CN108948604B - Gamma-type polyvinylidene fluoride/polybutylene adipate composite material and preparation method thereof - Google Patents
Gamma-type polyvinylidene fluoride/polybutylene adipate composite material and preparation method thereof 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
- 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
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- 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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- 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
Abstract
The gamma-type polyvinylidene fluoride/polybutylene adipate composite material comprises 30-70% of polyvinylidene fluoride and 30-70% of polybutylene adipate PBA. Wherein the polyvinylidene fluoride is gamma-type polyvinylidene fluoride, and may also include partial alpha-type polyvinylidene fluoride. The preparation method of the composite material comprises the following steps: dissolving polyvinylidene fluoride and polybutylene adipate in sufficient DMF; after complete dissolution, preparing a polyvinylidene fluoride/polybutylene adipate composite film; heating and melting the polyvinylidene fluoride/polybutylene adipate composite film to eliminate heat history, then quickly cooling to 155-160 ℃, and culturing at constant temperature until complete recrystallization is achieved to obtain the polyvinylidene fluoride/polybutylene adipate composite material with gamma-type polyvinylidene fluoride. The composite biodegradable material has simple and scientific preparation process, low cost and controllable flow.
Description
Technical Field
The invention belongs to the technical field of preparation of high polymer materials, and particularly relates to a gamma-type polyvinylidene fluoride/polybutylene adipate composite material and a preparation method thereof.
Background
Polyvinylidene fluoride (PVDF) has electrical properties such as piezoelectricity, dielectricity, and pyroelectric properties in addition to the properties of fluororesins and general-purpose resins, and thus has attracted much attention in the field of material science. The diversified service performance of PVDF has close relation with the complex and changeable crystal form structure of PVDF, and various crystal form crystals can be mutually transformed under certain conditions, so that various crystal form structures of PVDF and the mutual transformation mechanism and essence between the various crystal form structures are deeply researched, the influence of different crystal form structures on the performance is discussed, and the PVDF crystal has important theoretical significance and practical application value. The PVDF has alpha, beta, gamma and five crystal forms, wherein the alpha, beta and gamma are the most common crystal forms, and the PVDF with the alpha crystal form has excellent mechanical property and is a better photoelectric energy storage material. The beta crystal form is an important crystal form of PVDF, is widely applied to energy conversion devices such as photoelectricity, thermosensitive devices, pressure-sensitive devices and the like, and is the most successful piezoelectric polymer material applied at present. The molecular chain configuration of the gamma crystal form PVDF is similar to that of a beta phase, the molecular configuration is TTTG, two molecular chains in the same unit cell are arranged in parallel, the dipole moment direction is the same, the polarity is provided, but the polarity is smaller than that of the beta phase, and the piezoelectric, thermoelectric and other electrical properties are excellent.
Currently, the gamma crystal PVDF has the following preparation methods: PVDF melt is annealed at high temperature, and a second component nucleating agent is added. The gamma phase obtained by high-temperature annealing is actually formed by solid-solid phase transformation of alpha-PVDF crystals under the high-temperature condition, is called gamma ΄ -PVDF, and has higher melting temperature due to close arrangement.
The existing method for preparing gamma crystal PVDF needs a high-temperature thermal field, and the produced gamma phase PVDF is few in quantity and random in position. The preparation processes are complex, the related means are various, the unified standardized production and the industrial application are not facilitated, only theoretical technical bases can be provided, and a plurality of limitations exist in the future application field.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a gamma-type polyvinylidene fluoride (PVDF)/polybutylene adipate (PBA) composite material and a preparation method thereof.
