformance its further modification.
Fluoro containing polymers polymer, because of fluorine atom polarizability minimum in all elements, make C-F bond polarity stronger, between the polymer molecule that contains C-F key, active force is little, thereby has excellent surface property (resistance to water, oil resistivity, stain resistance, self-cleaning property), optical property (low-refraction), electric property (high insulation, low-k).Because fluorine atom distributes more symmetrically in molecular structure, perfluor side chain is orientated outwardly again, and main polymer chain is formed " shielding protection " and avoids the direct effect of extraneous factor.Therefore, fluoro containing polymers polymer has a lot of special performances, as excellent heat endurance, chemical stability and weatherability, UV resistant and high-energy radiation.
Nanometer SiO 2the inorganic nano-particle of a kind of excellent performance, wide material sources, can strengthen organic polymer hardness, improve its ABRASION RESISTANCE, scratch resistance, ultravioletlight screening performance etc.Nano-TiO 2, also claiming nanometer titanium dioxide, shielding ultraviolet rays effect is strong, has good dispersiveness and weatherability, has anti-line, antibacterial, self-cleaning, ageing resistace, is usually used in the fields such as cosmetics, functional fibre, plastics, ink, coating, paint, fine ceramics.
How fluorine-containing this Molecularly Imprinted Polymer, 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 nano-fiber material that possesses the function that intercepts Nanoparticle is target and the direction that material supplier author lays siege to always, but there is no at present successful story.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of method of preparing the nano-fiber composite material that contains PMMA is provided.
A method of preparing the nano-fiber composite material that contains PMMA, step is as follows:
1) under 70～90 DEG C of conditions, after nanometer PMMA is dried, join in solvent, uniform stirring 4～6h in confined conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10～24wt%;
2) add fluoro containing polymers polymer, stirring at normal temperature, fully dissolves it, obtains nanometer PMMA: fluoro containing polymers polymer quality is than the solution of 2.33-19;
3) get 10 mL ethanolic solutions, add 0.0075-0.03g nanometer oxide particle, ultrasonic oscillation 1～2h;
4) scattered nano-oxide solution is joined to 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 in at least one side on structure sheaf fabric by electrostatic spinning technique, obtains the nano-fiber composite material that contains PMMA.
Solvent described in step 1) is selected from acetone, 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 are dissolved in respectively in ethanol and make surface modification agent solution, coupling agent mass fraction is 1%, and structure sheaf fabric is carried out to surface treatment, 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 the function that intercepts Nanoparticle, has great application and industrialization value.
Brief description of the drawings
Fig. 1 is the ESEM spectrogram of the nano-fiber composite material that contains PMMA of embodiment 1;
Fig. 2 is the ESEM spectrogram of the nano-fiber composite material that contains PMMA of embodiment 4;
Fig. 3 is the ESEM spectrogram of the nano-fiber composite material that contains PMMA of embodiment 11;
Fig. 4 is the ESEM spectrogram of the nano-fiber composite material that contains PMMA of embodiment 18.
Detailed description of the invention
The step of the method for the nano-fiber composite material that preparation contains PMMA is as follows:
1) under 70～90 DEG C of conditions, nanometer PMMA is dried after 1～2h, join in a certain amount of solvent, uniform stirring 4～6h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10～24wt%;
2) add a certain amount of fluoro containing polymers polymer, stirring at normal temperature 0.5～1h, fully dissolves it, obtains the nanometer PMMA/ fluoro containing polymers polymer solution of mass ratio 7:3 ~ 19:1;
3) get 10 mL ethanolic solutions, 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 in at least one side on structure sheaf fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains 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.(silane resin acceptor kh-550, KH-560 and titanate coupling agent NDZ-201 are dissolved in respectively and in ethanol, make surface modification agent solution through certain processing for described structure sheaf fabric surface, coupling agent mass fraction is 1%, fabric is carried out to surface treatment, after through drying and processing).
embodiment 1
1) under 70 DEG C of conditions, 7g nanometer PMMA is dried after 2h, join in the DMAc solvent of 70g, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVDF, stirring at normal temperature 0.5h, fully dissolves it, obtains the nanometer PMMA/PVDF solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, add 0.0075g nanometer SiO 2particle, ultrasonic oscillation 1h;
4) by scattered nanometer SiO 2solution joins in PMMA/PVDF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.Fig. 1 is the ESEM spectrogram of the nano-fiber composite material that contains PMMA of embodiment 1.
embodiment 2
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the solvent that 70g mass ratio is DMAc/ acetone=7:3, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add the PVF of 3g, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PVF solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, add 0.0075g nanometer SiO 2particle, ultrasonic oscillation 1h;
4) by scattered nanometer SiO 2solution joins in PMMA/PVF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf nonwoven fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 3
1) under 90 DEG C of conditions, 9.5g nanometer PMMA is dried after 1h, join in the solvent that 40g mass ratio is DMAc/ acetone=7:3, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 0.5g PVDF, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/PVDF solution of mass ratio 19:1;
3) get 10 mL ethanolic solutions, 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 in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 4
1) under 90 DEG C of conditions, 9.5g nanometer PMMA is dried after 1h, join in the solvent that 40g mass ratio is DMF/ acetone=8:2, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 0.5g PVDF-co-HFP, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/PVDF solution of mass ratio 19:1;
3) get 10 mL ethanolic solutions, 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 in at least one side on structure sheaf glass fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.Fig. 2 is the ESEM spectrogram of the nano-fiber composite material that contains PMMA of embodiment 4.
embodiment 5
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the solvent that 70g mass ratio is NMP/ acetone=9:1, uniform stirring 6h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PTFE, stirring at normal temperature 0.5h, fully dissolves it, obtains the nanometer PMMA/PTFE solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, 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 in at least one side on structure sheaf glass fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 6
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the DMAc solvent of 70g, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVDF-co-AN, stirring at normal temperature 0.5h, fully dissolves it, obtains the nanometer PMMA/ PVDF-co-AN solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, 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 in at least one side on structure sheaf nonwoven fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 7
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the DMAc solvent of 70g, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVDF, stirring at normal temperature 0.5h, fully dissolves it, obtains the nanometer PMMA/ PVDF solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, 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 in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 8
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the DMAc solvent of 70g, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVF, stirring at normal temperature 0.5h, fully dissolves it, obtains the nanometer PMMA/ PVF solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, 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 in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 9
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the DMAc solvent of 70g, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PTFE, stirring at normal temperature 0.5h, fully dissolves it, obtains the nanometer PMMA/ PTFE solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, 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 in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 10
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the solvent that 70g mass ratio is DMAc/ acetone=7:3, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVDF, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/PVDF solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, adding 0.0075g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/PVDF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 11
1) under 90 DEG C of conditions, 9.5g nanometer PMMA is dried after 1h, join in the solvent that 40g mass ratio is DMAc/ acetone=7:3, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 24wt%;
2) add 0.5g PVDF, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/PVDF solution of mass ratio 19:1;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/PVDF solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.Fig. 3 is the ESEM spectrogram of the nano-fiber composite material that contains PMMA of embodiment 11.
embodiment 12
1) under 90 DEG C of conditions, 9.5g nanometer PMMA is dried after 1h, join in the solvent that 40g mass ratio is DMF/ acetone=8:2, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 24wt%;
2) add 0.5g PVF, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/PVF solution of mass ratio 19:1;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/PVF solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 13
1) under 90 DEG C of conditions, 9.5g nanometer PMMA is dried after 1h, join in the solvent that 40g mass ratio is DMF/ acetone=8:2, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 24wt%;
2) add 0.5g PVDF-co-HFP, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PVDF-co-HFP solution of mass ratio 19:1;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PVDF-co-HFP solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 14
1) under 90 DEG C of conditions, 9.5g nanometer PMMA is dried after 1h, join in the solvent that 40g mass ratio is DMF/ acetone=8:2, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 24wt%;
2) add 0.5g PTFE, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PTFE solution of mass ratio 19:1;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/PTFE solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf glass fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 15
1) under 90 DEG C of conditions, 9.5g nanometer PMMA is dried after 1h, join in the solvent that 40g mass ratio is DMF/ acetone=8:2, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 24wt%;
2) add 0.5g PVDF-co-AN, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PVDF-co-AN solution of mass ratio 19:1;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PVDF-co-AN solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 16
1) under 90 DEG C of conditions, 9.5g nanometer PMMA is dried after 1h, join in the solvent that 40g mass ratio is DMF/ acetone=8:2, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 24wt%;
2) add 0.5g PVDF-co-AN, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PVDF-co-AN solution of mass ratio 19:1;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PVDF-co-AN solution, obtains the spinning solution that concentration is 25wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 17
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the solvent that 70g mass ratio is DMF/ acetone=8:2, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVDF, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PVDF solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PVDF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 18
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the solvent that 70g mass ratio is DMF/ acetone=8:2, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVF, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PVF solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PVF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.Fig. 4 is the ESEM spectrogram of the nano-fiber composite material that contains PMMA of embodiment 18.
 
