CN113087947A - High-beta-crystal-content polyvinylidene fluoride unidirectional stretching film and preparation method thereof - Google Patents
High-beta-crystal-content polyvinylidene fluoride unidirectional stretching film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high beta crystal content polyvinylidene fluoride unidirectional stretching film and a preparation method thereof, PVDF raw material particles are subjected to high-temperature melt extrusion in a double-screw extruder and then subjected to online unidirectional stretching to prepare the high beta crystal content PVDF film with the beta crystal phase pair content not less than 87%.
Description
Technical Field
The invention belongs to the technical field of novel film material preparation, and particularly relates to a high-beta-crystal-content polyvinylidene fluoride unidirectional stretching film and a preparation method thereof.
Background
Polyvinylidene fluoride, known by the trade name Poly (vinylidene fluoride), abbreviated by PVDF, is a polymeric piezoelectric material whose linear polymer chain comprises repeating units of- [ CF2-CH2]Unit, hydrogen and fluorine side groups alternating, the pyroelectric, piezoelectric and ferroelectric properties of PVDF deriving from the dipole moment perpendicular to the polymer chain, caused by negatively charged fluorine atoms, the value of the electric dipole moment being about 7.58X 10-28C cm. PVDF as a polymer material has some distinct advantages: compared with inorganic materials, PVDF has high chemical stability and is resistant to acid and alkali corrosion; the prepared PVDF film has high transparency, and the light transmittance of the film can reach more than 90%; the Young modulus of PVDF is about 2500MPa, the bending and stretching properties are good, and the PVDF has certain flexibility; the biocompatibility is good, and the adhesiveness with soft tissues such as skin is good; compared with other piezoelectric materials, the PVDF has a large frequency response range, and can respond in a frequency range from Hz to GHz; the piezoelectric constant is high, and the piezoelectric sensor has high charge signal output for stress output, so that data acquisition and analysis are facilitated.
And the piezoelectric property of PVDF is mainly related to the crystal form. PVDF has multiple crystal forms, with the most common of these being 4: α, β, γ, and δ. Wherein, the molecular chain of the alpha crystal form is arranged in a TGTG mode, so the alpha crystal form is the most stable structure in 4 crystal forms; and the beta crystal molecular chain is arranged according to TTTT all-trans conformation, and the polar crystal structure plays a decisive role in the piezoelectric property of the PVDF polymer. Therefore, the key to preparing the PVDF piezoelectric film lies in the acquisition of beta crystals. In general, PVDF films prepared by solution crystallization film formation and melt crystallization film formation are both spherical crystalline α -phase PVDF films, and need to be converted into β -phase PVDF films with good piezoelectric properties by high temperature treatment or stretching process.
Chinese patent CN104877151A discloses a method for preparing PVDF film and PVDF film, which comprises dissolving PVDF powder raw material in a mixed solvent composed of benign and bad solvents, adjusting the width of the slit of the casting scraper, casting on a clean glass plate or polyester film belt, heating and drying through a bottom plate, and preparing PVDF film with high beta phase crystal content. The method has higher requirements on process conditions, complicated steps and difficult realization of mass production.
Chinese patent CN101045795A discloses a beta-phase polyvinylidene fluoride composite film and a preparation method thereof, according to a certain mass formula, polyvinylidene fluoride and inorganic hydrated salt are dissolved in a dimethylformamide solvent, are uniformly mixed and then are coated on a glass or silicon substrate in a spin mode, and are evaporated and crystallized for 24 hours at the temperature of 20-100 ℃, so that the polyvinylidene fluoride composite film is obtained. The method has high process requirement, long film forming time and difficult industrialization.
Chinese patent CN109762188A discloses a method for continuously preparing a PVDF film with high beta-crystal content by adopting melt extrusion-rolling, the PVDF film with high beta-crystal content is continuously produced by adopting a melt extrusion-rolling mode, common PVDF granules are used as raw materials, and mechanical force is applied in the rolling process to convert the configuration of PVDF molecules from an alpha crystal form to a beta crystal form; no other reagent is added, so that the preparation process is nontoxic and pollution-free, and the preparation method has the characteristics of easily obtained materials, simple process, easy control, convenient operation, low cost and the like. However, the die head used in the invention is only 5mm wide, the prepared finished film is less than 3mm, and the die head belongs to the field of laboratory research and is far away from equipment and processes required by industrial mass production. And the device is not provided with a melt pump, a die head, a thickness gauge and other parts, so that the thickness tolerance of the film cannot be accurately controlled.