The materials and the method relate to the following raw materials: polyvinylidene fluoride (PVDF), polybutylene adipate (PBA), N-Dimethylformamide (DMF). In the invention, PVDF is a main material and is completely dissolved in N, N-dimethylformamide, and PBA is uniformly dispersed in DMF solution of PVDF. The preparation method comprises the following steps: 1) respectively weighing a certain amount of PVDF, and respectively placing in 10ml volumetric flasks marked as No. 1, No. 2 and No. 3; 2) respectively weighing a certain amount of PBA, respectively placing the PBA in No. 1, No. 2 and No. 3 in the step 1), fixing the volume to 10ml by using good solvents DMF of PVDF and PBA, adding a magnetic stirring rotor, magnetically stirring at normal temperature for 30min, completely dissolving the PVDF and PBA in triplicate, and obtaining three blended solutions with the PVDF and PBA contents of 30wt%, 50wt% and 70wt% respectively; 3) preparing a film with uniform thickness by using the three PVDF/PBA solutions prepared in the step 2) with different ratios through a solution casting method, and placing the film in a vacuum drier for vacuum drying for 6 hours at 25 ℃ after the DMF solvent is completely volatilized at normal temperature; 4) placing the composite film prepared in the step 3) into a constant-temperature heating table at 200 ℃, culturing for 10min at constant temperature, rapidly reducing the culture temperature of the composite film after completely eliminating the heat history to 155-160 ℃, and culturing for 24h at constant temperature to completely recrystallize the composite film. The composite biodegradable material has simple and scientific manufacturing process, low cost and controllable flow, is expected to be produced industrially, and has great potential application prospect and economic benefit.
In order to achieve the purpose, the invention adopts the technical scheme that: a gamma-type polyvinylidene fluoride/polybutylene adipate composite material and a preparation method thereof comprise the following steps:
1) weighing PVDF =0.15g, 0.25g and 0.35g respectively, placing in 10ml volumetric flasks respectively marked as No. 1, No. 2 and No. 3;
2) weighing PBA =0.35g, 0.25g and 0.15g respectively, placing the PBA in No. 1, No. 2 and No. 3 in the step 1), fixing the volume to 10ml by using good solvent N, N-dimethylformamide of PVDF and PBA, adding a magnetic stirring rotor, and magnetically stirring at normal temperature for 30min to completely dissolve the PVDF and PBA in triplicate to obtain three blended solutions with the PVDF and PBA contents of 30wt%, 50wt% and 70wt% respectively;
3) preparing the PVDF/PBA solution prepared in the step 2) with different proportions into a film with uniform thickness by a solution casting method, and placing the film in a vacuum drier for vacuum drying for 6 hours at 25 ℃ after the solvent N, N-dimethylformamide is completely volatilized at normal temperature;
4) placing the composite film prepared in the step 3) into a constant-temperature heating table at 200 ℃, and culturing for 10min at constant temperature to ensure that the polymer film is fully melted to eliminate thermal history;
5) rapidly reducing the culture temperature of the composite film after the heat history is completely eliminated to 155-160 ℃, and culturing at constant temperature for 24h to completely recrystallize the composite film;
6) taking the product fully crystallized in the step 5) out of the constant-temperature heating table, cooling to room temperature, and detecting. By observation under a polarizing microscope, we found that we obtained a composite material with different nucleation densities and crystal morphologies.
Observing the PVDF/PBA composite film materials with different blending ratios prepared by the steps under a polarizing microscope, and finding that the spherulite size changes greatly according to the change of the crystallization temperature and the PBA content; the crystalline morphology of the PVDF also changes after the PBA is added into the PVDF in a comparative pure way, and changes along with the change of the content of the PBA.
The nucleation and growth of the samples were observed using a polarizing microscope. A differential scanning calorimeter is used for judging whether the crystallization temperature and the melting temperature of the compound are regularly changed.
The invention has the beneficial effects that:
compared with the prior art, the PBA component has excellent biocompatibility and biodegradability and wide application. The PBA is uniformly dispersed in the PVDF matrix, so that irreversible action on mechanical properties due to agglomeration is avoided in the crystallization growth process. And the molecular chain conformation of the alpha crystal type in the PVDF is converted to the gamma crystal type, so that the capacity of storing charges is increased for the mechanism, namely the dielectric property of the composite film is improved.
The invention adds PBA to carry out induced phase change on PVDF crystals, and prepares the film with uniform thickness by a solution casting method. Detection comparison shows that PVDF undergoes rapid phase change when the PBA composite film is added, and spherulites are uniform in size and distribution. Compared with pure PVDF, the phase change rate of PVDF is improved in the presence of PBA, and the relative content of gamma-phase crystals is greatly improved due to the induction effect of PBA on PVDF. Provides a crystal phase change mechanism, and the method shortens the preparation time and can prepare a stable composite film containing a large amount of gamma-phase crystals in a shorter time.
