CN114644791A - High-transparency modified polyolefin material and preparation process and application thereof - Google Patents
High-transparency modified polyolefin material and preparation process and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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Abstract
The invention relates to the technical field of polyolefin materials, in particular to a high-transparency modified polyolefin material and a preparation process and application thereof. The high-transparency modified polyolefin material is prepared from polyolefin, a polyolefin elastomer, a modified cyclic olefin copolymer and an auxiliary agent. The modified cycloolefin copolymer prepared by using the specific cycloolefin copolymer, the linear low-density polyethylene and the polyolefin elastomer can not only increase the transparency of the modified polyolefin material, but also improve the defect of high system rigidity caused by a cyclic structure.
Description
Technical Field
The invention relates to the technical field of polyolefin materials, in particular to a high-transparency modified polyolefin material and a preparation process and application thereof.
Background
The polyolefin material is a material using a polymer prepared by polymerization or copolymerization of one or more olefins as a base material, and the polyolefin material has advantages of abundant raw materials, low price, easy processing and molding, and the like, so that the polyolefin material can be widely applied to daily life and industry, for example, the polyolefin material can be applied to the aspects of insulating materials, rubber and plastic products, molds, signs, packaging, transportation and the like, and in recent years, the polyolefin material is also applied to solar back panels.
The transparent material is a material with excellent optical transmittance, the traditional transparent material is mainly inorganic glass, the transparent high polymer material continuously replaces the common inorganic glass along with the continuous development of the high polymer material, and compared with the glass material, the transparent high polymer material has higher toughness, lower operation temperature and lighter weight. At present, the most widely used transparent high polymer materials are methyl methacrylate, polystyrene and polycarbonate, but the components made of the materials are unstable and have poor aging resistance and low temperature resistance.
Therefore, it is necessary to prepare a highly transparent modified polyolefin material, from which materials having transparency, aging resistance and low temperature resistance can be prepared.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present invention provides a high-transparency modified polyolefin material, which is prepared from polyolefin, a polyolefin elastomer, a modified cyclic olefin copolymer, and an auxiliary agent.
As a preferred embodiment of the present invention, the polyolefin includes polypropylene and linear low density polyethylene.
As a preferred technical scheme of the invention, the molecular weight distribution index of the polypropylene is 1.5-4.
As a preferred technical scheme of the invention, the melt index of the linear low-density polyethylene at 190 ℃/2.16kg is 4-8g/10 min.
As a preferable technical scheme of the invention, the preparation raw materials of the modified cyclic olefin copolymer comprise the cyclic olefin copolymer, linear low density polyethylene and polyolefin elastomer, and the weight ratio is (70-80): (10-15): (10-15).
As a preferred embodiment of the present invention, the cycloolefin copolymer has a volume flow index of 2 to 6ml/10 min.
In a preferred embodiment of the present invention, the polyolefin elastomer is a polyethylene octene co-elastomer.
The second aspect of the invention provides a preparation process of a high-transparency modified polyolefin material, which comprises the following steps:
(1) weighing corresponding polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix;
(2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melt granulation to obtain the high-transparency modified polyolefin material.
The second aspect of the present invention provides a use of a high transparent modified polyolefin material, the use of the high transparent modified polyolefin material comprising: used for preparing single-layer or multi-layer composite back plates.
As a preferred technical scheme, the high-transparency modified polyolefin material is extruded by a rectangular die after being melted and plasticized by a backboard extruder to obtain a flaky melt, and the flaky melt is cooled, shaped and rolled by a cooling roller to obtain the single-layer solar backboard.
Has the beneficial effects that:
1. the modified cycloolefin copolymer prepared by using the specific cycloolefin copolymer, the linear low-density polyethylene and the polyolefin elastomer can not only increase the transparency of the modified polyolefin material, but also improve the defect of high system rigidity caused by a cyclic structure;
2. the modified polyolefin material and the linear low-density polyethylene in the invention act synergistically to realize the insertion of polypropylene spherulites to a certain extent, and the transparency of the modified cycloolefin copolymer can be exerted while the transparency of the polypropylene is influenced, so that the transparency of the modified polyolefin material is further improved;
3. the components of the invention interact with each other to form an interpenetrating network structure, and the denser structure improves the aging property at high and low temperature and the cooking aging property.
Detailed Description
The invention will be further understood by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definition provided in the present disclosure, the definition of the term provided in the present disclosure controls.
As used herein, a feature that does not define a singular or plural form is also intended to include a plural form of the feature unless the context clearly indicates otherwise. It will also be understood that the term "prepared from …," as used herein, is synonymous with "comprising," including, "comprising," "having," "containing," and/or "containing," when used in this specification denotes a stated composition, step, method, article, or apparatus, but does not preclude the presence or addition of one or more other compositions, steps, methods, articles, or apparatuses. Furthermore, the use of "preferred," "preferably," "more preferred," etc., when describing embodiments of the present invention, is meant to refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. In addition, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the above technical problems, a first aspect of the present invention provides a high-transparency modified polyolefin material, which is prepared from polyolefin, a polyolefin elastomer, a modified cyclic olefin copolymer, and an auxiliary agent.
Polyolefins
In one embodiment, the polyolefin comprises polypropylene and linear low density polyethylene.
Polypropylene
In one embodiment, the polypropylene has a molecular weight distribution index of 1.5 to 4; further preferably 2 to 4; still more preferably 3.8.
In one embodiment, the polypropylene is selected from at least one of block co-polypropylene, random co-polypropylene, homo-polypropylene.
