CN109694486A - The preparation method of 100% γ phase PVDF thin film - Google Patents
The preparation method of 100% γ phase PVDF thin film Download PDFInfo
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J5/18—Manufacture of films or sheets
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- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
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Abstract
The present invention relates to the preparation methods of 100% γ phase PVDF thin film, this method comprises: illite and PVDF pellet the first mixed processing of progress will be modified, the modified illite is by obtaining illite progress surface activation process；First mixed processing product is subjected to film process；Film process product is dried；Product will be dried and carry out melt process, to eliminate thermal history；Melt process product is subjected to isothermal crystal processing under conditions of temperature is 158~168 DEG C, to obtain the γ phase PVDF thin film.This method can prepare the PVDF material of 100% γ phase, and crystalline rate is fast, high-efficient, at low cost, be suitable for large-scale promotion application.
Description
Technical field
The present invention relates to Material Field, in particular it relates to the preparation method of 100% γ phase PVDF thin film, more
Body, the present invention relates to the preparation methods of γ phase PVDF thin film and modified illite to prepare the use in γ phase PVDF thin film
On the way.
Background technique
Kynoar (poly (vinylidene fluoride), PVDF) is a kind of typical heteromorphic polymer, is gathered around
There are five kinds of different crystal forms of α, β, γ, δ and ε.γ crystal form PVDF then have due to its special molecular conformation excellent piezoelectricity,
Pyroelectricity and ferroelectricity, the polymer with electrical property can be applied to sensor, execute as a kind of new intellectual material
The intellectual materials such as device, energy harvester field.However, at present preparation 100% γ phase polyvinylidene fluoride material method or
Condition is harsh, and crystal growth rate is slow or cost is excessively high, is unfavorable for promoting and applying.
Therefore, the method for preparing the polyvinylidene fluoride material of 100% γ phase also needs further to study.
Summary of the invention
The application is to be made based on inventor to the discovery of following facts and problem and understanding:
The preparation of γ crystal form PVDF is divided into two kinds at present, one is during high temperature crystallization low rate at karyogenesis
γ crystal form, usually with the α Xiang Bingcun of high-speed nucleating growth；Another kind is that alpha-crystal form changes to obtain γ crystal form by solid phase.
The former mainly pass through high annealing or Kynoar and other polymers or filler (carbon nanotube, graphene, silica,
Potassium bromide, nano montmorillonite) it is blended to promote the formation of γ polarity phase, but severe reaction conditions, it is not easy to form 100% γ phase material
Material；The latter by solid phase transformation need the time very it is long could change it is complete.To sum up, technology is difficult directly and quickly to prepare at present
Obtain the polyvinylidene fluoride material of 100% γ phase.
Based on the above issues, it is surprisingly found after inventor probes into through a large number of experiments, from the pure PVDF of α phase,
The illite that the organic modification of minute quantity (0.05wt%-10.0wt%) need to only be added, at certain temperature (158 DEG C -168 DEG C)
Under the conditions of melting recrystallization can prepare fast nucleation growth (POM characterization result show to add it is a certain amount of it is organically-modified she
Sharp stone can cover with the visual field in certain temperature isothermal crystal 10min) 100% γ phase PVDF material, and used in this method
Illite it is cheap (800~1500 yuan/ton), it is resourceful, be suitable for high-volume low cost production.
For this purpose, the invention proposes a kind of preparation methods of γ phase PVDF thin film in the first aspect of the present invention.According to this
The embodiment of invention, which comprises modified illite and PVDF pellet are subjected to the first mixed processing, the modified Erie
Stone is by obtaining illite progress surface activation process；First mixed processing product is subjected to film process；It will film forming
Processing product is dried；Product will be dried and carry out melt process, to eliminate thermal history；By melt process product
It is 158~168 DEG C in temperature, as carried out isothermal knot under conditions of 159,160,161,162,163,164,165,166 or 167 DEG C
Crystalline substance processing, to obtain the γ phase PVDF thin film.It should be noted that film process, elimination thermal history and isothermal crystal
Meaning understood according to this field common version.Wherein, film process can be by direct drop film in silicon wafer and red
It is carried out on outer silicon wafer, setting in the method for the drop film need to be according to specific polymer when liquid-transfering gun pipettes the volume of mixed solution
The concentration of blend and required area of base determine, for example, according to an embodiment of the present invention take 100 μ L mixed solution (concentration
It is dripped in 13mm*13mm substrate for 10mg/ml), average film thickness is 2 μm.Eliminate thermal history be meant that by melt process with
Just a variety of different crystal habits that high molecular polymer has been formed are eliminated, make high molecular polymer microcosmic upper in original
The state of random arrangement is conducive to subsequent recrystallization process.Isothermal crystal refers to the crystallization under isothermal condition
Journey, it is one of research and the characterization common experimental method of superpolymer crystal behavior.Illite is as a kind of (two layers of TOT structure
Oxygen-octahedron adds one layer of alumina octahedral) phyllosilicate, do not have substantially at present in terms of on polymer crystallization performance influence
Research.Inventors have found that the structure of the temperature and the γ phase PVDF thin film of preparation of the isothermal crystal processing is closely related: if waiting
The temperature of warm crystallization treatment is too low, can be only generated PVDF the α phase of α phase and the PVDF that γ is mixed；If isothermal crystal is handled
Temperature it is excessively high, polymer crystals nucleation is relatively difficult, is also unfavorable for the generation of γ phase PVDF, and isothermal crystal processing
At 158~168 DEG C of temperature, it in dynamics and is thermodynamically suitable for the formation of PVDF γ-phase conformation.In turn, according to this hair
The method of bright embodiment can prepare the PVDF material of 100% γ phase, and crystalline rate is fast, high-efficient, at low cost, be suitable for
Large-scale promotion application.
