CN107383799B - Special material for polybutylene terephthalate-polyvinylidene fluoride alloy - Google Patents
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- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- 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
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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
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- 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
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
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- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention discloses a special material for polybutylene terephthalate-polyvinylidene fluoride alloy. The components by weight portion are as follows: 5-95 parts of polybutylene terephthalate, 5-95 parts of polyvinylidene fluoride, 2-20 parts of a compatibilizer, 0.1-2 parts of an antioxidant and 10-20 parts of an inorganic filler. The polybutylene terephthalate (PBT)/polyvinylidene fluoride (PVDF) alloy film prepared by the invention has the characteristics of excellent ultraviolet blocking capability, low water permeability and good hydrolysis resistance of the PVDF film, and also has the advantages of low cost and easy degradation and recycling of the PBT film, and the novel outer layer protection material has extremely important significance for the photovoltaic backboard industry.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, relates to a material on a solar cell back plate, and particularly relates to a polyester alloy film material with excellent hydrolysis resistance, weather resistance and mechanical properties.
Background
The world's crisis of shortage of conventional energy supplies is becoming more severe, as exemplified by petroleum only, and the worldwide proven reserves have been available for recovery for only 45.7 years by the end of 2009. Moreover, the excessive exploitation and utilization of fossil energy has become one of the main intentions of natural environmental pollution and threatening human health. According to the prediction of the union of european union research center, the proportion of renewable energy sources will exceed that of traditional energy sources by 2050, and is about 52%, wherein the solar energy is 1/2-strong, and is about 28%, and the proportion of renewable energy sources will be 86% by the end of the century, and the solar energy will occupy about 67% of the solar energy sources.
Solar photovoltaic power generation constitutes an important component of solar energy strategy due to its advantages of no pollution, sustainability, large total amount, wide distribution, various utilization forms, and the like. Among them, crystalline silicon solar cells, which are semiconductor solar cells mainly composed of silicon, are dominant. The main structure of the crystalline silicon solar cell is a laminated structure formed by a high-transparency front plate, a packaging film, a silver paste or aluminum paste lead, a polycrystalline or monocrystalline silicon wafer, a packaging film, a cell back plate and other multilayer structures, the materials are molded in a heating laminating mode, and after the materials are assembled by using a sealing rubber strip and a frame, the crystalline silicon solar cell component can be obtained by matching with a junction box. The main functions of the back plate are excellent electrical insulation, mechanical stability, external environment corrosion resistance, weather resistance and low water vapor permeability, and the back plate is used for protecting and supporting the cell and has important influence on the performance of the crystalline silicon solar cell.
The solar cell back sheet is mainly classified into two types, one is a back sheet based on a fluoropolymer, and the other is a back sheet of a full polyethylene terephthalate (PET) structure. Among them, the fluoropolymer back sheet has excellent ultraviolet resistance, but the fluoropolymer has the problems of high price, high investment cost of production equipment, difficult recycling and the like, which greatly hinders the popularization and development of solar cells. The back sheet of the full PET structure is lower in price compared with the fluorine-containing back sheet, but still has the disadvantages of poor hydrolysis resistance and poor ultraviolet resistance, and because the crystallization rate of PET is slow, the crystallization is incomplete and uneven, the produced film needs to be biaxially stretched to improve the performance, and this also increases the production cost of the PET film. Therefore, the polyvinylidene fluoride (PVDF) film has excellent ultraviolet blocking capacity, low water permeability and good hydrolysis resistance, the polyethylene terephthalate (PET) film has low cost and is easy to degrade and recycle, and the novel outer-layer protection material has extremely important significance for the photovoltaic back plate industry.
Polybutylene terephthalate resin materials have the advantages of low water absorption, good dimensional stability, high dielectric strength, excellent chemical resistance and weather resistance, and the like, have been drawing attention as engineering plastics, and injection-molded parts thereof are widely applied to automobile parts, electrical, electronic and communication industries. Based on the consideration, the invention provides a special material for a polybutylene terephthalate/polyvinylidene fluoride alloy film, which is used for replacing a protective material of an outer layer of a traditional solar cell back plate, so that the aim of reducing the cost of a photovoltaic back plate is fulfilled.
