CN106432753B - A kind of preparation method of PVDF extended-chain crystals - Google Patents
A kind of preparation method of PVDF extended-chain crystals Download PDFInfo
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- CN106432753B CN106432753B CN201610857145.2A CN201610857145A CN106432753B CN 106432753 B CN106432753 B CN 106432753B CN 201610857145 A CN201610857145 A CN 201610857145A CN 106432753 B CN106432753 B CN 106432753B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/095—Oxygen containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/11—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids from solid polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- 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
Abstract
The present invention provides a kind of preparation method of PVDF extended-chain crystals, includes the following steps：(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；(2) it dissolves：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, connects heating power supply, and control heating rate is 10 DEG C/min, and heat temperature raising makes it completely dissolved, and keeps the temperature 10~60min；(3) cooling：Mold is cooled to soaking time after certain temperature；(4) it desorbs：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min, so that solvent desorption is removed, obtains PVDF extended-chain crystals.
Description
Technical field
The present invention relates to filed of functional, more specifically, the present invention provides a kind of preparation of PVDF extended-chain crystals
Method.
Background technology
Polyvinyladine floride (Poly (vinylidene fluoride), PVDF), is a kind of hemicrystalline high polymer, no
Only possess higher toughness and intensity, also there is outstanding heat resistance, weatherability and chemical resistance, thus it is wide by industrial circle
It is applied to the fields such as chemical industry, building, electric, mechanical and aerospace generally.Compared with traditional piezoceramic material, gather
Inclined fluorine ethylene has many advantages, such as that low acoustic impedance, light weight, flexible, machine-shaping is easy and cheap.
PVDF is a kind of heteromorphic polymer, at least there are five kinds of crystal forms of α, β, γ, δ and ε.PVDF is in process
Its Molecular connectivity indices or accumulation mode can be caused to change, thus can get different crystal types.Beta crystal belongs to six sides
Crystallographic system, strand are arranged according to flat serrations shape, and the dipole moment of each monomeric unit is flat along identical direction in beta crystal
Row arrangement has spontaneous polarization so that beta crystal possesses maximum piezoelectricity, thermoelectricity and ferroelectric properties to impart beta crystal.β is brilliant
The PVDF piezoelectric materials of type are applied to photoelectric instrument, sensor, piezoelectric actuator etc. in large quantities.
PVDF is crystallized at high temperature under high pressure will can be obtained β type extended-chain crystals, and the machinery for not only increasing PVDF matrixes is strong
Degree and thermal stability, and because polarity is most strong in the various crystal forms of PVDF for β types extended-chain crystal, can increase substantially PVDF's
Electromechanical coupling factor.
The extended-chain crystal for preparing PVDF in the prior art crystallizes at high temperature under high pressure, using HIGH PRESSURE TREATMENT, is prepared
The process industry degree-of-difficulty factor of the extended-chain crystal of PVDF is bigger and of high cost.
Therefore, now there is an urgent need for prepared with excellent mechanical strength, changed by solvent-induced formation eutectic under a kind of normal pressure
Learn the extended-chain crystal of the PVDF of characteristics such as stability, easy processing, good piezoelectricity, ferroelectricity.
Invention content
To solve the above-mentioned problems, the present invention provides a kind of preparation method of PVDF extended-chain crystals, includes the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；
(2) it dissolves：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, is connected and is added
Thermoelectric generator, control heating rate are 10 DEG C/min, and heat temperature raising makes it completely dissolved, and keep the temperature 10~60min；
(3) cooling：Mold is cooled to soaking time after certain temperature；
(4) it desorbs：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min,
So that solvent desorption is removed, obtains PVDF extended-chain crystals.
In one embodiment, the organic solvent is dimethyl sulfoxide (DMSO), diethylene glycol (DEG), acetamide, N, N- dimethyl second
Amide, n,N-Dimethylformamide, cyclohexanol, hexafluoroisopropanol, Isosorbide-5-Nitrae-dioxane, 1,3- dioxies Fourth Ring, hexamethyl phosphoric acid
It is one or more in triamine, acrylamide, acetone, tetrahydrofuran, cyclopentanone, butanone, 4-methyl-2 pentanone.
In one embodiment, the weight ratio of the PVDF and polar solvent is 1：(10~20).