Liu dong, et al, studied the effect of the stretching process on the morphology and structure of PVDF films by solution casting to obtain initial PVDF films, then fixing the initial films of a given size on a stretcher to stretch, and studied the effect of stretching times on the beta-form content with emphasis (Liudong, Jiangylin, Tongolyu, Jing vast. the effect of the stretching process on the morphology and structure of PVDF films. electronic components and materials, 2007.3, 26 (3): 12-14). The solution casting method is complicated in operation and long in time, organic solvent is not environment-friendly enough, off-line stretching is carried out in the second step after the sheet is cast, and the off-line stretching has the defects that the thickness tolerance of a film is difficult to accurately control, the stretching temperature is difficult to accurately regulate and control, the process is only suitable for laboratory research, and industrialization is difficult to realize.
Disclosure of Invention
The invention provides a polyvinylidene fluoride (PVDF) one-way stretching film with high beta-crystal content and a preparation method thereof, aiming at solving the technical problems that the process requirement for preparing the PVDF film by a tape casting method is high, the equipment composition is complex, the batch production is difficult, the existing PVDF film with high beta-crystal content prepared by one-way stretching is an off-line stretching process, the steps are complicated, the efficiency is slow and the like.
In order to achieve the purpose, the invention adopts the technical scheme that:
the polyvinylidene fluoride unidirectional stretching film with high beta crystal content has the beta crystal phase pair content of not less than 87%.
Preferably, the average thickness variation of the polyvinylidene fluoride uniaxially stretched film is within ± 5%.
Preferably, the polyvinylidene fluoride unidirectional stretching film has a width of 1000 to 1500mm and a thickness of 30 to 40 μm.
The invention also provides a preparation method of the high beta crystal content polyvinylidene fluoride unidirectional stretching film, which comprises the following steps:
(1) weighing PVDF raw material particles;
(2) adding the PVDF raw material particles weighed in the step (1) into a double-screw extruder for melt extrusion;
(3) and (3) performing on-line unidirectional stretching on the PVDF sheet to obtain the high-beta-crystal-content polyvinylidene fluoride unidirectional stretched film with beta-crystal phase pair content not less than 87%.
Preferably, the PVDF raw material has the particle number average molecular weight of 5-9 ten thousand and the melt index of 1-4 g/10 min.
Preferably, the temperature of the extruder is set to 160-250 ℃ and the rotation speed of the extruder is 100-300 rpm during melt extrusion. Pure and single PVDF raw material particles are added into a double-screw extruder, the temperature of each area of the extruder and the rotating speed of a screw of the extruder are accurately controlled, the high-efficiency high-quality melting plasticizing effect is realized, and a PVDF sheet is extruded by a die head.
Preferably, when the PVDF sheet is stretched in an on-line unidirectional mode, the distance is set to be 20-80 mm.
Stretching and polarization are two key steps for preparing a piezoelectric polyvinylidene fluoride (PVDF) film, and the selection of a proper stretching parameter in a stretching process can greatly convert an apolar alpha phase in the PVDF film into a strongly polar beta phase. The invention adopts the small-spacing quick stretching, thereby obviously improving the beta crystalline phase pair content and the thickness uniformity of the prepared PVDF film.
Preferably, when the PVDF sheet is subjected to on-line unidirectional stretching, the stretching temperature is 80-120 ℃, and the stretching rate is 1000-4000% s-1。
Preferably, the average thickness deviation of the polyvinylidene fluoride uniaxially stretched film is controlled within ± 5% by a die automatic adjusting device. By using a mapping matrix table formed by linkage of a self-developed die head automatic adjusting device (CN208324147U) and die head bolts, the thickness tolerance of the film can be accurately controlled, so that the average thickness deviation of the film is within +/-5%; the automatic die head adjusting device acts on the elastic die lips below the die head, the automatic die head adjusting device is formed by forming a mapping matrix table by surrounding the elastic die lips by a plurality of 60 fine adjustment mechanisms, the fine adjustment mechanisms are connected with the die head through independent mounting frames, the influence of high temperature of the die head is avoided, the adjusting precision is high, the positioning is accurate, the thickness tolerance of the film is accurately controlled on line, and the average thickness deviation of the film is within +/-5%; through continuous online uniaxial tension and online mapping matrix table linkage, the thickness tolerance of the uniaxial tension film is automatically and accurately controlled, the mass production of the PVDF film with excellent performance can be realized, the production efficiency is high, and the process steps are simple and controllable.