In one embodiment, the polypropylene is a combination of block co-polypropylene, random co-polypropylene, homo-polypropylene, in a weight ratio of (0.1-0.5): 1: (0.2-1.2); more preferably (0.1 to 0.3): 1: (0.5-1); still more preferably 0.2: 1: 0.8.
in the invention, the block copolymerization polypropylene, the random copolymerization polypropylene and the homopolymerization polypropylene in a certain weight ratio are used, so that the modified polyolefin material has good mechanical strength, and a product prepared by using the modified polyolefin material has good cohesiveness.
In one embodiment, the block co-polypropylene is delphinidin k 6712.
In one embodiment, the random copolymer polypropylene is mesopetrochemical M800E.
In one embodiment, the homopolypropylene is delphinized 1300.
Linear low density polyethylene
In one embodiment, the linear low density polyethylene has a melt index of 4 to 8g/10min at 190 ℃/2.16 kg; further preferably 5-6g/10 min; still more preferably 5.5g/10 min.
In one embodiment, the linear low density polyethylene is zipurite DNDB 7149U.
Modified cycloolefin copolymers
In one embodiment, the weight of the modified cyclic olefin copolymer is 10 to 20 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; preferably 12 to 17%; further preferably 14%.
In one embodiment, the raw materials for preparing the modified cyclic olefin copolymer comprise a cyclic olefin copolymer, linear low density polyethylene and a polyolefin elastomer, wherein the weight ratio of the cyclic olefin copolymer to the polyolefin elastomer is (70-80): (10-15): (10-15); preferably 65: 12: 13.
in one embodiment, the modified cycloolefin copolymer is prepared by a process comprising: and blending, melting and extruding the preparation raw materials of the modified cyclic olefin copolymer to obtain the modified cyclic olefin copolymer.
In one embodiment, the cyclic olefin copolymer has a volume flow index of 2 to 6ml/10min (test conditions HDT/B +115 ℃/2.16 kg); further preferably 5ml/10min, more specifically, cycloolefin copolymer 6017.
In order to improve the high temperature resistance and transparency of the modified polyolefin material, the applicant adds a certain amount of cycloolefin copolymer, but in the experimental process, the addition of the cycloolefin copolymer has poor effect on improving the transparency of the modified polyolefin material, and the toughness of the modified polyolefin material is reduced. It is possible that the rigidity of the system is increased due to the cyclic structure of the single cycloolefin copolymer, and that the properties of the cycloolefin copolymer itself are influenced to some extent by the presence of too much polyolefin in the system. The applicant finds that the modified cyclic olefin copolymer prepared by selecting the cyclic olefin copolymer with the volume flow index of 2-6ml/10min, the linear low density polyethylene with the melt index of 4-8g/10min and the polyolefin elastomer can not only increase the transparency of the modified polyolefin material, but also improve the defect of high system rigidity caused by a cyclic structure, probably because the polyolefin elastomer increases the compatibility of the cyclic olefin copolymer and the linear low density polyethylene to a certain extent, and the melt indexes of the cyclic olefin copolymer and the linear low density polyethylene are similar, and in the processing process, a certain proportion of the cyclic structure and the flexible structure of a molecular chain influence each other, so that the modified cyclic olefin copolymer has high temperature resistance and toughness and also has the transparency, and when the modified cyclic olefin is copolymerized with the polyolefin, The polyolefin elastomer is modified again, the modified cycloolefin copolymer contains a certain alkyl carbon chain, the modified cycloolefin copolymer can well react with the alkyl carbon chain of the polyolefin, the insertion of polypropylene spherulites is realized to a certain extent, the transparency of the modified cycloolefin copolymer can be brought into play while the transparency of the polypropylene is influenced, and the transparency of the modified polyolefin material is further improved.
Polyolefin elastomer
In one embodiment, the polyolefin elastomer is a polyethylene octene co-elastomer having a melt index (190 ℃,2.16kg) of 3g/10min, a density of 0.902g/cm3, and a Mooney viscosity (ML 1+4@121 ℃) of 10, specifically Dow 8450.
In one embodiment, the polypropylene, the linear low density polyethylene, and the polyolefin elastomer are present in a mass ratio of 0.8: (1.3-1.5): (0.1-0.3); preferably 0.8: 1.4: 0.2. the weight of the polyolefin elastomer herein does not include the weight of the polyolefin elastomer from which the modified cycloolefin copolymer was prepared.
The applicant has unexpectedly found in the experimental process that when polypropylene and linear low density polyethylene, especially polypropylene with a molecular weight distribution index of 1.5-4 and linear low density polyethylene with a melt index of 4-8g/10min at 190 ℃/2.16kg are used, the processing flowability is good and the cooking aging property is improved, but the high and low temperature aging property and the transparency are sometimes reduced, when a polyethylene octene co-elastomer with a melt index of 3g/10min, a density of 0.902g/cm3 and a Mooney viscosity (ML 1+4@121 ℃) of 10 is further added, and the mass ratio of the polypropylene, the linear low density polyethylene and the polyethylene octene co-elastomer is controlled to be 0.8: (1.3-1.5): (0.1-0.3), the two components interact with each other, so that the problems can be solved, and the cooking aging property is further improved, probably because the compatibility between the polyolefin and the polyolefin elastomer is better, on one hand, the linear low-density polyethylene in the system can fully realize the insertion, segmentation and refinement of polypropylene spherulites, the size of the polypropylene crystals is reduced, and the connection among the crystals is increased; on the other hand, the ethylene-octene substrate in amorphous state is embedded in a network of fine and evenly dispersed polyolefin crystals, and has higher transparency due to fine crystal grains and unit cell size smaller than the wavelength of visible light, and the components interact with each other to form an interpenetrating network structure, so that the high and low temperature aging property and the cooking aging property are improved due to a more compact structure.
