CN108948604A - A kind of γ type Kynoar/poly adipate succinic acid ester composite material and preparation method - Google Patents
A kind of γ type Kynoar/poly adipate succinic acid ester composite material and preparation method Download PDFInfo
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- CN108948604A CN108948604A CN201810617855.7A CN201810617855A CN108948604A CN 108948604 A CN108948604 A CN 108948604A CN 201810617855 A CN201810617855 A CN 201810617855A CN 108948604 A CN108948604 A CN 108948604A
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- acid ester
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
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- C08J2427/00—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
- C08J2427/02—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
- C08J2427/12—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
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
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- 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
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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Abstract
A kind of γ type Kynoar/poly adipate succinic acid ester composite material, including accounting for the polyvinylidene fluoride acid PVDF of gross mass 30% ~ 70% and accounting for the poly adipate succinic acid ester PBA of gross mass 30% ~ 70%.Wherein, polyvinylidene fluoride acid is γ type polyvinylidene fluoride acid, is furthermore also possible that part α type polyvinylidene fluoride acid.The preparation method of the composite material are as follows: be dissolved in Kynoar and poly adipate succinic acid ester in enough DMF；Kynoar/poly adipate succinic acid ester laminated film is produced after being completely dissolved；By Kynoar/poly adipate succinic acid ester laminated film heating melting to eliminate thermal history, then it is cooled to 155 DEG C ~ 160 DEG C rapidly, constant temperature incubation obtains the Kynoar with γ type Kynoar/poly adipate succinic acid ester composite material to complete recrystallization.The manufacture craft of this composite biodegradable material is simply scientific, and low in cost, process is controllable.
Description
Technical field
The invention belongs to field of polymer material preparing technology, and in particular to a kind of γ type Kynoar/polyadipate
Butanediol ester composite material and preparation method.
Background technique
Kynoar (PVDF) also has piezoelectricity, dielectric other than the characteristic with fluororesin and resins for universal use
The electrical properties such as property and pyroelectric, to cause the extensive concern of people in materials science field.The diversified usability of PVDF
Can the crystalline structure complicated and changeable with it have substantial connection, and can mutually turn under certain condition between various crystal form crystal
Become, therefore further investigate the various crystalline structures of PVDF and its mutual transition mechanisms between them and essence, inquires into the not isomorphous
The influence of type structure on performance, has important theoretical significance and practical application value.Known PVDF has five kinds of α, β, γ, δ and ε
Crystal form, wherein the most common one is α, β, γ, the excellent in mechanical performance of the PVDF of alpha-crystal form is preferable photoelectricity energy storage material.β
Crystal form is the important crystal form of PVDF, is widely used in the energy transducers such as photoelectricity, temperature-sensitive, pressure-sensitive, is at present using most successful
Class-1 piezoelectric high molecular material.The molecular chain configuration of the PVDF of γ crystal form is similar to the configuration of β phase, molecular configuration TTTG,
Two strands are arranged in parallel in same structure cell, have polarity since dipole moment direction is identical, but its polarity is less than β phase, tool
There are the electrical properties such as excellent piezoelectricity, thermoelectricity.
The PVDF of γ crystal form has following several preparation methods: PVDF melt high annealing, addition the second component nucleation at present
Agent.The γ phase that high annealing obtains is actually that α-PVDF crystal changes to be formed by solid solid phase under the high temperature conditions, referred to as
γ-PVDF, close due to arranging, melting temperature is higher.
The method for preparing γ crystal form PVDF at present, needs high temperature thermal field, the γ phase PVDF quantity of generation is few and position is random.
These preparation processes are complicated, are related to means multiplicity, are unfavorable for seek unity of standard metaplasia production and industrial applications, can only provide theoretical skill
Art foundation, in the following application field, there is also many limitations.
