CN107938169B - A kind of POSS modified nano fiber film and its preparation method and application - Google Patents
A kind of POSS modified nano fiber film and its preparation method and application Download PDFInfo
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- CN107938169B CN107938169B CN201711401095.8A CN201711401095A CN107938169B CN 107938169 B CN107938169 B CN 107938169B CN 201711401095 A CN201711401095 A CN 201711401095A CN 107938169 B CN107938169 B CN 107938169B
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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
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/10—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained by reactions only involving carbon-to-carbon unsaturated bonds as constituent
-
- 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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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Artificial Filaments (AREA)
Abstract
The invention belongs to micro/nano fibrous membrane material field, a kind of POSS modified nano fiber film and its preparation method and application is disclosed.PVDF and PMMA are dissolved in organic solvent and obtain electrostatic spinning solution；MA-POSS and OAPS function monomer is dissolved in organic solvent and obtains electrostatic solution；Photoinitiator is added into electrostatic spinning solution, then it is placed in electrostatic spinning machine together with electrostatic solution, electrostatic spinning and electrostatic spraying are started simultaneously under ultraviolet irradiation condition, it is after spinning that gained tunica fibrosa is dry, obtain POSS modified nano fiber film.The present invention is modified nano fibrous membrane using MA-POSS and OAPS function monomer, can significantly improve the thermal stability and mechanical strength of nano fibrous membrane；And spinning fibre film reaction activity and separation adsorption function etc. are assigned, increase the application field of spinning fibre film.
Description
Technical field
The invention belongs to micro/nano fibrous membrane material fields, and in particular to a kind of POSS modified nano fiber film and its preparation side
Method and application.
Background technique
Electrostatic spinning (Electrospinning) refers to polymer solution/melt drop under High Voltage electrostatic field
Itself surface tension and viscoplasticity power is overcome to form the special fibre that tip jet spinning occurs for conical (taylor cone) by spherical shape
Tie up manufacturing process.Electrostatic spinning is to prepare one of high polymer nanometer fiber membrane the most simple effective method now, can directly from
The nano-scale that there is other materials to be unable to reach for continuous fiber and prepared fiber is prepared in polymer and composite material,
Generally between tens nanometers to thousands of nanometers, the nano-fiber film of preparation exists generally in the form of non-woven fabrics, mainly
Feature is that the fiber of weaving has significant specific surface area advantage, higher porosity and preferable hole link, and is easy to get
To the nanofiber of good space three-dimensional structure.In addition, experimental facilities and cost is relatively low, spinning fibre has compared with high yield pulp1, is applicable in
In the preparation of a variety of different substrates and composite material, these remarkable advantages make electrostatic spinning in terms of the preparation of nano-fiber film
Extensive concern and further investigation with far-reaching potential using value, in recent decades by researcher.Although Static Spinning
Silk prepares fiber membrane technology with the above advantage, but since spinning fibre film is the non-woven form of haphazard packing, fiber base material
Most of is in chemical inertness, causes tunica fibrosa there are some obvious deficiencies, and general toughness is poor, and mechanical strength is lower, and reaction is lived
Property it is low, function is more single, it is difficult to have certain specific purposes, limit its application range significantly.
A kind of special shape of the electrostatic spraying as electrospinning can be divided small molecule spinning solution in a kind of spraying form
It dissipates, the unique mode of action enables small molecule uniformly to coat spinning fibre in conjunction with electrospinning, to promote the property of spinning film
Energy.Ultraviolet (UV) photocuring technology is that one kind causes intermolecular functional group's generation polymerization reaction generation friendship under ultraviolet irradiation condition
It is coupled the fast chemical reaction technology of structure.Fast with polymerization speed, efficiency of initiation is high, and operation is simple and easy to do, required energy consumption
It is low, energy-saving and environment friendly, it is applied widely the advantages that.The specific mode of action is photoinitiator under the irradiation of strong ultraviolet light, is drawn
Send out agent in a very short period of time (about 10-14S) intramolecule energy increases, from ground state transition to unstable excited singlet, place
May be released energy in a manner of relaxation or phosphorescent emissions etc. in the initiator molecule of excitation state and return to ground state, thus with unimolecule or
It interacts between polymolecular, in the activity for generating free radicals (Free-radical) or cationic (Cationic ion)
The heart, further to cause polymerization.