Auxiliary agent
In one embodiment, the weight of the auxiliary agent is 0.5-2% of the weight of the preparation raw material of the high-transparency modified polyolefin material; preferably 0.8 to 1.5%; further preferably 1.2%.
In one embodiment, the adjuvant is a uv absorber and/or an antioxidant.
In a preferred embodiment, the auxiliary agent is an ultraviolet absorber and an antioxidant, and the weight ratio of the auxiliary agent to the antioxidant is 1: (0.5-0.8); preferably 1: 0.72.
the ultraviolet absorber is not limited, and any ultraviolet absorber suitable for use in polyolefins is suitable for use in the system of the present invention, and examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers (for example, ultraviolet absorbers UV-P and UVP-327), hindered amine-based ultraviolet absorbers (for example, light stabilizer HPT), and benzophenone-based ultraviolet absorbers (for example, ultraviolet absorbers UV-O, ultraviolet absorbers UV-9, and ultraviolet absorbers UV-531).
In a preferred embodiment, the ultraviolet absorbent is a combination of an ultraviolet absorbent UV-O and an ultraviolet absorbent UV-531, and the weight ratio of the ultraviolet absorbent UV-O to the ultraviolet absorbent UV-531 is 1: (0.5-0.8), preferably 1: 0.65.
the antioxidant is not limited, and antioxidants suitable for use in polyolefins are suitable for use in the present system, and examples thereof include antioxidant 168, antioxidant 1098, antioxidant 1010, antioxidant 1098, and antioxidant 215, and preferably antioxidant 168.
The second aspect of the invention provides a preparation process of a high-transparency modified polyolefin material, which comprises the following steps:
(1) weighing corresponding polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix;
(2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melting granulation to obtain the high-transparency modified polyolefin material.
The third aspect of the present invention provides a use of a high-transparency modified polyolefin material, the use of the high-transparency modified polyolefin material comprising: used for preparing single-layer or multi-layer composite back plates.
In one embodiment, the high-transparency modified polyolefin material is subjected to melting and plasticizing by a backboard sheet extruder and then extruded by a rectangular die to obtain a sheet melt, and the sheet melt is cooled, shaped and rolled by a cooling roller to obtain the single-layer solar backboard.
In one embodiment, the multilayer composite backsheet comprises an EVA layer, a single layer solar backsheet as described above, and a reflective layer.
In one embodiment, the solar cell is composed of an upper cover plate, an adhesive film, a cell piece, the adhesive film and the single-layer solar back plate.
Several specific examples of the present invention are given below, but the present invention is not limited by the examples.
In addition, the starting materials in the present invention are commercially available unless otherwise specified.
Examples
Example 1
Embodiment 1 of the invention provides a high-transparency modified polyolefin material, which is prepared from polyolefin, a polyolefin elastomer, a modified cyclic olefin copolymer and an auxiliary agent;
the polyolefin comprises polypropylene and linear low density polyethylene;
the molecular weight distribution index of the polypropylene is 3.5; the polypropylene is a composition of block copolymerization polypropylene, random copolymerization polypropylene and homopolymerization polypropylene, and the weight ratio of the polypropylene to the polypropylene is 0.1: 1: 0.5; the block copolymerization polypropylene is Yanshan petrochemical k 6712; the random copolymerized polypropylene is mesopetrochemical M800E; the homopolymerized polypropylene is Yanshan petrochemical 1300;
the linear low density polyethylene has a melt index of 5.5g/10min at 190 ℃/2.16 kg; the linear low density polyethylene is zipuridylic DNDB 7149U;
the weight of the modified cycloolefin copolymer is 12 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the modified cycloolefin copolymer is prepared from the following raw materials in parts by weight of 70: 10: 10; the preparation method of the modified cycloolefin copolymer comprises the following steps: blending, melting and extruding the preparation raw materials of the modified cyclic olefin copolymer to obtain the modified cyclic olefin copolymer; the volume flow index of the cycloolefin copolymer is 5ml/10min (HDT/B +115 ℃/2.16 kg); specifically, cycloolefin copolymer 6017;
the polyolefin elastomer is a polyethylene octene co-elastomer, the melt index (190 ℃,2.16kg) of the polyolefin elastomer is 3g/10min, the density of the polyolefin elastomer is 0.902g/cm3, the Mooney viscosity (ML 1+4@121 ℃) of the polyolefin elastomer is 10, and the Dow-shaped polyolefin elastomer is specifically US 8450;
the mass ratio of the polypropylene to the linear low-density polyethylene to the polyolefin elastomer is 0.8: 1.3: 0.1;
the weight of the auxiliary agent is 0.8 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the auxiliary agent is an ultraviolet absorbent and an antioxidant, and the weight ratio of the auxiliary agent to the antioxidant is 1: 0.5; the ultraviolet absorbent is a composition of an ultraviolet absorbent UV-O and an ultraviolet absorbent UV-531, and the weight ratio of the ultraviolet absorbent to the ultraviolet absorbent is 1: 0.5; the antioxidant is antioxidant 168;
the preparation method of the high-transparency modified polyolefin material comprises the following steps:
(1) weighing corresponding polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix; (2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melt granulation to obtain the high-transparency modified polyolefin material.
