阅读说明：本技术 太阳能电池封装用快速交联型丙烯基聚烯烃的制备方法 (Preparation method of rapid crosslinking type propenyl polyolefin for packaging solar cell ) 是由 刘平伟 王文俊 罗理琼 李伯耿 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种太阳能电池封装用快速交联型丙烯基聚烯烃的制备方法,本发明利用连续溶液聚合,通过控制原料的停留时间和加入量,制备快速交联型的丙烯基聚烯烃材料,所述的交联基团为乙烯基,所合成的丙烯基聚烯烃中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的摩尔组成为0.001～10％。该交联型丙烯基聚烯烃材料制成的太阳能电池封装材料,145℃下总层压时间小于10min,层压后交联度大于70％。本发明制备的快速交联型太阳能电池封装聚烯烃可用于替代传统太阳能电池封装材料,且具有交联速度快、耐候性好等优点。(The invention discloses a preparation method of fast cross-linking type propenyl polyolefin for solar cell encapsulation, which utilizes continuous solution polymerization to prepare a fast cross-linking type propenyl polyolefin material by controlling the retention time and the addition amount of raw materials, wherein a cross-linking group is vinyl, 0-30 weight percent of the synthesized propenyl polyolefin does not contain the cross-linking group, and the molar composition of the cross-linking group of the 30-70 weight percent of the synthesized propenyl polyolefin is 0.001-10%. The total laminating time of the solar cell packaging material prepared from the crosslinking type propenyl polyolefin material is less than 10min at 145 ℃, and the crosslinking degree after laminating is more than 70%. The fast crosslinking type solar cell packaging polyolefin prepared by the invention can be used for replacing the traditional solar cell packaging material and has the advantages of fast crosslinking speed, good weather resistance and the like.)

1. A preparation method of rapid crosslinking type propenyl polyolefin for solar cell encapsulation is characterized by comprising the following steps: under the anhydrous and anaerobic conditions, adding a first part of propylene, a first part of alpha-olefin, a copolymerization catalyst and a cocatalyst into an organic solvent of a first reactor in a multistage continuous reactor, polymerizing at 50-300 ℃, keeping the time for 0.5-180min, then flowing into a subsequent reactor, adding a polyene monomer with a crosslinking group, a second part of propylene and a second part of alpha-olefin into the subsequent reactor, polymerizing at 50-300 ℃, keeping the time for 0.5-180min, and obtaining the fast crosslinking type propenyl polyolefin for packaging the solar cell. Based on the volume of the organic solvent, the addition amount of the first part of propylene, the first part of alpha-olefin, the second part of propylene, the second part of alpha-olefin and the polyene monomer with the crosslinking group is 0.001-10 mol/L, the concentration of the catalyst is 0.1-100 mu mol/L, and the molar ratio of the cocatalyst to the copolymerization catalyst is 50-10000: 1.

2. The preparation method according to claim 1, wherein the crosslinking group is vinyl, and the prepared fast crosslinking type acryl-based polyolefin for solar cell encapsulation has a weight average molecular weight of 1 to 500kg/mol, a molecular weight distribution index of 2.0 to 15.0, and consists 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 fast crosslinking allyl polyolefin for packaging the solar cell, the molar content of a crosslinking group is 0.001-10%.

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

4. The method according to claim 1, wherein the α -olefin is a linear or branched α -olefin having 4 to 20 carbon atoms, and includes butene, 1-hexene, 1-octene, isopentene, 2-methylpropene, and the like.

5. The process according to claim 1, wherein the polyene monomer comprises a linear diene monomer, a cyclic diene monomer, a linear triene monomer, a cyclic triene monomer, a olefin having a benzene ring, etc., 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, etc.

6. The preparation method of claim 1, wherein the copolymerization catalyst is one or two or more of metallocene catalyst and non-metallocene catalyst mixed 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.

7. The process of claim 1 wherein said promoter is selected from the group consisting of M (R)₁)₃、M(O)R₁Wherein M is aluminum, boron or lithium; r₁Is an alkyl group of 4 to 10 carbon atoms.

8. The method of claim 7, wherein R is₁Methyl, ethyl, isobutyl are preferred.

9. The method according to claim 1, wherein the organic solvent is a linear alkane, an isoparaffin, a cycloalkane, or an arylalkane having 3 to 10 carbon atoms.

10. The method according to claim 9, wherein the organic solvent is preferably n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoparaffin oil, toluene, xylene.

Technical Field

The invention belongs to the technical field of polyolefin preparation, and particularly relates to a preparation method of cross-linked polyolefin for solar cell encapsulation.