According to an embodiment of the invention, the above method can also further comprise at least one following additional technical feature:
According to an embodiment of the invention, the illitic mass fraction of modification be 0.05~10.0%, for example 0.07,
0.09,0.1,0.3,0.5,0.7,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0,6.0,7.0,8.0 or 9.0%.
It should be noted that the illitic mass fraction of modification (it is such as according to an embodiment of the present invention containing 0.1wt%, 0.5wt%,
1.0wt%, 2.0wt% or 5.0wt% organise illitic PVDF thin film) refer to the illitic quality of the modification with it is described
The ratio of the quality sum of modified illite and PVDF pellet.Inventors have found that if modified illitic mass fraction is too low,
The PVDF material of 100% γ phase can not be prepared, if modified illitic mass fraction is excessively high, can not only PVDF be hindered to tie
Crystalline substance makes PVDF crystallinity will be low, and can interfere to the performance of γ phase PVDF material.The modification is illitic as a result,
When mass fraction is 0.05~10.0%, the PVDF material of 100% γ phase can be prepared according to the method for the embodiment of the present invention
Material, and crystalline rate is faster, more efficient, modified illitic dosage is few.
According to an embodiment of the invention, the illitic mass fraction of modification is 0.1~5%.Inventors have found that described
When modified illitic mass fraction is 0.1~5%, 100% γ phase can be prepared according to the method for the embodiment of the present invention
PVDF material, and crystalline rate is faster, and more efficient, modified illitic dosage is less.
According to an embodiment of the invention, the mass-volume concentration of the first mixed processing product be 1~50mg/mL, for example 2,
3,4,5,7,9,10,13,15,17,19,20,25,30,35,40 or 45mg/mL.It should be noted that at first mixing
Manage product mass-volume concentration (blend solution concentration 5mg/mL, 10mg/mL such as according to an embodiment of the present invention, 20mg/mL,
40mg/mL or 50mg/mL) refer to the ratio of the quality sum of modified illite and PVDF pellet and the volume of the organic solvent
Value.Inventors have found that if the mass-volume concentration of the first mixed processing product is too low, prepare the rate of PVDF material compared with
Slowly, efficiency is lower；If the mass-volume concentration of the first mixed processing product is excessively high, organic solvent is unable to fully dissolution PVDF
Pellet and disperse modified illite.When the mass-volume concentration of the first mixed processing product is 1~50mg/mL as a result, have
Solvent can sufficiently dissolve PVDF pellet and disperse modified illite can be made according to the method for the embodiment of the present invention in turn
The standby PVDF material for obtaining 100% γ phase, and crystalline rate is faster, it is more efficient.
According to an embodiment of the invention, the mass-volume concentration of the first mixed processing product is 5~20mg/mL.Inventor
It was found that organic solvent can sufficiently dissolve when the mass-volume concentration of the first mixed processing product is 5~20mg/mL
Simultaneously disperse modified illite can prepare 100% γ phase in turn to PVDF pellet according to the method for the embodiment of the present invention
PVDF material, and crystalline rate is faster, it is more efficient.
According to an embodiment of the invention, it is 60~100 DEG C that first mixed processing, which is in temperature, such as 70,80,90 DEG C
Under the conditions of carry out.Inventors have found that being unable to fully dissolution PVDF pellet if the temperature of first mixed processing is too low and dividing
Dissipate modified illite；If the temperature of first mixed processing is excessively high, the structure of raw material may be destroyed.As a result, described first
When mixed processing carries out under conditions of temperature is 60~100 DEG C, organic solvent can sufficiently dissolve PVDF pellet and disperse to change
Property illite, and the structure of raw material will not be damaged, in turn, it can prepare according to the method for the embodiment of the present invention
The PVDF material of 100% γ phase, and crystalline rate is faster, it is more efficient.
According to an embodiment of the invention, first mixed processing carries out in organic solvent, the organic solvent
Including being selected from least one of N,N-dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone.
According to an embodiment of the invention, the modified illite is to provide in the form that is suspended in the organic solvent
's.
According to an embodiment of the invention, further comprising before carrying out first mixed processing: by modified illite
Suspension is ultrasonically treated.In turn, the dispersion of modified illite in organic solvent is more uniform.
According to an embodiment of the invention, the melt process is at 200~220 DEG C, under conditions of 205,210,215 DEG C
It carries out, to eliminate thermal history.
According to an embodiment of the invention, further comprising by melt process after the melt process, before isothermal crystal processing
Product carries out quickly cooling processing, to reach isothermal crystal treatment temperature.It should be noted that quickly cooling treated temperature, that is, isothermal
The temperature of crystallization.Wherein, the quickly cooling processing refers to is cooled down with speed as fast as possible, and rate of temperature fall is about 20 DEG C/s~50
℃/s。
According to an embodiment of the invention, the surface activation process include: by the illite and dilute hydrochloric acid and sun from
Sub- surfactant carries out the second mixed processing；Second mixed processing product is filtered processing, to obtain filter residue；By institute
It states filter residue to be dried, the filter residue after the drying process is the modified illite.Side according to an embodiment of the present invention
Method can prepare the PVDF material of 100% γ phase, and crystalline rate is faster, more efficient.
