CN109968762A - A kind of aluminum-plastic composite membrane cast polypropylene film and preparation method thereof - Google Patents

A kind of aluminum-plastic composite membrane cast polypropylene film and preparation method thereof Download PDF

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Publication number
CN109968762A
CN109968762A CN201811578425.5A CN201811578425A CN109968762A CN 109968762 A CN109968762 A CN 109968762A CN 201811578425 A CN201811578425 A CN 201811578425A CN 109968762 A CN109968762 A CN 109968762A
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layer
aluminum
composite membrane
plastic composite
polypropylene film
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CN109968762B (en
Inventor
程跃
陈滨
王小明
贾江恒
田俊斌
仲松华
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Jiangxi Tongrui New Energy Technology Development Co Ltd
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Jiangxi Tongrui New Energy Technology Development Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/085—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
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    • B32B7/08—Interconnection of layers by mechanical means
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    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C08L23/10—Homopolymers or copolymers of propene
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    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H01M50/124—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material having a layered structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B2037/1269—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives multi-component adhesive
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    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
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    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • C08L2205/00—Polymer mixtures characterised by other features
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of aluminum-plastic composite membrane cast polypropylene films and preparation method thereof, the three-layer co-extruded cast polypropylene film be cast by the way of three-layer co-extruded as three extrusion heads of melt extruder obtained by, it successively includes plasma treated layer, sandwich layer and hot sealing layer, and plasma treated layer is mainly made of atactic copolymerized polypropene, maleic anhydride modified polypropylene, polyolefin elastomer；Sandwich layer is mainly made of homopolypropylene, organic modification nano silica and polyolefin elastomer；And hot sealing layer is mainly made of random or block copolymerization polypropylene, polyolefin elastomer and slipping agent.The application heat conductivity and flexibility high due to the CPP film enhance the service life and purposes of aluminum-plastic composite membrane so that having by aluminum-plastic composite membrane made of thermal method process combining more resistant to scouring depth molding, being easier to low-temperature heat-sealing, more resistant to the performance of electrolyte.

Description

A kind of aluminum-plastic composite membrane cast polypropylene film and preparation method thereof
Technical field
The present invention relates to aluminum-plastic composite membrane production technical fields, are a kind of aluminum-plastic composite membrane curtain coatings poly- third specifically Alkene film and preparation method thereof.
Background technique
Lithium battery flexible packaging has become a using more and more extensive manner of packing, and primary structure is by trilamellar membrane Material cladding forms, and is followed successively by protective layer, aluminium foil layer and hot sealing layer from outside to inside, and usual protective layer is the nylon of biaxial tension Film, hot sealing layer are cast polypropylene (CPP).The electrolyte of lithium battery includes a variety of organic solvents and lithium salts, and lithium salts meets water meeting The hydrofluoric acid for generating strong corrosive rapidly, once having corroded CPP or even having destroyed the adhesive layer of plastic-aluminum combined film inner layer, and is destroyed Aluminium foil surface can be such that CPP interlayer heat-sealing effect variation and CPP separates with aluminium foil, and lithium battery flatulence, leakage failure etc. is caused to ask Topic.
Currently, a kind of heat-sealable material of the CPP film as aluminum-plastic composite membrane, there are still some problems.When such as scouring depth molding, Stress whitening easily occurs for toughness and the bad CPP film of intensity, or even the status broken through；High-temperature process can make CPP film surface Slipping agent change, the control of coefficient of friction between the surface hot sealing layer CPP and scouring depth mold is not easy, and is also influenced plastic-aluminum combined The scouring depth of film forms, and heat-sealing effect when heat-sealing between CPP film also can be bad, influences the electrolyte resistance performance of aluminum-plastic composite membrane.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of aluminum-plastic composite membrane cast polypropylene films And preparation method thereof.The caking property for improving adhesive layer and aluminium foil, improves the electrolyte resistance of aluminum-plastic composite membrane；Sandwich layer has height The organic modification nano silica of thermal conductivity, enhances plastic-aluminum combined film strength, flexibility and low temperature heat seal；Heat-sealing The high temperature resistant slipping agent contained in layer, so that the molding of aluminum-plastic composite membrane scouring depth is more stable, to keep lithium battery encapsulation plastic-aluminum multiple It is more excellent to close film properties of product.
The purpose of the present invention is achieved through the following technical solutions:
A kind of aluminum-plastic composite membrane cast polypropylene film, it is total using three layers by three extrusion heads of melt extruder Crowded mode is cast gained, successively includes plasma treated layer, sandwich layer and hot sealing layer.
The overall thickness of the aluminum-plastic composite membrane cast polypropylene film is 30~80 microns, and corona treatment Thickness ratio between every layer of layer, sandwich layer and hot sealing layer is 1: 3: 1.