Preferably, the polyvinylidene fluoride unidirectional stretching film has a width of 1000 to 1500mm and a thickness of 30 to 40 μm.
The invention has the beneficial effects that:
(1) the PVDF film is prepared by adopting a double-screw extrusion melting sheet casting method, the existing solution sheet casting method which has high process requirements, complicated steps and long time is replaced, single pure raw materials are used, no impurity is introduced into a raw material system, the production process is continuous, and industrial mass production can be realized;
(2) the invention adopts an on-line unidirectional stretching process instead of stepwise off-line stretching, which not only greatly improves the production efficiency, but also can well control the thickness tolerance of the film; the off-line stretching process, such as separate off-line stretching step by step after solution casting, can only achieve small-scale and is difficult to effectively control the thickness tolerance and uniformity of various properties of the film after off-line stretching; or the extruder extrudes the sheet material and then performs off-line stretching step by step, thereby increasing the complexity of the process and the time cost of production, and having poor thickness uniformity;
(3) the PVDF film prepared by the method has high beta crystalline phase relative content (not less than 87%), good film thickness uniformity and high production efficiency, and the prepared PVDF film has large width and is convenient to realize industrial production.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention. Those skilled in the art can and should understand that any simple changes or substitutions based on the spirit of the present invention should fall within the protection scope of the present invention.
Example 1
A preparation method of a polyvinylidene fluoride unidirectional stretching film with high beta crystal content comprises the following steps:
(1) weighing a certain amount of PVDF raw material particles (the number average molecular weight is 8.2 ten thousand, and the melt index is 2.3g/10min (230 ℃, 2.16 kg));
(2) weighing PVDF raw material particles in the step (1), adding the PVDF raw material particles into a double-screw extruder for melt extrusion, wherein the temperature of the extruder is set at 215 ℃, the rotating speed of the double screws is 230rpm, and performing melt extrusion on cast sheets, and precisely controlling the thickness tolerance of the film by using an automatic die head adjusting device to ensure that the average thickness deviation of the film is within +/-5%;
(3) on-line quick unidirectional stretching PVDF sheet with small space, the space is set at 57mm, the stretching temperature is 105 ℃, and the stretching speed is 3500% s-1And obtaining the PVDF unidirectional stretching film. The results of the measurements are reported in table 1.
Example 2
A preparation method of a polyvinylidene fluoride unidirectional stretching film with high beta crystal content comprises the following steps:
(1) weighing a certain amount of PVDF raw material particles (the number average molecular weight is 8.2 ten thousand, and the melt index is 2.3g/10min (230 ℃, 2.16 kg));
(2) adding the PVDF raw material particles weighed in the step (1) into a double-screw extruder for melt extrusion, wherein the temperature of the extruder is set at 210 ℃, the rotating speed of the double screws is 180rpm, the cast sheet is melt extruded, an automatic die head adjusting device and a die head bolt are linked and automatically adjusted, and the thickness tolerance of the film is accurately controlled, so that the average thickness deviation of the film is within +/-5%;
step three: on-line quick unidirectional stretching PVDF sheet with small space, the space is set at 40mm, the stretching temperature is 90 ℃, and the stretching speed is 1800% s-1And obtaining the PVDF unidirectional stretching film. The results of the measurements are reported in table 1.
Example 3
A preparation method of a polyvinylidene fluoride unidirectional stretching film with high beta crystal content comprises the following steps:
(1) weighing a certain amount of PVDF raw material particles (the number average molecular weight is 8.2 ten thousand, and the melt index is 2.3g/10min (230 ℃, 2.16 kg));
(2) adding the PVDF raw material particles weighed in the step (1) into a double-screw extruder for melt extrusion, wherein the temperature of the extruder is set at 230 ℃, the rotating speed of the double screws is 280rpm, the cast sheet is melt extruded, an automatic die head adjusting device is automatically adjusted in linkage with a die head bolt, and the thickness tolerance of the film is accurately controlled, so that the average thickness deviation of the film is within +/-5%;
(3) on-line quick unidirectional stretching PVDF (polyvinylidene fluoride) sheet with small space, the space is set at 80mm, and the stretching temperature isThe draw rate was 2400% s at 95 DEG C-1And obtaining the PVDF unidirectional stretching film. The results of the measurements are reported in table 1.