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 advantages of excellent weather resistance, PID effect resistance, difficult yellowing and the like due to a saturated hydrocarbon structure, and is a new type of photovoltaic packaging material (CN106206790A, CN105247689A, CN104995745A, CN104823285B and CN 104530994B). But the saturated hydrocarbon structure also results in slower crosslinking rates relative to ethylene-vinyl acetate copolymers.

At present on the marketFew commercial polyolefins have been specified for photovoltaic encapsulation films, and Dow introduced ENLIGHT using its INSITE process^TMThe series of polyolefins have strong bonding force with glass and no bubble in lamination, are very suitable for being applied to the encapsulation of thin film components, crystalline silicon components and flexible components, but the prepared polyolefins still have saturated chain structures and slow crosslinking speed. Therefore, the rapid crosslinking type propenyl polyolefin material comprising two crosslinking groups is prepared by adopting a continuous solution polymerization mode and controlling the retention time and the addition amount of raw materials, wherein the crosslinking groups are vinyl, the molar composition of the crosslinking groups in the synthesized polyolefin is 0.001-10%, the weight average molecular weight is 1-500 kg/mol, and the molecular weight distribution index is 2.0-15.0;

disclosure of Invention

The invention aims to provide a preparation method of rapid crosslinking type propenyl polyolefin for packaging a 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 rapid crosslinking type propenyl polyolefin for packaging a solar cell comprises the following steps: under the anhydrous and anaerobic conditions, adding a first part of propylene, a first part of alpha-olefin, a copolymerization catalyst and a cocatalyst into an organic solvent of a first reactor in a multistage continuous reactor, polymerizing at 50-300 ℃, keeping the time for 0.5-180min, then flowing into a subsequent reactor, adding a polyene monomer with a crosslinking group, a second part of propylene and a second part of alpha-olefin into the subsequent reactor, polymerizing at 50-300 ℃, keeping the time for 0.5-180min, and obtaining the fast crosslinking type propenyl polyolefin for packaging the solar cell. Based on the volume of the organic solvent, the addition amount of the first part of propylene, the first part of alpha-olefin, the second part of propylene, the second part of alpha-olefin and the polyene monomer with the crosslinking group is 0.001-10 mol/L, the concentration of the catalyst is 0.1-100 mu mol/L, and the molar ratio of the cocatalyst to the copolymerization catalyst is 50-10000: 1.

Further, the crosslinking group is vinyl, the weight average molecular weight of the prepared fast crosslinking propenyl polyolefin for solar cell encapsulation is 1-500 kg/mol, the molecular weight distribution index is 2.0-15.0, and the fast crosslinking propenyl polyolefin is composed of 0-30 wt% of olefin polymer without crosslinking group and 70-100 wt% of olefin polymer with crosslinking group; in the fast crosslinking allyl polyolefin for packaging the 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 linear or branched alpha-olefin with 4-20 carbon atoms, and comprises butylene, 1-hexene, 1-octene, isoamylene, 2-methylpropene and the like.

Further, the polyene monomer 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; r₁Is an alkyl group of 4 to 10 carbon atoms.

Further, said R₁Methyl, ethyl, isobutyl are preferred.

Further, the organic solvent is straight-chain alkane, isoparaffin, cycloalkane or aralkane with 3-10 carbon atoms.

Further, the organic solvent is preferably n-pentane, isopentane, n-hexane, cyclohexane, n-heptane, isoheptane, n-octane, isooctane, n-decane, isoparaffin oil, toluene, xylene. In another aspect, the invention also relates to a method for processing the fast crosslinking type allyl polyolefin material consisting of two crosslinking groups into the solar cell packaging material. Specifically, the sheet-shaped or film-shaped packaging material is prepared by one or more methods of calendaring, tape casting, film blowing and biaxial stretching. The solar cell packaging material processed by the synthesized propenyl polyolefin is laminated at 145 ℃, the laminating time is less than 10min, and the crosslinking degree of the polyolefin containing crosslinking groups after lamination is more than 70%.

The invention has the beneficial effects that: the continuous solution polymerization technology of the single-active-center-based metallocene catalyst system synthesizes the rapid crosslinking type propenyl polyolefin material by controlling the retention time and the addition amount of the raw materials, and overcomes the defect of low crosslinking speed of the metallocene polyolefin packaging material. The rapid crosslinking solar cell packaging propylene-based polyolefin material prepared by the invention can be used for replacing the traditional solar cell packaging material, has the advantages of high crosslinking speed, good weather resistance and the like, 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 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 solar module template was assembled by a vacuum laminator (TDCZ-Y-4) at a lamination temperature of 145 ℃.

The degree of crosslinking is calculated according to ASTM D2765-2016.