CN112175295A - Preparation method of polypropylene film layer for improving barrier property - Google Patents
Preparation method of polypropylene film layer for improving barrier property Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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- 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
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- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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Abstract
The invention discloses a preparation method of a polypropylene film layer for improving barrier property, which comprises the following steps: (1) in the presence of hydrogen, styrene derivatives are used as chain transfer agents, and a catalytic system consisting of metallocene catalysts and alkylaluminoxane cocatalyst is used for catalyzing propylene to polymerize to obtain isotactic polypropylene; (2) blending the isotactic polypropylene with random copolymerization polypropylene, isotactic polypropylene-b-polyethylene glycol diblock copolymer, polyvinyl alcohol, silicon dioxide modifier, nucleating agent and compatilizer, fully melting and blending in a screw extruder after blending, and then extruding and biaxially stretching to obtain the polypropylene film layer; the nucleating agent is a beta-crystal form nucleating agent. The aluminum plastic film prepared by the polypropylene film layer provided by the invention has the advantages of better gas-liquid barrier property, stronger safety, longer service life and good application prospect.
Description
Technical Field
The invention relates to the field of polypropylene packaging materials, in particular to a preparation method of a polypropylene film layer for improving barrier property.
Background
The green high-energy environment-friendly lithium ion battery appeared in 90 s of the 20 th century becomes one of the most spotlighted power sources due to the advantages of high energy density, long cycle life, high working voltage and the like. In recent years, with the increase of lithium battery technology and output, the demand of lithium battery packaging materials is increasing, at present, lithium battery packages can be divided into four types, namely a plastic shell, a steel shell, an aluminum shell and an aluminum-plastic film, and the aluminum-plastic film material becomes one of main packaging materials of the lithium battery due to the advantages of light weight, good formability and the like. The quality of lithium battery packaging directly relates to the yield and service life of the lithium battery, wherein the packaging is important for the barrier property of moisture, oxygen and the like.
The aluminum plastic film widely used at present is divided into three layers: the outer layer is a protective layer, the middle layer is an aluminum foil, and the inner layer is a bonding layer. Since polypropylene molecules are polymerized by non-polar propylene catalysis, and carbon-carbon and carbon-hydrogen saturated bonds are adopted in the molecular structure, the polypropylene has excellent electrical insulation and chemical stability, and thus, the polypropylene is widely used in adhesive layers. However, the gas barrier property of polypropylene is very poor, and most of the currently used high-barrier polymers are polar polymers, and the interaction between the high-barrier polymers and the non-polar polypropylene matrix interface is weak, so that a gap exists between the high-barrier polymers and the non-polar polypropylene matrix interface, and the gap increases the gas transmittance, so that the barrier property of the polypropylene film layer cannot be enhanced.
Therefore, how to provide a polypropylene film layer with barrier property is a technical problem to be solved urgently by those skilled in the art.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a polypropylene film layer with improved barrier property, which takes isotactic polypropylene and random copolymer polypropylene as raw materials, and realizes the purpose of enhancing the barrier property by adding other auxiliary agents for mutual matching.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a polypropylene film layer for improving barrier property specifically comprises the following steps:
(1) in the presence of hydrogen, styrene derivatives are used as chain transfer agents, and a catalytic system consisting of metallocene catalysts and alkylaluminoxane cocatalyst is used for catalyzing propylene to polymerize to obtain isotactic polypropylene;
(2) blending the isotactic polypropylene with random copolymerization polypropylene, isotactic polypropylene-b-polyethylene glycol diblock copolymer, polyvinyl alcohol, silicon dioxide modifier, nucleating agent and compatilizer, fully melting and blending in a screw extruder after blending, and then extruding and biaxially stretching to obtain the polypropylene film layer;
the nucleating agent is a beta-crystal form nucleating agent.