The cage-type silsesquioxane (POSS) of specific structure is referring to for a kind of cage-type silsesquioxane, also known as polyhedron
Oligomeric silsesquioxane is a kind of nanoscale molecular cluster.As the important construction unit of nano-hybrid material, POSS
Function monomer general molecular formula can be abbreviated as [RSiO3/2]n, there is determining three-dimensional cage structure and special topology geometric form
State, extremely strong MOLECULE DESIGN, internal structure are the inorganic kernel of polyhedron of Si-O-Si composition, and apex angle Si atom can link more
The different reactive or non-reacted R functional group of kind.Due to Si-O-Si structure class special in POSS function monomer molecule
Type makes it have good thermal stability and excellent mechanical strength, therefore the micro/nano fibrous membrane material that POSS is modified can be shown
Writing improves its mechanical property and calorifics intensity；On the other hand POSS function monomer can be carried out from molecule according to required function
Design, when apex angle R functional group difference, can assign the different response characteristic of POSS and further functionalization feasibility.But such as
What is compound by POSS and tunica fibrosa progress, and fiber film toughness is poor, mechanical strength is lower, reactivity is low to overcome, function compared with
It is the direction of those skilled in the art's research for single deficiency.
Summary of the invention
In place of the above shortcoming and defect of the existing technology, the primary purpose of the present invention is that providing a kind of POSS
The preparation method of modified nano fiber film.
Another object of the present invention is to provide a kind of POSS modified nano fiber films being prepared by the above method.
A further object of the present invention is to provide above-mentioned POSS modified nano fiber films in medical nano fiber, biological core
Piece, catalyst carrier, nano-sensor, battery dielectric material, flexible display material, photoelectric conversion material or supercapacitor etc.
Application in material or field.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of POSS modified nano fiber film, comprising the following steps:
(1) Kynoar (PVDF) and polymethyl methacrylate (PMMA) are added in organic solvent, heating is stirred
It mixes and is uniformly dissolved, obtain polymer electrostatic spinning solution；
(2) by gamma-methyl allyl acyloxypropyl cage-type silsesquioxane (MA-POSS) and eight anilino- cage model sesquialter silicon oxygen
Alkane (OAPS) function monomer is added in organic solvent, and stirring and dissolving is uniform, obtains POSS function monomer electrostatic solution；
(3) photoinitiator is added in polymer electrostatic spinning solution obtained by the step (1), then by its in step (2)
Gained POSS function monomer electrostatic solution is placed in electrostatic spinning machine together, starts simultaneously at electrostatic spinning under ultraviolet irradiation condition
And electrostatic spraying, EFI, which goes out POSS function monomer, while electrospinning high polymer nanometer fiber silk makes it be evenly distributed on tunica fibrosa
In, graft polymerization reaction occurs for the functional group on polymer matrix and POSS function monomer under the irradiation of ultraviolet light, and spinning is complete
It is after finishing that gained tunica fibrosa is dry, obtain POSS modified nano fiber film.
Preferably, organic solvent described in step (1) is the mixed solvent of n,N-dimethylacetamide and acetone；It is described
The volume ratio of DMAC N,N' dimethyl acetamide and acetone is preferably 4:6.
Preferably, the mass ratio of PVDF and PMMA described in step (1) is (1~5): 1；The polymer electrostatic spinning is molten
The total concentration of PVDF and PMMA is 18wt.% in liquid.
MA-POSS and OAPS function monomer structure described in step (2) is shown below respectively, and two kinds of function monomers can lead to
Existing disclosed method is crossed to be prepared.
Preferably, organic solvent described in step (2) is methylene chloride.
Preferably, the mass ratio of MA-POSS and OAPS described in step (2) is 1:(1~3).
Preferably, the total concentration of MA-POSS and OAPS is 2 in POSS function monomer electrostatic solution described in step (2)
~10wt.%.
Preferably, the volume of polymer electrostatic spinning solution described in step (3) and POSS function monomer electrostatic solution
Than for 1:1.
Preferably, electrostatic spinning described in step (3) and the condition of electrostatic spraying are as follows: syringe needle is with receiver board distance
15cm, spinning solution and spraying flow velocity are 3.5ml/h, spinning voltage 15kv.