According to an embodiment of the invention, the cationic surfactant and the illitic mass ratio are (1~10):
100, for example 2:100,3:100,4:100,5:100,6:100,7:100,8:100 or 9:100.It should be noted that the matter
Amount concentration (CTAB of 3wt%, 5wt%, 6wt% or 8wt% such as according to an embodiment of the present invention) refers to that cationic surface is living
Property agent quality and illitic mass ratio.Inventors have found that if the mass concentration of cationic surfactant is too small, it may
Illite surface alkyl chain can be reduced, and influence modified illite to the inducing action of polarity phase, so as to cause preparation modification she
Sharp stone can not obtain the PVDF material of 100% γ phase after mixing with the pure PVDF of α phase；If the quality of cationic surfactant is dense
It spends greatly, then needs to wash repeatedly to remove completely superfluous cationic surfactant, not only cause the waste of raw material, and
And unreacted a large amount of cationic surfactants can have an adverse effect to product properties；In addition, since illite interlayer is deposited
In potassium ion, the size of potassium ion is embedded just below the hole of oxygen atom grid protocol between adjacent crystal layer, around has 12 oxygen therewith
Coordination, therefore Coating combination ability is strong, illitic cation exchange capacity (CEC) is the every 100mg of 10-40 milliequivalent, works as use
When 15wt% surfactant, inventor is had found by oil absorbency and contact angle test, oil absorbency and contact angle variation compared to
10wt%, which differs the concentration for less showing to continue to improve surfactant, influences the compatibility for promoting illite and polymer
Less, and ion-exchange capacity has reached saturation, and there are excess surface activating agents in system, can also produce to product electric property
Raw adverse effect.As a result, inventors have found that by the minimal amount of modification illite obtained according to the method for the embodiment of the present invention with
The pure PVDF of α phase is mixed, and melting recrystallization can prepare 100% γ phase of fast nucleation growth under certain condition
PVDF material, and the illite used in the preparation method is cheap, resourceful, and it is raw to be suitable for high-volume low cost
It produces, this method not only substantially increases the crystalline rate of PVDF material, while illitic application field has also been enlarged.
According to an embodiment of the invention, the cationic surfactant and the illitic mass ratio are (3~8):
100.Inventors have found that the cationic surfactant and the illitic mass ratio are (3~8): when 100, according to this
The method of inventive embodiments can prepare the PVDF material of 100% γ phase, and crystalline rate is faster, more efficient.
According to an embodiment of the invention, the cationic surfactant include selected from cetyl trimethylammonium bromide,
At least one of Cetyltrimethylammonium bromide, didodecyldimethylammbromide bromide.
According to an embodiment of the invention, the temperature of second mixed processing is 60~100 DEG C, for example 70,80 or 90 DEG C.
Inventors have found that the structure of raw material may be destroyed if the temperature of the second mixed processing is excessively high；If the temperature of the second mixed processing
It is too low, then it reacts progress slowly, illite can not be carried out sufficiently modified.The temperature of second mixed processing is 60 as a result,
At~100 DEG C, it can be effectively modified illite, and then the 100% γ phase according to an embodiment of the present invention that can prepare
PVDF material, and crystalline rate is faster, it is more efficient.
According to an embodiment of the invention, the illite is provided in the form to suspend in water.
According to an embodiment of the invention, further comprising by illite suspension before carrying out the surface activation process
It is ultrasonically treated.In turn, the dispersion of illite in water is more uniform.
In the second aspect of the present invention, the invention proposes modified illites to prepare the purposes in γ phase PVDF thin film,
The modified illite is obtained by surface activation process described in any of the above-described.Illite is tied as a kind of TOT
Structure (two layers of oxygen-octahedron adds one layer of alumina octahedral) phyllosilicate, the current base in terms of on polymer crystallization performance influence
This is not studied.Inventor has found for the first time, minimal amount of to be changed by what surface activation process described in any of the above-described obtained
Property illite can be used to preparation 100% γ phase PVDF material, the possible reason is the positive CH in the part of PVDF2Dipole and band
The formation of ion-dipole interaction induced electrical polarity γ conformation between the clay nano layer of negative electrical charge.