embodiment 19
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the solvent that 70g mass ratio is DMF/ acetone=8:2, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PTFE, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PTFE solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PTFE solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 20
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the solvent that 70g mass ratio is DMF/ acetone=8:2, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVDF-co-HFP, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PVDF-co-HFP solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PVDF-co-HFP solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 21
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the solvent that 70g mass ratio is DMF/ acetone=8:2, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVDF-co-AN, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PVDF-co-AN solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PVDF-co-AN solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 22
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in the solvent of 70g DMAc, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVDF, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PVDF solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PVDF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 23
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in 70g DMAc solvent, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVF, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PVF solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PVF solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 24
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in 70g DMAc solvent, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PTFE, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PTFE solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PTFE solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 25
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in 70g DMAc solvent, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVDF-co-HFP, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PVDF-co-HFP solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PVDF-co-HFP solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.
embodiment 26
1) under 90 DEG C of conditions, 7g nanometer PMMA is dried after 1h, join in 70g DMAc solvent, uniform stirring 4h under 60 DEG C of airtight conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10wt%;
2) add 3g PVDF-co-AN, stirring at normal temperature 1h, fully dissolves it, obtains the nanometer PMMA/ PVDF-co-AN solution of mass ratio 7:3;
3) get 10 mL ethanolic solutions, adding 0.03g mass ratio is SiO 2/ TiO 2the nano particle of=4:1, ultrasonic oscillation 2h;
4) by scattered nanometer SiO 2/ TiO 2solution joins in PMMA/ PVDF-co-AN solution, obtains the spinning solution that concentration is 15wt%;
5) spinning solution is evenly coated in at least one side on structure sheaf spandex fibre fabric by electrostatic spinning technique, forms the nano-fiber composite material that contains PMMA.