Summary of the invention
In order to overcome the above-mentioned deficiencies of the prior art, the object of the present invention is to provide a kind of γ type Kynoar
(PVDF) it is fast, hot steady can to obtain crystallization by this method for/poly adipate succinic acid ester (PBA) composite material and preparation method
Qualitative polyester material high, degradation rate is fast, preparation method is simple.
The raw material that the material and method are related to: Kynoar (PVDF), poly adipate succinic acid ester (PBA), N,
Dinethylformamide (DMF).In the present invention, material based on PVDF is dissolved completely in n,N-Dimethylformamide, PBA
It is uniformly dispersed in the DMF solution of PVDF.1) preparation method the following steps are included: weigh a certain amount of PVDF, respectively respectively
It is placed in the volumetric flask of 10ml, is individually identified as No. 1, No. 2, No. 3；2) a certain amount of PBA is weighed respectively, is respectively placed in step 1)
In No. 1, No. 2, No. 3 in, be settled to 10ml with the good solvent DMF of PVDF and PBA, magnetic agitation rotor room temperature magnetic force be added and stirs
Mix 30min, be completely dissolved PVDF with PBA, in triplicate, obtain PVDF and PBA content be respectively 30wt%, 50wt%,
Three parts of blend solutions of 70wt%；3) the PVDF/PBA solution of three kinds of different ratios obtained by step 2 is passed through into solution-cast
Method, obtained thickness unify film, volatilize completely under room temperature to solvent DMF, are placed in vacuum drier and are dried in vacuo 6 in 25 DEG C
Hour；4) laminated film made from step 3) is placed in 200 DEG C of Thermostatic platform, constant temperature incubation 10min will completely eliminate heat
The cultivation temperature of above-mentioned laminated film after history is rapidly decreased to 155 DEG C ~ 160 DEG C, and constant temperature incubation recrystallizes it completely for 24 hours.
The manufacture craft of this composite biodegradable material is simply scientific, and low in cost, process is controllable, is expected to industrialized production, tool
There are great potential application foreground and economic benefit.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of γ type Kynoar/polyadipate fourth two
Alcohol ester composite material and preparation method, comprising the following steps:
1) PVDF=0.15g, 0.25g, 0.35g are weighed respectively, is respectively placed in the volumetric flask of 10ml, and No. 1,2 are individually identified as
Number, No. 3；
2) PBA=0.35g, 0.25g, 0.15g are weighed respectively, is respectively placed in No. 1 in step 1), No. 2, No. 3, with PVDF with
The good solvent n,N-Dimethylformamide of PBA is settled to 10ml, and magnetic agitation rotor room temperature magnetic agitation 30min is added, makes
PVDF is completely dissolved with PBA, in triplicate, obtain PVDF and PBA content be respectively three parts of 30wt%, 50wt%, 70wt% altogether
Miscible fluid；
3) it is unified that thickness is made by solution casting method in the PVDF/PBA solution of three kinds of different ratios obtained by step 2
Film volatilizees to solvent n,N-Dimethylformamide completely under room temperature, is placed in vacuum drier small in 25 DEG C of vacuum drying 6
When；
4) laminated film made from step 3) is placed in 200 DEG C of Thermostatic platform, constant temperature incubation 10min guarantees polymer thin
Film is sufficiently melted to eliminate thermal history；
5) cultivation temperature for completely eliminating the above-mentioned laminated film after thermal history is rapidly decreased to 155 DEG C ~ 160 DEG C, constant temperature incubation
Recrystallize it completely for 24 hours；
6) product after step 5) sufficient crystallising is taken out from heated at constant temperature platform, is cooled to room temperature, it is to be detected.By in polarisation
Microscopically observation finds that we obtain a kind of composite material with different nucleation densities and crystal morphology.
The PVDF/PBA composite film material of different mixture ratio obtained is placed under petrographic microscope through the above steps
Observation, discovery can also occur very big according to the variation of PBA content except spherulite size according to crystallization temperature in addition to changing
Variation；It compares pure PVDF crystallization shape of PVDF after PBA is added also to be changed, and with the change of PBA content
Change and changes.