Plasma treated layer is made of atactic copolymerized polypropene, maleic anhydride modified polypropylene and polyolefin elastomer, Composition ratio is 65~80%:10~15%:10~15%.
Sandwich layer is by homopolypropylene, and organic modification nano silica and polyolefin elastomer are made, composition ratio For 65~75%:5~10%:15~30%.
Hot sealing layer is made of random or block copolymerization polypropylene, polyolefin elastomer and slipping agent, composition ratio be 70~ 80%:15~25%:1~5%.
Film surface is carried out centainly by Surface Treatment with Plasma machine preferably, the corona treatment refers to Physical and chemical modified come change plasma treated layer surface surface roughness and surface molecular activity, improve plasma Handle the adhesive force of layer surface and aluminium foil.Compared with sided corona treatment, have treatment effeciency height, ozone etc. endanger gas discharge less, The advantages that not limited to by article size.Preferably, the maleic anhydride modified polypropylene in the plasma treated layer, tool There is high reactivity, improve the caking property of CPP film and aluminium foil, so that aluminum-plastic composite membrane is more resistant to electrolyte.
Preferably, the nanoscale organized improved silica in the sandwich layer containing high heat conductance, fast heat is passed Rate and high flexibility are led, mouldability when thermal conduction rate and scouring depth when improving aluminum-plastic composite membrane low-temperature heat-sealing.
The thermal conductivity of silica is 30 times of plain polypropylene or more, therefore can increase thermal conduction rate when heat-sealing, and Nanoscale silica also has the advantages that the large and small dimensional effect of surface area, macro quanta tunnel effect etc., and resin can be improved Intensity and flexibility.
The purpose of nanoscale silica organic modification is to be to reduce its polarity, improves its phase with resin matrix Capacitive, the key step of organic modification are as follows:
(3) preparation of nano silica:
Using sol-gel method, tetraethyl orthosilicate, ethyl alcohol, deionized water are configured to solution by volume at 1: 2: 2, 1h is stirred at 75 DEG C, it is uniformly mixed, adds cetylamine, the volume ratio of tetraethyl orthosilicate and cetylamine is 3: 2, continue to stir 1h, for control solution pH value 6 or so, room temperature, which is aged, is made milk white gel；Gel obtained is put into 650 DEG C Muffle furnace high temperature roast 1.5h, can be prepared by nano silica powder；
(4) activation of nano silica:
Dry silica is placed in 250 DEG C of high-temperature activation 5h in sand-bath under the protection of nitrogen, obtains activation nanometer Silica；
(3) organic modification of nano silica:
Octanol is added in activation nano silica, under the catalysis of p-methyl benzenesulfonic acid, 120 DEG C of heating stirring 1h, then It flows back after 1h, with washes of absolute alcohol product 3 times, drying obtains organic modification nano silica.
The mass ratio for activating nano silica and octanol is 1: 5；
Activate the mass ratio 25: 1 of nano silica and toluenesulfonic acid；
Preferably, the slipping agent in the hot sealing layer is that the silicone master batch using polypropylene as carrier makes more resistant to high temperature Its stable friction factor is obtained, the confficient of static friction for sealing layer surface is 0.12~0.2, and dynamic friction coefficient is 0.1~0.2, centainly Improve to degree the stability when molding of aluminum-plastic composite membrane scouring depth.
The component of slipping agent is atactic copolymerized polypropene and silicone, and the mass ratio of the two is 1: 1.1.
The preparation method of slipping agent is, the specific steps are that: mass ratio be 1: 1.1 polypropylene and silicone master batch one It is uniformly mixed under conditions of fixed, after adding respective additive, reaction is squeezed out and is granulated, and passes through chemical grafting method It is 50% using atactic copolymerized polypropene as the silicone slipping agent of carrier that silicone content, which is made, due to its characteristic resistant to high temperature, no It is easily precipitated, avoids influence of the high temperature to frosting coefficient of friction.
Polyolefin elastomer in the CPP film is that propylene-based elastomeric, based elastomers, ethylene-acrylic acid are total Polymers, the one of which of rubber modified polypropylene polymer or two kinds.
The CPP, which passes through aluminum-plastic composite membrane made of thermal method process combining, to be had more resistant to scouring depth molding, is easier to low-temperature heat-sealing, more The performance of electrolyte resistance.
A kind of preparation method of aluminum-plastic composite membrane cast polypropylene film, the specific steps are that:
(1) outer layer adhesive is applied to the acid passivation on double surfaces of liquid containing chromium passivating processing in the way of intaglio plate roller coating The aluminium foil dark face crossed, it is compound with BON biaxially oriented nylon film dry type after drying tunnel is dried.Aluminium foil passivation temperature is 200~220 DEG C, it is 80~150 DEG C that heat, which dries temperature, and compound hot pressing temperature is 100~150 DEG C:
The outer layer adhesive is polyurethane resin and polyisocyanate curing agent.