Claims (8)

1. prepare a method for the nano-fiber composite material that contains 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, uniform stirring 4～6h in confined conditions, fully dissolves it, and obtaining concentration is the PMMA solution of 10～24wt%;
2) add fluoro containing polymers polymer, stirring at normal temperature, fully dissolves it, obtains nanometer PMMA: fluoro containing polymers polymer quality is than the solution of 2.33-19;
3) get 10 mL ethanolic solutions, add 0.0075-0.03g nanometer oxide particle, ultrasonic oscillation 1～2h;
4) scattered nano-oxide solution is joined to 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 in at least one side on structure sheaf fabric by electrostatic spinning technique, obtains the nano-fiber composite material that contains PMMA.
2. method according to claim 1, is characterized in that, the solvent described in step 1) is selected from acetone, at least one in 1-METHYLPYRROLIDONE (NMP), dimethylacetylamide (DMAc), DMF (DMF).
3. method according to claim 1, it is characterized in that 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).
4. method according to claim 1, is characterized in that, the 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.
5. 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).
6. 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.
7. method according to claim 1, is characterized in that, the structure sheaf fabric surface described in step 5) is through modification.
8. method according to claim 7, it is characterized in that, described modification, silane resin acceptor kh-550, KH-560 and titanate coupling agent NDZ-201 are dissolved in respectively and in ethanol, make surface modification agent solution, coupling agent mass fraction is 1%, structure sheaf fabric is carried out to surface treatment, after through drying and processing.
CN201410078191.3A 2014-03-05 2014-03-05 The method of the nano-fiber composite material of preparation containing PMMA Active CN103898771B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410078191.3A CN103898771B (en) 2014-03-05 2014-03-05 The method of the nano-fiber composite material of preparation containing PMMA

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410078191.3A CN103898771B (en) 2014-03-05 2014-03-05 The method of the nano-fiber composite material of preparation containing PMMA

Publications (2)

Publication Number Publication Date
CN103898771A true CN103898771A (en) 2014-07-02
CN103898771B CN103898771B (en) 2016-03-09

Family

ID=50990329

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410078191.3A Active CN103898771B (en) 2014-03-05 2014-03-05 The method of the nano-fiber composite material of preparation containing PMMA

Country Status (1)