Preferably, the power level of ultraviolet lighting described in step (3) is 400-1000mW/cm2。
A kind of POSS modified nano fiber film, is prepared by the above method.
Above-mentioned POSS modified nano fiber film medical nano fiber, biochip, catalyst carrier, nano-sensor,
Application in the materials such as battery dielectric material, flexible display material, photoelectric conversion material or supercapacitor or field.
The principle of the present invention are as follows: the present invention is modified tunica fibrosa using grafting mono-/multi- function POSS function monomer.
MA-POSS (gamma-methyl allyl acyloxypropyl cage-type silsesquioxane) is a kind of methacrylate containing double bond functional group
Silsesquioxane, the active functional group on molecule can assign spinning fibre film reaction activity, make its can further functionalization it is derivative
Change；Meanwhile MA-POSS may act as cross-linking monomer, and cross-linked network structure is formed in tunica fibrosa, thus the boundary of the tunica fibrosa of enhancing
Face interaction, the performance of promote the calorifics and mechanical property of spinning film, and assign its distinct optical, electricity etc..OAPS
There is good lyophily because of the amido functional group on its molecule, unique separation adsorption function of spinning film etc. can be assigned,
Increase the application field of spinning fibre film.The present invention is used in electrospinning in combination with EFI mode, and the two, which synchronizes, to be carried out POSS
Function monomer is well dispersed on spinning fibre surface.Promote to be distributed in spinning fibre film using the cured reaction formation of ultraviolet light
On POSS function monomer and membrane material macromolecule occur graft reaction, function monomer is coated in film surface,
A stable organic whole is formed, and brings it about functionalization derivatization reaction further to prepare with special superiority
The functional film material of energy.
Preparation method of the invention and obtained product have the following advantages that and the utility model has the advantages that
(1) present invention carries out stable combination using POSS function monomer and nano fibrous membrane, can significantly improve
The thermal stability and mechanical strength of nano fibrous membrane.
(2) MA-POSS can assign spinning fibre film reaction activity as the active functional group on molecule, keep it further
Functionalization derivatization；OAPS has good lyophily because of the amido functional group on its molecule, and it is unique can to assign spinning film
Separation adsorption function etc., increase the application field of spinning fibre film.
Detailed description of the invention
Fig. 1 is the SEM figure of POSS modified nano fiber film obtained by the embodiment of the present invention.
Fig. 2 is the infrared spectrogram of POSS modified nano fiber film obtained by the embodiment of the present invention.
Specific embodiment
Present invention will now be described in further detail with reference to the embodiments and the accompanying drawings, but embodiments of the present invention are unlimited
In this.
Embodiment 1
(1) in 25ml serum bottle, 4ml n,N-dimethylacetamide (DMAc) and 6ml acetone are measured respectively with graduated cylinder
(ACE) prepare mixed solvent, according to the concentration of polymer solution of 18wt.% weigh respectively mass ratio be 5:1 PVDF 1.31g with
PMMA 0.26g, then the PVDF of weighing and PMMA are poured into the mixed solvent, it is put into magneton and is heated with magnetic stirring apparatus can be heated
It is stirred dissolution to 50 DEG C, room temperature is cooled to after completely dissolution and continues to stir 18h, it is molten to obtain uniform polymer electrostatic spinning
Liquid.
(2) it according to the gross mass of PVDF and PMMA, determines POSS function monomer mass concentration 2wt.%, weighs quality respectively
It is 15.7mg more each than for the MA-POSS and OAPS of 1:1, the methylene chloride (DCM) of 10ml is measured as solvent, by the MA- of weighing
POSS and OAPS function monomer dissolves in DCM, is put into magneton magnetic stirring apparatus stirring and dissolving 3h at room temperature, obtains uniform
POSS function monomer electrostatic solution.
