Search

CN-122011569-A - Method for catalytic degradation and plasticization of photovoltaic crosslinked material through polyvalent metal manganese/cerium compound

CN122011569ACN 122011569 ACN122011569 ACN 122011569ACN-122011569-A

Abstract

The invention discloses a method for catalytic degradation and plasticization of a photovoltaic cross-linked material by a polyvalent metal manganese/cerium compound, which aims at a thermosetting adhesive film with cross-linked molecular structure, uses a plasticizer and a cosolvent to thermally impregnate and pretreat the powder of the cross-linked adhesive film, uses the polyvalent metal manganese/cerium compound as a degradation catalyst of a system, then uniformly mixes the mixture after the thermal impregnation treatment with thermoplastic resin and a polymerization inhibitor, and carries out melt extrusion under strong mechanical shearing force of a double-screw extruder, wherein the obtained extrusion product has certain flowability. The invention can realize plasticization preparation of the photovoltaic crosslinked adhesive film aiming at the photovoltaic crosslinked material with certain crosslinking degree which is largely recovered in industries such as packaging adhesive films of crystalline silicon photovoltaic cells, functional greenhouse films, foaming shoe materials and the like, and the extrusion product can be used as a toughening filling material of traditional engineering plastics or used as an interface modifier in polymer alloy.

Inventors

  • MA JIAWEI
  • Hu Hanchu
  • ZOU XIANGPING
  • SONG YIHU
  • WU WUBIN

Assignees

  • 宁波甬复新材料科技有限公司

Dates

Publication Date
20260512
Application Date
20260319

Claims (10)

  1. 1. A method for catalytic degradation and plasticization of a photovoltaic cross-linked material by a polyvalent metal manganese/cerium compound is characterized by comprising, Crushing and grinding the recovered photovoltaic packaging adhesive film material to obtain adhesive film powder; mixing the adhesive film powder, the plasticizer and the cosolvent, and then sealing and placing in an oven for hot dipping treatment for 10-15 hours at 50-70 ℃ to obtain a pre-plasticized mixed material; Uniformly stirring the catalyst, the pre-plasticized mixed material, the thermoplastic resin and the polymerization inhibitor in a high-speed stirrer to obtain a mixture; Comprising, in mass percent of the mixture, 65-85% Of adhesive film powder, 10-20% of thermoplastic resin, 0-10% of plasticizer, 2-5% of cosolvent, 0.2-1% of catalyst and 0.01-0.2% of benzoquinone polymerization inhibitor; and (3) putting the mixture into a double-screw extruder for extrusion granulation, and cooling and granulating after extrusion to obtain a flowable recovered product.
  2. 2. The method for catalytic degradation and plasticization of a photovoltaic crosslinked material by a multi-valence Mn/Ce compound according to claim 1, wherein the crosslinking degree of the photovoltaic packaging film material is 65-90%, and the melt index is less than 0.1g/10 min under the conditions of 230 ℃ and 10 kg.
  3. 3. The method of catalytically degrading and plasticizing a photovoltaic cross-linked material with a polyvalent metal manganese/cerium compound according to claim 2, wherein the photovoltaic packaging film material comprises one or more of an ethylene-vinyl acetate film, an ethylene-polyolefin elastomer film; The plasticizer is an ester plasticizer with the boiling point of more than 180 ℃ and comprises one or more of aliphatic dibasic acid ester plasticizer and phthalic acid ester plasticizer, wherein the phthalic acid ester plasticizer comprises one or more of diphenyl phthalate and dioctyl terephthalate.
  4. 4. The method for catalytic degradation and plasticization of a photovoltaic cross-linked material by a polyvalent metal manganese/cerium compound according to claim 3, wherein the co-solvent comprises one or more of styrene, alpha-methylstyrene, ethylstyrene.
  5. 5. The method for catalytic degradation and plasticization of a photovoltaic cross-linked material by a polyvalent metal manganese/cerium compound according to claim 1, wherein the catalyst consists of manganese stearate and cerium acetate.
  6. 6. The method for catalytic degradation and plasticization of a photovoltaic cross-linked material according to claim 5, wherein the manganese stearate is contained in an amount of 0.1-0.5% and the cerium acetate is contained in an amount of 0.1-0.5% by mass of the mixture.
  7. 7. The method for catalytic degradation and plasticization of a photovoltaic cross-linked material by a polyvalent metal manganese/cerium compound according to claim 1, wherein the thermoplastic resin comprises one or more of EVA, PP, polyester-based resins.
  8. 8. The method for catalytic degradation and plasticization of photovoltaic cross-linked material by a polyvalent metal manganese/cerium compound according to claim 7, wherein the polymerization inhibitor is a benzoquinone polymerization inhibitor including one or more of benzoquinone and benzoquinone.
  9. 9. The method for catalytic degradation and plasticization of a photovoltaic cross-linked material by a multi-valence Mn/Ce compound according to claim 8, wherein the mixture is extruded and pelletized in a twin-screw extruder, wherein the screw host rotation speed is 100-300 r/min and the host current is 40-70%; The extrusion granulation is carried out, wherein the temperature of each section of the screw rod is respectively as follows: The temperature of the melt is 170-190 ℃, the temperature of the front section is 140-170 ℃, the temperature of the middle section is 170-180 ℃, the temperature of the rear section is 180-190 ℃, the residence time of the melt in a screw is 1-3 min, and the melt is cooled and pelletized after extrusion.
  10. 10. A blended modified product obtained by treatment according to the method of claim 1-9, wherein the melt index of the blended modified product after treatment is improved by more than 35 times under the condition of 230 ℃ and 10kg compared with that of an original photovoltaic cross-linked material.