Example 4
A preparation method of a polyvinylidene fluoride unidirectional stretching film with high beta crystal content comprises the following steps:
(1) weighing a certain amount of PVDF raw material particles (the number average molecular weight is 8.2 ten thousand, and the melt index is 2.3g/10min (230 ℃, 2.16 kg));
(2) and (2) adding the PVDF raw material particles weighed in the step (1) into a double-screw extruder for melt extrusion, wherein the temperature of the extruder is set at 215 ℃, the rotating speed of the double screws is 200rpm, the cast sheet is melt extruded, an automatic die head adjusting device and a die head bolt are linked for automatic adjustment, the thickness tolerance of the film is accurately controlled, and the average thickness deviation of the film is enabled to be within +/-5%.
Step three: on-line quick unidirectional stretching PVDF sheet with small space, the space is set at 45mm, the stretching temperature is 100 ℃, and the stretching speed is 3000% s-1And obtaining the PVDF unidirectional stretching film. The results of the measurements are reported in table 1.
Example 5
A preparation method of a polyvinylidene fluoride unidirectional stretching film with high beta crystal content comprises the following steps:
(1) weighing a certain amount of PVDF raw material particles (the number average molecular weight is 8.2 ten thousand, and the melt index is 2.3g/10min (230 ℃, 2.16 kg));
(2) and (2) adding the PVDF raw material particles weighed in the step (1) into a double-screw extruder for melt extrusion, wherein the temperature of the extruder is set at 220 ℃, the rotating speed of the double screws is 150rpm, the cast sheet is melt extruded, an automatic die head adjusting device and a die head bolt are linked for automatic adjustment, the thickness tolerance of the film is accurately controlled, and the average thickness deviation of the film is enabled to be within +/-5%.
(3) On-line small-spacing rapid unidirectional stretching PVDF (polyvinylidene fluoride) sheet, wherein the spacing is set at 65mm, the stretching temperature is 85 ℃, and the stretching speed is 1200% s-1And obtaining the PVDF unidirectional stretching film. The results of the measurements are reported in table 1.
Example 6
A preparation method of a polyvinylidene fluoride unidirectional stretching film with high beta crystal content comprises the following steps:
(1) weighing a certain amount of PVDF raw material particles (the number average molecular weight is 8.2 ten thousand, and the melt index is 2.3g/10min (230 ℃, 2.16 kg));
(2) adding the PVDF raw material particles weighed in the step (1) into a double-screw extruder for melt extrusion, wherein the temperature of the extruder is set at 215 ℃, the rotating speed of the double screws is 230rpm, the cast sheet is melt extruded, an automatic die head adjusting device and a die head bolt are linked and automatically adjusted, and the thickness tolerance of the film is accurately controlled, so that the average thickness deviation of the film is within +/-5%;
(3) on-line quick unidirectional stretching PVDF sheet with small space, the space is set at 70mm, the stretching temperature is 110 ℃, and the stretching speed is 4000% s-1And obtaining the PVDF unidirectional stretching film. The results of the measurements are reported in table 1.
Example 7
A preparation method of a polyvinylidene fluoride unidirectional stretching film with high beta crystal content comprises the following steps:
(1) weighing a certain amount of PVDF raw material particles (the number average molecular weight is 6.8 ten thousand, and the melt index is 2.9g/10min (230 ℃, 2.16 kg));
(2) adding the PVDF raw material particles weighed in the step (1) into a double-screw extruder for melt extrusion, wherein the temperature of the extruder is set at 215 ℃, the rotating speed of the double screws is 230rpm, the cast sheet is melt extruded, an automatic die head adjusting device and a die head bolt are linked and automatically adjusted, and the thickness tolerance of the film is accurately controlled, so that the average thickness deviation of the film is within +/-5%;
(3) on-line quick unidirectional stretching PVDF sheet with small space, the space is set at 70mm, the stretching temperature is 110 ℃, and the stretching speed is 4000% s-1And obtaining the PVDF unidirectional stretching film. The results of the measurements are reported in table 1.
Example 8
A preparation method of a polyvinylidene fluoride unidirectional stretching film with high beta crystal content comprises the following steps:
(1) weighing a certain amount of PVDF raw material particles (the number average molecular weight is 6.8 ten thousand, and the melt index is 2.9g/10min (230 ℃, 2.16 kg));
(2) adding the PVDF raw material particles weighed in the step (1) into a double-screw extruder for melt extrusion, wherein the temperature of the extruder is set at 210 ℃, the rotating speed of the double screws is 180rpm, the cast sheet is melt extruded, an automatic die head adjusting device and a die head bolt are linked and automatically adjusted, and the thickness tolerance of the film is accurately controlled, so that the average thickness deviation of the film is within +/-5%;
step three: on-line quick unidirectional stretching PVDF sheet with small space, the space is set at 40mm, the stretching temperature is 90 ℃, and the stretching speed is 1800% s-1And obtaining the PVDF unidirectional stretching film. The results of the measurements are reported in table 1.