Adopt above-mentioned technical scheme's beneficial effect:
according to the invention, polyvinyl alcohol is added in the preparation process of the polypropylene film layer, and the polyvinyl alcohol has excellent oxygen resistance;
the invention also adds modified silicon dioxide, under the action of biaxial tension, heterogeneous nucleation of the modified silicon dioxide promotes the crystallization of the polypropylene resin, bundles of columnar (fibrous) crystals are formed in the transverse direction and the longitudinal direction of the film, and the longitudinal fiber bundles and the transverse fiber bundles (columnar crystals) are interwoven into a net structure. The amorphous polypropylene is filled among the fiber bundles, so that on one hand, the mechanical strength of the polypropylene film is improved, and the number and the length of cracks on the surface of the modified polypropylene film are reduced; on the other hand, the polypropylene film is beneficial to forming a compact structure on the surface of the polypropylene film and reducing the diffusion of organic solvent, oxygen and water vapor from the outside to the inside of the film, thereby improving the barrier property of the polypropylene film;
through a large number of scientific experiments, the inventor of the invention also finds that the beta-crystal form nucleating agent is added in the preparation process of the polypropylene film layer, the proportion of refined crystals is improved through melting and stretching, gaps among the crystals can be reduced, and the barrier property of the product is improved.
Preferably, the chain transfer agent in the step (1) is any one of m-divinylbenzene, p-divinylbenzene, 1, 2-bis (4-vinylbenzene) ethane and 4, 4-divinylbiphenyl.
Preferably, the metallocene catalyst in the step (1) is rac-Me2C(2-t-Bu-Cp)2ZrCl2、 rac-Me2Si(2-Me-4-Naph-Ind)2ZrCl2、rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2、 rac-Me2Si(2-Me-Ind)2ZrCl2Any one of them.
Preferably, the preparation method of the isotactic polypropylene comprises the following steps: in the dry reactor, the amounts of the reaction raw materials and the catalyst added per 50ml of the toluene solvent were: adding 20-40 mmol of alkylaluminoxane, 10-15 mol of chain transfer agent and 0.01-0.02 mmol of metallocene catalyst, and introducing 5-10 mmol of hydrogen; introducing propylene gas at the reaction temperature of 15-50 ℃, and keeping the reaction pressure of the propylene at 1-8 atmospheric pressures; after the reaction is finished, the isotactic polypropylene is obtained.
Preferably, the compatilizer is isotactic polypropylene-b-polyethylene glycol diblock polymer.
Adopt above-mentioned technical scheme's beneficial effect: the isotactic polypropylene-b-polyethylene glycol diblock copolymer is used as a compatilizer, so that the isotactic polypropylene and polyvinyl alcohol have good compatibility, the polyvinyl alcohol phase can be uniformly dispersed in the polypropylene resin, a secondary continuous phase or lamellar structure is formed, and the barrier property of the polypropylene film is improved.
Preferably, the beta-crystal nucleating agent is one or more of aromatic amine nucleating agent, rare earth complex nucleating agent and fused ring compound nucleating agent.
Preferably, the beta crystal form nucleating agent is any one of 2, 6-cyclohexane dicarboxamide and N' N-dicyclohexyl-2, 6-naphthalene diamide.
Preferably, the preparation method of the silica modifier comprises the following steps:
s1, carrying out polymerization reaction by using vinyl acetate, allyl glycidyl ether and an initiator to obtain a vinyl acetate-allyl glycidyl ether copolymer;
s2, modifying silicon dioxide by using the vinyl acetate-allyl glycidyl ether copolymer to obtain the silicon dioxide modifier.
Preferably, the weight ratio of the vinyl acetate to the allyl glycidyl ether in the S1 is (95-97): 3-5; the mass ratio of the silicon dioxide to the vinyl acetate-allyl glycidyl ether copolymer in the S2 is (15-18): 82-85.
The initiator in the present invention may be an initiator commonly used in the art, such as benzoyl peroxide, lauroyl peroxide, etc.
