CN103509230B - Be applied to the modified master of polyethylene film and preparation thereof, using method - Google Patents

Be applied to the modified master of polyethylene film and preparation thereof, using method Download PDF

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CN103509230B
CN103509230B CN201210215556.3A CN201210215556A CN103509230B CN 103509230 B CN103509230 B CN 103509230B CN 201210215556 A CN201210215556 A CN 201210215556A CN 103509230 B CN103509230 B CN 103509230B
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antioxidant
film
modified master
polyethylene
master batch
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CN103509230A (en
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郭锐
王群涛
唐岩
王日辉
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China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The present invention relates to the polyethylene film manufacture fields such as plastic sheeting for farm use, packing film, stretch wrap film, be specifically related to a kind of be applied to polyethylene film modified master and preparation, using method, it is characterized in that being formed by the preparation of raw material of following parts by weight: polyethylene powder resin 100 parts, 0.025 ~ 0.15 part, oxidation inhibitor, nucleator A3 ~ 15 part and nucleator B3 ~ 15 part, wherein, nucleator A is selected from Metalsalts of hexahydrophthalic acid, and nucleator B is selected from glucitols and derivative thereof.The invention has the advantages that: the polyethylene composition containing modified master can be used as film article, comprise the fields such as agricultural film, packaging film and stretch wrap film, the tear-resistant power that polyvinyl resin prepares film after adding modified master of the present invention can improve more than 40%, mist degree is maximum reduces by more than 60%, film sharpness improves more than 10%, thus improves the over-all properties of film article.