In the third aspect of the present invention, the invention proposes a kind of preparation methods of γ phase PVDF thin film.According to the present invention
Embodiment, which comprises illite is suspended in water, and illite suspension is ultrasonically treated；It will be ultrasonic
Treated, and illite suspension carries out under conditions of temperature is 60~100 DEG C with dilute hydrochloric acid and cationic surfactant
Second mixed processing, the cationic surfactant and the illitic mass ratio are 3:100~8:100, the surface
Activating agent includes being selected from cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, double dodecyl dimethyl brominations
At least one of ammonium；Second mixed processing product is filtered processing, to obtain filter residue；Place is dried in the filter residue
Reason, the filter residue after the drying process are modified illite；The modified illite is suspended in organic solvent, and will be modified
Illite suspension is ultrasonically treated, and the organic solvent includes being selected from n,N-Dimethylformamide, dimethyl acetamide, N-
At least one of methyl pyrrolidone；By after ultrasonic treatment modification illite suspension and PVDF pellet temperature be 60~
The first mixed processing is carried out under conditions of 100 DEG C, the mass-volume concentration of the first mixed processing product is 5~20mg/mL, described
Modified illitic mass fraction is 0.1~5%, and first mixed processing is carried out in the organic solvent；By
One mixed processing product carries out film process；Film process product is dried；Product, which will be dried, in temperature is
Melt process is carried out under conditions of 200~220 DEG C, to eliminate thermal history；Melt process product is subjected to quickly cooling processing, so as to
Reach 158~168 DEG C, and melt process product is subjected to isothermal crystal processing under conditions of temperature is 158~168 DEG C, with
Just the γ phase PVDF thin film is obtained.The PVDF material of 100% γ phase can be prepared according to the method for the embodiment of the present invention,
And crystalline rate is faster, it is more efficient.
Detailed description of the invention
Fig. 1 is organic illitic PVDF material containing different quality containing according to the embodiment of the present invention in suitable temperature
Lower isothermal crystal characterizes schematic diagram until crystallizing complete X-ray diffractometer (XRD), wherein line 1 represents pure PVDF, line 2/3/4
Respectively represent the organic illitic PVDF material of 0.5wt% containing mass fraction/1.0wt%/2.0wt%, the results showed that, and it is pure
PVDF only exists α phase diffraction maximum and compares, remaining is added to the appropriate mass score illitic PVDF that organises and only exists γ phase
Diffraction maximum；
Fig. 2 is straight in 165 DEG C of isothermal crystals according to organic illitic PVDF material containing 0.5wt% of the embodiment of the present invention
Schematic diagram is characterized to the complete Fourier transform infrared spectroscopy figure (situ-FTIR) in situ of crystallization, the results showed that, in suitable temperature
Lower isothermal crystal only exists γ phase crystal form to crystallization since crystallization completely, will not generate α phase；
Fig. 3 is straight in 165 DEG C of isothermal crystals according to organic illitic PVDF material containing 2.0wt% of the embodiment of the present invention
Schematic diagram is characterized to complete differential scanning calorimeter (DSC) is crystallized, the results showed that, isothermal crystal is from crystallization at appropriate temperatures
Start to crystallization to only exist the melting peak of γ phase crystal form completely, α phase will not be generated；
Fig. 4 is organic illitic PVDF material containing 1.0wt% according to the embodiment of the present invention in 165 DEG C of isothermal crystal 5h
Selectively melted at 180 DEG C/183 DEG C afterwards petrographic microscope in situ (POM) characterization schematic diagram, selectivity melting the result shows that,
Isothermal crystal only exists γ phase crystal form until crystallizing completely at appropriate temperatures, will not generate α phase, and compared to pure PVDF in phase
Synthermal isothermal crystal 6-8h can just start to crystallize, and γ phase is nucleated to be significantly improved with growth rate,
Wherein: A indicates schematic diagram of the organic illitic PVDF material containing 1.0wt% in 165 DEG C of isothermal crystal 5h, B
Indicate that the petrographic microscope in situ (POM) selectively melted after isothermal crystal 5h at 180 DEG C characterization schematic diagram, C indicate isothermal knot
Petrographic microscope in situ (POM) the characterization schematic diagram selectively melted after brilliant 5h at 183 DEG C；
Fig. 5 is straight in 160 DEG C of isothermal crystals according to organic illitic PVDF material containing 2.0wt% of the embodiment of the present invention
Schematic diagram is characterized to complete atomic force (AFM) is crystallized, the results showed that, isothermal crystal is until crystallization is complete only at appropriate temperatures
There are γ phase flat-on crystal forms, and there is no edge-on, flat-on of the torsion of typical platelet zonary structures being alternately present
α phase；
Fig. 6 is according to the modified illitic polyvinylidene fluoride composite film of the addition 1.0wt% of the embodiment of the present invention 140
After DEG C isothermal crystal 10min, respectively at 160 DEG C, 170 DEG C, 175 DEG C, 178 DEG C of melting infrared line schematic diagrames in situ.
Specific embodiment
The embodiment of the present invention is described below in detail, examples of the embodiments are shown in the accompanying drawings.Below with reference to
The embodiment of attached drawing description is exemplary, it is intended to is used to explain the present invention, and is not considered as limiting the invention.
It should be noted that unless otherwise instructed, solvent, reagent or the raw material used in the present invention commercially available can obtain
, and each solvent, the title of reagent or raw material and its meaning are understood according to this field common version.
The purpose of the present invention is to provide a kind of methods of 100% polarity γ phase PVDF crystal film of low cost preparation.This
Another of invention is designed to provide a kind of method for promoting γ phase crystal fast nucleation and growth.Another mesh of the invention
Be to provide a kind of illite in the method for regulation polymer crystallization field application.The invention also discloses the PVDF crystal is thin
Purposes of the film in piezoelectricity, thermoelectricity and ferro-electric device.
The invention is realized by the following technical scheme, a kind of to prepare inexpensive fast nucleation to grow 100% γ phase PVDF thin
The method of film includes following technology: illite and cationic surfactant is blended the illite that organises is made first, then
Preparation organises illitic PVDF solution containing 0.1wt% to 5.0wt%, and after solution blending is complete, using drop film method, vacuum is dry
Obtained film after dry, later in 158 DEG C to 168 DEG C isothermal crystals for a period of time until crystallization completely, can be obtained 100% γ phase
PVDF thin film.