Example 2
Embodiment 2 of the present invention provides a high-transparency modified polyolefin material, which comprises the following raw materials of polyolefin, a polyolefin elastomer, a modified cyclic olefin copolymer, and an auxiliary agent;
the polyolefin comprises polypropylene and linear low density polyethylene;
the polypropylene has a molecular weight distribution index of 3.5; the polypropylene is a composition of block copolymerization polypropylene, random copolymerization polypropylene and homopolymerization polypropylene, and the weight ratio of the polypropylene to the polypropylene is 0.3: 1: 1; the block copolymerization polypropylene is Yanshan petrochemical k 6712; the random copolymerized polypropylene is mesopetrochemical M800E; the homopolymerized polypropylene is Yanshan petrochemical 1300;
the linear low density polyethylene has a melt index of 5.5g/10min at 190 ℃/2.16 kg; the linear low density polyethylene is zipurite DNDB 7149U;
the weight of the modified cycloolefin copolymer is 17 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the preparation raw materials of the modified cyclic olefin copolymer comprise a cyclic olefin copolymer, linear low-density polyethylene and a polyolefin elastomer, wherein the weight ratio of the cyclic olefin copolymer to the linear low-density polyethylene is 80: 15: 15; the preparation method of the modified cycloolefin copolymer comprises the following steps: blending, melting and extruding the preparation raw materials of the modified cyclic olefin copolymer to obtain the modified cyclic olefin copolymer; the cycloolefin copolymer had a volume flow index of 5ml/10min (HDT/B +115 ℃/2.16 kg); specifically, cycloolefin copolymer 6017;
the polyolefin elastomer is a polyethylene octene co-elastomer, the melt index (190 ℃,2.16kg) of the polyolefin elastomer is 3g/10min, the density of the polyolefin elastomer is 0.902g/cm3, the Mooney viscosity (ML 1+4@121 ℃) of the polyolefin elastomer is 10, and the Dow-shaped polyolefin elastomer is specifically US 8450;
the mass ratio of the polypropylene to the linear low-density polyethylene to the polyolefin elastomer is 0.8: 1.5: 0.3;
the weight of the auxiliary agent is 01.5 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the auxiliary agent is an ultraviolet absorbent and an antioxidant, and the weight ratio of the auxiliary agent to the antioxidant is 1: 0.8; the ultraviolet absorbent is a composition of an ultraviolet absorbent UV-O and an ultraviolet absorbent UV-531, and the weight ratio of the ultraviolet absorbent to the ultraviolet absorbent is 1: 0.8; the antioxidant is antioxidant 168;
the preparation method of the high-transparency modified polyolefin material comprises the following steps:
(1) weighing corresponding polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix; (2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melt granulation to obtain the high-transparency modified polyolefin material.
Example 3
Embodiment 3 of the present invention provides a high transparent modified polyolefin material, which comprises the following raw materials of polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent;
the polyolefin comprises polypropylene and linear low density polyethylene;
the molecular weight distribution index of the polypropylene is 3.5; the polypropylene is a composition of block copolymerization polypropylene, random copolymerization polypropylene and homopolymerization polypropylene, and the weight ratio of the polypropylene to the polypropylene is 0.2: 1: 0.8; the block copolymerization polypropylene is Yanshan petrochemical k 6712; the random copolymerized polypropylene is mesopetrochemical M800E; the homopolymerized polypropylene is Yanshan petrochemical 1300;
the linear low density polyethylene has a melt index of 5.5g/10min at 190 ℃/2.16 kg; the linear low density polyethylene is zipuridylic DNDB 7149U;
the weight of the modified cycloolefin copolymer is 14 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the preparation raw materials of the modified cyclic olefin copolymer comprise a cyclic olefin copolymer, linear low-density polyethylene and a polyolefin elastomer, wherein the weight ratio of the cyclic olefin copolymer to the linear low-density polyethylene is 65: 12: 13; the preparation method of the modified cycloolefin copolymer comprises the following steps: blending, melting and extruding the preparation raw materials of the modified cyclic olefin copolymer to obtain the modified cyclic olefin copolymer; the cycloolefin copolymer had a volume flow index of 5ml/10min (HDT/B +115 ℃/2.16 kg); specifically, cycloolefin copolymer 6017;
the polyolefin elastomer is a polyethylene octene co-elastomer, the melt index (190 ℃,2.16kg) of the polyolefin elastomer is 3g/10min, the density of the polyolefin elastomer is 0.902g/cm3, the Mooney viscosity (ML 1+4@121 ℃) of the polyolefin elastomer is 10, and the Dow-shaped polyolefin elastomer is specifically US 8450;
the mass ratio of the polypropylene to the linear low-density polyethylene to the polyolefin elastomer is 0.8: 1.4: 0.2;
the weight of the auxiliary agent is 1.2 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the auxiliary agent is an ultraviolet absorbent and an antioxidant, and the weight ratio of the auxiliary agent to the antioxidant is 1: 0.72; the ultraviolet absorbent is a composition of an ultraviolet absorbent UV-O and an ultraviolet absorbent UV-531, and the weight ratio of the ultraviolet absorbent to the ultraviolet absorbent is 1: 0.65; the antioxidant is an antioxidant 168;
the preparation method of the high-transparency modified polyolefin material comprises the following steps:
(1) weighing corresponding polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix; (2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melt granulation to obtain the high-transparency modified polyolefin material.