(2) the extrusion coated bright face of aluminium foil to composite nylon of inner layer resin adhesive is squeezed out using melt extruder Temperature is 160~240 DEG C, so that aluminum-plastic composite membrane be made.
The inner layer resin adhesive is acid-modified polyolefin resin and epoxy curing agent.
Compared with prior art, the positive effect of the present invention is:
The plasma treated layer of the application CPP film and the adhesion strength of aluminium foil layer enhance；There is sandwich layer high heat to pass The property led, more preferably intensity and flexibility；Heat-sealing layer surface has the advantages that the coefficient of friction more stable to temperature, so that being made Aluminum-plastic composite membrane has the characteristics that form more resistant to scouring depth, is easier to low-temperature heat-sealing, more resistant to electrolyte.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of embodiments of the present invention.
Description of drawing identification:
1 nylon layer,
2 outer layer glue adhesive layers,
3 aluminium foil layers,
4 inner layer resin gluing oxidant layer,
5CPP layers,
6 plasma treated layers,
7 sandwich layers,
8 hot sealing layers.
Specific embodiment
A kind of specific embodiment party of aluminum-plastic composite membrane cast polypropylene film of the present invention presented below and preparation method thereof Formula.
Embodiment 1
A kind of aluminum-plastic composite membrane is by molten with cast polypropylene film (CPP), the three-layer co-extruded cast polypropylene film Three extrusion heads for melting extruder are cast gained by the way of three-layer co-extruded, it successively includes plasma treated layer, core Layer and hot sealing layer.Plasma treated layer is mainly by atactic copolymerized polypropene, maleic anhydride modified polypropylene and polyolefin bullet Property system at, substantially composition ratio be 75%:10%:15%；Sandwich layer is mainly by homopolypropylene, organic modification nanometer two Silica and polyolefin elastomer are made, and substantially composition ratio is 65%:5%:30%；And hot sealing layer is mainly by random or embedding Section copolymer polypropylene, polyolefin elastomer and slipping agent are made, and substantially composition ratio is 80%:18%:2%.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane cast polypropylene film (CPP), the plasma treated layer Refer to that the surface CPP carries out certain physical and chemical modified to film surface by Surface Treatment with Plasma machine.
The key step of organic modification are as follows:
(1) preparation of nano silica:
Using sol-gel method, tetraethyl orthosilicate, ethyl alcohol, deionized water are configured to solution by volume at 1: 2: 2, 1h is stirred at 75 DEG C, it is uniformly mixed, adds cetylamine, the volume ratio of tetraethyl orthosilicate and cetylamine is 3: 2, continue to stir 1h, for control solution pH value 6 or so, room temperature, which is aged, is made milk white gel.Gel obtained is put into 650 DEG C Muffle furnace high temperature roast 1.5h, can be prepared by nano silica powder.
(2) activation of nano silica:
Dry silica is placed in 250 DEG C of high-temperature activation 5h in sand-bath under the protection of nitrogen, obtains activation nanometer Silica；
(3) organic modification of nano silica:
Octanol is added in activation nano silica, under the catalysis of p-methyl benzenesulfonic acid, 120 DEG C of heating stirring 1h, then It flows back after 1h, with washes of absolute alcohol product 3 times, drying obtains organic modification nano silica.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane with cast polypropylene film (CPP), contains in the CPP sandwich layer The nanoscale organized improved silica of high heat conductance has fast thermal conduction rate and high flexibility.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane cast polypropylene film (CPP), the plasma treated layer In maleic anhydride modified polypropylene, have high reactivity, improve the caking property of CPP film and aluminium foil.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane is with cast polypropylene film (CPP), it is smooth in the hot sealing layer Agent is the silicone master batch using atactic copolymerized polypropene as carrier, more resistant to high temperature, so that its stable friction factor, seals layer surface Confficient of static friction is 0.12~0.2, and dynamic friction coefficient is 0.1~0.2.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane is with cast polypropylene film (CPP), it is poly- in the CPP film Olefin elastomer is propylene-based elastomeric, based elastomers, ethylene-acrylic acid copolymer, rubber modified polypropylene polymer One of which or two kinds.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane cast polypropylene film (CPP), the total thickness of the CPP film Degree is 40 microns, and the ratio between plasma treated layer, sandwich layer and hot sealing layer thickness are 1: 3: 1.
The application is the promotion for bringing performance by adding nanoparticle in the sandwich layer of CPP；Second is that passing through plasma Processing and high temperature resistant slipping agent bring composite layer and stablizing for hot sealing layer surface property to be promoted, to make aluminum plastic film made from CPP Performance optimization.
