CN119285815B - Modified catalyst and preparation method thereof, polyolefin elastomer and preparation method and application thereof - Google Patents
Modified catalyst and preparation method thereof, polyolefin elastomer and preparation method and application thereof Download PDFInfo
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- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
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- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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Abstract
The invention provides a modified catalyst and a preparation method thereof, a polyolefin elastomer and a preparation method and application thereof, wherein the modified catalyst comprises a catalyst matrix and a coating layer coated on the outer surface of the catalyst matrix, the catalyst matrix is a metallocene catalyst, the metallocene catalyst comprises a zirconocene chloride main catalyst and a butyl aluminoxane cocatalyst, and the coating layer is made of a low-carbon olefin homopolymer. The polyolefin elastomer prepared by the method improves the uniformity of comonomer insertion molecular chain segments, improves the light transmittance of products and has wider industrial application prospect.
Description
Technical Field
The application relates to the technical field of polyolefin elastomers, in particular to a modified catalyst and a preparation method thereof, a polyolefin elastomer and a preparation method and application thereof.
Background
Polyolefin elastomer (POE) is prepared by introducing a large amount of comonomer, alpha-olefin, into the ethylene backbone, disrupting the original crystalline state and forming more short chain branches, causing the polymer to tend towards a "plasticizing effect". Thereby reducing the crystallinity of ethylene on the branched chain and enabling the material to have better optical performance. Moreover, POE has the advantages of low volume resistivity, low water vapor transmittance, good ageing resistance, small Potential Induced Degradation (PID) and the like, and is generally used for producing an EPE structure (EVA-POE-EVA) adhesive film or a pure POE adhesive film by a three-layer coextrusion casting method with EVA (ethylene and vinyl acetate copolymer).
At present, the proportion of POE in the raw materials of the photovoltaic module packaging adhesive film is 20-30%, and the proportion of POE further improves the space. Along with the progress of photovoltaic technology, the photovoltaic module takes an N-type battery as a leading material in the future, the module type is developed from single-glass single-sided power generation to double-glass double-sided power generation, different batteries and module types need corresponding packaging materials, and an EPE adhesive film and a POE adhesive film are indispensable packaging materials of novel batteries in the future. The continuous increase of the demand of the global photovoltaic module can promote the generation of EVA and greatly increase the demand of POE packaging materials.
From the application angle analysis, in order to ensure higher photoelectric conversion efficiency of the photovoltaic power generation assembly, the photovoltaic film must have higher light transmittance, and according to energy industry standard NB/T10200-2019 polyolefin elastomer (POE) packaging insulating film for crystalline silicon solar cell assemblies, the light transmittance requirement of the POE film is more than or equal to 70% at 290-380 nm, the light transmittance requirement of the POE film is more than or equal to 90% at 380-1100 nm, and the actual purchase quality requirement of the photovoltaic film enterprise for the POE is more than or equal to 85% at 290-380 nm, and the light transmittance of the POE film at 380-1100 nm is more than or equal to 90%. The POE for the photovoltaic adhesive film is produced by two processes of solution polymerization and gas phase polymerization at present, the POE for the photovoltaic adhesive film which is stable and mature in the market is higher in general light transmittance, the problem that the solution POE with poor quality stability or the gas phase POE with higher density possibly has insufficient light transmittance occurs, the gas phase POE with the density of 0.8750-0.8880 g/cm 3 is taken as an example, the influence of factors such as microstructure and the like is caused, the full-wave-band light transmittance (0.5 mm sample) is generally 84-88%, the application proportion of the full-wave-band light transmittance (0.5 mm sample) in the photovoltaic adhesive film POE is seriously influenced, and the advantages of low production cost and low product smell of the gas phase POE are not exerted. In addition, the gas phase method POE with lower light transmittance can have high-melting-point microcomponents, can not be effectively plasticized in the processing temperature range of the photovoltaic adhesive film, so that the prepared photovoltaic adhesive film has holes or the number of crystal points is over-standard, and quality events occur.