Example 4
Embodiment 4 of the present invention provides a high-transparency modified polyolefin material, which comprises the following raw materials of polyolefin, a polyolefin elastomer, a cyclic olefin copolymer, and an auxiliary agent;
the polyolefin comprises polypropylene and linear low density polyethylene;
the molecular weight distribution index of the polypropylene is 3.5; the polypropylene is a composition of block copolymerization polypropylene, random copolymerization polypropylene and homopolymerization polypropylene, and the weight ratio of the polypropylene to the polypropylene is 0.2: 1: 0.8; the block copolymerization polypropylene is Yanshan petrochemical k 6712; the random copolymerized polypropylene is mesopetrochemical M800E; the homopolypropylene is Yanshan petrochemical 1300;
the linear low density polyethylene has a melt index of 5.5g/10min at 190 ℃/2.16 kg; the linear low density polyethylene is zipurite DNDB 7149U;
the weight of the cycloolefin copolymer is 14 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the cycloolefin copolymer had a volume flow index of 5ml/10min (HDT/B +115 ℃/2.16 kg); specifically, cycloolefin copolymer 6017;
the polyolefin elastomer is a polyethylene octene co-elastomer, the melt index (190 ℃,2.16kg) of the polyolefin elastomer is 3g/10min, the density of the polyolefin elastomer is 0.902g/cm3, the Mooney viscosity (ML 1+4@121 ℃) of the polyolefin elastomer is 10, and the Dow-shaped polyolefin elastomer is specifically US 8450;
the mass ratio of the polypropylene to the linear low-density polyethylene to the polyolefin elastomer is 0.8: 1.4: 0.2;
the weight of the auxiliary agent is 1.2 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the auxiliary agent is an ultraviolet absorbent and an antioxidant, and the weight ratio of the auxiliary agent to the antioxidant is 1: 0.72; the ultraviolet absorbent is a composition of an ultraviolet absorbent UV-O and an ultraviolet absorbent UV-531, and the weight ratio of the ultraviolet absorbent to the ultraviolet absorbent is 1: 0.65; the antioxidant is antioxidant 168;
the preparation method of the high-transparency modified polyolefin material comprises the following steps:
(1) weighing corresponding polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix; (2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melt granulation to obtain the high-transparency modified polyolefin material.
Example 5
Embodiment 5 of the present invention provides a high transparent modified polyolefin material, which comprises the following raw materials of polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent;
the polyolefin comprises polypropylene and linear low density polyethylene;
the molecular weight distribution index of the polypropylene is 3.5; the polypropylene is a composition of block copolymerization polypropylene, random copolymerization polypropylene and homopolymerization polypropylene, and the weight ratio of the polypropylene to the polypropylene is 0.2: 1: 0.8; the block copolymerization polypropylene is Yanshan petrochemical k 6712; the random copolymerized polypropylene is mesopetrochemical M800E; the homopolymerized polypropylene is Yanshan petrochemical 1300;
the linear low density polyethylene has a melt index of 5.5g/10min at 190 ℃/2.16 kg; the linear low density polyethylene is zipuridylic DNDB 7149U;
the weight of the modified cycloolefin copolymer is 14 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the preparation raw materials of the modified cyclic olefin copolymer comprise a cyclic olefin copolymer, linear low-density polyethylene and a polyolefin elastomer, wherein the weight ratio of the cyclic olefin copolymer to the linear low-density polyethylene is 65: 12: 13; the preparation method of the modified cycloolefin copolymer comprises the following steps: blending, melting and extruding the preparation raw materials of the modified cyclic olefin copolymer to obtain the modified cyclic olefin copolymer; the volume flow index of the cycloolefin copolymer is 24ml/10min (the test condition is HDT/B +115 ℃/2.16kg), and the cycloolefin copolymer is specifically 5013;
the polyolefin elastomer is a polyethylene octene co-elastomer, the melt index (190 ℃,2.16kg) of the polyolefin elastomer is 3g/10min, the density of the polyolefin elastomer is 0.902g/cm3, the Mooney viscosity (ML 1+4@121 ℃) of the polyolefin elastomer is 10, and the Mooney viscosity is specifically Dow 8450;
the mass ratio of the polypropylene to the linear low-density polyethylene to the polyolefin elastomer is 0.8: 1.4: 0.2;
in one embodiment, the weight of the auxiliary agent is 1.2% of the weight of the preparation raw material of the high-transparency modified polyolefin material; the auxiliary agent is an ultraviolet absorbent and an antioxidant, and the weight ratio of the auxiliary agent to the antioxidant is 1: 0.72; the ultraviolet absorbent is a composition of an ultraviolet absorbent UV-O and an ultraviolet absorbent UV-531, and the weight ratio of the ultraviolet absorbent to the ultraviolet absorbent is 1: 0.65; the antioxidant is antioxidant 168;
the preparation method of the high-transparency modified polyolefin material comprises the following steps:
(1) weighing corresponding polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix; (2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melt granulation to obtain the high-transparency modified polyolefin material.