In one embodiment, the mass ratio of the organic solvent-acetone and tetrahydrofuran, cyclopentanone is (1~5)：(2
~10)：1.
In one embodiment, the mass ratio of the organic solvent-acetone and tetrahydrofuran, cyclopentanone is (1~4)：(2
~6)：1.
In one embodiment, holding temperature is 50~80 DEG C in the step (2).
In one embodiment, cooling velocity described in the step (3) is 0.1~1 DEG C/s.
In one embodiment, holding temperature described in the step (3) be 0~20 DEG C, soaking time be 10~
24h。
In one embodiment, holding temperature described in the step (4) be 80~130 DEG C, soaking time be 5~
12h。
In one embodiment, the weight average molecular weight of the PVDF is 5000~500000.
The above-mentioned of the application and other features, aspect and advantage is more readily understood with reference to following detailed description.
Specific implementation mode
The detailed description for preferred implementation method of the invention below of participating in the election of and including embodiment this hair can be more easily understood
Bright content.Unless otherwise defined, all technologies used herein and scientific terminology have common with fields of the present invention
The normally understood identical meaning of technical staff.When there is a conflict, the definition in this specification shall prevail.
As used herein term " by ... prepare " it is synonymous with "comprising".Term "comprising" used herein, " comprising ",
" having ", " containing " or its any other deformation, it is intended that cover non-exclusionism includes.For example, the combination comprising listed elements
Object, step, method, product or device are not necessarily limited to those elements, but may include not expressly listed other elements or
Such composition, step, method, product or the intrinsic element of device.
Conjunction " Consists of " excludes any element that do not point out, step or component.If in claim, this
Phrase will make claim be closed, so that it is not included the material in addition to the material of those descriptions, but relative normal
Except rule impurity.When being rather than immediately following after theme in the clause that phrase " Consists of " appears in claim main body,
It is only limited to the element described in the clause；Other elements are not excluded except the claim as a whole.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1 to 5 ", described range should be interpreted as including range " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to
5 ", " 1 to 3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end
Value and all integers and score in the range.
Singulative includes that plural number discusses object, unless the context clearly dictates otherwise." optional " or it is " arbitrary
It is a kind of " refer to that the item described thereafter or event may or may not occur, and the description include situation that event occurs and
The situation that event does not occur.
Approximate term in specification and claims is used for modifying quantity, and it is specific to indicate that the present invention is not limited to this
Quantity further includes the modified part of the acceptable change without lead to related basic function close to the quantity.Phase
It answers, modifies a numerical value with " about ", " about " etc., mean that the present invention is not limited to the exact numericals.In some examples, approximate
Term likely corresponds to the precision of the instrument of measured value.In present specification and claims, range limits can be with
Combination and/or exchange, these ranges include all subranges contained therebetween if not stated otherwise.
In addition, indefinite article "an" before element of the present invention or component and "one" quantitative requirement to element or component
(i.e. occurrence number) unrestriction.Therefore "one" or "an" should be read as including one or at least one, and odd number
The element or component of form also include plural form, unless the apparent purport of the quantity refers to singulative.
" polymer " means the polymerizable compound prepared by the monomer by the identical or different type of polymerization.Generic term
" polymer " includes term " homopolymer ", " copolymer ", " terpolymer " and " copolymer ".
" copolymer " means the polymer prepared by polymerizeing at least two different monomers.Generic term " copolymer " includes
(it is general with term " terpolymer " for term " copolymer " (its generally to refer to the polymer prepared by two kinds of different monomers)
To refer to the polymer prepared by three kinds of different monomers).It also includes the polymer manufactured by polymerizeing more kinds of monomers.
" blend " means the polymer that two or more polymer is formed by mixing jointly by physics or chemical method.
The present invention provides a kind of preparation method of PVDF extended-chain crystals, includes the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；
(2) it dissolves：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, is connected and is added
Thermoelectric generator, control heating rate are 10 DEG C/min, and heat temperature raising makes it completely dissolved, and keep the temperature 10~60min；
(3) cooling：Mold is cooled to soaking time after certain temperature；
(4) it desorbs：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min,
So that solvent desorption is removed, obtains PVDF extended-chain crystals.