Country Link
CN (1) CN103898771B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106939471A (en) * 2016-01-05 2017-07-11 新材料与产业技术北京研究院 A kind of silica nano fibrous membrane and its preparation method and application
CN108103666A (en) * 2017-12-29 2018-06-01 平潭诚信智创科技有限公司 A kind of preparation method for the three-dimensional nanofiber membrane for being used to filter PM2.5
CN110453372A (en) * 2019-08-01 2019-11-15 合肥国轩高科动力能源有限公司 Composite diaphragm and preparation method and application thereof
CN114232108A (en) * 2021-11-25 2022-03-25 中原工学院 Three-dimensional porous micro-nano composite material and preparation method and application thereof
CN114575000A (en) * 2022-02-25 2022-06-03 楚能新能源股份有限公司 Porous conductive fiber with PVDF as carbon source, and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101084052A (en) * 2004-11-19 2007-12-05 切夫里昂美国公司 Mixed matrix membrane with mesoporous particles and methods for making the same
CN101249387A (en) * 2008-04-09 2008-08-27 湖北工业大学 High flow and overpressure resistant hyperfiltration membrane with laminar hole structure and method of preparing the same
CN101534667A (en) * 2006-11-03 2009-09-16 纳幕尔杜邦公司 Liquid water resistant and water vapor permeable garments
CN101855069A (en) * 2007-11-13 2010-10-06 纳幕尔杜邦公司 The breathable waterproof garment
CN101990493A (en) * 2008-01-08 2011-03-23 纳幕尔杜邦公司 Liquid water resistant and water vapor permeable garments comprising hydrophobic treated nonwoven made from nanofibers
CN101992030A (en) * 2010-08-27 2011-03-30 东华大学 Organic and inorganic matter modified polyvinylidene fluoride five-hole fiber ultrafiltration membrane and preparation thereof
CN102430352A (en) * 2011-09-07 2012-05-02 三达膜科技（厦门）有限公司 Polyvinylidene fluoride organic-inorganic hybrid membrane and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101084052A (en) * 2004-11-19 2007-12-05 切夫里昂美国公司 Mixed matrix membrane with mesoporous particles and methods for making the same
CN101534667A (en) * 2006-11-03 2009-09-16 纳幕尔杜邦公司 Liquid water resistant and water vapor permeable garments
CN101855069A (en) * 2007-11-13 2010-10-06 纳幕尔杜邦公司 The breathable waterproof garment
CN101990493A (en) * 2008-01-08 2011-03-23 纳幕尔杜邦公司 Liquid water resistant and water vapor permeable garments comprising hydrophobic treated nonwoven made from nanofibers
CN101249387A (en) * 2008-04-09 2008-08-27 湖北工业大学 High flow and overpressure resistant hyperfiltration membrane with laminar hole structure and method of preparing the same
CN101992030A (en) * 2010-08-27 2011-03-30 东华大学 Organic and inorganic matter modified polyvinylidene fluoride five-hole fiber ultrafiltration membrane and preparation thereof
CN102430352A (en) * 2011-09-07 2012-05-02 三达膜科技（厦门）有限公司 Polyvinylidene fluoride organic-inorganic hybrid membrane and preparation method thereof