Example 6
Embodiment 6 of the present invention provides a highly transparent modified polyolefin material, which comprises the following raw materials of polyolefin, a polyolefin elastomer, a modified cycloolefin copolymer, and an auxiliary agent;
the polyolefins include polypropylene and linear low density polyethylene;
the polypropylene has a molecular weight distribution index of 3.5; the polypropylene is a composition of block copolymerization polypropylene, random copolymerization polypropylene and homopolymerization polypropylene, and the weight ratio of the polypropylene to the polypropylene is 0.2: 1: 0.8; the block copolymerization polypropylene is Yanshan petrochemical k 6712; the random copolymerized polypropylene is mesopetrochemical M800E; the homopolymerized polypropylene is Yanshan petrochemical 1300;
the linear low density polyethylene has a melt index of 5.5g/10min at 190 ℃/2.16 kg; the linear low density polyethylene is zipurite DNDB 7149U;
the weight of the modified cycloolefin copolymer is 14 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the modified cycloolefin copolymer is prepared from the following raw materials in parts by weight of 65: 13; the preparation method of the modified cycloolefin copolymer comprises the following steps: blending, melting and extruding the preparation raw materials of the modified cyclic olefin copolymer to obtain the modified cyclic olefin copolymer; the cycloolefin copolymer had a volume flow index of 5ml/10min (HDT/B +115 ℃/2.16 kg); specifically, cycloolefin copolymer 6017;
the polyolefin elastomer is a polyethylene octene co-elastomer, the melt index (190 ℃,2.16kg) of the polyolefin elastomer is 3g/10min, the density of the polyolefin elastomer is 0.902g/cm3, the Mooney viscosity (ML 1+4@121 ℃) of the polyolefin elastomer is 10, and the Mooney viscosity is specifically Dow 8450;
the mass ratio of the polypropylene to the linear low-density polyethylene to the polyolefin elastomer is 0.8: 1.4: 0.2;
the weight of the auxiliary agent is 1.2 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the auxiliary agent is an ultraviolet absorbent and an antioxidant, and the weight ratio of the auxiliary agent to the auxiliary agent is 1: 0.72; the ultraviolet absorbent is a composition of an ultraviolet absorbent UV-O and an ultraviolet absorbent UV-531, and the weight ratio of the ultraviolet absorbent to the ultraviolet absorbent is 1: 0.65; the antioxidant is antioxidant 168;
the preparation method of the high-transparency modified polyolefin material comprises the following steps:
(1) weighing corresponding polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix; (2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melt granulation to obtain the high-transparency modified polyolefin material.
Example 7
Embodiment 7 of the present invention provides a high-transparency modified polyolefin material, which comprises the following raw materials of polyolefin, a polyolefin elastomer, a modified cyclic olefin copolymer, and an auxiliary agent;
the polyolefin comprises polypropylene and linear low density polyethylene;
the molecular weight distribution index of the polypropylene is 3.5; the polypropylene is a composition of block copolymer polypropylene, random copolymer polypropylene and homopolymerized polypropylene, and the weight ratio of the polypropylene to the homopolymerized polypropylene is 0.2: 1: 0.8; the block copolymerization polypropylene is Yanshan petrochemical k 6712; the random copolymerized polypropylene is mesopetrochemical M800E; the homopolymerized polypropylene is Yanshan petrochemical 1300;
the linear low density polyethylene has a melt index of 5.5g/10min at 190 ℃/2.16 kg; the linear low density polyethylene is zipuridylic DNDB 7149U;
the weight of the modified cycloolefin copolymer is 14 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the preparation raw materials of the modified cyclic olefin copolymer comprise a cyclic olefin copolymer and linear low-density polyethylene, wherein the weight ratio of the cyclic olefin copolymer to the linear low-density polyethylene is 65: 12; the preparation method of the modified cycloolefin copolymer comprises the following steps: blending, melting and extruding the preparation raw materials of the modified cyclic olefin copolymer to obtain the modified cyclic olefin copolymer; the volume flow index of the cycloolefin copolymer is 5ml/10min (HDT/B +115 ℃/2.16 kg); in particular cycloolefin copolymer 6017;
the polyolefin elastomer is a polyethylene octene co-elastomer, the melt index (190 ℃,2.16kg) of the polyolefin elastomer is 3g/10min, the density of the polyolefin elastomer is 0.902g/cm3, the Mooney viscosity (ML 1+4@121 ℃) of the polyolefin elastomer is 10, and the Dow-shaped polyolefin elastomer is specifically US 8450;
the mass ratio of the polypropylene to the linear low-density polyethylene to the polyolefin elastomer is 0.8: 1.4: 0.2;
the weight of the auxiliary agent is 1.2 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the auxiliary agent is an ultraviolet absorbent and an antioxidant, and the weight ratio of the auxiliary agent to the antioxidant is 1: 0.72; the ultraviolet absorbent is a composition of an ultraviolet absorbent UV-O and an ultraviolet absorbent UV-531, and the weight ratio of the ultraviolet absorbent to the ultraviolet absorbent is 1: 0.65; the antioxidant is antioxidant 168;
the preparation method of the high-transparency modified polyolefin material comprises the following steps:
(1) weighing corresponding polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix; (2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melt granulation to obtain the high-transparency modified polyolefin material.