Drawings
FIG. 1 is a polarization microscope photograph of PVDF and PBA composite samples cultured at 155 ℃ for 24 hours.
FIG. 2 is a differential scanning calorimetry thermogram of a sample of PVDF/PBA composite material of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1:
a preparation method of a polyvinylidene fluoride/polybutylene adipate composite material comprises the following steps:
1) weighing PVDF =0.15g, placing in a 10ml volumetric flask, and marking as No. 1;
2) weighing PBA =0.35g, placing in No. 1 in the step 1), fixing the volume to 10ml by using good solvent N, N-dimethylformamide of PVDF and PBA, adding a magnetic stirring rotor, and magnetically stirring at normal temperature for 30min to completely dissolve the PVDF and PBA in triplicate to obtain a blending solution with the content of the PVDF and the PBA being 30 wt%;
3) preparing a film with uniform thickness from the PVDF/PBA solution prepared in the step 2) by a solution casting method, completely volatilizing the N, N-dimethylformamide solvent at normal temperature, and then placing the film in a vacuum drier for vacuum drying for 6 hours at 25 ℃;
4) placing the composite film prepared in the step 3) into a constant-temperature heating table at 200 ℃, and culturing for 10min at constant temperature to ensure that the polymer film is fully melted to eliminate thermal history;
5) rapidly reducing the culture temperature of the composite film after completely eliminating the thermal history to 155 ℃, and culturing for 24 hours at constant temperature to completely recrystallize the composite film;
6) taking the product fully crystallized in the step 5) out of the constant-temperature heating table, cooling to room temperature, and detecting.
Example 2:
a preparation method of a polyvinylidene fluoride/polybutylene adipate composite material comprises the following steps:
1) weighing PVDF =0.25g, placing in a 10ml volumetric flask, and marking as No. 2;
2) weighing PBA =0.25g, placing in No. 2 in the step 1), fixing the volume to 10ml by using good solvent N, N-dimethylformamide of PVDF and PBA, adding a magnetic stirring rotor, and magnetically stirring at normal temperature for 30min to completely dissolve the PVDF and PBA to obtain a blended solution with the PVDF and PBA content of 50 wt%;
3) preparing a film with uniform thickness from the PVDF/PBA solution prepared in the step 2) by a solution casting method, completely volatilizing the N, N-dimethylformamide solvent at normal temperature, and then placing the film in a vacuum drier for vacuum drying for 6 hours at 25 ℃;
4) placing the composite film prepared in the step 3) into a constant-temperature heating table at 200 ℃, and culturing for 10min at constant temperature to ensure that the polymer film is fully melted to eliminate thermal history;
5) rapidly reducing the culture temperature of the composite film after completely eliminating the thermal history to 155 ℃, and culturing for 24 hours at constant temperature to completely recrystallize the composite film;
6) taking the product fully crystallized in the step 5) out of the constant-temperature heating table, cooling to room temperature, and detecting.
Example 3:
a preparation method of a polyvinylidene fluoride/polybutylene adipate composite material comprises the following steps:
1) weighing PVDF =0.35g, placing in a 10ml volumetric flask, and marking as No. 3;
2) weighing PBA =0.15g, placing in No. 3 in the step 1), fixing the volume to 10ml by using good solvent N, N-dimethylformamide of PVDF and PBA, adding a magnetic stirring rotor, and magnetically stirring at normal temperature for 30min to completely dissolve the PVDF and PBA to obtain a blended solution with the PVDF and PBA content of 70 wt%;
3) preparing a film with uniform thickness from the PVDF/PBA solution prepared in the step 2) by a solution casting method, completely volatilizing the N, N-dimethylformamide solvent at normal temperature, and then placing the film in a vacuum drier for vacuum drying for 6 hours at 25 ℃;
4) placing the composite film prepared in the step 3) into a constant-temperature heating table at 200 ℃, and culturing for 10min at constant temperature to ensure that the polymer film is fully melted to eliminate thermal history;
5) rapidly reducing the culture temperature of the composite film after completely eliminating the thermal history to 160 ℃, and culturing for 24 hours at constant temperature to completely recrystallize the composite film;
6) taking the product fully crystallized in the step 5) out of the constant-temperature heating table, cooling to room temperature, and detecting.