Disclosure of Invention
The invention aims to provide a polybutylene terephthalate/polyvinylidene fluoride alloy film with low cost, good dimensional stability, hydrolysis resistance, mechanical property and weather resistance, so as to replace the traditional reinforced BO-PET or fluorine-containing back film and reduce the preparation cost of a solar cell back plate. The polybutylene terephthalate/polyvinylidene fluoride alloy film provided by the invention has the advantages of excellent hydrolysis resistance, weather resistance, thermal stability, electrical insulation and lower cost, and more importantly, the polybutylene terephthalate/polyvinylidene fluoride alloy film is easy to recycle and has far lower environmental hazard than polyvinylidene fluoride.
In order to achieve the above object, the invention adopts a reactive compatibilization technology, and prepares the high-performance polybutylene terephthalate/polyvinylidene fluoride alloy special material by adjusting the proportion of polybutylene terephthalate, polyvinylidene fluoride (PVDF), a compatibilizer, an antioxidant and an inorganic filler and carrying out a blending reaction in a double-screw extruder under proper process conditions, and the specific technical scheme is as follows:
the special material for the polybutylene terephthalate-polyvinylidene fluoride alloy comprises the following raw material components in parts by weight: 5-95 parts of polybutylene terephthalate, 5-95 parts of polyvinylidene fluoride, 2-20 parts of compatibilizer, 0.1-2 parts of antioxidant and 10-20 parts of inorganic filler.
Then, the materials are uniformly mixed in a high-speed mixer, then the uniformly mixed mixture is extruded and granulated in a double-screw extruder, and finally, a polybutylene terephthalate/polyvinylidene fluoride alloy film sheet with the thickness of 10-200 mu m is prepared by a tape casting process.
Preferably, the polybutylene terephthalate has an intrinsic viscosity of 0.5 to 1.3 dl/g.
Preferably, the weight average molecular weight of the polyvinylidene fluoride is 20-150 ten thousand.
Preferably, the compatibilizer is a functional group graft modified acrylic block copolymer, and the sum of the proportions of the components is 100%. Wherein the functional group comprises glycidyl methacrylate (-GMA), maleic anhydride (-MAH) or amino (-NH)2) Of 1 to 10% in an acrylic block copolymer, or a mixture thereof. The acrylic block copolymer comprises two or more block copolymers of acrylic acid or acrylic acid alkyl C1-C4 ester polymers, methacrylic acid or methacrylic acid alkyl C1-C4 ester polymers and ethacrylic acid or ethacrylic acid alkyl C1-C4 ester polymers, and the sum of the proportion of the components in the acrylic block copolymer is 90-99%.
Preferably, the functional group comprises one or more of glycidyl methacrylate, maleic anhydride or amino.
Preferably, the acrylic block copolymer comprises two or more block copolymers of acrylic acid or alkyl acrylate C1-C4 ester polymers, methacrylic acid or alkyl methacrylate C1-C4 ester polymers, and ethacrylic acid or alkyl ethacrylate C1-C4 ester polymers.
Preferably, the solubilizer is glycidyl methacrylate grafted modified methyl methacrylate (MMA-g-GMA) or amino grafted modified butyl methacrylate (MBA-g-NH)2) Glycidyl methacrylate grafted butyl methacrylate-methyl acrylate copolymer (MBA-MA-g-GMA) and maleic anhydride grafted modified methyl methacrylate (MMA-g-MAH).
Preferably, the inorganic filler is nano-scale silicon dioxide, nano-scale calcium carbonate or nano-scale titanium dioxide, and the average particle size of the inorganic filler is 1-500 nanometers.
