CN108164889B - High-strength high-toughness PVDF solar backboard film material and preparation method thereof - Google Patents

High-strength high-toughness PVDF solar backboard film material and preparation method thereof Download PDF

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CN108164889B
CN108164889B CN201711175465.0A CN201711175465A CN108164889B CN 108164889 B CN108164889 B CN 108164889B CN 201711175465 A CN201711175465 A CN 201711175465A CN 108164889 B CN108164889 B CN 108164889B
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titanium dioxide
toughness
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pvdf
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王汉利
韩瑞芹
杜延华
马丽
唐妮
李秀芬
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Shandong Huaxia Shenzhou New Material Co Ltd
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Abstract

The invention belongs to the field of solar backboard film materials, and particularly relates to a high-strength high-toughness PVDF solar backboard film material and a preparation method thereof. Comprises the following components: polyvinylidene fluoride, polymethyl methacrylate, titanium dioxide, nano inorganic whisker, a coupling agent, a heat stabilizer and a flow modifier. The diameter of the inorganic nano-whisker is 0.1-0.5 μm, the length is 2-50 μm, and the length-diameter ratio is 20-100. The strength and toughness of the PVDF back plate film are improved, the problem that the strength and toughness are insufficient when only PMMA and titanium dioxide are added is solved, the tensile strength of the prepared PVDF back plate film material in the MD direction is more than or equal to 50MPa, and the elongation at break is more than or equal to 350 percent; the tensile strength in the TD direction is more than or equal to 40MPa, and the elongation at break is more than or equal to 250%; the luminousness is low, the reflectivity of sunlight is improved, and then the utilization rate of the backboard component to the sunlight is improved.

Description

High-strength high-toughness PVDF solar backboard film material and preparation method thereof
Technical Field
The invention belongs to the field of solar backboard film materials, and particularly relates to a high-strength high-toughness PVDF solar backboard film material and a preparation method thereof.
Background
PVDF has outstanding excellent performances such as chemical corrosion resistance, high and low temperature resistance, weather resistance and the like, and the excellent performances of PVDF make PVDF especially suitable for being used as solar backboard film materials. However, pure PVDF raw material has the defects of difficult film formation, high film formation shrinkage rate, high light transmittance and the like, PMMA is usually added to carry out film formation modification on PVDF, and the light transmittance of the film is reduced by adding titanium dioxide, but the problems of insufficient strength and toughness, particularly low tensile strength and low elongation at break of the film in TD direction, still exist by adding PMMA and titanium dioxide.
In order to solve the problem of reinforcing, toughening and modifying the solar backboard film, patent CN106159010 discloses a PVDF solar backboard film with high tensile strength, which is prepared from PVDF/PMMA/TiO2On the basis of compounding, the anti-impact modifier is added, the solar back panel film is prepared by adopting an intersolubility blending technology, the tensile strength (MD) is more than or equal to 50MPa, the tensile strength (TD) is more than or equal to 37MPa, and the tensile strength of the PVDF resin is effectively improved. However, the formula provided by the patent does not contain a heat stabilizer or an antioxidant, and the added titanium dioxide can not well inhibit the thermal decomposition promotion effect of the PVDF resin. Patent CN201010536756.X discloses a special material for polyvinylidene fluoride film, which uses reinforced resin (acrylate) to plasticize and toughen PVDF and improve the tear resistance of the film.
Chinese patent CN 103240008A discloses a whisker reinforced polyvinylidene fluoride hollow fiber membrane and a preparation process thereof, which are applied to the hollow fiber membrane and adopt the form of membrane casting solution for spinning. Chinese patent CN 107236232 a discloses a polyvinylidene fluoride resin polymer and a preparation method thereof, wherein at least one of sodium silicate material, magnesium oxysulfate whisker and potassium titanate whisker is used as a composite nucleating agent compounded with mica powder, so as to reduce the shrinkage rate of injection molding and improve the impact strength.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a PVDF solar backboard film material with high strength and high toughness, which improves the strength and toughness of a PVDF backboard film master batch, solves the problems of insufficient strength and toughness of the prior art, has high tensile strength and elongation at break, low light transmittance and improved sunlight reflectivity; the invention also provides a preparation method of the composition.
The PVDF solar backboard film material with high strength and high toughness comprises the following components: polyvinylidene fluoride, polymethyl methacrylate, titanium dioxide, nano inorganic whisker, a coupling agent, a heat stabilizer and a flow modifier.