Use the nucleation and growing state of polarized light microscope observing sample.Compound is judged with differential scanning calorimeter
Whether crystallization temperature and melting temperature are regularly changing.
The beneficial effects of the present invention are:
Compared with prior art, the component PBA in the present invention has excellent biocompatible property and biodegradability, answers
With extensive.PBA is uniformly dispersed in PVDF matrix, and ensure that will not be because of agglomeration and to mechanics during crystalline growth
Performance causes irreversible effect.And the Molecular connectivity indices that can be alpha-crystal type in PVDF change to γ crystal type, to be
The mechanism increases the ability of storage charge, that is, improves the dielectric properties of the laminated film.
The present invention carries out induced transformation to PVDF crystal by addition PBA, and thickness unification is made by solution casting method
Film.Detection comparison discovery, in PBA laminated film is added, quick phase transformation is had occurred in PVDF, and spherulite size is unified,
It is evenly distributed.Pure PVDF is compared, the transformation rate of PVDF improves in the presence of PBA, and the relative amount of γ phase crystal is significantly
It improves, this is because inducing action of the PBA to PVDF.A kind of crystal-phase transformation mechanism is provided, this method shortens preparation time,
And the stable laminated film containing a large amount of γ phase crystal can be prepared in the short period.
Detailed description of the invention
Fig. 1 is inclined after the composite sample of PVDF and PBA different ratio in the present invention is cultivated 24 hours at 155 DEG C
Light microscope figure.
Fig. 2 is PVDF/PBA composite sample differential scanning calorimetry heat release figure of the present invention.
Specific embodiment
Invention is further described in detail combined with specific embodiments below.
Embodiment 1:
A kind of preparation method of Kynoar/poly adipate succinic acid ester composite material, comprising the following steps:
1) PVDF=0.15g is weighed, is placed in the volumetric flask of 10ml, is identified as No. 1；
2) PBA=0.35g is weighed, is placed in in step 1) No. 1, it is fixed with the good solvent n,N-Dimethylformamide of PVDF and PBA
Hold to 10ml, magnetic agitation rotor room temperature magnetic agitation 30min is added, is completely dissolved PVDF with PBA, in triplicate, obtains
The content of PVDF and PBA is the blend solution of 30wt%；
3) by PVDF/PBA solution obtained by step 2 by solution casting method, obtained thickness unifies film, to molten under room temperature
Agent n,N-Dimethylformamide is volatilized completely, is placed in vacuum drier and is dried in vacuo 6 hours in 25 DEG C；
4) laminated film made from step 3) is placed in 200 DEG C of Thermostatic platform, constant temperature incubation 10min guarantees polymer thin
Film is sufficiently melted to eliminate thermal history；
5) cultivation temperature for completely eliminating the above-mentioned laminated film after thermal history is rapidly decreased to 155 DEG C, constant temperature incubation makes it for 24 hours
Recrystallization completely；
6) product after step 5) sufficient crystallising is taken out from heated at constant temperature platform, is cooled to room temperature, it is to be detected.
Embodiment 2:
A kind of preparation method of Kynoar/poly adipate succinic acid ester composite material, comprising the following steps:
1) PVDF=0.25g is weighed, is placed in the volumetric flask of 10ml, is identified as No. 2；
2) PBA=0.25g is weighed, is placed in in step 1) No. 2, it is fixed with the good solvent n,N-Dimethylformamide of PVDF and PBA
Hold to 10ml, magnetic agitation rotor room temperature magnetic agitation 30min is added, is completely dissolved PVDF with PBA, obtains PVDF and PBA
Content be 50wt% blend solution；
3) by PVDF/PBA solution obtained by step 2 by solution casting method, obtained thickness unifies film, to molten under room temperature
Agent n,N-Dimethylformamide is volatilized completely, is placed in vacuum drier and is dried in vacuo 6 hours in 25 DEG C；
4) laminated film made from step 3) is placed in 200 DEG C of Thermostatic platform, constant temperature incubation 10min guarantees polymer thin
Film is sufficiently melted to eliminate thermal history；
5) cultivation temperature for completely eliminating the above-mentioned laminated film after thermal history is rapidly decreased to 155 DEG C, constant temperature incubation makes it for 24 hours
Recrystallization completely；
6) product after step 5) sufficient crystallising is taken out from heated at constant temperature platform, is cooled to room temperature, it is to be detected.