The chemical formula of PVDFPVDF is a kind of heteromorphic polymer, at least there is α, β, γ, δ and ε five
Kind crystal form.PVDF can cause its Molecular connectivity indices or accumulation mode to change in process, thus can get difference
Crystal type:Alpha-crystal form is the crystal form that PVDF is most often obtained in crystallization process；And β and γ crystal forms are needed in specific condition
It is lower just to prepare；Two kinds of crystal forms of δ and ε are compared for first three crystal form, and the condition of preparation is harsher.α, β, γ of PVDF
Three kinds of crystal forms under certain conditions can phase co-conversion.
Beta crystal belongs to hexagonal crystal system, and strand is arranged according to flat serrations shape, the F of H and aobvious negative electricity due to showing positive electricity
Atom is arranged separately on that the both sides of carbochain and dipole moment direction are identical, in beta crystal the dipole moment of each monomeric unit along
Identical direction is arranged in parallel, to impart beta crystal have spontaneous polarization so that beta crystal possess maximum piezoelectricity, thermoelectricity and
Ferroelectric properties.The PVDF piezoelectric materials of beta crystal are applied to the side such as photoelectric instrument, sensor, piezoelectric actuator in large quantities
Face.
In the present invention, what the PVDF can be enumerated has：Like that rich FR901, Shanghai three love rich FR902, Shanghai three in Shanghai three
Love richness FR903, Shanghai three like rich FR904, Shanghai three like rich FR905, Shanghai three like rich FR906, Shanghai three like rich FR907, on
Hai Sanai richnesses FR921-1, Shanghai three like rich FR921-2, U.S. 3M11008/0001, U.S. 3M 11008/0003, the U.S.
11010/0000, U.S. 3M 31508/0003, U.S. 3M 31508/0009, U.S. 3M 32008/0009, U.S. 3M
60512/0000, U.S. 3M 6008, U.S. Su Wei 1015 (powder), U.S. Su Wei 11010, U.S. Su Wei 21510, U.S. Su Wei
31508, U.S. Su Wei 41308, U.S. Su Wei 460/461, U.S. Su Wei 5130, U.S. Su Wei 6012, U.S. Su Wei 6020, U.S.
State Su Wei 60512, U.S. Su Wei 9007, U.S. Su Wei 9009, U.S. Su Wei 20810-0.1, U.S. Su Wei 20810-19, the U.S.
Su Wei 20810-20, U.S. Su Wei 20810-3, U.S. Su Wei 20810-30, U.S. Su Wei 20810-32, U.S. Su Wei 20810-
47, U.S. Su Wei 20810-55, U.S. Su Wei 21216 (powder), U.S. Su Wei 21508/0001, U.S. Su Wei 460-NC, the U.S.
Su Wei 6008, U.S. Su Wei 6008/0001, U.S. Su Wei 6010 (powder), U.S. Su Wei 6010NC, U.S. Su Wei 720, Soviet Union of the U.S.
Prestige HR460, France A Kema 2750, France A Kema 2800-00, France A Kema 2801, France A Kema 2850, French Ah
Kerma (unit of kinetic energy) 450, France A Kema 460, France A Kema 500, France A Kema 720, France A Kema 740, France A Kema
761, France A Kema 761A, France A Kema 9000HD, France A Kema HR761, France A Kema HSV900, France A Ke
Agate KR761.
Extended-chain crystal
Extended-chain crystal (ECC) is presently believed to be the crystal of thermodynamicaHy most stable.It is to be directed to folded-chain crystal
(FCC) for, i.e., the Molecular connectivity indices for not having in platelet or slightly folding, thickness is more than or equal to molecular chain length.
By comparing lamellae thickness distribution short chain molecule (molecular weight≤10 are can be inferred that with molecular weight distribution4) can reach under high pressure
To stretching completely, and the folded form of long-chain molecule all in various degree is present in platelet.
The formation mechenism of extended-chain crystal：
The extended-chain crystal of polymer can both be reset by folded-chain crystal, and control solvent desorption forms, also can be direct
It is formed from melt crystallization.Which kind of specific form accounts for leading, it is necessary to crystallization temperature, soaking time during Binding experiment, crystallization
Pressure and the warming and cooling rate of experiment specifically consider.
In one embodiment, the weight ratio of the PVDF and organic solvent is 1：(10~20)；Preferably, described
The weight ratio of PVDF and organic solvent is 1：(10~18)；Preferably, the weight ratio of the PVDF and organic solvent is 1：15.