In the prior art, the publication number of China patent No. 118221858A discloses a preparation method of polyolefin elastomer POE for photovoltaic packaging, wherein ethylene, comonomer, organic solvent, main catalyst and cocatalyst are added into a polymerization stirring reaction kettle under the anhydrous and anaerobic condition to react to obtain the elastomer POE, namely the solution process production. The Chinese patent publication No. CN116789883A discloses a polyolefin elastomer and application thereof in a photovoltaic packaging film, wherein in the preparation step of the elastomer, the solvent and the alpha-olefin are mixed and then injected into a reaction kettle, namely a solution polymerization process, and the composition prepared by the elastomer is used for the photovoltaic packaging film and has more excellent optical performance, electrical insulation performance and PID resistance. The Chinese patent publication No. CN116041598A discloses an olefin polymer for a photovoltaic film and a solution polymerization method thereof, and the method obtains the olefin polymer for the photovoltaic film with improved PID resistance. The Chinese patent publication No. CN115746746A discloses a polyolefin elastomer composition for a photovoltaic packaging film, wherein the polyolefin elastomer is obtained by adopting a solution polymerization method. The relation between the POE structure and the properties of the polyolefin elastomer composition is found through analysis, so that the properties such as light transmittance, water vapor transmittance, volume resistivity and the like of the polyolefin elastomer composition are ensured to be kept at a higher level. The Chinese patent publication No. CN117567961B discloses an ethylene/alpha-olefin random copolymer for a photovoltaic film and application thereof, wherein the copolymer has high crosslinking speed and crosslinking degree in the application of the photovoltaic film and the photovoltaic film has high light transmittance, and the copolymer is prepared by a kettle-type reactor and a solution polymerization process.
Based on this, in the above prior art, POE for photovoltaic film is mainly produced by solution polymerization process, and the solution process is complex and complicated, however, POE produced by gas phase polymerization process has the defect of low light transmittance, and there is an urgent need to provide a modified catalyst, a preparation method thereof, a polyolefin elastomer and a preparation method thereof, so as to improve the above problems.
Disclosure of Invention
The invention mainly aims to provide a modified catalyst and a preparation method thereof, a polyolefin elastomer and a preparation method and application thereof, so as to solve the technical problem that the polyolefin elastomer in the existing gas phase polymerization process technology has lower light transmittance.
In order to achieve the above objective, according to one aspect of the present invention, there is provided a modified catalyst, the modified catalyst includes a catalyst substrate and a coating layer coated on an outer surface of the catalyst substrate, wherein the catalyst substrate is a metallocene catalyst, the metallocene catalyst includes a zirconocene chloride main catalyst and a butyl aluminoxane cocatalyst, and the coating layer is made of a low carbon olefin homopolymer.
Further, the thickness of the coating layer is 40-140 mu m, the modified catalyst is granular, and the grain size D50 is 130-330 mu m.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a modified catalyst, comprising subjecting a catalyst substrate, an olefin, nitrogen and a solvent to a micro-polymerization reaction to form a coating layer on an outer surface of the catalyst substrate, thereby obtaining the modified catalyst.
Further, the olefin is selected from one or more of ethylene, propylene or 1-butene, the solvent is preferably selected from one or more of cyclopentane, propane, butane, pentane or hexane, the temperature of the micro-polymerization reaction is preferably 25-45 ℃, the reaction pressure is 0.2-0.5 MPa, and the reaction time is 20-50 min.
According to another aspect of the present invention, there is provided a method for preparing a polyolefin elastomer, comprising the step of using a modified catalyst, which is obtained by the above method for preparing a modified catalyst, comprising mixing a modified catalyst, ethylene, 1-butene, hydrogen, nitrogen, and a condensing agent in a gas-phase fluidized-bed reactor, and polymerizing the modified catalyst and an antistatic agent in a fluidized-bed layer of the gas-phase fluidized-bed reactor to obtain the polyolefin elastomer.