Embodiment 3:
A kind of preparation method of Kynoar/poly adipate succinic acid ester composite material, comprising the following steps:
1) PVDF=0.35g is weighed, is placed in the volumetric flask of 10ml, is identified as No. 3；
2) PBA=0.15g is weighed, is placed in step 1) in No. 3, with the good solvent n,N-Dimethylformamide constant volume of PVDF and PBA
To 10ml, magnetic agitation rotor room temperature magnetic agitation 30min is added, is completely dissolved PVDF with PBA, obtains PVDF's and PBA
Content is the blend solution of 70wt%；
3) by PVDF/PBA solution obtained by step 2 by solution casting method, obtained thickness unifies film, to molten under room temperature
Agent n,N-Dimethylformamide is volatilized completely, is placed in vacuum drier and is dried in vacuo 6 hours in 25 DEG C；
4) laminated film made from step 3) is placed in 200 DEG C of Thermostatic platform, constant temperature incubation 10min guarantees polymer thin
Film is sufficiently melted to eliminate thermal history；
5) cultivation temperature for completely eliminating the above-mentioned laminated film after thermal history is rapidly decreased to 160 DEG C, constant temperature incubation makes it for 24 hours
Recrystallization completely；
6) product after step 5) sufficient crystallising is taken out from heated at constant temperature platform, is cooled to room temperature, it is to be detected.
Embodiment 4:
Referring to Fig. 1,24 hours polarisations are cultivated at 155 DEG C for the PVDF/PBA composite material of different ratio prepared by this experiment
Microscope figure.A is the sample of PVDF/PBA=3/7, passes through polarized light microscope observing, it can be seen that complete spherulitic crystal structure, from figure
In it can be seen that α spherocrystal has apparent zonary structure, and it is wherein also unobvious and without zonary structure containing birefringent phenomenon
γ spherocrystal.B is the sample of PVDF/PBA=5/5, passes through polarized light microscope observing, it can be seen that spherulite size is larger (about
400 μm) and α spherocrystal zonary structure it is obvious, wherein unobvious containing birefringent phenomenon and γ spherocrystal without zonary structure, compare a
It is obvious to become large-sized annulus spacing for spherocrystal from the point of view of figure.C is that the sample of PVDF/PBA=3/7 becomes smaller (about compared to a figure with b figure spherulite size
It is 100 μm) this is because the increase of PBA content hinders the growth of PVDF spherocrystal.
Sample prepared by embodiment 1 ~ 3 is placed in differential scanning calorimeter and carries out heat analysis, test result is referring to fig. 2.
Fig. 2 is the differential scanning calorimetry heat release figure of the PVDF/PBA composite material of different mixture ratio, wherein corresponding 3/7 in figure
There are four melting peaks in the melting behavior of the PVDF/PBA of compound system, can not judge system according to the temperature of melting peak
The crystallization situation of middle PVDF.This may be because PBA content it is more in the case where, the crystallization of PVDF melt receives huge limit
System, it is complete there is no crystallizing under this crystallization condition, so complicated melting peak is showed in subsequent temperature-rise period.Phase
Than under, the melting behavior for the compound system that mass ratio is 5/5 and 7/3 is just very regular, and PVDF melt is crystallized in film
Completely.Such as scheme to compare melting curve b and c, all occur very strong melting peak at 185 DEG C, illustrates PVDF in the two proportions
In all generate the more regular structure of structure, thus macroscopic property stablize, need to absorb amount of heat during heating
It is that strand comes back to active state.Unlike, in 7/3 compound system, the melting peak intensity at 170 DEG C is in 185
It is suitable that peak intensity is melted at DEG C.In the compound system that mass ratio is 5/5, the melting peak at 170 DEG C is almost without appearance.This is
The arrangement of PVDF strand can be promoted to pile up faster because enough PBA are added into PVDF matrix, make its structure more
Stablize.This result is consistent with the result of study of POM, in PVDF/PBA compound system, increases containing for PBA in a certain range
Amount increases birefringent weaker PVDF crystal relative amount.