Description

Modified master batch applied to polyethylene film and preparation and use methods thereof
Technical Field
The invention relates to the field of processing of polyethylene films such as agricultural films, packaging films, stretch wrap films and the like, in particular to a modified master batch applied to the polyethylene films and preparation and use methods thereof.
Background
Film products are an important area of application of Polyethylene (PE) resins today, and about more than half of the polyethylene resins are used in the film field. The polyethylene film is widely applied to the fields of agriculture, packaging industry and the like, and the requirement on the comprehensive performance of the polyethylene film is higher and higher along with the development of society and science and technology. The tearing resistance is an important index for measuring the performance of the film, the film product can be torn due to the action of external force in the using process, and the sufficient tearing resistance and the sufficient stretching resistance can reduce the transmission of tearing and improve the performance of the film. The optical performance is also one of the evaluation indexes of the film, the better optical performance can improve the appearance quality of the film, and when the film is used as a packaging film, the lower haze and the higher definition are also one of the indexes required by users. It is becoming more common to improve the performance of polyethylene films by using various additives.
Patent CN101268132 "film and its manufacturing method" describes a polyethylene composition for film, which comprises polyethylene resin, antioxidant, metal dicarboxylate, and stearate. The compositions disclosed therein comprise LLDPE, antioxidant 1010, antioxidant 168, calcium hexahydrophthalate, and zinc stearate, and films blown from the compositions exhibit improved haze and gloss, but reduced tear and dart impact compared to control films without the addition of calcium hexahydrophthalate.
Disclosure of Invention
The invention aims to provide a modified master batch applied to a polyethylene film and preparation and use methods thereof, wherein a novel polyethylene composition is obtained by mixing polyethylene resin and the modified master batch, and compared with the existing polyethylene composition, the modified master batch can improve the mechanical property and the optical property of a film product, thereby improving the comprehensive performance of the film product.
The invention relates to a modified master batch applied to a polyethylene film, which is characterized by being prepared from the following raw materials in parts by weight: 100 parts of polyethylene powder resin, 0.025-0.15 part of antioxidant, 3-15 parts of nucleating agent A and 3-15 parts of nucleating agent B, wherein the nucleating agent A is selected from hexahydrophthalic acid metal salt, and the nucleating agent B is selected from sorbitol and derivatives thereof.
The polyethylene powder resin is preferably a copolymer of ethylene and butene-1 or a copolymer of ethylene and hexene-1, the density of the polyethylene powder resin is 0.910-0.960 g/cm3, the melt Mass Flow Rate (MFR) of the polyethylene powder resin is 0.1-50 g/10min, the melting temperature range of the polyethylene resin measured by a differential scanning calorimeter is 110-140 ℃, and the branching degree range of the polyethylene resin is 0.1-3.0.
The weight part of the antioxidant is preferably 0.03-0.1 part, and more preferably 0.05-0.08 part.
The antioxidant is preferably selected from hindered phenol antioxidants, or hindered phenol antioxidants and phosphite antioxidant systems, or hindered phenol antioxidants, phosphite antioxidants and thioester antioxidant systems, wherein the mass ratio of the hindered phenol antioxidants to the phosphite antioxidants in the hindered phenol antioxidants and phosphite antioxidant systems is 1: 0.1 to 5, preferably 1: 0.3 to 3; in a hindered phenol antioxidant, phosphite antioxidant and thioester antioxidant system, the mass ratio of the phosphite antioxidant to the thioester antioxidant to the hindered phenol antioxidant is 0.1-15: 1, preferably 0.3-10: 1, wherein the mass ratio of the phosphite antioxidant to the thioester antioxidant is 1: 0.1 to 4.
The hindered phenolic antioxidant has a melting point of between 100 ℃ and 260 ℃, and is preferably selected from pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, (2, 4, 6-trioxo-1, 3, 5-triazine-1, 3, 5 (2H, 4H, 6H) -triyl) trivinyltris [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) acrylate, 1, 3, 5-trimethyl-2, 4, 6-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) benzene or 1, 3, 5-tris (4-tert-butyl-3-hydroxy-2, one or more than two of 6-dimethylbenzyl) -1, 3, 5-triazine-2, 4, 6- (1H, 3H, 5H) -trione are mixed in any proportion.
The phosphite antioxidant has a melting point of 160-250 ℃, and is preferably selected from tris (2, 4-di-tert-butylphenyl) phosphite or pentaerythritol diphosphite bis (2, 4-di-tert-butylphenyl).
The thioester antioxidant is preferably selected from dioctadecyl thiodipropionate or dilauryl thiodipropionate.
The antioxidant system can play a good synergistic effect in the preparation process of the modified master batch, and resin degradation caused by high temperature in the preparation process of the modified master batch is avoided.
The nucleating agent A is preferably calcium hexahydrophthalate.
The nucleating agent B is preferably Millad3988 from Milliken company or dibenzylidene sorbitol and its derivatives.
The preparation method of the modified master batch applied to the polyethylene film comprises the steps of adding the raw materials into a high-speed stirrer, mixing for 5-10 min, adding the uniformly mixed materials into a double-screw extruder, and melting, plasticizing, extruding and granulating according to a conventional process.