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
M. SETHUPATHY ET AL.: "《Preparation of PVDF/SiO2 Composite Nanofiber Membrane Using Electrospinning for Polymer Electrolyte Analysis》", 《SOFT NANOSCIENCE LETTERS》 *
M. STOLARSKA ET AL.: "《Structure, transport properties and interfacial stability of PVdF/HFP electrolytes containing modified inorganic filler》", 《ELECTROCHIMICA ACTA》 *
XUEJUAN ZHAO ET AL.: "《Hydrophilicity and crystallization behavior of PVDF/PMMA/TiO2(SiO2) composites prepared by in situ polymerization》", 《J POLYM RES》 *
任彦彦: "《纳米二氧化硅纤维的制备及其对聚偏二氟乙烯结晶结构的影响》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *
傅政: "《橡胶材料及工艺学》", 30 November 2013, 化学工业出版社 *
孙鸿: "《纳米TiO2+Al2O3/PVDF超滤膜的制备及应用研究》", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 *
曹江: "《双亲性纳米TiO2复合体的制备及其在聚偏氟乙烯(PVDF)超滤膜中的应用研究》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *
李晓云: "《锂离子电池用PVDF/PMMA电纺膜的制备及电化学性能研究》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 *
盛夏: "《织布支撑聚偏氟乙烯/纳米TiO2共混模的制备及其在MBR中抗污染性能的研究》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *
钱苗根: "《现代表面工程》", 30 September 2012, 上海交通大学出版社 *
韩领: "《静电纺丝法制备无机改性锂离子电池隔膜》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》 *
顾宜等: "《高分子材料设计与应用》", 31 May 2011, 化学工业出版社 *
马吉全: "《聚偏氟乙烯—全氟磺酸共混超滤膜及电纺聚醚砜纳米纤维微滤膜的制备》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106939471A (en) * 2016-01-05 2017-07-11 新材料与产业技术北京研究院 A kind of silica nano fibrous membrane and its preparation method and application
CN108103666A (en) * 2017-12-29 2018-06-01 平潭诚信智创科技有限公司 A kind of preparation method for the three-dimensional nanofiber membrane for being used to filter PM2.5
CN110453372A (en) * 2019-08-01 2019-11-15 合肥国轩高科动力能源有限公司 Composite diaphragm and preparation method and application thereof
CN114232108A (en) * 2021-11-25 2022-03-25 中原工学院 Three-dimensional porous micro-nano composite material and preparation method and application thereof
CN114232108B (en) * 2021-11-25 2022-11-22 中原工学院 Three-dimensional porous micro-nano composite material and preparation method and application thereof
CN114575000A (en) * 2022-02-25 2022-06-03 楚能新能源股份有限公司 Porous conductive fiber with PVDF as carbon source, and preparation method and application thereof

Also Published As

Publication number Publication date
CN103898771B (en) 2016-03-09

Similar Documents

Publication Publication Date Title
CN103898771B (en) The method of the nano-fiber composite material of preparation containing PMMA
Xu et al. Preparation and properties of hydrophobically modified nano-SiO2 with hexadecyltrimethoxysilane
Chen et al. Electrospinning fabrication of high strength and toughness polyimide nanofiber membranes containing multiwalled carbon nanotubes
Ahmadpoor et al. The optical properties of PVA/TiO2 composite nanofibers
CN101165083A (en) Ultra-hydrophobic polystyrene thin film enhanced by nano silicon dioxide particles and preparation method thereof
Gong et al. Electrospun nanofibrous membranes: a versatile medium for waterproof and breathable application
CN106823866B (en) A kind of separating and filtering film and its preparation method and application
CN104073116A (en) Preparation method of super-amphiphobic coating
Abdelmoez et al. Electrospun PDA‐CA nanofibers toward hydrophobic coatings
Wu et al. Improving electrical, mechanical, thermal and hydrophobic properties of waterborne acrylic resin-glycidyl methacrylate (GMA) by adding multi-walled carbon nanotubes
Chagas et al. UV-induced switchable wettability between superhydrophobic and superhydrophilic polypropylene surfaces with an improvement of adhesion properties
CN104073084A (en) PVDF (Polyvinylidene Fluoride) coating material with self-cleaning property and preparation method and application thereof
CN107383708A (en) A kind of high molecule plastic master batch and its preparation technology
Zhang et al. Superhydrophobic and breathable polyacrylonitrile/silica/perfluoroalkyl ethyl methacrylate nanofiber membranes prepared by solution blow spinning
CN104356584A (en) Fiber composite material
CN106519641A (en) Electrostrictive composite material, and preparation method and applications thereof
CN106633299B (en) A kind of polyethylene/montmorillonite carried titanium dioxide composite material and preparation method
KR102281404B1 (en) Coating method of super-hydrophobic surface
Yang et al. Dispersion stability of nano-Sb2O3 particles modified with polyethylene glycol
CN105062149B (en) A kind of method of modifying of nano titanium oxide
Maharani et al. Nanosilica‐Chitosan Composite Coating on Cotton Fabrics
CN107313246A (en) A kind of anti-ultraviolet ageing method of modifying of polyester fiber
KR20170049704A (en) High durable nanoparticles having water repellent and antibiotic, and coating composition comprising the same, and preparation method thereof
CN104845165A (en) Enhanced PET/PTT/nano bamboo carbon-based composite material
CN104230230A (en) Antimicrobial architectural paint

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Fu Simin

Inventor after: Fei Hui

Inventor after: Wang Long

Inventor before: Fu Simin

Inventor before: Fei Hui

Inventor before: Zhou Jianwei

Inventor before: Liu Chuang