Example 8
Embodiment 8 of the present invention provides a highly transparent modified polyolefin material, which comprises the following raw materials of polyolefin, modified cycloolefin copolymer, and auxiliary agent;
the polyolefin comprises polypropylene and linear low density polyethylene;
the polypropylene has a molecular weight distribution index of 3.5; the polypropylene is a composition of block copolymerization polypropylene, random copolymerization polypropylene and homopolymerization polypropylene, and the weight ratio of the polypropylene to the polypropylene is 0.2: 1: 0.8; the block copolymerization polypropylene is Yanshan petrochemical k 6712; the random copolymerized polypropylene is mesopetrochemical M800E; the homopolymerized polypropylene is Yanshan petrochemical 1300;
the linear low density polyethylene has a melt index of 5.5g/10min at 190 ℃/2.16 kg; the linear low density polyethylene is zipurite DNDB 7149U;
the weight of the modified cycloolefin copolymer is 14 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the preparation raw materials of the modified cyclic olefin copolymer comprise a cyclic olefin copolymer, linear low-density polyethylene and a polyolefin elastomer, wherein the weight ratio of the cyclic olefin copolymer to the linear low-density polyethylene is 65: 12: 13; the preparation method of the modified cycloolefin copolymer comprises the following steps: blending, melting and extruding the preparation raw materials of the modified cycloolefin copolymer to obtain the modified cycloolefin copolymer; the volume flow index of the cycloolefin copolymer is 5ml/10min (HDT/B +115 ℃/2.16 kg); in particular cycloolefin copolymer 6017;
the polyolefin elastomer is a polyethylene octene co-elastomer, the melt index (190 ℃,2.16kg) of the polyolefin elastomer is 3g/10min, the density of the polyolefin elastomer is 0.902g/cm3, the Mooney viscosity (ML 1+4@121 ℃) of the polyolefin elastomer is 10, and the Mooney viscosity is specifically Dow 8450;
the mass ratio of the polypropylene to the linear low density polyethylene is 0.8: 1.4;
the weight of the auxiliary agent is 1.2 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the auxiliary agent is an ultraviolet absorbent and an antioxidant, and the weight ratio of the auxiliary agent to the antioxidant is 1: 0.72; the ultraviolet absorbent is a composition of an ultraviolet absorbent UV-O and an ultraviolet absorbent UV-531, and the weight ratio of the ultraviolet absorbent to the ultraviolet absorbent is 1: 0.65; the antioxidant is antioxidant 168;
the preparation method of the high-transparency modified polyolefin material comprises the following steps:
(1) weighing corresponding polyolefin, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix; (2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melt granulation to obtain the high-transparency modified polyolefin material.
Example 9
Embodiment 9 of the present invention provides a high transparent modified polyolefin material, which is prepared from polyolefin, a polyolefin elastomer, a modified cyclic olefin copolymer, and an auxiliary agent;
the polyolefin comprises polypropylene and linear low density polyethylene;
the polypropylene has a molecular weight distribution index of 3.5; the polypropylene is a composition of block copolymerization polypropylene, random copolymerization polypropylene and homopolymerization polypropylene, and the weight ratio of the polypropylene to the polypropylene is 0.2: 1: 0.8; the block copolymerization polypropylene is Yanshan petrochemical k 6712; the random copolymerized polypropylene is mesopetrochemical M800E; the homopolymerized polypropylene is Yanshan petrochemical 1300;
the linear low density polyethylene has a melt index of 5.5g/10min at 190 ℃/2.16 kg; the linear low density polyethylene is zipuridylic DNDB 7149U;
the weight of the modified cycloolefin copolymer is 14 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the preparation raw materials of the modified cyclic olefin copolymer comprise a cyclic olefin copolymer, linear low-density polyethylene and a polyolefin elastomer, wherein the weight ratio of the cyclic olefin copolymer to the linear low-density polyethylene is 65: 12: 13; the preparation method of the modified cycloolefin copolymer comprises the following steps: blending, melting and extruding the preparation raw materials of the modified cyclic olefin copolymer to obtain the modified cyclic olefin copolymer; the volume flow index of the cycloolefin copolymer is 5ml/10min (HDT/B +115 ℃/2.16 kg); specifically, cycloolefin copolymer 6017;
the polyolefin elastomer is a polyethylene octene co-elastomer, the melt index (190 ℃,2.16kg) of the polyolefin elastomer is 3g/10min, the density of the polyolefin elastomer is 0.902g/cm3, the Mooney viscosity (ML 1+4@121 ℃) of the polyolefin elastomer is 10, and the Dow-shaped polyolefin elastomer is specifically US 8450;
the mass ratio of the polypropylene to the linear low-density polyethylene to the polyolefin elastomer is 0.8: 1.4: 0.05
The weight of the auxiliary agent is 1.2 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the auxiliary agent is an ultraviolet absorbent and an antioxidant, and the weight ratio of the auxiliary agent to the antioxidant is 1: 0.72; the ultraviolet absorbent is a composition of an ultraviolet absorbent UV-O and an ultraviolet absorbent UV-531, and the weight ratio of the ultraviolet absorbent to the ultraviolet absorbent is 1: 0.65; the antioxidant is antioxidant 168;
the preparation method of the high-transparency modified polyolefin material comprises the following steps:
(1) weighing corresponding polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix; (2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melt granulation to obtain the high-transparency modified polyolefin material.
Example 9
Embodiment 9 of the present invention provides a high transparent modified polyolefin material, which is prepared from polyolefin, a polyolefin elastomer, a modified cyclic olefin copolymer, and an auxiliary agent;
the polyolefin comprises polypropylene and linear low density polyethylene;
the molecular weight distribution index of the polypropylene is 3.5; the polypropylene is a composition of block copolymerization polypropylene, random copolymerization polypropylene and homopolymerization polypropylene, and the weight ratio of the polypropylene to the polypropylene is 0.2: 1: 0.8; the block copolymerization polypropylene is Yanshan petrochemical k 6712; the random copolymerized polypropylene is mesopetrochemical M800E; the homopolymerized polypropylene is Yanshan petrochemical 1300;
the linear low density polyethylene has a melt index of 5.5g/10min at 190 ℃/2.16 kg; the linear low density polyethylene is zipuridylic DNDB 7149U;
the weight of the modified cycloolefin copolymer is 14 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the preparation raw materials of the modified cyclic olefin copolymer comprise a cyclic olefin copolymer, linear low-density polyethylene and a polyolefin elastomer, wherein the weight ratio of the cyclic olefin copolymer to the linear low-density polyethylene is 65: 12: 13; the preparation method of the modified cycloolefin copolymer comprises the following steps: blending, melting and extruding the preparation raw materials of the modified cyclic olefin copolymer to obtain the modified cyclic olefin copolymer; the volume flow index of the cycloolefin copolymer is 5ml/10min (HDT/B +115 ℃/2.16 kg); in particular cycloolefin copolymer 6017;
the polyolefin elastomer is a polyethylene octene co-elastomer, the melt index (190 ℃,2.16kg) of the polyolefin elastomer is 3g/10min, the density of the polyolefin elastomer is 0.902g/cm3, the Mooney viscosity (ML 1+4@121 ℃) of the polyolefin elastomer is 10, and the Dow-shaped polyolefin elastomer is specifically US 8450;
the mass ratio of the polypropylene to the linear low-density polyethylene to the polyolefin elastomer is 0.8: 0.8: 0.2;
the weight of the auxiliary agent is 1.2 percent of the weight of the preparation raw material of the high-transparency modified polyolefin material; the auxiliary agent is an ultraviolet absorbent and an antioxidant, and the weight ratio of the auxiliary agent to the antioxidant is 1: 0.72; the ultraviolet absorbent is a composition of an ultraviolet absorbent UV-O and an ultraviolet absorbent UV-531, and the weight ratio of the ultraviolet absorbent to the ultraviolet absorbent is 1: 0.65; the antioxidant is an antioxidant 168;
the preparation method of the high-transparency modified polyolefin material comprises the following steps:
(1) weighing corresponding polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix; (2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melt granulation to obtain the high-transparency modified polyolefin material.