In one embodiment, the organic solvent is dimethyl sulfoxide (DMSO), diethylene glycol (DEG), acetamide, N, N- dimethyl second
Amide, n,N-Dimethylformamide, cyclohexanol, hexafluoroisopropanol, Isosorbide-5-Nitrae-dioxane, 1,3- dioxies Fourth Ring, hexamethyl phosphoric acid
It is one or more in triamine, acrylamide, acetone, tetrahydrofuran, cyclopentanone, butanone, 4-methyl-2 pentanone；Preferably, described
Organic solvent is dimethyl sulfoxide (DMSO), n,N-Dimethylformamide, cyclohexanol, hexafluoroisopropanol, Isosorbide-5-Nitrae-dioxane, 1,3- dioxies
It is one or more in Fourth Ring, acetone, tetrahydrofuran, cyclopentanone, butanone, 4-methyl-2 pentanone.
In one embodiment, the mass ratio of the organic solvent-acetone and tetrahydrofuran, cyclopentanone is (1~5)：(2
~10)：1；Preferably, the mass ratio of the organic solvent-acetone and tetrahydrofuran, cyclopentanone is (1~4)：(2~6)：1.
In one embodiment, the weight average molecular weight of the PVDF is 5000~500000；Preferably, the PVDF
Weight average molecular weight is 10000~300000；Preferably, the weight average molecular weight of the PVDF is 280000.
After weight average molecular weight carries out polystyrene conversion based on gel permeation chromatography (referred to as " GPC ") measurement
Value.The determination condition of GPC uses the condition test of this field routine, tests to obtain for example, following modes can be used.
Column：Following columns are connected in series with and are used.
" TSKgelG5000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG4000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG3000 " (7.8mmI.D. × 30cm) × 1 piece
" TSKgelG2000 " (7.8mmI.D. × 30cm) × 1 piece
Detector：RI (differential refractometer)；Column temperature：40℃；Eluent：Tetrahydrofuran (THF)；Flow velocity：1.0mL/ point
Clock；Injection rate：100 μ L (tetrahydrofuran solution of sample solution concentration 4mg/mL)；Standard sample：Use following monodisperse polystyrenes
Alkene makes standard curve.
In one embodiment, the rotating speed of step (1) the high speed mixing machine is 20000~25000r/min.
In one embodiment, holding temperature is 50~80 DEG C in the step (2)；Preferably, in the step (2)
Holding temperature is 50~70 DEG C.
In one embodiment, cooling velocity described in the step (3) is 0.1~1 DEG C/s；Preferably, the step
Suddenly cooling velocity described in (3) is 0.5~1 DEG C/s.
In one embodiment, holding temperature described in the step (3) be 0~20 DEG C, soaking time be 10~
24h；Preferably, holding temperature described in the step (3) is 0~15 DEG C, and soaking time is 10~20h.
In one embodiment, holding temperature described in the step (4) be 80~130 DEG C, soaking time be 5~
12h；Preferably, holding temperature described in the step (4) is 100~130 DEG C, and soaking time is 5~12h.
PVDF forms eutectic with organic solvent, adjusts crystallization process by the diffusion of the solvent of glassy state PVDF, leads to
The interaction crossed between solvent molecule reduces the micro Brownian motion of the glass transition temperature induction amorphous chain of polymer, this widens
Glass transition temperature and melting temperature, are conducive to polymer and crystallize at a lower temperature.
When PVDF is precipitated from solvent, PVDF tends to generate alpha-crystal, is desorbed, is promoted to solvent by controlling temperature
It is discharged again into PVDF lattices, obtains the crystal of the orientation with chain, i.e. β crystal.
The present invention forms eutectic by PVDF and organic solvent, and knot is adjusted by the diffusion of the solvent of glassy state PVDF
Brilliant process, control mixed solvent acetone and tetrahydrofuran, cyclopentanone desorption (evaporation) rate regulate and control the crystallization rate of PVDF
And crystal type (β crystal), the PVDF extended-chain crystals to be had excellent performance in atmospheric conditions, and it is suitble to industrial metaplasia
Production.
In one embodiment, the thickness of the PVDF extended-chain crystals is 100~420 μm.
The present invention is specifically described below by embodiment.It is necessarily pointed out that following embodiment is only used
In the invention will be further described, it should not be understood as limiting the scope of the invention, professional and technical personnel in the field
Some the nonessential modifications and adaptations made according to the content of aforementioned present invention, still fall within protection scope of the present invention.