Further, the condensing agent is one or more selected from propane, pentane or cyclopentane, and the addition amount of the antistatic agent accounts for 0.001-0.010% of the addition amount of ethylene.
Further, the polymerization temperature is 40-70 ℃, the polymerization pressure is 1.5-5.5 MPa, the polymerization time is 12-18 h, and the yield of the modified catalyst is 6000-9900 g of product/g of catalyst.
According to another aspect of the present invention, there is provided a polyolefin elastomer obtained by the above-mentioned method for producing a polyolefin elastomer.
Further, the polyolefin elastomer has a density of 0.8750 to 0.8880g/cm 3, a melt mass flow rate of 4 to 14g/10min, a molecular weight distribution width PDI of 2.0 to 2.3, and when the polyolefin elastomer has a thickness of 0.5mm, the polyolefin elastomer has a light transmittance of 85 to 90% at a wavelength of 290 to 380nm and a light transmittance of 90 to 93.5% at a wavelength of 380 to 1100 nm.
According to another aspect of the invention, there is provided an application of a polyolefin elastomer in the field of POE pure adhesive films or EPE structured photovoltaic adhesive films, wherein the polyolefin elastomer is the polyolefin elastomer.
The polyolefin elastomer prepared by the invention has the advantages that the uniformity of comonomer insertion molecular chain segments is improved, the light transmittance of the product is improved, and the industrial application prospect is wider.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present application more apparent, the technical solutions in the embodiments of the present application will be clearly and completely described in the following in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
According to the technical problem that the polyolefin elastomer in the prior gas phase polymerization process technology has low light transmittance, the invention provides a modified catalyst, which comprises a catalyst matrix and a coating layer coated on the outer surface of the catalyst matrix, wherein the catalyst matrix is a metallocene catalyst, the metallocene catalyst comprises a zirconocene chloride main catalyst and a butyl aluminoxane cocatalyst, and the coating layer is made of a low-carbon olefin homopolymer.
At present, the microstructure factors influencing the light transmittance of polyolefin are mainly the crystallinity, grain size and uniformity of distribution of the comonomer alpha-olefin, when the comonomer alpha-olefin is inserted more uniformly on an ethylene molecular chain, the uniformity of distribution is higher, and the grain size displayed by the comonomer alpha-olefin is more uniform, so that the light transmittance of the comonomer alpha-olefin is higher. However, when the comonomer α -olefin is inserted more unevenly in the ethylene molecular chain, the distribution thereof is uneven, and the large crystal grains therein are more or finer crushed grains are more, and the crystal grain size is uneven, so that the light transmittance is poor. The invention adopts a novel modified catalyst to reduce the activity of the original catalyst and slow down the instantaneous explosion degree generated by the polymerization reaction by adding the catalyst, so that the copolymerized monomer can be more orderly and uniformly distributed on the main chain of ethylene molecules, thereby improving the light transmittance. Specifically, the modified catalyst provided by the invention is coated on the basis of a catalyst matrix metallocene catalyst to obtain a coating layer, and the coating layer is made of a low-carbon olefin homopolymer, so that the structural stability of the catalyst can be further improved. The modified catalyst solves the problem that the ethylene and alpha-olefin raw materials are instantaneously exploded and polymerized when encountering the unmodified catalyst in the process of preparing the polyolefin elastomer by a gas phase method, so that the comonomer is unevenly inserted in an ethylene molecular chain and distributed.
In a preferred embodiment, the thickness of the coating layer is 40-140 μm, the weight average molecular weight of the coating layer material is 100-2000 g/mol, the modified catalyst is in the form of particles, and the particle size D50 is 130-330 μm, so that the light transmittance of the polyolefin elastomer is further improved. Preferably, the metallocene catalyst is a commercial metallocene catalyst, the main catalyst component is zirconocene chloride, and the cocatalyst is butyl aluminoxane. Wherein, in the metallocene catalyst, the mass ratio of the zirconium element is 0.48 percent, and the mass ratio of the aluminum element is 19.2 percent.