(3) take the polymer electrostatic spinning solution prepared in 5ml step (1) with aluminium foil cladding syringe, and to its
Spinning solution matrix is made in the middle photoinitiator that 1wt.% is added, and connects needle tubing and syringe needle, and wherein needle tubing need to all be wrapped with aluminium foil
Winding is covered to be protected from light, then preparation POSS function monomer electrostatic in the step of using another syringe draws equal amounts of the same race (2)
Solution, connects needle tubing and syringe needle is latter with being placed on electrostatic spinning machine, is covered on spinning machine cylinder and is made with an aluminium foil greatly
For fiber bearing plate, control syringe needle and receiver board be maintained at distance be 15cm, the spinning flow velocity set and hydrojet speed as
3.5ml/h and spinning voltage are 15kv, and electrospinning and EFI identical flow velocity synchronize completion simultaneously, are opened after setting completed purple
Outer lamp, setting intensity of illumination are 400mW/cm2Start to prepare nano fibrous membrane, aluminium foil is taken off after spinning and is put into high temperature baking
It is dry in case, obtain POSS modified nano fiber film.
Embodiment 2
(1) in 25ml serum bottle, 4ml n,N-dimethylacetamide (DMAc) and 6ml acetone are measured respectively with graduated cylinder
(ACE) prepare mixed solvent, according to the concentration of polymer solution of 18wt.% weigh respectively mass ratio be 5:1 PVDF 1.31g with
PMMA 0.26g, then the PVDF of weighing and PMMA are poured into the mixed solvent, it is put into magneton and is heated with magnetic stirring apparatus can be heated
It is stirred dissolution to 50 DEG C, room temperature is cooled to after completely dissolution and continues to stir 18h, it is molten to obtain uniform polymer electrostatic spinning
Liquid.
(2) it according to the gross mass of PVDF and PMMA, determines POSS function monomer mass concentration 5wt.%, weighs quality respectively
Than MA-POSS 19.62mg and the OAPS 58.88mg for 1:3, the methylene chloride (DCM) of 10ml is measured as solvent, will be weighed
MA-POSS and OAPS function monomer dissolve in DCM, be put into magneton magnetic stirring apparatus stirring and dissolving 3h at room temperature, obtain
One POSS function monomer electrostatic solution.
(3) take the polymer electrostatic spinning solution prepared in 5ml step (1) with aluminium foil cladding syringe, and to its
Spinning solution matrix is made in the middle photoinitiator that 1wt.% is added, and connects needle tubing and syringe needle, and wherein needle tubing need to all be wrapped with aluminium foil
Winding is covered to be protected from light, then preparation POSS function monomer electrostatic in the step of using another syringe draws equal amounts of the same race (2)
Solution, connects needle tubing and syringe needle is latter with being placed on electrostatic spinning machine, is covered on spinning machine cylinder and is made with an aluminium foil greatly
For fiber bearing plate, control syringe needle and receiver board be maintained at distance be 15cm, the spinning flow velocity set and hydrojet speed as
3.5ml/h and spinning voltage are 15kv, and electrospinning and EFI identical flow velocity synchronize completion simultaneously, are opened after setting completed purple
Outer lamp, setting intensity of illumination are that 1000mW/cm2 starts to prepare nano fibrous membrane, take aluminium foil off after spinning and are put into high temperature
It is dry in baking oven, obtain POSS modified nano fiber film.
Embodiment 3
(1) in 25ml serum bottle, 4ml n,N-dimethylacetamide (DMAc) and 6ml acetone are measured respectively with graduated cylinder
(ACE) mixed solvent is prepared, weighs the PVDF 1.20g that mass ratio is 3.2:1 respectively according to the concentration of polymer solution of 18wt.%
With PMMA 0.37g, then the PVDF of weighing and PMMA poured into the mixed solvent, is put into magneton and is added with magnetic stirring apparatus can be heated
Heat is stirred dissolution to 50 DEG C, is cooled to room temperature after completely dissolution and continues to stir 18h, obtains uniform polymer electrostatic spinning
Solution.
(2) it according to the gross mass of PVDF and PMMA, determines POSS function monomer mass concentration 8wt.%, weighs quality respectively
Than MA-POSS 41.87mg and the OAPS 83.73mg for 1:2, the methylene chloride (DCM) of 10ml is measured as solvent, will be weighed
MA-POSS and OAPS function monomer dissolve in DCM, be put into magneton magnetic stirring apparatus stirring and dissolving 3h at room temperature, obtain
One POSS function monomer electrostatic solution.