In the present invention, described for be modified that illitic amphipathic reagent selects is cationic surfactant, one
In a little embodiments are as follows: cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, didodecyldimethylammbromide bromide
Deng.
In the present invention, the solvent for dissolving polymer selects organic solvent, in some embodiments are as follows: N, N- bis-
Methylformamide (DMF), dimethyl acetamide (DMAc), the mixing of N-Methyl pyrrolidone (NMP) or optional two kinds of solvents
Solvent etc..
In the present invention, the concentration of the polymer blend solution is 1mg/mL~50mg/mL, in some embodiments concentration
For 5mg/mL~20mg/mL.
In the present invention, prepared film thickness is adjusted between 200nm to 10 μm, in some embodiments with a thickness of
500nm to 8 μm, in further embodiments with a thickness of 1 μm -5 μm.
In the present invention, the electromagnetic agitation temperature and mixing time, vacuum drying oven drying temperature and time need to select conjunction
Reason.
The invention also discloses the mechanism that the illite induction PVDF that organises generates γ polarity phase.Mechanism is the part of PVDF
Positive CH2The formation of ion-dipole interaction induced electrical polarity γ conformation between dipole and negatively charged clay nano layer.
The specific method is as follows:
One, the illitic preparation method of organic modification
Illite is ultrasonically treated first, after be placed on certain temperature magnetic stirrer and stir, be slowly added hydrochloric acid
The cationic surfactant of weak solution and certain mass score, stirring stands activation after a certain period of time makes fully reacting.It will hang
Supernatant liquid vacuum filtration, repeatedly with deionized water and dehydrated alcohol, alternately washing removes unreacted ion during suction filtration, through true
Modified silicate clay is ground up, sieved bottling by empty oven drying.The organic modification illite that the present invention produces is preferred
Whipping temp is 60-100 DEG C, and preferred cationic surfactant is cetyl trimethylammonium bromide, octadecyl trimethyl
Ammonium bromide, didodecyldimethylammbromide bromide etc..Preferred surfactant concentration is 1wt%-10wt%, more preferable 3wt%-
8wt%.
Two, organise illite/PVDF laminated film preparation method
The organically-modified illite of certain mass is weighed in a certain amount of solvent, after ultrasonic disperse, load weighted PVDF is added
Pellet carries out solution mixing with the certain revolving speed electromagnetic agitation instrument of certain temperature.Using drop film method, (liquid-transfering gun is pipetted after mixing completely
Liquid to 13mm*13mm silicon wafer substrate), after vacuum drying oven is dried be made film.Solvent for dissolving polymer is selected
Conventional solvents, preferably: n,N-Dimethylformamide (DMF), dimethyl acetamide (DMAc), N-Methyl pyrrolidone (NMP) or
The mixed solvent etc. of the optional two kinds of solvents of person.The modified illitic mass fraction of addition is 0.05wt%-10.0wt%, is preferably changed
Property illitic mass fraction be 0.1wt%--5wt%.The concentration of polymer blend solution is 1mg/mL~50mg/mL, preferably
5mg/mL~20mg/mL.It is 60 DEG C -100 DEG C that solution used, which mixes preferred whipping temp,.Prepared film thickness is adjusted
Between 200nm to 10 μm, preferably 500nm to 8 μm, more preferable 1 μm to 4 μm.
Obtained sample is in 200 DEG C~220 DEG C holding 10min to eliminate thermal history, and then quickly cooling is at 158 DEG C -168 DEG C
Between specific temperature isothermal processes certain time until crystallization is complete.X-ray diffractometer (XRD) is used respectively, polarized light microscopy
Mirror (POM), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimeter (DSC) and atomic force (AFM) characterization.
Technical effect: the present invention provide it is a kind of it is easy to operate, can big yield preparation, low cost and 100% γ-phase
The preparation method of PVDF material.From the pure PVDF of α-phase, organising for minute quantity (0.1wt%-5.0wt%) need to be only added
Modified illite can prepare fast nucleation growth (POM characterization in certain temperature (158 DEG C -168 DEG C) melting recrystallization
As a result the visual field can be covered with to add a certain amount of organically-modified illite in certain temperature isothermal crystal 10min) 100%
The PVDF material of γ-phase.The illite used in the method is cheap, is suitable for high-volume low cost production.
Explanation is further expalined to the present invention below in conjunction with specific embodiment.
Embodiment 1
The first step is the modified illite of cetyl trimethylammonium bromide (CTAB) preparation.10g illite is added to
In 150mL deionized water, be ultrasonically treated 2h, after be put on 80 DEG C of magnetic stirrers and stir, by 4mL in whipping process
(0.1mol/L) hydrochloric acid weak solution and 5wt%CTAB are added slowly in slurry.Mixed solution electromagnetism at 80 DEG C stirs
2h is mixed, standing activates fully reacting for 24 hours.Suspension is filtered by vacuum, and is alternately and repeatedly washed with deionized water and dehydrated alcohol
It washs 3 times, it is ensured that be free in the CTAB removal on illite surface.Then drying in 70 DEG C of vacuum drying ovens is placed on for 24 hours, to take out, will do
Dry organically-modified illite is ground up, sieved bottling.