The metallocene catalyst is used as a catalyst matrix to further improve the catalytic performance of the modified catalyst.
The invention also provides a preparation method of the modified catalyst, which comprises the step of carrying out micro-polymerization reaction on the catalyst matrix, olefin, nitrogen and solvent to form a coating layer on the outer surface of the catalyst matrix, thereby obtaining the modified catalyst.
The modified catalyst is obtained by first performing a micro-polymerization reaction on a catalyst substrate, olefin, nitrogen and a solvent to form a coating layer on the outer surface of the catalyst substrate. The modified catalyst can moderately inhibit the initial activity of the catalyst in the process of entering a reactor for subsequent polymerization reaction, thereby further improving the light transmittance of the product.
In a preferred embodiment, the olefin is selected from one or more of ethylene, propylene or 1-butene, the solvent is selected from one or more of cyclopentane, propane, butane, pentane or hexane, the temperature of the micro-polymerization reaction is 25-45 ℃, preferably 35-40 ℃, the reaction pressure is 0.2-0.5 MPa, and the reaction time is 20-50 min, preferably 30-40 min.
The invention also provides a preparation method of the polyolefin elastomer, which comprises the step of using the modified catalyst, wherein the modified catalyst is obtained by the preparation method of the modified catalyst, and the preparation method of the polyolefin elastomer comprises the steps of mixing the modified catalyst, ethylene, 1-butene, hydrogen, nitrogen and condensing agent in a gas-phase fluidized bed reactor, and then carrying out polymerization reaction on the modified catalyst and the antistatic agent in a fluidized bed layer of the gas-phase fluidized bed reactor to obtain the polyolefin elastomer.
The modified catalyst, ethylene, 1-butene, hydrogen, nitrogen and condensing agent are firstly mixed in a gas-phase fluidized bed reactor by a person skilled in the art, and then the modified catalyst and the antistatic agent are polymerized in a fluidized bed layer of the gas-phase fluidized bed reactor to obtain the polyolefin elastomer. The polyolefin elastomer has better optical performance and higher light transmittance.
In a preferred embodiment, the polymerization temperature is 40-70 ℃, the polymerization pressure is 1.5-5.5 MPa, the polymerization time is 12-18 h, and the yield of the modified catalyst is 6000-9900 g of product/g of catalyst, so that the polyolefin elastomer product with better performance is prepared.
The invention also provides a polyolefin elastomer obtained by the preparation method of the polyolefin elastomer. The density is 0.8750-0.8880 g/cm 3, the melt mass flow rate is 4-14 g/10min, the molecular weight distribution width PDI is 2.0-2.3, when the thickness of the polyolefin elastomer is 0.5mm, the light transmittance of 290-380 nm is 85-90%, and the light transmittance of 380-1100 nm is 90-93.5%.
The polyolefin elastomer prepared in the invention has the following microstructure:
a) The content of the comonomer 1-butene is 11.0-15.0 mol%;
b) Ternary sequence distribution of molecular chain segments ：[EEE]=0.600~0.700、[EEB]=0.170~0.180、[EBE]=0.110~0.160、[BEB]=0.012~0.024、[BBE]=0.005~0.045、[BBB]=0~0.003;
C) Ethylene average sequence length ne=8.7 to 9.4;
d) 1-butene average sequence length nb=1.05 to 1.12;
Wherein [ EEE ] represents the fraction of ethylene triplets, [ EEB ] represents the fraction of ethylene triplets, [ EBE ] represents the fraction of ethylene meta-sequences, [ BEB ] represents the fraction of butene-1 meta-sequences, [ BBE ] represents the fraction of 1-butene triplets, [ BBB ] represents the fraction of 1-butene triplets, and the microstructure of the polyolefin elastomer described above characterizes the uniformity of the inserted molecular segments of 1-butene.