(3) take the polymer electrostatic spinning solution prepared in 5ml step (1) with aluminium foil cladding syringe, and to its
Spinning solution matrix is made in the middle photoinitiator that 1wt.% is added, and connects needle tubing and syringe needle, and wherein needle tubing need to all be wrapped with aluminium foil
Winding is covered to be protected from light, then preparation POSS function monomer electrostatic in the step of using another syringe draws equal amounts of the same race (2)
Solution, connects needle tubing and syringe needle is latter with being placed on electrostatic spinning machine, is covered on spinning machine cylinder and is made with an aluminium foil greatly
For fiber bearing plate, control syringe needle and receiver board be maintained at distance be 15cm, the spinning flow velocity set and hydrojet speed as
3.5ml/h and spinning voltage are 15kv, and electrospinning and EFI identical flow velocity synchronize completion simultaneously, and it is post-opening that setting completed
Ultraviolet lamp, setting intensity of illumination are that 400mW/cm2 starts to prepare nano fibrous membrane, take aluminium foil off after spinning and are put into high temperature
It is dry in baking oven, obtain POSS modified nano fiber film.
Embodiment 4
(1) in 25ml serum bottle, 4ml n,N-dimethylacetamide (DMAc) and 6ml acetone are measured respectively with graduated cylinder
(ACE) prepare mixed solvent, according to the concentration of polymer solution of 18wt.% weigh respectively mass ratio be 3:1 PVDF 1.18g with
PMMA 0.39g, then the PVDF of weighing and PMMA are poured into the mixed solvent, it is put into magneton and is heated with magnetic stirring apparatus can be heated
It is stirred dissolution to 50 DEG C, room temperature is cooled to after completely dissolution and continues to stir 18h, it is molten to obtain uniform polymer electrostatic spinning
Liquid.
(2) it according to the gross mass of PVDF and PMMA, determines POSS function monomer mass concentration 2wt.%, weighs quality respectively
It is 15.7mg more each than for the MA-POSS and OAPS of 1:1, the methylene chloride (DCM) of 10ml is measured as solvent, by the MA- of weighing
POSS and OAPS function monomer dissolves in DCM, is put into magneton magnetic stirring apparatus stirring and dissolving 3h at room temperature, obtains uniform
POSS function monomer electrostatic solution.
(3) take the polymer electrostatic spinning solution prepared in 5ml step (1) with aluminium foil cladding syringe, and to its
Spinning solution matrix is made in the middle photoinitiator that 2wt.% is added, and connects needle tubing and syringe needle, and wherein needle tubing need to all be wrapped with aluminium foil
Winding is covered to be protected from light, then preparation POSS function monomer electrostatic in the step of using another syringe draws equal amounts of the same race (2)
Solution, connects needle tubing and syringe needle is latter with being placed on electrostatic spinning machine, is covered on spinning machine cylinder and is made with an aluminium foil greatly
For fiber bearing plate, control syringe needle and receiver board be maintained at distance be 15cm, the spinning flow velocity set and hydrojet speed as
3.5ml/h and spinning voltage are 15kv, and electrospinning and EFI identical flow velocity synchronize completion simultaneously, are opened after setting completed purple
Outer lamp, setting intensity of illumination are that 400mW/cm2 starts to prepare nano fibrous membrane, take aluminium foil off after spinning and are put into high temperature baking
It is dry in case, obtain POSS modified nano fiber film.
Embodiment 5
(1) in 25ml serum bottle, 4ml n,N-dimethylacetamide (DMAc) and 6ml acetone are measured respectively with graduated cylinder
(ACE) prepare mixed solvent, according to the concentration of polymer solution of 18wt.% weigh respectively mass ratio be 3:1 PVDF 1.18g with
PMMA 0.39g, then the PVDF of weighing and PMMA are poured into the mixed solvent, it is put into magneton and is heated with magnetic stirring apparatus can be heated
It is stirred dissolution to 50 DEG C, room temperature is cooled to after completely dissolution and continues to stir 18h, it is molten to obtain uniform polymer electrostatic spinning
Liquid.
(2) it according to the gross mass of PVDF and PMMA, determines POSS function monomer mass concentration 8wt.%, weighs quality respectively
Than MA-POSS 31.40mg and the OAPS 94.20mg for 1:3, the methylene chloride (DCM) of 10ml is measured as solvent, will be weighed
MA-POSS and OAPS function monomer dissolve in DCM, be put into magneton magnetic stirring apparatus stirring and dissolving 3h at room temperature, obtain
One POSS function monomer electrostatic solution.