Second step is that solution blending preparation organises illitic PVDF thin film containing 2.0wt%.6mg is weighed, her is organised
Sharp stone dimethyl acetamide (DMAc) in 30mL, ultrasonic disperse 2h weigh 294mg PVDF pellet and are added in conical flask, be blended
Solution concentration 10mg/mL, electromagnetic agitation 4h keeps mixing complete at 100 DEG C.Direct drop film (takes in silicon wafer and infrasil on piece
100 μ L mixed solutions drip to 13mm*13mm substrate, and average film thickness is 2 μm), then drying is made for 24 hours in 90 DEG C of vacuum drying ovens
PVDF/CTAB-Illite film.
For obtained sample in 210 DEG C of holdings, 10 minutes elimination thermal histories, quickly cooling is extremely straight in 165 DEG C of isothermal processes certain times
It is complete to crystallization.It is characterized respectively with X-ray diffractometer (XRD) and differential scanning calorimeter (DSC).
As a result: with reference to the line 4 and Fig. 3 in Fig. 1 it is found that this method can quickly prepare 100% γ phase PVDF material.
Embodiment 2
The first step is to prepare Cetyltrimethylammonium bromide (STAB) modified illite.10g illite is added to
In 150mL deionized water, be ultrasonically treated 2h, after be put on 60 DEG C of magnetic stirrers and stir, by 4mL in whipping process
(0.1mol/L) hydrochloric acid weak solution and 3wt%CTAB are added slowly in slurry.Mixed solution electromagnetism at 60 DEG C stirs
2h is mixed, standing activates fully reacting for 24 hours.Suspension is filtered by vacuum, and is alternately and repeatedly washed with deionized water and dehydrated alcohol
It washs 3 times, it is ensured that be free in the STAB removal on illite surface.Then drying in 60 DEG C of vacuum drying ovens is placed on for 24 hours, to take out, will do
Dry organically-modified illite is ground up, sieved bottling.
Second step is that solution blending preparation organises illitic PVDF thin film containing 0.1wt%.0.25mg is weighed to organise
Illite is in 50mL n,N-Dimethylformamide (DMF), ultrasonic disperse 2h, weighs 249.75mg PVDF pellet and is added to cone
Shape bottle, blend solution concentration are 5mg/mL, and electromagnetic agitation 2h keeps mixing complete at 60 DEG C.Direct drop film is in silicon wafer and infrasil
On piece (takes 50 μ L mixed solutions to drip to 13mm*13mm substrate, average film thickness 500nm), then does in 90 DEG C of vacuum drying ovens
It is dry that PVDF/STAB-Illite film is made for 24 hours.
Obtained sample in 210 DEG C of holdings, 10 minutes elimination thermal histories, quickly cooling in 168 DEG C of isothermal processes certain times until
Crystallization is complete.X-ray diffractometer (XRD) is used respectively, petrographic microscope (POM), Fourier transform infrared spectroscopy (FTIR) shows difference
Scan calorimeter (DSC) and atomic force (AFM) characterization.
As a result: this method can quickly prepare 100% γ phase PVDF material.
Embodiment 3
The first step is to prepare cetyl trimethylammonium bromide (CTAB) modified illite.10g illite is added to
In 150mL deionized water, be ultrasonically treated 2h, after be put on 70 DEG C of magnetic stirrers and stir, by 4mL in whipping process
(0.1mol/L) hydrochloric acid weak solution and 5wt%CTAB are added slowly in slurry.Mixed solution electromagnetism at 70 DEG C stirs
2h is mixed, standing activates fully reacting for 24 hours.Suspension is filtered by vacuum, and is alternately and repeatedly washed with deionized water and dehydrated alcohol
It washs 3 times, it is ensured that be free in the CTAB removal on illite surface.Then drying in 70 DEG C of vacuum drying ovens is placed on for 24 hours, to take out, will do
Dry organically-modified illite is ground up, sieved bottling.
Second step is that solution blending preparation organises illitic PVDF thin film containing 0.5wt%.1.5mg is weighed, is organised
Illite is in 30mL N-Methyl pyrrolidone (NMP), ultrasonic disperse 2h, weighs 298.5mg PVDF pellet and conical flask is added
In, blend solution concentration 10mg/mL, electromagnetic agitation 4h keeps mixing complete at 70 DEG C.Direct drop film is in silicon wafer and infrared silicon wafer
It goes up and (takes 50 μ L mixed solutions to drip to 13mm*13mm substrate, average film thickness is 1 μm), then dried for 24 hours in 90 DEG C of vacuum drying ovens
PVDF/CTAB-Illite film is made.
Obtained sample in 210 DEG C of holdings, 10 minutes elimination thermal histories, quickly cooling in 165 DEG C of isothermal processes certain times until
Crystallization is complete.It is characterized respectively with X-ray diffractometer (XRD) and Fourier transform infrared spectroscopy (FTIR).
As a result: with reference to the line 2 and Fig. 2 in Fig. 1 it is found that this method can quickly prepare 100% γ phase PVDF material.