Preferably, the composition comprises the following components in parts by weight:
wherein:
the diameter of the inorganic nano-whisker is 0.1-0.5 μm, the length is 2-50 μm, and the length-diameter ratio is 20-100. The nano crystal whisker has different diameters, lengths and length-diameter ratios than the reinforcing and toughening effects of the composite material, the length-diameter ratio is increased in a certain range, the tensile strength of the composite material is increased, but when the length-diameter ratio is too large, the dispersion is poor, stress concentration is generated in the material, the reinforcing and toughening are not facilitated, and the crystal whisker with the size is selected, so that the reinforcing and toughening effects are best. The nano inorganic crystal whisker is one or more of titanium dioxide crystal whisker, silicon carbide crystal whisker, potassium titanate crystal whisker, aluminum borate crystal whisker, calcium sulfate crystal whisker, calcium carbonate crystal whisker, aluminum oxide crystal whisker or zinc oxide crystal whisker. The whisker is a fiber mainly grown in a single crystal form, has a very small diameter (micro-nano scale), does not contain defects existing in common materials, has highly ordered atomic arrangement, has high strength, high modulus and high elongation due to the highly oriented structure, has the strength far higher than that of other chopped fibers, and can reduce the shrinkage rate of the material and optimize the strength and the toughness of the material by adding the whisker into a polymer matrix.
The polyvinylidene fluoride is at least one of a vinylidene fluoride monomer homopolymer or a copolymer of the vinylidene fluoride monomer and other fluorine-containing monomers.
The mass flow rate of the melt of polyvinylidene fluoride at 230 ℃ and 5kg is 5-30 g/10 min.
The mass flow rate of the melt of polymethyl methacrylate at 230 ℃ and 5kg is 0.5-25 g/10min, preferably 2-15 g/10 min.
The titanium dioxide is rutile type titanium dioxide or anatase type titanium dioxide, preferably rutile type titanium dioxide.
The particle size of the titanium dioxide is 100-500 nm, preferably 200-400 nm.
The coupling agent is one or more of silane coupling agent, titanate coupling agent or aluminate coupling agent.
The flow modifier is one or more of erucamide, stearic acid amide, octadecyl erucamide, calcium stearate or zinc stearate.
The heat stabilizer is hindered phenol antioxidant 1010 and phosphite ester auxiliary antioxidant 168 according to the weight ratio of 0.5: 1-3: 1. 1010 is a main antioxidant, 168 is an auxiliary antioxidant, and the compounding synergistic effect of the two is good, so that the processing thermal stability and the oxidation resistance of the material in the using process can be effectively improved.
The preparation method of the PVDF solar backboard film material with high strength and high toughness comprises the following steps:
(1) pretreating titanium dioxide and nano inorganic whiskers by using a coupling agent: mixing the coupling agent, the titanium dioxide and the nano inorganic crystal whisker in a high-speed mixer to obtain a pretreated product;
(2) mixing polyvinylidene fluoride, polymethyl methacrylate, the pretreated product obtained in the step (1), a heat stabilizer and a flow modifier in a high-speed mixer; carrying out melt processing granulation on the obtained mixture on a double-screw extruder to obtain master batches special for the back plate film;
(3) and (3) casting or blow molding the master batch special for the back plate film on a single-screw extruder to form a film.
Wherein:
the mixing time in the step (1) is 5-20min, the mixing temperature is 60-80 ℃, and the rotating speed is 800-2000 r/min.
The mixing time in the step (2) is 10-30min, the mixing temperature is 40-80 ℃, the rotating speed is 800-2000r/min, and the granulation temperature is 180-220 ℃.
The extrusion temperature in step (3) is 170-210 ℃.
As a preferable technical scheme, the preparation method of the PVDF solar back panel film material with high strength and high toughness comprises the following steps:
(1) pretreating titanium dioxide and nano inorganic whiskers by using a coupling agent: mixing the coupling agent, the titanium dioxide and the nano inorganic whisker in a high-speed mixer for 5-20min at the mixing temperature of 60-80 ℃ and the rotating speed of 800-;
(2) mixing polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), the pretreated titanium dioxide obtained in the step (1), the nano inorganic crystal whisker, the heat stabilizer and the flow modifier in a high-speed mixer for 10-30min at the mixing temperature of 40-80 ℃ and the rotating speed of 800-2000 r/min; carrying out melting processing granulation on the obtained mixture on a double-screw extruder at the granulation temperature of 180 ℃ and 220 ℃ to obtain master batches special for the backboard membrane;
(3) the master batch special for the backboard film is subjected to tape casting or blow molding to form a film on a single-screw extruder, and the extrusion temperature is 170-210 ℃.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, the nano inorganic whiskers are added, the strength and toughness of the PVDF back plate membrane master batch are improved by utilizing the special reinforcing and toughening effect of the nano inorganic whiskers, the problem that the strength and toughness are insufficient when only PMMA and titanium dioxide are added is solved, the tensile strength of the prepared PVDF back plate membrane material in the MD direction is not less than 50MPa, and the elongation at break is not less than 350%; the tensile strength in the TD direction is more than or equal to 40MPa, and the elongation at break is more than or equal to 250%; meanwhile, the added nano inorganic whiskers are white, have low light transmittance, and can be used for preparing a backboard film with lower light transmittance compared with other reinforcing and toughening modifiers with high light transmittance, so that the reflectivity of sunlight is improved, and the utilization rate of the backboard component to the sunlight is further improved. The invention is a melt extrusion method, and the added crystal whisker not only has the function of strengthening and toughening, but also realizes other comprehensive functions, such as lower light transmittance and improved processing thermal stability of the back plate film material.