The application method of the modified master batch applied to the polyethylene film comprises the steps of adding polyethylene granular resin and the modified master batch into a high-speed stirrer, mixing for 5-10 min, adding the uniformly mixed materials into a double-screw extruder for melting, plasticizing, extruding and granulating, wherein the length-diameter ratio of a screw in the double-screw extruder influences the plasticizing performance and the conveying performance of the materials, is 28-40, and is preferably 30-35; the shear blocks in the screw combination in the double-screw extruder influence the plasticizing performance and the degradation degree of the material, the screw combination adopted by the invention comprises 3-9 sections of shear blocks, wherein the 3 sections of shear blocks comprise 1-5 sections of reverse shear blocks, preferably 6 sections of shear blocks, and the 3 sections of shear blocks are reverse shear blocks; the processing temperature for preparing the composition is too high, so that the material is easily degraded, the temperature is too low, the plasticization and the extrusion are not facilitated, and the processing temperature adopted by the invention is 180-220 ℃, and preferably 200 ℃.
And the other method is that after the polyethylene granular resin and the modified master batch are added into a high-speed stirrer to be mixed for 5-10 min, the materials are discharged and directly blown for use.
Wherein, the polyethylene pellet resin and the polyethylene powder resin in the modified master batch are the same chemical component, and only have different physical forms.
When the polyethylene pellet resin and the modified master batch are used, the content of the nucleating agent A in the total material of the polyethylene pellet resin and the modified master batch is 300-2000 ppm, preferably 500-1500 ppm and more preferably 1000ppm, and the content of the nucleating agent B in the total material of the polyethylene pellet resin and the modified master batch is 300-2000 ppm, preferably 500-1500 ppm and more preferably 1000 ppm.
The invention has the advantages that: the polyethylene composition containing the modified master batch can be used as film products in the fields of agricultural films, packaging films, stretch winding films and the like, the tearing resistance of the film prepared by adding the modified master batch into the polyethylene resin can be improved by more than 40%, the haze can be reduced by more than 60% to the maximum extent, and the film definition is improved by more than 10%, so that the comprehensive performance of the film products is improved.
Detailed Description
The present invention is further illustrated by the following examples.
Four modified masterbatches were prepared and used in the examples.
Masterbatch 1 (all parts by weight, the same below):
masterbatch 2:
masterbatch 3:
masterbatch 4:
example 1:
polyethylene pellet resin (ethylene, butene-1 copolymerized, MFR =2.0g/10 mm, density 0.920g/cm3) 99 portions of
11 parts of modified master batch
Length-diameter ratio of screw: 30
Screw combination: 8-section shear block and 3-section reverse shear
Processing temperature: 190 deg.C
Example 2:
polyethylene pellet resin (ethylene, butene-1 copolymerization, slurry catalyst synthesis, MFR =2.0g/10 mm, density 0.918g/cm3）
99 portions of
21 parts of modified master batch
High-stirring blending direct blown film
Example 3:
polyethylene pellet resin (ethylene, hexene-1 copolymerization, slurry catalyst synthesis, MFR =2.0g/10 mm, density 0.920g/cm3）
98 portions of
32 parts of modified master batch
Length-diameter ratio of screw: 35
Screw combination: 6-section shear block and 3-section reverse shear
Processing temperature: 200 deg.C
Example 4:
98.5 parts of polyethylene pellet resin (copolymerized with ethylene and butene-1, MFR =2.0g/10 mm, density 0.918g/cm 3)
41.5 parts of modified master batch
Length-diameter ratio of screw: 40
Screw combination: 5-section shear block and 3-section reverse shear
Processing temperature: 180 deg.C
Example 5:
polyethylene pellet resin (ethylene, butene-1 copolymerization, slurry catalyst synthesis, MFR =2.0g/10 mm, density 0.920g/cm3）
98.5 portions
11.5 parts of modified master batch
High mixing ratio
Example 6:
polyethylene pellet resin (ethylene, hexene-1 copolymerization, slurry catalyst synthesis, MFR =2.0g/10 mm, density 0.920g/cm3）
98 portions of
Modified master batch 22 parts
Length-diameter ratio of screw: 30
Screw combination: 7-section shear block and 3-section reverse shear
Processing temperature: 190 deg.C
Example 7:
polyethylene pellet resin (ethylene, butene-1 copolymerization, slurry catalyst synthesis, MFR =2.0g/10 mm, density 0.920g/cm3）
99 portions of
31 parts of modified master batch
Screw length-diameter ratio 35 parts
Screw combination: 5-section shear block and 4-section reverse shear
Processing temperature: 180 deg.C
Example 8:
polyethylene pellet resin (ethylene, hexene-1 copolymerized, MFR =2.0g/10 mm, density 0.920g/cm3) 98 portions of
42 parts of modified master batch
High mixing ratio
Comparative example 1:
after mixing, high-speed stirring and section mixing, performing double-screw granulation, and combining screws: 5-section fast shearing and 3-section reverse shearing
Comparative example 2:
granulating by using a double screw after mixing by using a high-speed stirrer, and combining screws: 8-section fast shearing and 3-section reverse shearing
Comparative example 3:
granulating by using a double screw after mixing by using a high-speed stirrer, and combining screws: 6-section fast shearing and 3-section reverse shearing
Comparative example 4:
granulating by using a double screw after mixing by using a high-speed stirrer, and combining screws: 6-section fast shearing and 3-section reverse shearing
The performance evaluation of the films prepared in examples 1 to 8 and comparative examples 1 to 4 is shown in Table 1.
Table 1: comparison of film Properties
As can be seen from Table 1, the optical properties and tear strength of the film prepared from the polyethylene composition containing A, B two kinds of nucleating agents are higher than those of the film prepared from the polyethylene composition containing no nucleating agent or only one kind of nucleating agent, wherein the haze can be reduced by more than 60% at most, and the tear strength can be improved by more than 40%, which indicates that the combination properties of the film can be improved well by adding the two kinds of nucleating agents into the film.