Embodiment 4
The first step is the modified illite of didodecyldimethylammbromide bromide (DDAB) preparation.10g illite is added
Into 150mL deionized water, be ultrasonically treated 2h, after be put on 80 DEG C of magnetic stirrers and stir, by 4mL in whipping process
(0.1mol/L) hydrochloric acid weak solution and 6wt%CTAB are added slowly in slurry.Mixed solution electromagnetism at 80 DEG C stirs
2h is mixed, standing activates fully reacting for 24 hours.Suspension is filtered by vacuum, and is alternately and repeatedly washed with deionized water and dehydrated alcohol
It washs 3 times, it is ensured that be free in the DDAB removal on illite surface.Then drying in 90 DEG C of vacuum drying ovens is placed on for 24 hours, to take out, will do
Dry organically-modified illite is ground up, sieved bottling.
Second step is that solution blending preparation organises illitic PVDF thin film containing 1.0wt%.4mg is weighed, her is organised
Sharp stone dimethyl acetamide (DMAc) in 20mL, ultrasonic disperse 2h weigh 396mg PVDF pellet and are added in conical flask, be blended
Solution concentration 20mg/mL, electromagnetic agitation 4h keeps mixing complete at 80 DEG C, and direct drop film (takes 50 μ in silicon wafer and infrasil on piece
L mixed solution drips to 13mm*13mm substrate, and average film thickness is 2 μm), then drying is made for 24 hours in 80 DEG C of vacuum drying ovens
PVDF/DDAB-Illite film.
Obtained sample in 210 DEG C of holdings, 10 minutes elimination thermal histories, quickly cooling in 163 DEG C of isothermal processes certain times until
Crystallization is complete.It is characterized respectively with X-ray diffractometer (XRD) and petrographic microscope (POM).
As a result: with reference to the line 3 and Fig. 4 in Fig. 1 it is found that this method can quickly prepare 100% γ phase PVDF material.
Embodiment 5
The first step is the modified illite of didodecyldimethylammbromide bromide (DDAB) preparation.10g illite is added
Into 150mL deionized water, be ultrasonically treated 2h, after be put on 90 DEG C of magnetic stirrers and stir, by 4mL in whipping process
(0.1mol/L) hydrochloric acid weak solution and 5wt%CTAB are added slowly in slurry.Mixed solution electromagnetism at 90 DEG C stirs
2h is mixed, standing activates fully reacting for 24 hours.Suspension is filtered by vacuum, and is alternately and repeatedly washed with deionized water and dehydrated alcohol
It washs 3 times, it is ensured that be free in the DDAB removal on illite surface.Then drying in 50 DEG C of vacuum drying ovens is placed on for 24 hours, to take out, will do
Dry organically-modified illite is ground up, sieved bottling.
Second step is that solution blending preparation organises illitic PVDF thin film containing 2.0wt%.16mg is weighed, her is organised
Sharp stone dimethyl acetamide (DMAc) in 20mL, ultrasonic disperse 2h weigh 784mg PVDF pellet and are added in conical flask, be blended
Solution concentration 40mg/mL, electromagnetic agitation 4h keeps mixing complete at 90 DEG C.Direct drop film (takes 50 μ in silicon wafer and infrasil on piece
L mixed solution drips to 13mm*13mm substrate, and average film thickness is 4 μm), then drying is made for 24 hours in 80 DEG C of vacuum drying ovens
PVDF/DDAB-Illite film.
Obtained sample in 210 DEG C of holdings, 10 minutes elimination thermal histories, quickly cooling in 160 DEG C of isothermal processes certain times until
Crystallization is complete.It is characterized with atomic force (AFM).
As a result: with reference to Fig. 5 it is found that this method can quickly prepare 100% γ phase PVDF material.
Embodiment 6
The first step is the modified illite of cetyl trimethylammonium bromide (CTAB) preparation.10g illite is added to
In 150mL deionized water, be ultrasonically treated 2h, after be put on 100 DEG C of magnetic stirrers and stir, by 4mL in whipping process
(0.1mol/L) hydrochloric acid weak solution and 8wt%CTAB are added slowly in slurry.Mixed solution electromagnetism at 100 DEG C stirs
2h is mixed, standing activates fully reacting for 24 hours.Suspension is filtered by vacuum, and is alternately and repeatedly washed with deionized water and dehydrated alcohol
It washs 3 times, it is ensured that be free in the CTAB removal on illite surface.Then drying in 70 DEG C of vacuum drying ovens is placed on for 24 hours, to take out, will do
Dry organically-modified illite is ground up, sieved bottling.
Second step is that solution blending preparation organises illitic PVDF thin film containing 5.0wt%.25mg is weighed, her is organised
Sharp stone dimethyl acetamide (DMAc) in 10mL, ultrasonic disperse 2h weigh 475mg PVDF pellet and are added in conical flask, be blended
Solution concentration 50mg/mL, electromagnetic agitation 4h keeps mixing complete at 100 DEG C.Direct drop film (takes 80 in silicon wafer and infrasil on piece
μ L mixed solution drips to 13mm*13mm substrate, and average film thickness is 8 μm), then drying is made for 24 hours in 80 DEG C of vacuum drying ovens
PVDF/CTAB-Illite film.
Obtained sample in 210 DEG C of holdings, 10 minutes elimination thermal histories, quickly cooling in 158 DEG C of isothermal processes certain times until
Crystallization is complete.X-ray diffractometer (XRD) is used respectively, petrographic microscope (POM), Fourier transform infrared spectroscopy (FTIR) shows difference
Scan calorimeter (DSC) and atomic force (AFM) characterization.