(2) According to the invention, the nano inorganic crystal whiskers are added, the strength and toughness of the PVDF back plate film master batch are improved by utilizing the special reinforcing and toughening effect of the nano inorganic crystal whiskers, and the problem of insufficient strength and toughness caused by only adding PMMA and titanium dioxide is solved; the titanium dioxide and the nano inorganic crystal whiskers act together, so that the prepared backboard film is lower in light transmittance, the reflectivity of sunlight is improved, and the utilization rate of the backboard component to the sunlight is further improved. Meanwhile, the use of a heat stabilizer and the replacement of part of the addition amount of the titanium dioxide by the inorganic crystal whisker improve the processing heat stability of the back plate film material.
Detailed Description
The present invention will be further described with reference to the following examples.
The parts of the materials in the following examples are parts by weight; the extrusion temperature in the examples below refers to the screw melt zone temperature.
Comparative example
Mixing 0.5 part of silane coupling agent and 10 parts of titanium dioxide in a high-speed mixer for 15min at the mixing temperature of 60 ℃ and the rotating speed of the mixer of 1200r/min to obtain coupling agent pre-treated titanium dioxide; 70 parts of PVDF, 20 parts of PMMA, pretreated titanium dioxide, 1 part of octadecyl erucamide and 1.5 parts of antioxidant (1010:168 is equal to 1:0.5) are mixed in a high-speed mixer for 20min, the mixing temperature is 50 ℃, the rotating speed of the mixer is 1500r/min, the obtained mixture is subjected to melt processing and granulation on a double-screw extruder, the temperature is 195 ℃, the master batch special for the back plate film is obtained, and the master batch is cast into a film on a single-screw extruder, the temperature is 195 ℃, and the film thickness is 25 mu m.
Example 1
Mixing 0.5 part of silane coupling agent, 10 parts of titanium dioxide and 5 parts of calcium sulfate whisker in a high-speed mixer for 15min at the mixing temperature of 60 ℃ and the rotating speed of the mixer of 800r/min to obtain coupling agent pretreated titanium dioxide and calcium sulfate whisker; 60 parts of PVDF, 25 parts of PMMA, the obtained pretreated titanium dioxide and titanium dioxide whiskers, 1 part of octadecyl erucamide and 1.5 parts of antioxidant (1010:168 is 1:0.5) are mixed in a high-speed mixer for 10min at the mixing temperature of 50 ℃ and the rotating speed of the mixer of 1200r/nim, the obtained mixture is subjected to melt processing and granulation on a double-screw extruder at the temperature of 200 ℃, the master batch special for the back plate film is obtained, and the master batch is subjected to tape casting on a single-screw extruder to form a film at the temperature of 200 ℃ and the film thickness of 25 mu m.
Example 2
Mixing 1 part of silane coupling agent, 5 parts of titanium dioxide and 10 parts of titanium dioxide whiskers in a high-speed mixer for 10min at the mixing temperature of 65 ℃ and the rotating speed of the mixer of 1000r/min to obtain coupling agent pretreated titanium dioxide and titanium dioxide whiskers; 65 parts of PVDF, 20 parts of PMMA, the obtained pretreated titanium dioxide and titanium dioxide whiskers, 1.5 parts of octadecyl erucamide and 1.8 parts of antioxidant (1010: 168: 1:0.8) are mixed in a high-speed mixer for 15min, the mixing temperature is 60 ℃, the rotating speed of the mixer is 1500r/nim, the obtained mixture is subjected to melt processing granulation on a double-screw extruder, the temperature is 210 ℃, the master batch special for the back plate film is obtained, and the master batch is subjected to tape casting on a single-screw extruder to form a film, the temperature is 190 ℃, and the film thickness is 25 mu m.