(3) take the polymer electrostatic spinning solution prepared in 5ml step (1) with aluminium foil cladding syringe, and to its
Spinning solution matrix is made in the middle photoinitiator that 2wt.% is added, and connects needle tubing and syringe needle, and wherein needle tubing need to all be wrapped with aluminium foil
Winding is covered to be protected from light, then preparation POSS function monomer electrostatic in the step of using another syringe draws equal amounts of the same race (2)
Solution, connects needle tubing and syringe needle is latter with being placed on electrostatic spinning machine, is covered on spinning machine cylinder and is made with an aluminium foil greatly
For fiber bearing plate, control syringe needle and receiver board be maintained at distance be 15cm, the spinning flow velocity set and hydrojet speed as
3.5ml/h and spinning voltage are 15kv, and electrospinning and EFI identical flow velocity synchronize completion simultaneously, are opened after setting completed purple
Outer lamp, setting intensity of illumination are that 1000mW/cm2 starts to prepare nano fibrous membrane, take aluminium foil off after spinning and are put into high temperature
It is dry in baking oven, obtain POSS modified nano fiber film.
Embodiment 6
(1) in 25ml serum bottle, 4ml n,N-dimethylacetamide (DMAc) and 6ml acetone are measured respectively with graduated cylinder
(ACE) prepare mixed solvent, according to the concentration of polymer solution of 18wt.% weigh respectively mass ratio be 1:1 PVDF 0.78g with
PMMA 0.78g, then the PVDF of weighing and PMMA are poured into the mixed solvent, it is put into magneton and is heated with magnetic stirring apparatus can be heated
It is stirred dissolution to 50 DEG C, room temperature is cooled to after completely dissolution and continues to stir 18h, it is molten to obtain uniform polymer electrostatic spinning
Liquid.
(2) it according to the gross mass of PVDF and PMMA, determines POSS function monomer mass concentration 10wt.%, weighs matter respectively
Amount measures the methylene chloride (DCM) of 10ml as solvent, will claim than MA-POSS 52.0mg and the OAPS 104.0mg for being 1:2
MA-POSS the and OAPS function monomer of amount dissolves in DCM, is put into magneton magnetic stirring apparatus stirring and dissolving 3h at room temperature, obtains
Uniform POSS function monomer electrostatic solution.
(3) take the polymer electrostatic spinning solution prepared in 5ml step (1) with aluminium foil cladding syringe, and to its
Spinning solution matrix is made in the middle photoinitiator that 2wt.% is added, and connects needle tubing and syringe needle, and wherein needle tubing need to all be wrapped with aluminium foil
Winding is covered to be protected from light, then preparation POSS function monomer electrostatic in the step of using another syringe draws equal amounts of the same race (2)
Solution, connects needle tubing and syringe needle is latter with being placed on electrostatic spinning machine, is covered on spinning machine cylinder and is made with an aluminium foil greatly
For fiber bearing plate, control syringe needle and receiver board be maintained at distance be 15cm, the spinning flow velocity set and hydrojet speed as
3.5ml/h and spinning voltage are 15kv, and electrospinning and EFI identical flow velocity synchronize completion simultaneously, are opened after setting completed purple
Outer lamp, setting intensity of illumination are that 20%400mW/cm2 starts to prepare nano fibrous membrane, take aluminium foil off after spinning and are put into height
It is dry in warm baking oven, obtain POSS modified nano fiber film.
Embodiment 7
(1) in 25ml serum bottle, 4ml n,N-dimethylacetamide (DMAc) and 6ml acetone are measured respectively with graduated cylinder
(ACE) prepare mixed solvent, according to the concentration of polymer solution of 18wt.% weigh respectively mass ratio be 1:1 PVDF 0.78g with
PMMA 0.78g, then the PVDF of weighing and PMMA are poured into the mixed solvent, it is put into magneton and is heated with magnetic stirring apparatus can be heated
It is stirred dissolution to 50 DEG C, room temperature is cooled to after completely dissolution and continues to stir 18h, it is molten to obtain uniform polymer electrostatic spinning
Liquid.