Adopt above-mentioned technical scheme's beneficial effect: both the polyvinyl acetate chain segment and the allyl glycidyl ether contain polar groups, so that the polyvinyl acetate chain segment and the allyl glycidyl ether have good compatibility with silicon dioxide. The copolymer of allyl glycidyl ether and polyvinyl acetate is used for coating and modifying the nano silicon dioxide, which is beneficial to improving the dispersibility of the modifying agent silicon dioxide.
Preferably, the raw materials comprise the following components in parts by weight: 25-45 parts of isotactic polypropylene, 15-35 parts of random copolymerization polypropylene, 5-15 parts of isotactic polypropylene-b-polyethylene glycol diblock copolymer, 15-25 parts of polyvinyl alcohol, 3-5 parts of silicon dioxide modifier, 1-3 parts of nucleating agent and 1-5 parts of compatilizer.
The invention further provides the polypropylene film layer with the improved barrier property, which is prepared by the preparation method of the polypropylene film layer with the improved barrier property.
Through the technical scheme, compared with the prior art, the beneficial effects of the invention comprise the following points:
(1) according to the invention, by optimizing the formula and the preparation method, the components have good intermiscibility, uniform dispersion and interaction, and the barrier property of the polypropylene film layer is improved;
(2) the preparation method is simple, the raw materials are easy to obtain, the cost is low, the production period is short, and the method is suitable for large-scale popularization;
(3) the aluminum plastic film prepared by the polypropylene film layer provided by the invention has the advantages of better gas-liquid barrier property, stronger safety, longer service life and good application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a preparation method of a polypropylene film layer for improving barrier property, which specifically comprises the following steps:
(1) preparing isotactic polypropylene: in the dry reactor, the amounts of the reaction raw materials and the catalyst added per 50ml of the toluene solvent were: adding 25mmol of alkylaluminoxane, 15mol of chain transfer agent and 0.02mmol of metallocene catalyst, and introducing 10mmol of hydrogen; introducing propylene gas at the reaction temperature of 50 ℃, and keeping the reaction pressure of the propylene at 1 atmospheric pressure; after the reaction is finished, isotactic polypropylene is obtained; wherein the chain transfer agent is m-divinylbenzene, and the metallocene catalyst is rac-Me2C(2-t-Bu-Cp) 2ZrCl2The cocatalyst is methylaluminoxane;
(2) preparing a silicon dioxide modifier:
s1, carrying out polymerization reaction by using vinyl acetate, allyl glycidyl ether and an initiator to obtain a vinyl acetate-allyl glycidyl ether copolymer;
s2, modifying silicon dioxide by using the vinyl acetate-allyl glycidyl ether copolymer to obtain a silicon dioxide modifier, wherein the weight ratio of vinyl acetate to allyl glycidyl ether is 97: 3; the mass ratio of the silicon dioxide to the vinyl acetate-allyl glycidyl ether copolymer is 15: 85;
(3) 25 parts of isotactic polypropylene, 15 parts of random copolymer polypropylene, 5 parts of isotactic polypropylene-b-polyethylene glycol diblock copolymer, 15 parts of polyvinyl alcohol, 3 parts of silicon dioxide modifier, 1 part of 2, 6-phthalic acid cyclohexylamide and 1 part of isotactic polypropylene-b-polyethylene glycol diblock copolymer, fully melting and blending in a screw extruder after blending, and then extruding and biaxially stretching to obtain the polypropylene film layer with the thickness of 30 microns.