As a result: this method can quickly prepare 100% γ phase PVDF material.
Comparative example 1
For experimental method with embodiment 4, difference is only that isothermal crystal temperature is 140 DEG C.
As a result with conclusion:
The modified illitic polyvinylidene fluoride composite film of 1.0wt% is added after 140 DEG C of isothermal crystal 10min, respectively
At 160 DEG C, 170 DEG C, 175 DEG C, 178 DEG C of melting INFRARED SPECTRUM line charts in situ refer to Fig. 6.Infrared absorption peak in Fig. 6 shows
It can be only generated α phase when 140 DEG C of isothermal crystals, the γ crystal form of PVDF needs the isothermal crystal within the scope of relatively high suitable temperature
It could generate.
In addition, term " first ", " second " are used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance
Or implicitly indicate the quantity of indicated technical characteristic.Define " first " as a result, the feature of " second " can be expressed or
Implicitly include at least one this feature.In the description of the present invention, the meaning of " plurality " is at least two, such as two, three
It is a etc., unless otherwise specifically defined.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of preparation method of γ phase PVDF thin film characterized by comprising
Illite will be modified and PVDF pellet carries out the first mixed processing, the modified illite is by the way that illite is carried out table
What face was activated；
First mixed processing product is subjected to film process；
Film process product is dried；
Product will be dried and carry out melt process, to eliminate thermal history；
Melt process product is subjected to isothermal crystal processing under conditions of temperature is 158~168 DEG C, to obtain the γ phase
PVDF thin film.
2. the method according to claim 1, wherein the illitic mass fraction of the modification be 0.05~
10.0%, it is preferable that the illitic mass fraction of modification is 0.1~5%；
Optionally, the mass-volume concentration of the first mixed processing product is 1~50mg/mL, it is preferable that mass-volume concentration 5
~20mg/mL.
3. the method according to claim 1, wherein it is 60~100 DEG C that first mixed processing, which is in temperature,
Under conditions of carry out；
Optionally, first mixed processing carries out in organic solvent, and the organic solvent includes being selected from N, N- diformazan
At least one of base formamide, dimethyl acetamide, N-Methyl pyrrolidone.
4. the method according to claim 1, wherein the modified illite is to be suspended in the organic solvent
In form provide；
Optionally, before carrying out first mixed processing, further comprise: modified illite suspension is carried out at ultrasound
Reason；
Optionally, the melt process is carried out under conditions of 200~220 DEG C；
It optionally, further comprise carrying out melt process product at quickly cooling after the melt process, before isothermal crystal processing
Reason, to reach isothermal crystal treatment temperature.
5. the method according to claim 1, wherein the surface activation process includes:
The illite and dilute hydrochloric acid and cationic surfactant are subjected to the second mixed processing；
Second mixed processing product is filtered processing, to obtain filter residue；
The filter residue is dried, the filter residue after the drying process is the modified illite.
6. according to the method described in claim 5, it is characterized in that, the cationic surfactant and the illitic matter
Amount is than being 1:100~10:100；Preferably, the cationic surfactant and the illitic mass ratio be 3:100~
8:100.
7. according to right to go 5 described in method, which is characterized in that the cationic surfactant include be selected from cetyl
At least one of trimethylammonium bromide, Cetyltrimethylammonium bromide, didodecyldimethylammbromide bromide；
Optionally, the temperature of second mixed processing is 60~100 DEG C.
8. according to the method described in claim 5, it is characterized in that, the illite is provided in the form to suspend in water
's；
It optionally, further comprise being ultrasonically treated illite suspension before carrying out the surface activation process.
9. modified illite is preparing the purposes in γ phase PVDF thin film, the modified illite is by claim 5~8 times
What surface activation process defined by one obtained.
10. a kind of preparation method of γ phase PVDF thin film characterized by comprising
Illite is suspended in water, and illite suspension is ultrasonically treated；
By after ultrasonic treatment illite suspension and dilute hydrochloric acid and cationic surfactant in temperature be 60~100 DEG C
Under the conditions of carry out the second mixed processing, the cationic surfactant and the illitic mass ratio are 3:100~8:
100, the surfactant includes being selected from cetyl trimethylammonium bromide, Cetyltrimethylammonium bromide, double dodecanes
At least one of base ditallowdimethyl ammonium bromide；
Second mixed processing product is filtered processing, to obtain filter residue；
The filter residue is dried, the filter residue after the drying process is modified illite；
The modified illite is suspended in organic solvent, and modified illite suspension is ultrasonically treated, it is described to have
Solvent includes being selected from least one of N,N-dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone；
Modification illite suspension after ultrasonic treatment is carried out first under conditions of temperature is 60~100 DEG C with PVDF pellet
Mixed processing, the mass-volume concentration of the first mixed processing product are 5~20mg/mL, the illitic mass fraction of modification
It is 0.1~5%, first mixed processing is carried out in the organic solvent；
First mixed processing product is subjected to film process；
Film process product is dried；
Product will be dried and carry out melt process under conditions of temperature is 200~220 DEG C, to eliminate thermal history；
Melt process product is subjected to quickly cooling processing, to reach 158~168 DEG C, and is 158 in temperature by melt process product
Isothermal crystal processing is carried out under conditions of~168 DEG C, to obtain the γ phase PVDF thin film.
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