阅读说明：本技术 一种高透光太阳能电池封装用交联型聚烯烃的制备方法 (Preparation method of cross-linked polyolefin for packaging high-light-transmittance solar cell ) 是由 王文俊 罗理琼 刘平伟 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种高透光太阳能电池封装用交联型聚烯烃的制备方法,本发明利用溶液聚合,通过控制原料的加入方式、时间和加入量,制备含两种交联基团组成的聚烯烃,所述的交联基团为乙烯基,所合成的聚烯烃中,0-30重量百分比聚烯烃不含交联基团,30-70重量百分比的聚烯烃的交联基团摩尔组成为0.001–10。该交联型聚烯烃制成的太阳能电池封装材料,在380-780nm的波长范围内透光率大于93％。本发明制备的高透光太阳能电池封装用交联型聚烯烃可以用于替代传统太阳能电池封装材料,且具有交联时间短、耐候性好等优点。(The invention discloses a preparation method of cross-linking polyolefin for high-light-transmission solar cell encapsulation, which utilizes solution polymerization to prepare polyolefin consisting of two cross-linking groups by controlling the adding mode, time and adding amount of raw materials, wherein the cross-linking groups are vinyl, 0-30 weight percent of the synthesized polyolefin does not contain the cross-linking groups, and the molar composition of the cross-linking groups of the polyolefin of 30-70 weight percent is 0.001-10. The light transmittance of the solar cell packaging material prepared from the cross-linked polyolefin is greater than 93% in the wavelength range of 380-780 nm. The cross-linking type polyolefin for packaging the high-light-transmission solar cell, which is prepared by the invention, can be used for replacing the traditional solar cell packaging material and has the advantages of short cross-linking time, good weather resistance and the like.)

1. A preparation method of cross-linked polyolefin for packaging a high-light-transmission solar cell is characterized by comprising the following steps: dissolving ethylene in an organic solvent of a semicontinuous reactor under the anhydrous and oxygen-free conditions, adding alpha-olefin, a copolymerization catalyst and a cocatalyst, polymerizing for 0.1-21h at 30-300 ℃, then adding a polyene monomer with a crosslinking group for reaction, and further polymerizing for 0-4h to prepare the crosslinking polyolefin for packaging the high-light-transmission solar cell; based on the volume of the organic solvent in the semi-continuous reactor, the concentrations of ethylene and alpha-olefin are both 0.001-10 mol/L, the concentration of the alkene monomer with the crosslinking group is 0.001-10 mol/L, the concentration of the copolymerization catalyst is 0.1-100 mu mol/L, and the molar ratio of the cocatalyst to the copolymerization catalyst is 50-10000: 1.

2. A preparation method of cross-linked polyolefin for packaging a high-light-transmission solar cell is characterized by comprising the following steps: dissolving ethylene in an organic solvent of a first reactor of a multistage continuous reactor under anhydrous and anaerobic conditions, adding a first part of alpha-olefin, a copolymerization catalyst and a cocatalyst, polymerizing at 30-300 ℃, keeping the time for 0.5-180min, then flowing into a subsequent reactor, adding a polyene monomer with a crosslinking group into the subsequent reactor, reacting with a second part of alpha-olefin, polymerizing at 30-300 ℃, keeping the time for 0.5-180min, and obtaining the crosslinking polyolefin for packaging the high-light-transmission solar cell consisting of the two crosslinking groups. Based on the volume of the organic solvent, the concentrations of the ethylene and the first part of alpha-olefin are both 0.001-10 mol/L, the concentration of the catalyst is 0.1-100 mu mol/L, the molar ratio of the cocatalyst to the copolymerization catalyst is 50-10000: 1, the concentration of the second part of alpha-olefin is 0.001-10 mol/L, and the concentration of the vinyl monomer with the crosslinking group is 0.001-10 mol/L.

3. The preparation method according to claim 1 or 2, wherein the crosslinking group is vinyl, and the prepared crosslinked polyolefin for encapsulating the high-light-transmittance solar cell has a weight average molecular weight of 1 to 500kg/mol and a molecular weight distribution index of 2.0 to 15.0, and is composed of 0 to 30% by weight of an olefin polymer containing no crosslinking group and 70 to 100% by weight of an olefin polymer containing a crosslinking group; in the crosslinking polyolefin for packaging the high-light-transmission solar cell, the molar content of a crosslinking group is 0.001-10%.

4. The process according to claim 1 or 2, wherein the reactor is a tubular reactor or a tank reactor, and the polymerization is a solution polymerization.

5. The method according to claim 1 or 2, wherein the α -olefin is a linear or branched α -olefin of 3 to 20 carbon atoms.