In addition, if without other explanations, it is raw materials used to be all commercially available, it is purchased from traditional Chinese medicines chemical reagent.
Embodiment 1
The preparation method of PVDF extended-chain crystals includes the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；The PVDF with have
The weight ratio of solvent is 1：20；The mass ratio of the organic solvent-acetone and tetrahydrofuran is 1：10；The weight of the PVDF is equal
Molecular weight is 100000；
(2) it melts：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, is connected and is added
Thermoelectric generator, control heating rate are 10 DEG C/min, and heat temperature raising makes it be completely melt, and keeps the temperature 45min；The holding temperature is
50℃；
(3) cooling：Mold is cooled to soaking time after certain temperature, the cooling velocity is 0.2 DEG C/s；The heat preservation
Temperature is 20 DEG C；The soaking time is 20h；
(4) dry：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min,
So that solvent desorption is removed, obtains PVDF extended-chain crystals；The holding temperature is 80 DEG C, soaking time 10h.
Embodiment 2
The preparation method of PVDF extended-chain crystals includes the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；The PVDF with have
The weight ratio of solvent is 1：18；The mass ratio of the organic solvent-acetone and cyclopentanone is 10：1；The PVDF's divides equally again
Son amount is 200000；
(2) it melts：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, is connected and is added
Thermoelectric generator, control heating rate are 10 DEG C/min, and heat temperature raising makes it be completely melt, and keeps the temperature 45min；The holding temperature is
60℃；
(3) cooling：Mold is cooled to soaking time after certain temperature, the cooling velocity is 0.2 DEG C/s；The heat preservation
Temperature is 20 DEG C；The soaking time is 20h；
(4) dry：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min,
So that solvent desorption is removed, obtains PVDF extended-chain crystals；The holding temperature is 100 DEG C, soaking time 10h.
Embodiment 3
The preparation method of PVDF extended-chain crystals includes the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；The PVDF with have
The weight ratio of solvent is 1：16；The mass ratio of the organic solvent-acetone and tetrahydrofuran, cyclopentanone is 1：10：1；It is described
The weight average molecular weight of PVDF is 300000；
(2) it melts：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, is connected and is added
Thermoelectric generator, control heating rate are 10 DEG C/min, and heat temperature raising makes it be completely melt, and keeps the temperature 45min；The holding temperature is
80℃；
(3) cooling：Mold is cooled to soaking time after certain temperature, the cooling velocity is 0.2 DEG C/s；The heat preservation
Temperature is 15 DEG C；The soaking time is 20h；
(4) dry：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min,
So that solvent desorption is removed, obtains PVDF extended-chain crystals；The holding temperature is 110 DEG C, soaking time 10h.
Embodiment 4
The preparation method of PVDF extended-chain crystals includes the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；The PVDF with have
The weight ratio of solvent is 1：12；The mass ratio of the organic solvent-acetone and tetrahydrofuran, cyclopentanone is 5：6：1；It is described
The weight average molecular weight of PVDF is 400000；
(2) it melts：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, is connected and is added
Thermoelectric generator, control heating rate are 10 DEG C/min, and heat temperature raising makes it be completely melt, and keeps the temperature 45min；The holding temperature is
70℃；
(3) cooling：Mold is cooled to soaking time after certain temperature, the cooling velocity is 0.2 DEG C/s；The heat preservation
Temperature is 0 DEG C；The soaking time is 20h；
(4) dry：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min,
So that solvent desorption is removed, obtains PVDF extended-chain crystals；The holding temperature is 130 DEG C, soaking time 10h.
Embodiment 5
The preparation method of PVDF extended-chain crystals includes the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；The PVDF with have
The weight ratio of solvent is 1：15；The mass ratio of the organic solvent-acetone and tetrahydrofuran, cyclopentanone is 4：3：1；It is described
The weight average molecular weight of PVDF is 500000；
(2) it melts：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, is connected and is added
Thermoelectric generator, control heating rate are 10 DEG C/min, and heat temperature raising makes it be completely melt, and keeps the temperature 45min；The holding temperature is
70℃；
(3) cooling：Mold is cooled to soaking time after certain temperature, the cooling velocity is 0.2 DEG C/s；The heat preservation
Temperature is 10 DEG C；The soaking time is 20h；
(4) dry：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min,
So that solvent desorption is removed, obtains PVDF extended-chain crystals；The holding temperature is 130 DEG C, soaking time 10h.