Preferably, the antioxidant is dilauryl thiodipropionate, 2, 6-di-tert-butyl-4-methylphenol, tris (2, 4-di-tert-butylphenyl) phosphite or tris (2, 4-di-tert-butylphenyl) phosphite, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-octadecyl beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate or N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine or a mixture of several thereof.
Preferably, the processing mode of the special material for the polybutylene terephthalate-polyvinylidene fluoride alloy comprises hollow blow molding preparation, casting preparation or calendaring; the thickness of the prepared film sheet is 10-200 μm.
The invention has the beneficial effects that: the invention adopts the reactive compatilizer, improves the interface state between the PBT and the PVDF by utilizing the in-situ reaction, and improves the compatibility of the PBT and the PVDF, thereby obtaining the polybutylene terephthalate (PBT)/polyvinylidene fluoride (PVDF) alloy film with excellent dimensional stability, hydrolysis resistance, mechanical property and weather resistance.
Detailed Description
The technical solution of the present invention is further described below by means of specific examples.
Unless otherwise specified, the raw materials used in the examples of the present invention are all those commonly used in the art, and the methods used in the examples are all those conventional in the art.
Polybutylene terephthalate with an intrinsic viscosity of 0.5 to 1.3 dl/g.
The weight average molecular weight of the polyvinylidene fluoride is 20-150 ten thousand.
Comparative example 1
The raw material components by weight: 80 parts of polybutylene terephthalate, 20 parts of polyvinylidene fluoride, 0.2 part of antioxidant 1010, 0.1 part of antioxidant 168 and 10 parts of nano titanium dioxide. Firstly weighing the materials according to the formula, uniformly mixing the materials in a high-speed mixer, then extruding and granulating the uniformly mixed mixture in a double-screw extruder, and finally preparing the dried particles into a film sheet with the thickness of 30 mu m by a tape casting process.
Example one
The raw material components by weight: 95 parts of polybutylene terephthalate, 5 parts of polyvinylidene fluoride, 2 parts of glycidyl methacrylate grafted and modified methyl methacrylate (MMA-g-GMA), 0.05 part of antioxidant 1010, 0.05 part of antioxidant 168 and 10 parts of nano titanium dioxide inorganic filler. Firstly weighing the materials according to the formula, uniformly mixing the materials in a high-speed mixer, then extruding and granulating the uniformly mixed mixture in a double-screw extruder, and finally preparing the dried particles into a film sheet with the thickness of 10 mu m by a tape casting process.
Example two
The raw material components by weight: 50 parts of polybutylene terephthalate, 50 parts of polyvinylidene fluoride and 10 parts of amino graft modified butyl methallylate (MBA-g-NH)2) 0.2 part of antioxidant 1010, 0.1 part of antioxidant 168 and 15 parts of nano silicon dioxide. Firstly weighing the materials according to the formula, uniformly mixing the materials in a high-speed mixer, then extruding and granulating the uniformly mixed mixture in a double-screw extruder, and finally preparing the dried particles into a film sheet with the thickness of 30 mu m by a tape casting process.
EXAMPLE III
The raw material components by weight: 20 parts of polybutylene terephthalate, 80 parts of polyvinylidene fluoride, 15 parts of glycidyl methacrylate grafted butyl methacrylate-methyl acrylate (MBA-MA-g-GMA), 0.2 part of antioxidant 1010, 0.1 part of antioxidant 168 and 20 parts of nano calcium carbonate. Firstly weighing the materials according to the formula, uniformly mixing the materials in a high-speed mixer, then extruding and granulating the uniformly mixed mixture in a double-screw extruder, and finally preparing the dried particles into a film sheet with the thickness of 50 microns by a tape casting process.