The invention also provides application of the polyolefin elastomer in the field of POE pure adhesive films or EPE structure photovoltaic adhesive films, wherein the polyolefin elastomer is the polyolefin elastomer.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Example 1
And carrying out micro-polymerization reaction on the catalyst matrix, olefin, nitrogen and solvent to form a coating layer on the outer surface of the catalyst matrix, thereby obtaining the modified catalyst. Wherein the catalyst matrix is a metallocene catalyst, the olefin is propylene, the solvent is cyclopentane, the micro-polymerization reaction is carried out in a tubular container, the capacity is 10L, the micro-polymerization reaction temperature is 40 ℃, the pressure is 0.35MPa, and the reaction time is 30min. The coating layer material is low-carbon olefin homopolymer, the weight average molecular weight of the coating layer material is 2000g/mol, the thickness of the coating layer is 140 mu m, the modified catalyst is granular, and the grain size D50 of the modified catalyst is 330 mu m.
Mixing the modified catalyst, ethylene, 1-butene, hydrogen, nitrogen and condensing agent in a gas-phase fluidized bed reactor, and taking the modified catalyst and the antistatic agent to carry out polymerization reaction in a fluidized bed layer of the gas-phase fluidized bed reactor to obtain the polyolefin elastomer. Wherein the polymerization temperature is 68 ℃, the polymerization pressure is 1.55MPa, the catalyst yield is 9300g of product per g of catalyst, the addition amount of the antistatic agent accounts for 0.0012% of the addition amount of ethylene, the condensing agent is cyclopentane, and the polymerization time is 12h, so as to obtain the polyolefin product. The polyolefin elastomer has a product density of 0.8870g/cm 3, a melt mass flow rate MFR (190 ℃, 2.16 kg) of 4.9g/10min, a molecular weight distribution width PDI of 2.25, a comonomer 1-butene content of 11.0mol% in the product, a molecular segment ternary sequence distribution of [ EEE ] = 0.699, [ EEB ] = 0.173, [ EBE ] = 0.111, [ BEB ] = 0.012, [ BBE ] = 0.007, [ BBB ] = 0.002, an average ethylene sequence length nE= 9.3,1-butene average sequence length nB=1.07, wherein [ EEE ] represents a fraction of ethylene triples, [ EEB ] represents a fraction of ethylene triples, [ EEE ] represents a fraction of ethylene meta-sequences, [ BEB ] represents a fraction of butene-1 meta-sequences, [ BBE ] represents a fraction of 1-butene triples. The polyolefin product with the thickness of 0.5mm is obtained by tabletting and sample preparation, the light transmittance of the polyolefin product with the wavelength of 290-380 nm is 87.2%, the light transmittance of the polyolefin product with the wavelength of 380-1100 nm is 90.1%, and the polyolefin product is used for blending application in POE raw materials of photovoltaic packaging adhesive films, wherein the blending proportion is 20%.
Example 2
The only difference from example 1 is that the micro-polymerization temperature was 38℃and the pressure was 0.20MPa. The coating layer material is low-carbon olefin homopolymer, the weight average molecular weight is 1400g/mol, the thickness of the coating layer is 105 mu m, the modified catalyst is granular, and the grain size D50 is 260 mu m.