Embodiment 6
The preparation method of PVDF extended-chain crystals includes the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；The PVDF with have
The weight ratio of solvent is 1：16；The mass ratio of the organic solvent-acetone and tetrahydrofuran, cyclopentanone is 3：5：1；It is described
The weight average molecular weight of PVDF is 280000；
(2) it melts：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, is connected and is added
Thermoelectric generator, control heating rate are 10 DEG C/min, and heat temperature raising makes it be completely melt, and keeps the temperature 45min；The holding temperature is
70℃；
(3) cooling：Mold is cooled to soaking time after certain temperature, the cooling velocity is 0.2 DEG C/s；The heat preservation
Temperature is 3 DEG C；The soaking time is 20h；
(4) dry：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min,
So that solvent desorption is removed, obtains PVDF extended-chain crystals；The holding temperature is 100 DEG C, soaking time 10h.
Comparative example 1
The preparation method of PVDF extended-chain crystals includes the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；The PVDF with have
The weight ratio of solvent is 1：16；The organic solvent is tetrahydrofuran；The weight average molecular weight of the PVDF is 280000；
(2) it melts：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, is connected and is added
Thermoelectric generator, control heating rate are 10 DEG C/min, and heat temperature raising makes it be completely melt, and keeps the temperature 45min；The holding temperature is
64℃；
(3) cooling：Mold is cooled to soaking time after certain temperature, the cooling velocity is 0.2 DEG C/s；The heat preservation
Temperature is 3 DEG C；The soaking time is 20h；
(4) dry：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min,
So that solvent desorption is removed, obtains PVDF extended-chain crystals；The holding temperature is 90 DEG C, soaking time 10h.
Comparative example 2
The preparation method of PVDF extended-chain crystals includes the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；The PVDF with have
The weight ratio of solvent is 1：16；The organic solvent is acetone；The weight average molecular weight of the PVDF is 280000；
(2) it melts：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, is connected and is added
Thermoelectric generator, control heating rate are 10 DEG C/min, and heat temperature raising makes it be completely melt, and keeps the temperature 45min；The holding temperature is
55℃；
(3) cooling：Mold is cooled to soaking time after certain temperature, the cooling velocity is 0.2 DEG C/s；The heat preservation
Temperature is 3 DEG C；The soaking time is 20h；
(4) dry：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min,
So that solvent desorption is removed, obtains PVDF extended-chain crystals；The holding temperature is 80 DEG C, soaking time 10h.
Comparative example 3
The preparation method of PVDF extended-chain crystals includes the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；The PVDF with have
The weight ratio of solvent is 1：16；The organic solvent is DMSO；The weight average molecular weight of the PVDF is 280000；
(2) it melts：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, is connected and is added
Thermoelectric generator, control heating rate are 10 DEG C/min, and heat temperature raising makes it be completely melt, and keeps the temperature 45min；The holding temperature is
70℃；
(3) cooling：Mold is cooled to soaking time after certain temperature, the cooling velocity is 0.2 DEG C/s；The heat preservation
Temperature is 3 DEG C；The soaking time is 20h；
(4) dry：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min,
So that solvent desorption is removed, obtains PVDF extended-chain crystals；The holding temperature is 130 DEG C, soaking time 10h.
Comparative example 4
The preparation method of PVDF extended-chain crystals includes the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；The PVDF with have
The weight ratio of solvent is 1：16；The organic solvent is DMF；The weight average molecular weight of the PVDF is 280000；
(2) it melts：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, is connected and is added
Thermoelectric generator, control heating rate are 10 DEG C/min, and heat temperature raising makes it be completely melt, and keeps the temperature 45min；The holding temperature is
70℃；
(3) cooling：Mold is cooled to soaking time after certain temperature, the cooling velocity is 0.2 DEG C/s；The heat preservation
Temperature is 3 DEG C；The soaking time is 20h；
(4) dry：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min,
So that solvent desorption is removed, obtains PVDF extended-chain crystals；The holding temperature is 130 DEG C, soaking time 10h.