Performance testing
The high-transparency modified polyolefin materials prepared in the embodiments 1 to 10 are respectively extruded through a rectangular die after being melted and plasticized by a backboard extruder to obtain a flaky melt, and the flaky melt is cooled, shaped and rolled by a cooling roller to obtain the single-layer solar backboard.
The following performance tests were performed on the single layer solar back panel:
1. and (3) testing the transparency:
the light transmittance of the transparent back sheet in examples 1 to 10 was measured by a light transmittance meter, and a value of a light transmittance of 80% or more was recorded as A; the light transmittance is greater than or equal to 68 percent and less than 80 percent is marked as B; the transmittance of less than 68% was designated as C.
2. Low temperature aging resistance test
Under the same preparation conditions, solar cells are respectively prepared by using the single-layer solar back panels prepared in the embodiments 1 to 10 (the only difference of the prepared cells is that different single-layer solar back panels are used), and according to the IEC61215:2005 standard, the power change test is carried out under TC200, wherein under TC200, the power change is marked as A, which is less than or equal to 0.35%; the power change is more than 0.35 percent, and less than 1 percent is marked as B; the change in power is 1% or more and is denoted as C.
3. Test of resistance to cooking aging
Carrying out a PCT96h cooking aging test according to GB/T2423.40-201, and recording the average value of the retention rate of the longitude and latitude elongation at break of the single-layer solar back panel of the embodiment 1-10, wherein the retention rate of the elongation at break is greater than or equal to 95% and is marked as A; the retention rate of elongation at break is less than 95 percent, and the mark B is more than or equal to 85 percent; the retention of elongation at break is less than 85% and is denoted as C.
The test results are shown in table 1:
TABLE 1
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The high-transparency modified polyolefin material is characterized in that the preparation raw materials comprise polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent.
2. The high transparency modified polyolefin material according to claim 1, wherein the polyolefin comprises polypropylene and linear low density polyethylene.
3. The high-transparency modified polyolefin material according to claim 2, wherein the polypropylene has a molecular weight distribution index of 1.5-4.
4. The high-transparency modified polyolefin material according to claim 2 or 3, wherein the linear low-density polyethylene has a melt index of 4-8g/10min at 190 ℃/2.16 kg.
5. The high-transparency modified polyolefin material according to claim 1, wherein the modified cyclic olefin copolymer is prepared from the following raw materials, by weight, of the cyclic olefin copolymer, linear low density polyethylene and polyolefin elastomer, and the weight ratio of the raw materials is (70-80): (10-15): (10-15).
6. The high-transparency modified polyolefin material according to claim 5, wherein the volume flow index of the cyclic olefin copolymer is 2-6ml/10 min.
7. The high-transparency modified polyolefin material according to claim 1, wherein the polyolefin elastomer is a polyethylene octene co-elastomer.
8. A process for preparing a high-transparency modified polyolefin material according to any one of claims 1 to 7, comprising the steps of:
(1) weighing corresponding polyolefin, polyolefin elastomer, modified cycloolefin copolymer and auxiliary agent, stirring and mixing to obtain a premix;
(2) and (2) conveying the premix obtained in the step (1) to a double-screw extruder, and carrying out melt granulation to obtain the high-transparency modified polyolefin material.
9. The use of the high-transparency modified polyolefin material according to any one of claims 1 to 7, wherein the use of the high-transparency modified polyolefin material comprises: used for preparing single-layer or multi-layer composite back plates.
10. The application of the high-transparency modified polyolefin material according to claim 9, wherein the high-transparency modified polyolefin material is subjected to melting and plasticizing by a backboard sheet extruder, and then is extruded by a rectangular die to obtain a sheet melt, and the sheet melt is cooled, shaped and rolled by a cooling roller to obtain the single-layer solar backboard.
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| US20060199915A1 (en) * | 2003-04-04 | 2006-09-07 | Soken Chemical & Engineering Co., Ltd. | Modified cycloolefin copolymer, process for producing the same, and use of the polymer |
| US20180072878A1 (en) * | 2015-04-10 | 2018-03-15 | Apple Inc. | Chemically resistant and tough cyclic olefin copolymer compounds |
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| US20180072878A1 (en) * | 2015-04-10 | 2018-03-15 | Apple Inc. | Chemically resistant and tough cyclic olefin copolymer compounds |
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