Description

Method for catalytic degradation and plasticization of photovoltaic crosslinked material through polyvalent metal manganese/cerium compound Technical Field The invention belongs to the technical field of high polymer materials, and particularly relates to a method for catalytic degradation and plasticization of a photovoltaic cross-linked material through a multivalent metal manganese/cerium compound. Background The main components of the photovoltaic packaging adhesive film material are an ethylene-vinyl acetate (EVA) adhesive film, an ethylene-polyolefin elastomer (POE) adhesive film and a mixed adhesive film, and the photovoltaic packaging adhesive film material is used for connecting a glass plate and a crystalline silicon battery. EVA is a nontoxic, odorless and transparent thermoplastic elastomer which is obtained by copolymerizing nonpolar, crystalline vinyl monomer and noncrystalline vinyl acetate monomer in the presence of various additives such as cross-linking agent, antioxidant, stabilizer, etc., and has excellent flexibility, impact resistance, elasticity, optical transparency, corrosion resistance, etc. POE is a thermoplastic elastomer prepared by in-situ polymerization of ethylene and alpha-olefin (such as 1-octene), and has excellent weather resistance, ozone resistance, ultraviolet linearity resistance and aging resistance, and can keep stable performance under severe environmental conditions. In practical application, after the crosslinking agent, the coupling agent and other conditions and oxidation and other conditions, certain crosslinking structure is generated in the molecular chain, so that the original thermoplastic property is lost. The cross-linked materials can not be further reused by traditional melt reprocessing after being recycled due to the loss of the melt processable flow characteristics, and can only be treated by landfill or incineration at present, but the treatment method can cause serious ecological environmental pollution. Therefore, a processing method is explored, which is used for degrading and plasticizing the crosslinked photovoltaic adhesive film, and obtaining a new material capable of being melt processed, and has great environmental protection value and market value. Disclosure of Invention This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application. The present invention has been made in view of the above and/or problems occurring in the prior art. It is therefore an object of the present invention to overcome the deficiencies of the prior art by providing a method for the catalytic degradation and plasticization of a photovoltaic cross-linked material by a polyvalent metal manganese/cerium compound. In order to solve the technical problems, the invention provides a method for catalyzing, degrading and plasticizing a photovoltaic crosslinking material by using a polyvalent metal manganese/cerium compound, which comprises the following steps of, And mixing the adhesive film powder, the plasticizer and the cosolvent, sealing, and placing in an oven for hot dipping treatment to obtain a pre-plasticized mixed material. The catalyst, the pre-plasticized mixture, the thermoplastic resin and the polymerization inhibitor are stirred uniformly in a high-speed stirrer to obtain a mixture. And crushing and grinding the recovered photovoltaic packaging adhesive film material to obtain adhesive film powder. And mixing the adhesive film powder, the plasticizer and the cosolvent, and then sealing and placing in an oven for hot dipping treatment for 10-15 h at 50-70 ℃ to obtain a pre-plasticized mixed material. The catalyst, the pre-plasticized mixture, the thermoplastic resin and the polymerization inhibitor are stirred uniformly in a high-speed stirrer to obtain a mixture. The adhesive film comprises, by mass, 65-85% of adhesive film powder, 10-20% of thermoplastic resin, 0-10% of plasticizer, 2-5% of cosolvent, 0.2-1% of catalyst and 0.01-0.2% of benzoquinone polymerization inhibitor. And (3) putting the mixture into a double-screw extruder for extrusion granulation, and cooling and granulating after extrusion to obtain a flowable recovered product. As a preferred embodiment of the method for catalytic degradation and plasticization of a photovoltaic cross-linked material by a polyvalent metal manganese/cerium compound according to the present invention, the photovoltaic packaging film material comprises one or more of ethylene-vinyl acetate film, ethylene-polyolefin elastomer film. The plasticizer is an ester plasticizer with a boiling point of more than 180 ℃ and comprises one or more of an aliphatic dibasic acid ester plasticizer and a phthalate plasticizer, wherein the phthalate plastic