Example 3
Mixing 1.5 parts of silane coupling agent, 12 parts of titanium dioxide and 3 parts of alumina whisker in a high-speed mixer for 20min at the mixing temperature of 70 ℃ at the rotating speed of 1200r/min to obtain coupling agent pretreated titanium dioxide and alumina whisker; 70 parts of PVDF, 15 parts of PMMA, the obtained pretreated titanium dioxide and alumina whiskers, 0.5 part of octadecyl erucamide and 1.0 part of antioxidant (1010: 168: 0.5) are mixed in a high-speed mixer for 30min at the mixing temperature of 40 ℃ and the rotating speed of the mixer of 1800r/nim, the obtained mixture is subjected to melt processing granulation on a double-screw extruder at the temperature of 220 ℃ to obtain master batches special for the back plate film, and the master batches are subjected to tape casting on a single-screw extruder to form the film at the temperature of 210 ℃ and the film thickness of 25 mu m.
Example 4
Mixing 2 parts of silane coupling agent, 15 parts of titanium dioxide and 1 part of silicon carbide whisker in a high-speed mixer for 25min at the mixing temperature of 75 ℃ at the rotating speed of 1500r/min to obtain coupling agent pretreated titanium dioxide and silicon carbide whisker; 75 parts of PVDF, 9 parts of PMMA, the obtained pretreated titanium white and silicon carbide whiskers, 2 parts of octadecyl erucamide and 3 parts of antioxidant (1010:168 is 2:1) are mixed in a high-speed mixer for 10min at the mixing temperature of 80 ℃ and the rotating speed of the mixer of 800r/nim, the obtained mixture is subjected to melt processing and granulation on a double-screw extruder at the temperature of 200 ℃ to obtain master batches special for the back plate film, and the master batches are cast into a film on a single-screw extruder at the temperature of 195 ℃ and the thickness of the film is 25 mu m.
Example 5
Mixing 3 parts of silane coupling agent, 10 parts of titanium dioxide, 3 parts of titanium dioxide whiskers and 2 parts of alumina whiskers in a high-speed mixer for 30min at the mixing temperature of 80 ℃ and the rotating speed of the mixer of 1800r/min to obtain a coupling agent pretreatment product; 80 parts of PVDF, 5 parts of PMMA, the obtained pretreatment product, 3 parts of octadecyl erucamide and 2.5 parts of antioxidant (1010:168 is 1.5:1) are mixed in a high-speed mixer for 25min at the mixing temperature of 60 ℃ and the rotating speed of the mixer of 1500r/nim, the obtained mixture is subjected to melt processing and granulation on a double-screw extruder at the temperature of 200 ℃ to obtain master batch special for the back plate film, and the master batch is subjected to tape casting on a single-screw extruder to form a film at the temperature of 195 ℃ and the thickness of the film of 25 mu m.
Example 6
Mixing 0.5 part of silane coupling agent, 5 parts of titanium dioxide whiskers and 5 parts of alumina whiskers in a high-speed mixer at the temperature of 70 ℃ for 15min, wherein the mixing temperature is 60 ℃, and the rotating speed of the mixer is 1200r/min to obtain a coupling agent pretreatment product; 65 parts of PVDF, 20 parts of PMMA, the obtained pretreatment product, 1 part of octadecyl erucamide and 2 parts of antioxidant (1010:168 ═ 1:1) are mixed in a high-speed mixer for 15min, the mixing temperature is 60 ℃, the rotating speed of the mixer is 1500r/nim, the obtained mixture is subjected to melt processing and granulation on a double-screw extruder, the temperature is 205 ℃, the master batch special for the back plate film is obtained, and the master batch is subjected to tape casting on a single-screw extruder to form a film, the temperature is 195 ℃, and the film thickness is 25 mu m.
Example 7
Mixing 0.5 part of silane coupling agent, 15 parts of titanium dioxide and 5 parts of calcium carbonate crystal whisker in a high-speed mixer for 20min at the mixing temperature of 80 ℃ at the rotating speed of 1000r/min to obtain coupling agent pretreated titanium dioxide and calcium carbonate crystal whisker; 70 parts of PVDF, 10 parts of PMMA, the obtained pretreated titanium white powder and calcium carbonate whiskers, 1 part of octadecyl erucamide and 1.5 parts of antioxidant (1010:168 is 0.5:1) are mixed in a high-speed mixer for 20min at the mixing temperature of 70 ℃ and the rotating speed of the mixer of 1800r/nim, the obtained mixture is subjected to melt processing and granulation on a double-screw extruder at the temperature of 205 ℃ to obtain master batches special for the back plate film, the master batches are subjected to tape casting on a single-screw extruder to form a film at the temperature of 195 ℃ and the film thickness of 25 mu m.