The polymerization temperature was 58℃and the polymerization pressure was 2.05MPa, the catalyst yield was 8400g of product per g of catalyst, the addition of antistatic agent was 0.0045% of the addition of ethylene, the condensing agent was pentane and the polymerization time was 14h. Polyolefin elastomer product density 0.8826g/cm 3, melt mass flow rate MFR (190 ℃, 2.16 kg) 9.7g/10min, molecular weight distribution width PDI 2.12, comonomer 1-butene content 12.23mol% in the product, molecular segment ternary sequence distribution: [ EEE ] = 0.675, [ EEB ] = 0.171, [ EBE ] = 0.121, [ BEB ] = 0.017, [ BBE ] = 0.014, [ BBB ] = 0.002, ethylene average sequence length n E = 9.1,1-butene average sequence length n B = 1.09. Wherein [ EEE ] represents the fraction of ethylene triplets, [ EEB ] represents the fraction of ethylene triplets, [ EBE ] represents the fraction of ethylene meta-sequences, [ BEB ] represents the fraction of butene-1 meta-sequences, [ BBE ] represents the fraction of 1-butene triplets, and [ BBB ] represents the fraction of 1-butene triplets. The product is pressed into a sample with the thickness of 0.5mm, the light transmittance of the sample with the wavelength of 290-380 nm is 87.7%, the light transmittance of the sample with the wavelength of 380-1100 nm is 90.9%, and the product is used for mixing and applying the POE raw materials of the photovoltaic packaging adhesive film, wherein the mixing proportion is 30%.
Example 3
The only difference from example 1 is that the micro-polymerization temperature was 35℃and the reaction time was 40min. The coating layer material is a low-carbon olefin homopolymer, the weight average molecular weight of the coating layer material is 800g/mol, the thickness of the coating layer is 75 mu m, the modified catalyst is granular, and the grain size D50 of the modified catalyst is 200 mu m.
The polymerization temperature is 45 ℃, the polymerization pressure is 4.5MPa, the catalyst yield is 6000g of product per g of catalyst, the addition amount of the antistatic agent accounts for 0.009% of the addition amount of ethylene, the condensing agent is propane, and the polymerization time is 18h. Polyolefin elastomer product density 0.8785g/cm 3, melt mass flow rate MFR (190 ℃, 2.16 kg) 13.9g/10min, molecular weight distribution width PDI 2.10, comonomer 1-butene content 14.40mol% in the product, molecular segment ternary sequence distribution: [ EEE ] = 0.607, [ EEB ] = 0.170, [ EBE ] = 0.159, [ BEB ] = 0.022, [ BBE ] = 0.042, [ BBB ] = 0, ethylene average sequence length n E = 8.8,1-butene average sequence length n B = 1.11. Wherein [ EEE ] represents the fraction of ethylene triplets, [ EEB ] represents the fraction of ethylene triplets, [ EBE ] represents the fraction of ethylene meta-sequences, [ BEB ] represents the fraction of butene-1 meta-sequences, [ BBE ] represents the fraction of 1-butene triplets, and [ BBB ] represents the fraction of 1-butene triplets. The product is subjected to tabletting sample preparation to obtain the polyolefin elastomer, wherein the thickness of the polyolefin elastomer is 0.5mm, the light transmittance of the polyolefin elastomer at the wavelength of 290-380 nm is 89.3%, the light transmittance at the wavelength of 380-1100 nm is 92.8%, and the polyolefin elastomer is used for blending application in POE raw materials of photovoltaic packaging adhesive films, and the blending proportion is 35%.
Example 4
The only difference from example 2 is that the micropolymerization olefin was 1-butene and the reaction time was 40min. The coating layer material is low-carbon olefin homopolymer, the weight average molecular weight of the coating layer material is 1200g/mol, the thickness of the coating layer is 110 mu m, the modified catalyst is granular, and the grain size D50 of the modified catalyst is 270 mu m.
The catalyst yield was 7500g product/g catalyst and the polymerization time was 16h. The polyolefin elastomer has the density of 0.8854g/cm 3, the melt mass flow rate MFR (190 ℃ and 2.16 kg) of 10.0g/10min, the molecular weight distribution width PDI of 2.18, the content of 1-butene as a comonomer in the product of 11.83mol%, the thickness of the polyolefin elastomer obtained by tabletting and sample preparation of the product is 88.2% of light transmittance with the wavelength of 290-380 nm and 91.5% of light transmittance with the wavelength of 380-1100 nm, and the product is used for blending in POE raw materials of photovoltaic packaging films, wherein the blending proportion is 25%.