(2) it according to the gross mass of PVDF and PMMA, determines POSS function monomer mass concentration 2wt.%, weighs quality respectively
It is 15.6mg more each than for the MA-POSS and OAPS of 1:1, the methylene chloride (DCM) of 10ml is measured as solvent, by the MA- of weighing
POSS and OAPS function monomer dissolves in DCM, is put into magneton magnetic stirring apparatus stirring and dissolving 3h at room temperature, obtains uniform
POSS function monomer electrostatic solution.
(3) take the polymer electrostatic spinning solution prepared in 5ml step (1) with aluminium foil cladding syringe, and to its
Spinning solution matrix is made in the middle photoinitiator that 2wt.% is added, and connects needle tubing and syringe needle, and wherein needle tubing need to all be wrapped with aluminium foil
Winding is covered to be protected from light, then preparation POSS function monomer electrostatic in the step of using another syringe draws equal amounts of the same race (2)
Solution, connects needle tubing and syringe needle is latter with being placed on electrostatic spinning machine, is covered on spinning machine cylinder and is made with an aluminium foil greatly
For fiber bearing plate, control syringe needle and receiver board be maintained at distance be 15cm, the spinning flow velocity set and hydrojet speed as
3.5ml/h and spinning voltage are 15kv, and electrospinning and EFI identical flow velocity synchronize completion simultaneously, are opened after setting completed purple
Outer lamp, setting intensity of illumination are that 400mW/cm2 starts to prepare nano fibrous membrane, take aluminium foil off after spinning and are put into high temperature baking
It is dry in case, obtain POSS modified nano fiber film.
Embodiment 8
(1) in 25ml serum bottle, 4ml n,N-dimethylacetamide (DMAc) and 6ml acetone are measured respectively with graduated cylinder
(ACE) prepare mixed solvent, according to the concentration of polymer solution of 18wt.% weigh respectively mass ratio be 1:1 PVDF 0.78g with
PMMA 0.78g, then the PVDF of weighing and PMMA are poured into the mixed solvent, it is put into magneton and is heated with magnetic stirring apparatus can be heated
It is stirred dissolution to 50 DEG C, room temperature is cooled to after completely dissolution and continues to stir 18h, it is molten to obtain uniform polymer electrostatic spinning
Liquid.
(2) it according to the gross mass of PVDF and PMMA, determines POSS function monomer mass concentration 8wt.%, weighs quality respectively
Than MA-POSS 31.40mg and the OAPS 94.20mg for 1:3, the methylene chloride (DCM) of 10ml is measured as solvent, will be weighed
MA-POSS and OAPS function monomer dissolve in DCM, be put into magneton magnetic stirring apparatus stirring and dissolving 3h at room temperature, obtain
One POSS function monomer electrostatic solution.
(3) take the polymer electrostatic spinning solution prepared in 5ml step (1) with aluminium foil cladding syringe, and to its
Spinning solution matrix is made in the middle photoinitiator that 3wt.% is added, and connects needle tubing and syringe needle, and wherein needle tubing need to all be wrapped with aluminium foil
Winding is covered to be protected from light, then preparation POSS function monomer electrostatic in the step of using another syringe draws equal amounts of the same race (2)
Solution, connects needle tubing and syringe needle is latter with being placed on electrostatic spinning machine, is covered on spinning machine cylinder and is made with an aluminium foil greatly
For fiber bearing plate, control syringe needle and receiver board be maintained at distance be 15cm, the spinning flow velocity set and hydrojet speed as
3.5ml/h and spinning voltage are 15kv, and electrospinning and EFI identical flow velocity synchronize completion simultaneously, are opened after setting completed purple
Outer lamp, setting intensity of illumination are that 1000mW/cm2 starts to prepare nano fibrous membrane, take aluminium foil off after spinning and are put into high temperature
It is dry in baking oven, obtain POSS modified nano fiber film.