Example 2
(1) Preparing isotactic polypropylene: in the dry reactor, the amounts of the reaction raw materials and the catalyst added per 50ml of the toluene solvent were: adding 30mmol of alkylaluminoxane, 12mol of chain transfer agent and 0.015mmol of metallocene catalyst, and introducing 5mmol of hydrogen; introducing propylene gas at the reaction temperature of 15 ℃, and keeping the reaction pressure of the propylene at 8 atmospheric pressures; after the reaction is finished, isotactic polypropylene is obtained; wherein the chain transfer agent is p-divinylbenzene, and the metallocene catalyst is rac-Me2Si(2-Me-4-Naph-Ind)2ZrCl2The cocatalyst is ethyl aluminoxane;
(2) preparing a silicon dioxide modifier:
s1, carrying out polymerization reaction by using vinyl acetate, allyl glycidyl ether and an initiator to obtain a vinyl acetate-allyl glycidyl ether copolymer;
s2, modifying silicon dioxide by using the vinyl acetate-allyl glycidyl ether copolymer to obtain a silicon dioxide modifier, wherein the weight ratio of vinyl acetate to allyl glycidyl ether is 96: 4; the mass ratio of the silicon dioxide to the vinyl acetate-allyl glycidyl ether copolymer is 16: 84;
(3) 35 parts of isotactic polypropylene, 25 parts of random copolymer polypropylene, 10 parts of isotactic polypropylene-b-polyethylene glycol diblock copolymer, 20 parts of polyvinyl alcohol, 4 parts of silicon dioxide modifier, 2 parts of N' N-dicyclohexyl-2, 6-naphthalene diamide and 3 parts of isotactic polypropylene-b-polyethylene glycol diblock copolymer, fully melting and blending in a screw extruder after blending, and then extruding and biaxially stretching to obtain the polypropylene film layer with the thickness of 28 microns.
Example 3
(1) Preparing isotactic polypropylene: in the dry reactor, the amounts of the reaction raw materials and the catalyst added per 50ml of the toluene solvent were: adding 20mmol of alkylaluminoxane and 10mol of chain transferTransferring agent and 0.01mmol metallocene catalyst, and introducing 5mmol hydrogen; introducing propylene gas at the reaction temperature of 20 ℃, and keeping the reaction pressure of the propylene at 2 atmospheric pressures; after the reaction is finished, isotactic polypropylene is obtained; wherein the chain transfer agent is 1, 2-bis (4-vinyl benzene) ethane, and the metallocene catalyst is rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2The cocatalyst is isobutyl aluminoxane;
(2) preparing a silicon dioxide modifier:
s1, carrying out polymerization reaction by using vinyl acetate, allyl glycidyl ether and an initiator to obtain a vinyl acetate-allyl glycidyl ether copolymer;
s2, modifying silicon dioxide by using the vinyl acetate-allyl glycidyl ether copolymer to obtain a silicon dioxide modifier, wherein the weight ratio of vinyl acetate to allyl glycidyl ether is 96: 4; the mass ratio of the silicon dioxide to the vinyl acetate-allyl glycidyl ether copolymer is 17: 83;
(3) 40 parts of isotactic polypropylene, 20 parts of random copolymer polypropylene, 12 parts of isotactic polypropylene-b-polyethylene glycol diblock copolymer, 23 parts of polyvinyl alcohol, 4 parts of silicon dioxide modifier, 1.5 parts of 2, 6-cyclohexane diformate and 2.5 parts of isotactic polypropylene-b-polyethylene glycol diblock copolymer, fully melting and blending in a screw extruder after blending, and then extruding and biaxially stretching to obtain the polypropylene film layer with the thickness of 25 micrometers.