The indexes of the thickness, elongation at break, thermal shrinkage, beta crystal phase pair content and the like of the film in the above examples are evaluated according to the method in the company enterprise standard Q/ZZC 03.40-2021 "piezoelectric material polyvinylidene fluoride unidirectional stretching film". In particular, the heat shrinkage test was evaluated using an index of shrinkage at 65 ℃ for 1 hour; the calculation of the beta crystalline phase relative content adopts total reflection infrared spectroscopy ATR test, and 764cm in an infrared spectrogram-1The peak area A (alpha) of (A) represents alpha crystal, 840cm-1The peak area A (β) represents β crystal, and the relative content (%) of β crystal form is calculated according to formula (1).
The results of the measurements of the properties of the PVDF films prepared in examples 1 to 8 are shown in Table 1.
TABLE 1
The results show that the PVDF unidirectional stretching film which has high beta crystal form content and can be used for preparing excellent piezoelectric materials is prepared by adopting a double-screw high-temperature melt extrusion online unidirectional stretching production process, the technical requirements are met, the production process is environment-friendly, the production efficiency is high, and the industrial production is convenient.
The present invention is described in detail with reference to the examples, but the description is only a specific embodiment of the present invention, and the present invention is not to be construed as being limited to the claims. It should be noted that, for those skilled in the art, variations and modifications made within the scope of the present invention shall fall within the scope of the claims of the present invention without departing from the spirit of the present invention.
Claims (10)
1. A high beta crystal content polyvinylidene fluoride unidirectional stretching film is characterized in that: the beta crystalline phase pair content of the polyvinylidene fluoride unidirectional stretching film is not less than 87%.
2. The high beta crystal content polyvinylidene fluoride uniaxially oriented film of claim 1, wherein: the average thickness deviation of the polyvinylidene fluoride unidirectional stretching film is within +/-5%.
3. The high β crystal content polyvinylidene fluoride uniaxially stretched film according to claim 1 or 2, characterized in that: the polyvinylidene fluoride unidirectional stretching film has the width of 1000-1500 mm and the thickness of 30-40 mu m.
4. A preparation method of a polyvinylidene fluoride unidirectional stretching film with high beta crystal content is characterized by comprising the following steps:
(1) weighing PVDF raw material particles;
(2) adding the PVDF raw material particles weighed in the step (1) into a double-screw extruder for melt extrusion;
(3) and (3) performing on-line unidirectional stretching on the PVDF sheet to obtain the high-beta-crystal-content polyvinylidene fluoride unidirectional stretched film with beta-crystal phase pair content not less than 87%.
5. The method for preparing the high beta crystal content polyvinylidene fluoride unidirectional stretching film according to claim 4, characterized in that: the PVDF raw material has the particle number average molecular weight of 5-9 ten thousand and the melt index of 1-4 g/10 min.
6. The method for preparing the high beta crystal content polyvinylidene fluoride unidirectional stretching film according to claim 4, characterized in that: during melt extrusion, the temperature of the extruder is set to be 160-250 ℃, and the rotating speed of the extruder is 100-300 rpm.
7. The method for preparing the high beta crystal content polyvinylidene fluoride unidirectional stretching film according to claim 4, characterized in that: when the PVDF sheet is stretched in an on-line unidirectional mode, the distance is set to be 20-80 mm.
8. The method for preparing the high beta crystal content polyvinylidene fluoride unidirectional stretching film according to claim 5, characterized in that: when the PVDF sheet is subjected to on-line unidirectional stretching, the stretching temperature is 80-120 ℃, and the stretching speed is 1000-4000% s-1。
9. The method for preparing the high beta crystal content polyvinylidene fluoride unidirectional stretching film according to claim 4, characterized in that: the average thickness deviation of the polyvinylidene fluoride unidirectional stretching film is controlled within +/-5 percent through a die head automatic adjusting device.
10. The method for preparing the high beta crystal content polyvinylidene fluoride unidirectional stretching film according to claim 4, characterized in that: the polyvinylidene fluoride unidirectional stretching film has the width of 1000-1500 mm and the thickness of 30-40 mu m.
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