The formulations of the above examples are shown in Table 1.
Table 1 example formulations
The films obtained in comparative examples and examples 1 to 7 were subjected to mechanical property, light transmittance and weather resistance (yellowing index) tests, and the test results are shown in Table 2:
TABLE 2 test results of comparative example and examples 1-7

Claims (8)

1. The PVDF solar backboard film material with high strength and high toughness is characterized in that: the composition comprises the following components in parts by weight:
polyvinylidene fluoride 60 ~ 80 parts
Polymethyl methacrylate 5 ~ 25 parts
Titanium dioxide 5 ~ 15 parts
Nano inorganic whisker 1 ~ 10 parts
0.5 ~ 3 parts of coupling agent
0.5 part of heat stabilizer 0.5 ~ 3
0.5 ~ 3 parts of flow modifier;
the diameter of the nano inorganic whisker is 0.1 ~ 0.5.5 μm, the length is 2 ~ 50 μm, and the length-diameter ratio is 20 ~ 100.
2. The high strength high toughness PVDF solar back sheet film material as claimed in claim 1, wherein: the nano inorganic crystal whisker is one or more of titanium dioxide crystal whisker, silicon carbide crystal whisker, potassium titanate crystal whisker, aluminum borate crystal whisker, calcium sulfate crystal whisker, calcium carbonate crystal whisker, aluminum oxide crystal whisker or zinc oxide crystal whisker.
3. The high-strength high-toughness PVDF solar back panel film material as claimed in claim 1, wherein the polyvinylidene fluoride is at least one of a vinylidene fluoride monomer homopolymer or a copolymer of the vinylidene fluoride monomer and other fluorine-containing monomers, and the melt mass flow rate of the polyvinylidene fluoride at 230 ℃ and 5kg is 5 ~ 30g/10 min.
4. The high-strength high-toughness PVDF solar back panel film material as claimed in claim 1, wherein the melt mass flow rate of 5kg at 230 ℃ of polymethyl methacrylate is 0.5 ~ 25g/10 min.
5. The PVDF solar back panel film material with high strength and high toughness as claimed in claim 1, wherein the titanium dioxide is rutile titanium dioxide or anatase titanium dioxide, and the particle size of the titanium dioxide is 100 ~ 500nm and 500 nm.
6. The PVDF solar back panel film material with high strength and high toughness as claimed in claim 1, wherein the coupling agent is one or more of silane coupling agent, titanate coupling agent or aluminate coupling agent, the flow modifier is one or more of erucamide, stearamide, octadecylerucamide, calcium stearate or zinc stearate, and the heat stabilizer is a mixture of hindered phenol antioxidant 1010 and phosphite ester auxiliary antioxidant 168 in a weight ratio of 0.5:1 ~ 3: 1.
7. A preparation method of the high-strength high-toughness PVDF solar back panel film material as defined in any one of claims 1-6, wherein: the method comprises the following steps:
(1) pretreating titanium dioxide and nano inorganic whiskers by using a coupling agent: mixing the coupling agent, the titanium dioxide and the nano inorganic crystal whisker in a high-speed mixer to obtain a pretreated product;
(2) mixing polyvinylidene fluoride, polymethyl methacrylate, the pretreated product obtained in the step (1), a heat stabilizer and a flow modifier in a high-speed mixer; carrying out melt processing granulation on the obtained mixture on a double-screw extruder to obtain master batches special for the back plate film;
(3) and (3) casting or blow molding the master batch special for the back plate film on a single-screw extruder to form a film.
8. The preparation method of the high-strength high-toughness PVDF solar back panel film material as claimed in claim 7, is characterized in that:
the mixing time in the step (1) is 5-20min, the mixing temperature is 60-80 ℃, and the rotating speed is 800-;
the mixing time in the step (2) is 10-30min, the mixing temperature is 40-80 ℃, the rotating speed is 800-;
the extrusion temperature in step (3) is 170-210 ℃.
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CN109560165A (en) * 2018-11-14 2019-04-02 宁波高新区州致科技有限公司 A kind of composite membrane used for solar batteries and preparation method thereof
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CN112768542B (en) * 2021-01-05 2022-12-02 浙江中聚材料有限公司 Insulated solar photovoltaic backboard and preparation process thereof

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