Example 5
The only difference from example 3 is that the micropolymerized olefin was ethylene and the reaction time was 35min. The coating layer material is low-carbon olefin homopolymer, the weight average molecular weight of the coating layer material is 500g/mol, the thickness of the coating layer is 40 mu m, the modified catalyst is granular, and the grain size D50 of the modified catalyst is 130 mu m.
The polymerization pressure is 5.05MPa, the catalyst yield is 6800g of product/g of catalyst, the polyolefin elastomer product density is 0.8755g/cm 3, the melt mass flow rate MFR (190 ℃ C., 2.16 kg) is 14.0g/10min, the molecular weight distribution width PDI is 2.02, the content of comonomer 1-butene in the product is 14.93mol%, the product is subjected to tabletting sample preparation, the thickness of the polyolefin elastomer is 0.5mm, the light transmittance of the polyolefin elastomer with the wavelength of 290-380 nm is 89.4%, the light transmittance with the wavelength of 380-1100 nm is 93.3%, and the product is used for mixing application in POE raw materials of photovoltaic packaging adhesive films and the mixing proportion is 45%.
Comparative example 1
The only difference from example 1 is that the micro-polymerization temperature was 60℃and the propylene feed ratio was increased. The coating layer material is a low-carbon olefin homopolymer, the weight average molecular weight of the coating layer material is 4300g/mol, the thickness of the coating layer is 260 mu m, the modified catalyst is granular, and the grain size D50 of the modified catalyst is 570 mu m.
The catalyst yield was 8200g of product per g of catalyst, the mass ratio of antistatic agent to ethylene was 0.0030%, and the polymerization time was 16 hours. The obtained polyolefin elastomer has a density of 0.8848g/cm 3, a melt mass flow rate MFR (190 ℃, 2.16 kg) of 4.90g/10min, a molecular weight distribution width PDI of 2.56, a comonomer 1-butene content of 12.04mol% in the product, a molecular chain segment ternary sequence distribution of [ EEE ] = 0.693, [ EEB ] = 0.175, [ EBE ] = 0.093, [ BEB ] = 0.014, [ BBE ] = 0.013, [ BBB ] = 0.012, an ethylene average sequence length n E = 9.5,1-butene average sequence length n B =1.11, wherein [ EEE ] represents a fraction of ethylene triple sequence, [ EEB ] represents a fraction of ethylene triple sequence, [ BEB ] represents a fraction of butene-1 meta sequence, [ BBE ] represents a fraction of 1-butene triple sequence. The average sequence length of ethylene is too large, and the distribution uniformity of 1-butene in a molecular chain segment is poor. The product is subjected to tabletting sample preparation to obtain the polyolefin elastomer with the thickness of 0.5mm, the light transmittance of 84.0% at the wavelength of 290-380 nm and the light transmittance of 87.6% at the wavelength of 380-1100 nm, and the product is mixed with the POE raw material for the photovoltaic packaging adhesive film to obtain the polyolefin elastomer with the light transmittance of 88.8% at the wavelength of 380-1100 nm, wherein the light transmittance of Fu Jiaomo can not meet the standard requirement of 90%.