Example 4:
referring to FIG. 1, a polarizing microscope image of PVDF/PBA composites of different formulations prepared for this experiment was incubated at 155 ℃ for 24 hours. a is a sample of PVDF/PBA =3/7, and a complete spherulite structure can be seen through observation by a polarization microscope, and alpha spherulites can be seen from the figure to have a clear ring-shaped structure and also contain gamma spherulites which have no obvious birefringence and have no ring-shaped structure. b is a sample of PVDF/PBA =5/5, and when observed by a polarizing microscope, the spherulite size is large (about 400 μm) and the alpha spherulite ring structure is obvious, wherein gamma spherulites without a ring structure and without a birefringence phenomenon are contained, and the spherulite size is obviously larger than the ring spacing when observed in a diagram. c is PVDF/PBA =3/7 sample compared to the spherulite size of panels a and b (about 100 μm) because increasing PBA content hinders the growth of PVDF spherulites.
The samples prepared in examples 1-3 were subjected to thermal analysis in a differential scanning calorimeter, and the test results are shown in FIG. 2. FIG. 2 is a differential scanning calorimetry and heat release diagram of PVDF/PBA composite materials with different blending ratios, wherein the melting behavior of the PVDF/PBA of the composite system of 3/7 in the diagram is shown, four melting peaks appear, and the crystallization of PVDF in the system can not be judged according to the temperatures of the melting peaks. This is probably because the crystallization of PVDF melts is greatly restricted in the case of high PBA contents, and does not crystallize completely under this condition, so that complex melting peaks appear during subsequent temperature increases. In contrast, the melting behavior of the composite systems with mass ratios of 5/5 and 7/3 was very regular, and the PVDF melt in the film had crystallized completely. As the graph compares melting curves b and c, a strong melting peak appears at 185 ℃, which indicates that PVDF generates a more regular structure in the two compositions, so that the thermodynamic property is stable, and a large amount of heat needs to be absorbed in the heating process to ensure that the molecular chain returns to an active state again. Except that in the 7/3 composite system, the melting peak intensity at 170 ℃ was comparable to the melting peak intensity at 185 ℃. In the composite system having the mass ratio of 5/5, a melting peak at 170 ℃ hardly appeared. This is because the addition of sufficient PBA to the PVDF matrix can promote the alignment and packing of PVDF molecular chains more rapidly, and make the structure more stable. This result is consistent with the research result of POM, and in the PVDF/PBA composite system, increasing the content of PBA within a certain range increases the relative content of PVDF crystals with weak birefringence.
Claims (1)
1. The preparation method of the gamma-type polyvinylidene fluoride/polybutylene adipate composite material is characterized by comprising the following steps of:
1) weighing polyvinylidene fluoride (PVDF) accounting for 70% of the total mass and polybutylene adipate (PBA) accounting for 30% of the total mass according to the formula proportion, adding the PVDF and the PBA into a volumetric flask, using N, N-dimethylformamide to fix the volume to 10ml, adding a magnetic stirring rotor, and magnetically stirring at normal temperature for 30min to completely dissolve the PVDF and the PBA;
2) preparing a PVDF/PBA solution prepared in the step 1) into a film with uniform thickness by a solution casting method, completely volatilizing N, N-dimethylformamide serving as a solvent at normal temperature, and then placing the film in a vacuum drier for vacuum drying for 6 hours at 25 ℃ to obtain a PVDF/PBA composite film;
3) placing the composite film prepared in the step 2) into a constant-temperature heating table at 200 ℃, and culturing for 10min at constant temperature to ensure that the polymer film is fully melted to eliminate thermal history;
4) rapidly cooling the composite film in the step 3) for completely eliminating the heat history to 155-160 ℃, and culturing at constant temperature for 24h to completely recrystallize the composite film;
5) and (3) taking out the fully crystallized product obtained in the step 4) from a constant-temperature heating table, and cooling to room temperature to obtain the gamma-type polyvinylidene fluoride/polybutylene adipate composite material.
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