Claims (6)
1. a kind of γ type Kynoar/poly adipate succinic acid ester composite material, it is characterised in that: including accounting for gross mass 30%
~ the 70% polyvinylidene fluoride acid PVDF and poly adipate succinic acid ester PBA for accounting for gross mass 30% ~ 70%；The polyvinylidene fluoride acid
PVDF includes γ type polyvinylidene fluoride acid.
2. a kind of γ type Kynoar/poly adipate succinic acid ester composite material according to claim 1, feature exist
In: polyvinylidene fluoride acid PVDF further includes α type polyvinylidene fluoride acid.
3. the preparation method of γ type Kynoar/poly adipate succinic acid ester composite material of any of claims 1 or 2,
It is characterized in that, comprising the following steps:
Kynoar and poly adipate succinic acid ester are dissolved in enough N,N-dimethylformamides；After being completely dissolved
Produce Kynoar/poly adipate succinic acid ester laminated film；By Kynoar/poly adipate succinic acid ester laminated film
Then heating melting is cooled to rapidly 155 DEG C ~ 160 DEG C, constant temperature incubation is had to complete recrystallization to eliminate thermal history
The Kynoar of γ type Kynoar/poly adipate succinic acid ester composite material.
4. a kind of preparation side of γ type Kynoar/poly adipate succinic acid ester composite material according to claim 3
Method, it is characterised in that: Kynoar is white pellet, and glass transition temperature is -39 DEG C, and fusing point is 170 DEG C.
5. a kind of preparation side of γ type Kynoar/poly adipate succinic acid ester composite material according to claim 3
Method, it is characterised in that: poly adipate succinic acid ester is white pellet, and glass transition temperature is -60 DEG C, 54 DEG C of fusing point.
6. a kind of γ type Kynoar/poly adipate succinic acid ester composite material according to claim 3 and its preparation
Method, it is characterised in that:
1) PVDF and PBA are weighed by formula rate and be added in volumetric flask, be settled to 10ml with n,N-Dimethylformamide, be added
Magnetic agitation rotor room temperature magnetic agitation 30min, is completely dissolved PVDF with PBA；
2) by PVDF/PBA solution obtained by step 1) by solution casting method, obtained thickness unifies film, to molten under room temperature
Agent n,N-Dimethylformamide is volatilized completely, is placed in vacuum drier and is dried in vacuo 6 hours in 25 DEG C, obtains PVDF/PBA
Meet film；
3) laminated film made from step 2 is placed in 200 DEG C of Thermostatic platform, constant temperature incubation 10min guarantees polymer thin
Film is sufficiently melted to eliminate thermal history；
4) the rapid of laminated film of stating for completely eliminating thermal history is cooled to 155 DEG C ~ 160 DEG C, constant temperature incubation makes it completely for 24 hours
Recrystallization；
5) product after step 4) sufficient crystallising is taken out from heated at constant temperature platform, is cooled to room temperature, obtain γ type polyvinylidene fluoride
Alkene/poly adipate succinic acid ester composite material.
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| CN112708154A (en) * | 2021-01-08 | 2021-04-27 | 陕西科技大学 | Nucleation method for improving polyvinylidene fluoride gamma phase |
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