Claims (9)

1. A modified master batch applied to a polyethylene film is characterized by being prepared from the following raw materials in parts by weight: 100 parts of polyethylene powder resin, 0.025-0.15 part of antioxidant, 3-15 parts of nucleating agent A and 3-15 parts of nucleating agent B, wherein the nucleating agent A is selected from hexahydrophthalic acid metal salt, and the nucleating agent B is selected from sorbitol and derivatives thereof;
wherein,
the antioxidant is selected from hindered phenol antioxidants, or hindered phenol antioxidants and phosphite antioxidant systems, or hindered phenol antioxidants, phosphite antioxidants and thioester antioxidant systems, wherein the mass ratio of the hindered phenol antioxidants to the phosphite antioxidants in the hindered phenol antioxidants and phosphite antioxidant systems is 1: 0.1 to 5; in a hindered phenol antioxidant, phosphite antioxidant and thioester antioxidant system, the mass ratio of the phosphite antioxidant to the thioester antioxidant to the hindered phenol antioxidant is 0.1-15: 1, wherein the mass ratio of the phosphite antioxidant to the thioester antioxidant is 1: 0.1 to 4.
2. The modified master batch applied to the polyethylene film as claimed in claim 1, wherein the antioxidant is 0.03-0.1 part by weight.
3. The modified masterbatch applied to polyethylene film as claimed in claim 1, wherein the phosphite antioxidant has a melting point of 160-250 ℃ and is selected from tris (2, 4-di-tert-butylphenyl) phosphite or pentaerythritol bis (2, 4-di-tert-butylphenyl) phosphite.
4. The modified master batch for polyethylene film according to claim 1, wherein the thioester antioxidant is selected from the group consisting of dioctadecyl thiodipropionate and dilauryl thiodipropionate.
5. The modified master batch for polyethylene films as claimed in claim 1, wherein the nucleating agent A is calcium hexahydrophthalate.
6. A preparation method of the modified master batch applied to the polyethylene film as claimed in claim 1, wherein the raw materials are added into a high-speed stirrer to be mixed for 5-10 min, and then the uniformly mixed materials are added into a double-screw extruder to be melted, plasticized, extruded and granulated according to the conventional process.
7. A using method of the modified master batch applied to the polyethylene film, as claimed in claim 1, is characterized in that the polyethylene pellet resin and the modified master batch are added into a high-speed stirrer, mixed for 5-10 min, and then the uniformly mixed materials are added into a double-screw extruder for melting, plasticizing, extruding and granulating, wherein the length-diameter ratio of screws of the double-screw extruder is 28-40; the screw combination is provided with 3-9 sections of shear blocks, wherein the shear blocks comprise 1-5 sections of reverse shear blocks; the processing temperature is 180-220 ℃.
8. A using method of the modified master batch applied to the polyethylene film as claimed in claim 1, wherein the polyethylene pellet resin and the modified master batch are added into a high-speed stirrer to be mixed for 5-10 min, and then the materials are discharged for direct film blowing.
9. The use method of the modified master batch applied to the polyethylene film as claimed in claim 7 or 8, wherein the content of the nucleating agent A is 300-2000 ppm and the content of the nucleating agent B is 300-2000 ppm in the total material of the polyethylene pellet resin and the modified master batch.
CN201210215556.3A 2012-06-27 2012-06-27 Be applied to the modified master of polyethylene film and preparation thereof, using method Active CN103509230B (en)

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CN104231400A (en) * 2014-09-24 2014-12-24 句容市给力包装制品厂 Plastic packaging film and preparation method thereof
CN106496802B (en) * 2015-09-07 2019-09-03 中国石油天然气股份有限公司 High-density polyethylene resin for melt-blown composite fiber
CN111100347A (en) * 2018-10-25 2020-05-05 中国石油化工股份有限公司 High-pressure polyethylene resin composition for repackaging film and preparation method thereof
CN111100233B (en) * 2018-10-25 2023-07-25 中国石油化工股份有限公司 Synthetic method of high-pressure polyethylene for repackaging film
CN110577702A (en) * 2019-09-30 2019-12-17 东华能源(宁波)新材料有限公司 Transparent rigidity-toughness balanced thermoforming homo-polypropylene resin and preparation method and application thereof
CN112759814B (en) * 2019-11-01 2022-09-20 中国石油化工股份有限公司 Polyethylene film and preparation method thereof
CN114426726A (en) * 2020-10-29 2022-05-03 中国石油化工股份有限公司 Polyethylene material and preparation method and application thereof

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