Example four
The raw material components by weight: 5 parts of polybutylene terephthalate, 95 parts of polyvinylidene fluoride, 20 parts of maleic anhydride grafted modified methyl methacrylate (MMA-g-MAH), 1.2 parts of antioxidant 1010, 0.8 part of antioxidant 168 and 20 parts of nano titanium dioxide. Firstly weighing the materials according to the formula, uniformly mixing the materials in a high-speed mixer, then extruding and granulating the uniformly mixed mixture in a double-screw extruder, and finally preparing the dried particles into a film sheet with the thickness of 200 mu m by a tape casting process.
The mechanical properties of the invention were measured according to ASTM D882-83 for preparing and testing bars, the heat resistance was measured according to ASTM D1204 for testing samples, and the test properties of the comparative examples and the examples of the invention are shown in the following table (the test directions are all MD directions):
Claims (6)
1. the material special for the polybutylene terephthalate-polyvinylidene fluoride alloy is characterized by comprising the following raw material components in parts by weight: 5-95 parts of polybutylene terephthalate, 5-95 parts of polyvinylidene fluoride, 2-20 parts of compatibilizer, 0.1-2 parts of antioxidant and 10-20 parts of inorganic filler; the compatibilizer is one of amino grafted and modified butyl methacrylate, glycidyl methacrylate grafted butyl methacrylate-methyl acrylate and maleic anhydride grafted and modified methyl methacrylate.
2. The special material for polybutylene terephthalate-polyvinylidene fluoride alloy according to claim 1, wherein the polybutylene terephthalate has an intrinsic viscosity of 0.5 to 1.3 dl/g.
3. The special material for the polybutylene terephthalate-polyvinylidene fluoride alloy as claimed in claim 1, wherein the weight average molecular weight of the polyvinylidene fluoride is 20-150 ten thousand.
4. The special material for the polybutylene terephthalate-polyvinylidene fluoride alloy according to claim 1, wherein the inorganic filler is nano-silica, nano-calcium carbonate or nano-titanium dioxide, and the average particle size of the inorganic filler is 1-500 nm.
5. The special material for polybutylene terephthalate-polyvinylidene fluoride alloy according to claim 1, wherein the antioxidant is dilauryl thiodipropionate, 2, 6-di-tert-butyl-4-methylphenol, tris (2, 4-di-tert-butylphenyl) phosphite, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-octadecyl beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate or N, N-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine or a mixture of several of them.
6. The special material for the polybutylene terephthalate-polyvinylidene fluoride alloy according to claim 1, wherein the special material for the polybutylene terephthalate-polyvinylidene fluoride alloy is prepared by hollow blow molding, casting or calendering; the thickness of the prepared film sheet is 10-200 μm.
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| CN108264738B (en) * | 2018-01-19 | 2020-11-17 | 合肥宸翊商贸有限公司 | Master batch of solar back panel film for adding high-recovery material and preparation method thereof |
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| CN109181243B (en) * | 2018-08-24 | 2021-09-07 | 杭州福禧新材料有限公司 | Method for recycling waste film and leftover materials of solar cell backboard |
| CN109367146A (en) * | 2018-08-29 | 2019-02-22 | 绍兴福膜新材料有限公司 | A kind of extra-weather-proof protecting solar cell film and preparation method thereof |
| CN109486150B (en) * | 2018-11-07 | 2022-11-08 | 万华化学集团股份有限公司 | Hydrolysis-resistant PC/ASA alloy material and preparation method thereof |
| CN109749313A (en) * | 2018-11-29 | 2019-05-14 | 常州回天新材料有限公司 | Solar panel notacoria |
| CN110126379A (en) * | 2019-04-29 | 2019-08-16 | 江苏派恩新型材料有限公司 | A kind of precoated metal watt of high-strength and high-weather-resistance |
| CN110746753B (en) * | 2019-10-16 | 2022-01-04 | 苏州市新广益电子有限公司 | PET film blowing bag and preparation method thereof |
| CN111592741B (en) * | 2020-05-27 | 2022-09-23 | 合复新材料科技(无锡)有限公司 | Melt blending modification method of solar aged fluorine-containing back plate membrane material and product thereof |
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