Comparative example 2
The difference from example 1 was only that polymerization was carried out using an unmodified catalyst, the catalyst yield was 13200g of product/g of catalyst, the mass ratio of the antistatic agent to ethylene was 0.0010%, and the polymerization time was 9 hours. The polyolefin elastomer has a product density of 0.8905g/cm 3, a melt mass flow rate MFR (190 ℃, 2.16 kg) of 5.0g/10min, a molecular weight distribution width PDI of 2.72, a comonomer 1-butene content of 10.2mol% in the product, a molecular chain segment ternary sequence distribution of [ EEE ] = 0.772, [ EEB ] = 0.123, [ EBE ] = 0.081, [ BEB ] = 0.007, [ BBE ] = 0.011, [ BBB ] = 0.006, an ethylene average sequence length n E = 9.9, and a butene-1 average sequence length n B = 1.02, wherein [ EEE ] represents a fraction of ethylene triples, [ EEB ] represents a fraction of ethylene triples, [ EBE ] represents a fraction of ethylene meta-sequences, [ BEB ] represents a fraction of butene-1 meta-sequences, and [ E ] represents a fraction of 1-butene triples. The product is subjected to tabletting sample preparation, the thickness of the obtained polyolefin elastomer is 0.5mm, the light transmittance of the polyolefin elastomer is 82.6% when the wavelength is 290-380 nm, the light transmittance of the polyolefin elastomer is 85.3% when the wavelength is 380-1100 nm, and the light transmittance of the polyolefin elastomer is far lower than the index requirement of 90% of the photovoltaic adhesive film when the wavelength is 380-1100 nm, so that the polyolefin elastomer cannot be used for blending application.
Comparative example 3
The difference from example 3 was only that polymerization was carried out using an unmodified catalyst, the catalyst yield was 10500g of product/g of catalyst, the mass ratio of the antistatic agent to ethylene was 0.0010%, and the polymerization time was 12 hours. The molecular weight distribution width PDI of the polyolefin elastomer product is 2.44, the content of the comonomer butene-1 in the product is 14.20mol%, the molecular chain segment ternary sequence distribution is [ EEE ] =0.607, [ EEB ] =0.173, [ EBE ] =0.143, [ BEB ] =0.023, [ BBE ] =0.044, [ BBB ] =0.010, the ethylene average sequence length n E = 8.4,1-butene average sequence length n B =1.17, wherein [ EEE ] represents the fraction of ethylene triple sequence, [ EEB ] represents the fraction of ethylene double-linked sequence, [ E ] represents the fraction of ethylene meta-sequence, [ BEB ] represents the fraction of butene-1 meta-sequence, and [ BBE ] represents the fraction of 1-butene double-linked sequence. The average sequence length of the 1-butene is too large, the distribution uniformity of the 1-butene in a molecular chain segment is poor, the product is subjected to tabletting and sample preparation, the thickness of the obtained polyolefin elastomer is 0.5mm, the light transmittance of the polyolefin elastomer with the wavelength of 290-380 nm is 84.7%, the light transmittance of the polyolefin elastomer with the wavelength of 380-1100 nm is 88.9%, the product is used for blending and applying in POE raw materials of a photovoltaic packaging adhesive film, the blending proportion is 10%, and the application value is low.
From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:
The test results of the embodiment and the comparative example show that in the gas phase polymerization process, the uniformity of comonomer insertion into a molecular chain segment is improved by adopting the modified catalyst, the POE light transmittance is improved, the product quality is improved by process optimization, and the application proportion of the gas phase POE in the photovoltaic adhesive film is improved, so that the application prospect is wider.
While this specification contains many specific implementation details, these should not be construed as limitations on the scope of any invention or of what may be claimed, but rather as descriptions of features of specific embodiments of particular inventions. Certain features that are described in this specification in the context of separate embodiments can also be implemented in combination in a single embodiment. On the other hand, the various features described in the individual embodiments may also be implemented separately in the various embodiments or in any suitable subcombination. Furthermore, although features may be acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a subcombination or variation of a subcombination.
Thus, particular embodiments of the subject matter have been described. Other embodiments are within the scope of the following claims. In some cases, the actions recited in the claims can be performed in a different order and still achieve desirable results. In some implementations, multitasking and parallel processing may be advantageous.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises an element.
The foregoing is only a specific embodiment of the application to enable those skilled in the art to understand or practice the application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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