Example 4
(1) Preparing isotactic polypropylene: in the dry reactor, the amounts of the reaction raw materials and the catalyst added per 50ml of the toluene solvent were: adding 40mmol of alkylaluminoxane, 15mol of chain transfer agent and 0.02mmol of metallocene catalyst, and introducing 10mmol of hydrogen; introducing propylene gas at the reaction temperature of 40 ℃, and keeping the reaction pressure of the propylene at 4 atmospheric pressures; after the reaction is finished, isotactic polypropylene is obtained; wherein the chain transfer agent is 4, 4-divinyl biphenyl, and the metallocene catalyst is rac-Me2Si(2-Me-Ind)2ZrCl2The cocatalyst is isobutyl aluminoxane;
(2) preparing a silicon dioxide modifier:
s1, carrying out polymerization reaction by using vinyl acetate, allyl glycidyl ether and an initiator to obtain a vinyl acetate-allyl glycidyl ether copolymer;
s2, modifying silicon dioxide by using the vinyl acetate-allyl glycidyl ether copolymer to obtain a silicon dioxide modifier, wherein the weight ratio of vinyl acetate to allyl glycidyl ether is 95: 5; the mass ratio of the silicon dioxide to the vinyl acetate-allyl glycidyl ether copolymer is 18: 82;
(3) 45 parts of isotactic polypropylene, 35 parts of random copolymer polypropylene, 15 parts of isotactic polypropylene-b-polyethylene glycol diblock copolymer, 25 parts of polyvinyl alcohol, 5 parts of silicon dioxide modifier, 3 parts of 2, 6-phthalic acid cyclohexylamide and 5 parts of isotactic polypropylene-b-polyethylene glycol diblock copolymer, fully melting and blending in a screw extruder after blending, and then extruding and biaxially stretching to obtain the polypropylene film layer with the thickness of 20 microns.
Test examples
The polypropylene film layers obtained in examples 1 to 4 were tested for their properties.
Preparing the aluminum-plastic composite film: the thickness of the aluminum foil is 50 microns, the thickness of the nylon is 30 microns, after the two sides of the aluminum foil are passivated, the dark side of the aluminum foil is coated with an outer layer adhesive to be in dry compounding with the nylon, then an inner layer petroleum resin adhesive is extruded to the bright side of the aluminum foil through a melting extruder, and the aluminum foil is thermally compounded with the polypropylene film layers in the embodiments 1-4, so that the prepared aluminum-plastic composite film is obtained.
Electrolyte resistance performance test: cutting the aluminum-plastic film into samples with the diameter of 15mm multiplied by 100mm, soaking the samples in electrolyte with the composition of EC/DEC/DMC of 1:1:1+1mol/L LiFeF for 14 days at 80 DEG C6+1000ppm H2And O, taking out the sample, washing the residual electrolyte, and testing the peel strength between the polypropylene film and the aluminum foil of the sample at the testing speed of 100 mm/min.
Barrier properties: according to the GB/T1037 plastic film sheet water vapor permeability pattern method, the aluminum-plastic composite film is formed with humidity difference at 35 ℃ and 90% RH humidity, the water vapor permeates the sample in the moisture permeable cup and enters the dry side, and the change of the weight of the moisture permeable cup along with the time is measured, so that the water vapor transmission coefficient of the sample is obtained.
The oxygen transmission is measured in ASTM D3985-1995 test method for oxygen transmission on plastic films and sheets using an electric quantity sensor.
The results of the performance tests of the aluminum-plastic films obtained by thermal compounding the polypropylene films of examples 1-4 are shown in Table 1:
table 1: test results of aluminum-plastic composite film performance
As can be seen from the data in the table, the aluminum-plastic films prepared from the polypropylene film layers prepared in examples 1 to 4 have low water vapor and oxygen transmission coefficients, so that the barrier property of the aluminum-plastic film and the sealing property after packaging of the lithium battery are remarkably improved.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. 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 invention. Thus, the present invention 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.
Claims (10)
1. A preparation method of a polypropylene film layer for improving barrier property is characterized by comprising the following steps:
(1) in the presence of hydrogen, styrene derivatives are used as chain transfer agents, and a catalytic system consisting of metallocene catalysts and alkylaluminoxane cocatalyst is used for catalyzing propylene to polymerize to obtain isotactic polypropylene;
(2) blending the isotactic polypropylene with random copolymerization polypropylene, polyvinyl alcohol, a silicon dioxide modifier, a nucleating agent and a compatilizer, fully melting and blending in a screw extruder after blending, and then extruding and biaxially stretching to obtain the polypropylene film layer;
the nucleating agent is a beta-crystal form nucleating agent.