6. The method for preparing the cross-linked polyolefin material for encapsulating the high-light-transmission solar cell according to claim 5, wherein the alpha-olefin is preferably propylene, butylene, 1-hexene, 1-octene, isopentene, 2-methylpropene.

7. The method for preparing the cross-linked polyolefin material for encapsulating a high light-transmitting solar cell according to claim 1 or 2, wherein the polyene monomer having a cross-linking group includes a straight chain type diene monomer, a cyclic diene monomer, a straight chain triene monomer, a cyclic triene monomer, a alkene having a benzene ring, and the like, preferably butadiene, 1, 5-hexadiene, 1, 4-hexadiene, 1, 7-octadiene, 1, 9-decadiene, 1, 4-isoprene, cyclopentadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinylbicyclo [2.2.1] hept-2-ene, styrene, cyclohexadiene, and the like.

8. The preparation method according to claim 1 or 2, wherein the copolymerization catalyst is prepared by mixing one or two or more of metallocene catalyst and non-metallocene catalyst in any proportion. The metallocene catalyst comprises bis-indenyl dimethyl zirconium, 2,3, 4-trihydro-8-diphenyl phosphorus-quinolyl) tribenzyl zirconium bis (3-methyl salicylidene-pentafluoro-imido) titanium dichloride, dimethyl silicon bridge group-bis indenyl, dimethyl silicon bridge group-tetramethyl cyclopentadienyl-tert-butylamino-dimethyl titanium, bis-indenyl zirconium dichloride, dicyclopentadienyl dimethyl hafnium, dicyclopentadienyl-bis phenoxy zirconium, [ N- (3, 5-di-tert-butyl salicylidene) -2-diphenyl phosphorus-imido ] titanium trichloride, ethylene bridge group-bis indenyl zirconium dichloride, diphenyl carbon bridge group-cyclopentadienyl-fluorenyl zirconium dichloride, Dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, dimethylsilyl-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium, bis [2- (3',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, bis (2-methyl-4, 5-phenyl-indenyl) zirconium dichloride, dimethylsilyl-bisindenyl zirconium dichloride, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, (pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride, bis (salicylidene-phenylimino) titanium dichloride and the like, and the non-metallocene catalysts include bisiminopyrrole ligand vanadium catalyst, bis (iminomethyl) titanium dichloride, bis (3 '-pyrrolylidenyl-tert-butylamino-dimethyltitanium dichloride, bis (2, 5' -di-tert-butylphenyl, Pyridine amino hafnium catalyst, palladium diimine catalyst, neutral salicylaldimine nickel, phenoxyimine ligand catalyst and limited geometric configuration catalyst.

9. The process according to claim 1 or 2, wherein the cocatalyst is selected from M (R)₁)₃、M(O)R₁Wherein M is aluminum, boron or lithium; r₁Alkyl of 4 to 10 carbon atoms, preferably methyl, ethyl, isobutyl, etc.

10. The method according to claim 1 or 2, wherein the organic solvent is a linear alkane, an isoparaffin, a cycloalkane, or an arylalkane having 4 to 10 carbon atoms; preference is given to n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoparaffin oils, toluene, xylene.

Technical Field

The invention belongs to the technical field of polyolefin preparation, and particularly relates to a preparation method of a cross-linked polymer adhesive film for packaging a high-light-transmittance solar cell.

Background

The polyolefin has the advantages of rich raw materials, low price, easy processing and forming and excellent comprehensive performance, and can be applied to the fields of automobiles, aviation, food, medical appliances and the like. The preparation method comprises a gas phase method, a slurry method, a bulk method and a solution method, and the solution polymerization process is widely applied along with the success of the industrialization of the metallocene catalyst in the last 90 th century. Typical solution polymerization processes include the INSITE process by Dow and the Exxon adiabatic solution polymerization process by Exxon Mobil chemical, under the trade names Engage, respectively^TMAnd Exact^TM. The molecular weight and distribution of the polymer and the composition and distribution of the copolymer can be regulated and controlled by regulating and controlling the feeding strategy of each monomer in the polymerization process, so that the polyolefin product with more excellent performance and wider application range is obtained.

Ethylene-vinyl acetate copolymers and polyolefins are widely used as solar cell sealing materials because of their advantages such as transparency, flexibility and insulation properties. The ethylene-vinyl acetate copolymer is easy to degrade and yellow in the long-term use process of the solar cell module, so that the service life of the photovoltaic module in power generation is shortened, and the power generation efficiency is greatly reduced. The polyolefin material has the characteristics of excellent weather resistance, PID (proportion integration differentiation) effect resistance, difficult yellowing and the like, and is a new type of photovoltaic packaging material (CN106206790A, CN105247689A, CN104995745A, CN104823285B and CN 104530994B). The light transmittance of the solar cell packaging material determines the photoelectric conversion efficiency of the solar cell packaging material, and the light transmittance of the polyolefin packaging film is lower than that of the ethylene-vinyl acetate copolymer, so that the application of the polyolefin packaging film is limited to a certain extent.