The observation figure of POSS modified nano fiber environmental microbes obtained by above embodiments (SEM) is as shown in Figure 1, can from figure
Spun filament diameter be will become apparent from dozens to a few hundred nanometers size；Infrared spectrum (IR) analysis is as shown in Figure 2, it can be seen that
There is 1717cm on film-1Locate the characteristic peak C=O, 1182cm of PMMA-1Locate the characteristic peak CF of PVDF2And 1125cm-1Locate POSS function
The Si-O-Si characteristic peak of energy monomer, the results showed that successfully prepare the modified specific function nano fibrous membrane of POSS function monomer
Material.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of POSS modified nano fiber film, it is characterised in that the following steps are included:
(1) PVDF and PMMA are added in organic solvent, heating stirring is uniformly dissolved, and obtains polymer electrostatic spinning solution；
(2) MA-POSS and OAPS function monomer is added in organic solvent, stirring and dissolving is uniform, obtains POSS function monomer
Electrostatic solution；
(3) photoinitiator is added into step (1) gained polymer electrostatic spinning solution, then by gained in itself and step (2)
POSS function monomer electrostatic solution is placed in electrostatic spinning machine together, and electrostatic spinning and quiet is started simultaneously under ultraviolet irradiation condition
Electrospray, EFI, which goes out POSS function monomer, while electrospinning high polymer nanometer fiber silk is evenly distributed on it in tunica fibrosa,
Graft polymerization reaction occurs for the functional group on polymer matrix and POSS function monomer under the irradiation of ultraviolet light, after spinning
Gained tunica fibrosa is dry, obtain POSS modified nano fiber film.
2. a kind of preparation method of POSS modified nano fiber film according to claim 1, it is characterised in that: step (1)
Described in organic solvent be DMAC N,N' dimethyl acetamide and acetone mixed solvent；Organic solvent described in step (2) is two
Chloromethanes.
3. a kind of preparation method of POSS modified nano fiber film according to claim 1, it is characterised in that: step (1)
Described in PVDF and PMMA mass ratio be (1~5): 1；The total concentration of PVDF and PMMA in the polymer electrostatic spinning solution
For 18wt.%.
4. a kind of preparation method of POSS modified nano fiber film according to claim 1, it is characterised in that: step (2)
Described in MA-POSS and OAPS mass ratio be 1:(1~3).
5. a kind of preparation method of POSS modified nano fiber film according to claim 1, it is characterised in that: step (2)
Described in POSS function monomer electrostatic solution the total concentration of MA-POSS and OAPS be 2~10wt.%.
6. a kind of preparation method of POSS modified nano fiber film according to claim 1, it is characterised in that: step (3)
Described in the volume ratio of polymer electrostatic spinning solution and POSS function monomer electrostatic solution be 1:1.
7. a kind of preparation method of POSS modified nano fiber film according to claim 1, it is characterised in that in step (3)
The electrostatic spinning and the condition of electrostatic spraying are as follows: apart from being 15cm, spinning solution and spraying flow velocity are for syringe needle and receiver board
3.5ml/h, spinning voltage 15kv.
8. a kind of preparation method of POSS modified nano fiber film according to claim 1, it is characterised in that: step (3)
Described in ultraviolet lighting power level be 400-1000mW/cm2。
9. a kind of POSS modified nano fiber film, it is characterised in that: prepared by method according to any one of claims 1 to 8
It obtains.
10. a kind of POSS modified nano fiber film as claimed in claim 9 is carried in medical nano fiber, biochip, catalyst
Application in body, nano-sensor, battery dielectric material, flexible display material, photoelectric conversion material or supercapacitor.
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| CN110212227B (en) * | 2019-05-17 | 2022-07-15 | 天津工业大学 | Preparation method of metal organic framework modified nanofiber proton exchange membrane |
| EP3789523A1 (en) * | 2019-09-05 | 2021-03-10 | SABIC Global Technologies B.V. | Nanofibers formed from a blend of photoactive thermoplastic polymer and trifluoropropyl polyhedral silsesquioxane and methods for using them |
| CN111197184B (en) * | 2020-01-17 | 2022-04-05 | 西安交通大学 | Electrostatic spinning device |
| CN113279139B (en) * | 2021-04-26 | 2022-06-17 | 杭州诗蓝过滤科技有限公司 | Preparation method of high-strength fluffy melt-blown fabric |
| CN113797649B (en) * | 2021-08-12 | 2022-03-25 | 浙江大学 | Antibacterial and antivirus air filtering material and preparation method thereof |
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