Test method
1, sample fusing point (Tm) is tested：
TEM is the Tecnai G2F20S-TWIN type transmission electron microscopes using FEI Co. of the U.S..
About 6mg polymer samples are sealed in aluminium crucible, 250 DEG C are heated to 10 DEG C/min heating rates, to
Determine the molten point of sample.
2, the type and content of crystal form
FTIR tests are to load onto ATR attachmentes on the Nieolet5700 type infrared spectrometers that power ＆ light company of the U.S. produces,
The wave-number range of outer red scanning 32 times, spectrum is 700~4000cm-1, it is distinguished as 4cm-1, α, β and γ crystal of PVDF it is opposite
Content can be calculated by ATR-FTIR data quantitatives：
F (beta, gamma)=A840/(A840+1.26×A764)(1)
The relative amount that β and γ crystal is occupied in total crystal in wherein PVDF, A840It is 840cm-1The face of characteristic peak
Product, A764It is 764cm-1The area of characteristic peak.
F (β)=A1280/(A1280+A1234)(2)
Wherein F (β) is the relative amount that β crystal accounts for β and γ crystal in PVDF, A1280It is 1280cm-1The area of characteristic peak,
A1234It is 1234cm-1The area of characteristic peak.
3, micro-hardness testing
Indentation test is carried out to (001) face of the PVDF crystal obtained after cleavage using intelligent microhardness testers,
According to the Vickers hardness of the size of impression sample to calculate.
1 the performance test results of table
It can be seen from the results above that compared with single solvent DMF, DMSO, acetone and tetrahydrofuran, it is provided by the invention
The β type extended-chain crystals that PVDF extended-chain crystals obtain have spontaneous polarization so that beta crystal possess maximum piezoelectricity, thermoelectricity and
Ferroelectric properties can increase substantially the electromechanical coupling factor of PVDF.
Example above-mentioned is merely illustrative, some features for explaining the method for the invention.Appended right is wanted
The range as wide as possible for being intended to require to be contemplated that is sought, and embodiments as presented herein is only according to all possible implementation
The explanation of the embodiment of the selection of the combination of example.Therefore, the purpose of applicant is that the attached claims are not illustrated this hair
The exemplary selectional restriction of bright feature.Some numberical ranges used also include sub- model in the claims
It encloses, the variation in these ranges should also be construed to be covered by the attached claims in the conceived case.
Claims (7)
1. a kind of preparation method of PVDF extended-chain crystals, which is characterized in that include the following steps：
(1) it is blended：It is premixed by weight PVDF to be added with organic solvent in high-speed mixer；
(2) it dissolves：Batch mixing is put into specified mold, the mold that then will be filled with material is fitted into heating furnace, connects heating electricity
Source, control heating rate are 10 DEG C/min, and heat temperature raising makes it completely dissolved, and keep the temperature 10~60min；
(3) cooling：Mold is cooled to soaking time after certain temperature；
(4) it desorbs：The sample that step (3) obtains is warming up to certain temperature heat preservation, control heating rate is 1 DEG C/min, is made molten
Agent desorption removes, and obtains PVDF extended-chain crystals；
Wherein, the weight ratio of the PVDF and organic solvent is 1：(10~20)；The organic solvent-acetone and tetrahydrofuran, ring
The mass ratio of pentanone is (1~5)：(2~10)：1.
2. the preparation method of PVDF extended-chain crystals according to claim 1, which is characterized in that the organic solvent-acetone with
Tetrahydrofuran, cyclopentanone mass ratio be (1~4)：(2~6)：1.
3. the preparation method of PVDF extended-chain crystals according to claim 1, which is characterized in that heat preservation in the step (2)
Temperature is 50~80 DEG C.
4. the preparation method of PVDF extended-chain crystals according to claim 1, which is characterized in that described in the step (3)
Cooling velocity is 0.1~1 DEG C/s.
5. the preparation method of PVDF extended-chain crystals according to claim 1, which is characterized in that described in the step (3)
Holding temperature be 0~20 DEG C, soaking time be 10~for 24 hours.
6. the preparation method of PVDF extended-chain crystals according to claim 1, which is characterized in that described in the step (4)
Holding temperature is 80~130 DEG C, and soaking time is 5~12h.
7. the preparation method of PVDF extended-chain crystals according to claim 1, which is characterized in that the Weight-average molecular of the PVDF
Amount is 5000~500000.
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