Methods for improving the transmittance of photovoltaic materials have appeared at present, but the methods (CN107502232A, CN107312468A and CN102945879A) for adding modifiers and changing the packaging process of photovoltaic modules are adopted, and the microstructure of polyolefin is rarely customized from the synthesis method through the design and regulation of a polymer chain structure. Therefore, the method adopts a semi-continuous or continuous solution polymerization process, and synthesizes the polyolefin containing two crosslinking groups by controlling the addition mode, time and addition amount of the raw materials, so as to prepare the crosslinking type polyolefin for sealing the solar cell, which has high light transmittance, short crosslinking time and good weather resistance.

Disclosure of Invention

The invention aims to provide a preparation method of a cross-linking type polyolefin material for sealing a high-light-transmission solar cell, aiming at the defects of the existing production products and technologies.

The purpose of the invention is realized by the following technical scheme: a preparation method of cross-linked polyolefin for packaging a high-light-transmission solar cell comprises the following steps: dissolving ethylene in an organic solvent of a semicontinuous reactor under the anhydrous and oxygen-free conditions, adding alpha-olefin, a copolymerization catalyst and a cocatalyst, polymerizing for 0.1-21h at 30-300 ℃, then adding a polyene monomer with a crosslinking group for reaction, and further polymerizing for 0-4h to prepare the crosslinking polyolefin for packaging the high-light-transmission solar cell; based on the volume of the organic solvent in the semi-continuous reactor, the concentrations of ethylene and alpha-olefin are both 0.001-10 mol/L, the concentration of the alkene monomer with the crosslinking group is 0.001-10 mol/L, the concentration of the copolymerization catalyst is 0.1-100 mu mol/L, and the molar ratio of the cocatalyst to the copolymerization catalyst is 50-10000: 1.

A preparation method of cross-linked polyolefin for packaging a high-light-transmission solar cell comprises the following steps: dissolving ethylene in an organic solvent of a first reactor of a multistage continuous reactor under anhydrous and anaerobic conditions, adding a first part of alpha-olefin, a copolymerization catalyst and a cocatalyst, polymerizing at 30-300 ℃, keeping the time for 0.5-180min, then flowing into a subsequent reactor, adding a polyene monomer with a crosslinking group into the subsequent reactor, reacting with a second part of alpha-olefin, polymerizing at 30-300 ℃, keeping the time for 0.5-180min, and obtaining the crosslinking polyolefin for packaging the high-light-transmission solar cell consisting of the two crosslinking groups. Based on the volume of the organic solvent, the concentrations of the ethylene and the first part of alpha-olefin are both 0.001-10 mol/L, the concentration of the catalyst is 0.1-100 mu mol/L, the molar ratio of the cocatalyst to the copolymerization catalyst is 50-10000: 1, the concentration of the second part of alpha-olefin is 0.001-10 mol/L, and the concentration of the vinyl monomer with the crosslinking group is 0.001-10 mol/L.

Further, the crosslinking group is vinyl, the prepared crosslinking polyolefin for packaging the high-light-transmission solar cell has the weight-average molecular weight of 1-500 kg/mol and the molecular weight distribution index of 2.0-15.0, and consists of 0-30 wt% of olefin polymer without the crosslinking group and 70-100 wt% of olefin polymer with the crosslinking group; in the crosslinking polyolefin for packaging the high-light-transmission solar cell, the molar content of a crosslinking group is 0.001-10%.

Further, the reactor is a tubular reactor or a kettle type reactor, and the polymerization mode is solution polymerization.

Further, the alpha-olefin is a linear or branched alpha-olefin of 3 to 20 carbon atoms.

Further, the α -olefin is preferably propylene, butene, 1-hexene, 1-octene, isopentene, 2-methylpropene.

Further, the polyene monomer having a crosslinking group includes a linear diene monomer, a cyclic diene monomer, a linear triene monomer, a cyclic triene monomer, a alkene having a benzene ring and the like, and preferably butadiene, 1, 5-hexadiene, 1, 4-hexadiene, 1, 7-octadiene, 1, 9-decadiene, 1, 4-isoprene, cyclopentadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinylbicyclo [2.2.1] hept-2-ene, styrene, cyclohexadiene and the like.