2. The method for preparing a polypropylene film layer with improved barrier property as claimed in claim 1, wherein the chain transfer agent in step (1) is any one of m-divinylbenzene, p-divinylbenzene, 1, 2-bis (4-vinylbenzene) ethane and 4, 4-divinylbiphenyl.
3. The method for preparing a polypropylene film layer with improved barrier property according to claim 2, wherein the metallocene catalyst in the step (1) is rac-Me2C(2-t-Bu-Cp)2ZrCl2、rac-Me2Si(2-Me-4-Naph-Ind)2ZrCl2、rac-Me2Si(2-Me-4-Ph-Ind)2ZrCl2、rac-Me2Si(2-Me-Ind)2ZrCl2Any one of them.
4. The method for preparing a polypropylene film layer with improved barrier property as claimed in claim 1, wherein the compatibilizer is isotactic polypropylene-b-polyethylene glycol diblock copolymer.
5. The preparation method of the polypropylene film layer with the improved barrier property according to claim 1, wherein the beta-crystalline nucleating agent is one or more of aromatic amine nucleating agents, rare earth complex nucleating agents and condensed ring compound nucleating agents.
6. The method for preparing a polypropylene film layer with improved barrier property as claimed in claim 5, wherein the beta-crystalline nucleating agent is 2, 6-cyclohexane dicarboxamide or N' N-dicyclohexyl-2, 6-naphthalene diamide.
7. The method for preparing a polypropylene film layer with improved barrier property according to claim 1, wherein the method for preparing the silica modifier comprises the following steps:
s1, carrying out polymerization reaction by using vinyl acetate, allyl glycidyl ether and an initiator to obtain a vinyl acetate-allyl glycidyl ether copolymer;
s2, modifying silicon dioxide by using the vinyl acetate-allyl glycidyl ether copolymer to obtain the silicon dioxide modifier.
8. The method as claimed in claim 7, wherein the weight ratio of vinyl acetate to allyl glycidyl ether in S1 is (95-97): 3-5); the mass ratio of the silicon dioxide to the vinyl acetate-allyl glycidyl ether copolymer in the S2 is (15-18): 82-85.
9. The preparation method of the polypropylene film layer with the improved barrier property according to any one of claims 1 to 8, wherein the raw materials comprise, by weight: 25-45 parts of isotactic polypropylene, 15-35 parts of random copolymerization polypropylene, 5-15 parts of isotactic polypropylene-b-polyethylene glycol diblock copolymer, 15-25 parts of polyvinyl alcohol, 3-5 parts of silicon dioxide modifier, 1-3 parts of nucleating agent and 1-5 parts of compatilizer.
10. A barrier property-improved polypropylene film layer, wherein the polypropylene film layer is prepared by the barrier property-improved polypropylene film layer preparation method of any one of claims 1 to 9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851305A (en) * | 2009-04-03 | 2010-10-06 | 中国科学院化学研究所 | Isotactic polypropylene capped with styrene group and preparation method thereof |
| CN107586413A (en) * | 2017-09-15 | 2018-01-16 | 北京印刷学院 | Modified polypropene film and preparation method thereof |
| CN109293958A (en) * | 2018-09-25 | 2019-02-01 | 宁波瑞成包装材料有限公司 | A kind of production method of low haze high barrier polypropylene screen |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851305A (en) * | 2009-04-03 | 2010-10-06 | 中国科学院化学研究所 | Isotactic polypropylene capped with styrene group and preparation method thereof |
| CN107586413A (en) * | 2017-09-15 | 2018-01-16 | 北京印刷学院 | Modified polypropene film and preparation method thereof |
| CN109293958A (en) * | 2018-09-25 | 2019-02-01 | 宁波瑞成包装材料有限公司 | A kind of production method of low haze high barrier polypropylene screen |
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Application publication date: 20210105 |