Furthermore, the copolymerization catalyst is mixed by one or two or more of metallocene catalyst and non-metallocene catalyst according to any proportion. The metallocene catalyst comprises bis-indenyl dimethyl zirconium, 2,3, 4-trihydro-8-diphenyl phosphorus-quinolyl) tribenzyl zirconium bis (3-methyl salicylidene-pentafluoro-imido) titanium dichloride, dimethyl silicon bridge group-bis indenyl, dimethyl silicon bridge group-tetramethyl cyclopentadienyl-tert-butylamino-dimethyl titanium, bis-indenyl zirconium dichloride, dicyclopentadienyl dimethyl hafnium, dicyclopentadienyl-bis phenoxy zirconium, [ N- (3, 5-di-tert-butyl salicylidene) -2-diphenyl phosphorus-imido ] titanium trichloride, ethylene bridge group-bis indenyl zirconium dichloride, diphenyl carbon bridge group-cyclopentadienyl-fluorenyl zirconium dichloride, Dimethylsilyl-tetramethylcyclopentadienyl-tert-butylamino-dimethyltitanium, dimethylsilyl-3-pyrrolylindenyl-tert-butylamino-dimethyltitanium, bis [2- (3',5' -di-tert-butylphenyl) -indenyl ] zirconium dichloride, bis (2-methyl-4, 5-phenyl-indenyl) zirconium dichloride, dimethylsilyl-bisindenyl zirconium dichloride, pentamethylcyclopentadienyl- (2-phenylphenoxy) -titanium dichloride, (pentamethylcyclopentadienyl- (2, 6-diisopropylphenoxy) -titanium dichloride, bis (salicylidene-phenylimino) titanium dichloride and the like, and the non-metallocene catalysts include bisiminopyrrole ligand vanadium catalyst, bis (iminomethyl) titanium dichloride, bis (3 '-pyrrolylidenyl-tert-butylamino-dimethyltitanium dichloride, bis (2, 5' -di-tert-butylphenyl, Pyridine amino hafnium catalyst, palladium diimine catalyst, neutral salicylaldimine nickel, phenoxyimine ligand catalyst and limited geometric configuration catalyst.

Further, the cocatalyst is selected from M (R)₁)₃、M(O)R₁Wherein M is aluminum, boron or lithium; r₁Alkyl of 4 to 10 carbon atoms, preferably methyl, ethyl, isobutyl, etc.

Further, the organic solvent is straight-chain alkane, isoparaffin, cycloparaffin or arene with 4-10 carbon atoms; preference is given to n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoparaffin oils, toluene, xylene. In still another aspect, the invention also relates to a solar cell packaging material prepared from the polyolefin containing two crosslinking groups. The processing method of the film prepared from the polyolefin material comprises one or more of calendering molding, tape casting molding, film blowing method and biaxial stretching, and the processed film is used for sealing protection of a solar cell module comprising a front side/back side protection member.

The light transmittance of the solar cell packaging material which is processed by the processing method of the synthesized polyolefin is more than 93% in the wavelength range of 380-780 nm. The total vacuum lamination time of the film made of the polyolefin material is less than 20min at 145 ℃, and the crosslinking degree of the laminated packaging material is more than 60%.

The invention has the beneficial effects that: the solution polymerization technology of the single-active-center-based metallocene catalyst system is used for preparing the high-light-transmittance polyolefin containing two crosslinking groups by controlling the addition mode, time and addition amount of raw materials and regulating and controlling the copolymer composition of the polyolefin chain, can be used for replacing the application field of the polyolefin for packaging the solar cell, and has high industrial value.

Detailed Description

The present invention is illustrated by the following specific examples, which are merely exemplary and should not be construed as limiting the invention.

The feed molar concentration to be used in the present invention means the initial concentration of ethylene monomer, olefin of 3 to 20 carbon atoms, as fed to the reactor, based on the volume of the organic solvent.

The molecular weights (Mw and Mn) of the polymers and their distribution indices (PDI) were determined by high temperature gel permeation chromatography (PL-GPC 220). 1, 2, 4-trichlorobenzene is used as a solvent to prepare 0.1-0.3 wt% of polymer solution at 150 ℃, polystyrene with narrow molecular weight distribution is used as a standard sample to measure at 150 ℃, and the flow rate of the solvent is 1.0 ml/min.

The light transmittance of the solar cell packaging film is measured by a spectrophotometer (Variancary 5000) according to IEC 62788-1-4 test standards, and the crosslinking degree is calculated according to ASTM D2765-2016 test standards.

The solar module template was assembled by a vacuum laminator (TDCZ-Y-4) at a lamination temperature of 145 ℃.