Embodiment 2
A kind of aluminum-plastic composite membrane with cast polypropylene film (CPP), the CPP film is squeezed by three of melt extruder Head is cast gained by the way of three-layer co-extruded out, successively includes corona layer, sandwich layer and hot sealing layer.Plasma treated layer master If being made of atactic copolymerized polypropene and polyolefin elastomer, composition ratio 75%:25%；Sandwich layer is mainly gathered by homopolymerization Propylene and polyolefin elastomer are made, composition ratio 80%:20%；And hot sealing layer is mainly by random or block copolymerization poly- third Alkene, polyolefin elastomer and thermostable silicone slipping agent are made, composition ratio 80%:18%:2%.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane is with cast polypropylene film (CPP), polyene in the CPP film Olefin elastomer is propylene-based elastomeric, based elastomers, ethylene-acrylic acid copolymer, rubber modified polypropylene polymer It is one of or two kinds.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane cast polypropylene film (CPP), the plasma treated layer Refer to that the surface CPP carries out certain physical and chemical modified to film surface by Surface Treatment with Plasma machine.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane is with cast polypropylene film (CPP), it is smooth in the hot sealing layer Agent is the silicone master batch using atactic copolymerized polypropene as carrier, more resistant to high temperature, so that its stable friction factor, seals layer surface Confficient of static friction is 0.12~0.2, and dynamic friction coefficient is 0.1~0.2.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane is with cast polypropylene film (CPP), it is poly- in the CPP film Olefin elastomer is propylene-based elastomeric, based elastomers, ethylene-acrylic acid copolymer, rubber modified polypropylene polymer One of which or two kinds.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane cast polypropylene film (CPP), the total thickness of the CPP film Degree is 40 microns, and the ratio between plasma treated layer, sandwich layer and hot sealing layer thickness are 1: 3: 1.
Embodiment 3
A kind of aluminum-plastic composite membrane is by molten with cast polypropylene film (CPP), the three-layer co-extruded cast polypropylene film Three extrusion heads for melting extruder are cast gained by the way of three-layer co-extruded, it successively includes plasma treated layer, core Layer and hot sealing layer.Plasma treated layer is mainly by atactic copolymerized polypropene, maleic anhydride modified polypropylene and polyolefin bullet Property system at, substantially composition ratio be 75%:10%:15%；Sandwich layer is mainly by homopolypropylene, organic modification nanometer two Silica and polyolefin elastomer are made, and substantially composition ratio is 65%:5%:30%；And hot sealing layer is mainly by random or embedding Section copolymer polypropylene, polyolefin elastomer and slipping agent are made, and substantially composition ratio is 80%:18%:2%.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane cast polypropylene film (CPP), the plasma treated layer Refer to that the surface CPP carries out certain physical and chemical modified to film surface by Surface Treatment with Plasma machine.
The key step of organic modification are as follows:
(1) preparation of nano silica:
Using sol-gel method, tetraethyl orthosilicate, ethyl alcohol, deionized water are configured to solution by volume at 1: 2: 2, 1h is stirred at 75 DEG C, it is uniformly mixed, adds cetylamine, the volume ratio of tetraethyl orthosilicate and cetylamine is 3: 2, continue to stir 1h, for control solution pH value 6 or so, room temperature, which is aged, is made milk white gel.Gel obtained is put into 650 DEG C Muffle furnace high temperature roast 1.5h, can be prepared by nano silica powder.
(2) activation of nano silica:
Dry silica is placed in 250 DEG C of high-temperature activation 5h in sand-bath under the protection of nitrogen, obtains activation nanometer Silica；
(3) organic modification of nano silica:
Octanol is added in activation nano silica, under the catalysis of p-methyl benzenesulfonic acid, 120 DEG C of heating stirring 1h, then It flows back after 1h, with washes of absolute alcohol product 3 times, drying obtains organic modification nano silica.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane with cast polypropylene film (CPP), contains in the CPP sandwich layer The nanoscale organized improved silica of high heat conductance has fast thermal conduction rate and high flexibility.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane cast polypropylene film (CPP), the plasma treated layer In maleic anhydride modified polypropylene, have high reactivity, improve the caking property of CPP film and aluminium foil.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane cast polypropylene film (CPP), the CPP film hot sealing layer In the erucamide slip agent containing non-refractory, the confficient of static friction for sealing layer surface is 0.2~0.3, and dynamic friction coefficient is 0.2~0.3.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane is with cast polypropylene film (CPP), it is poly- in the CPP film Olefin elastomer is propylene-based elastomeric, based elastomers, ethylene-acrylic acid copolymer, rubber modified polypropylene polymer One of which or two kinds.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane cast polypropylene film (CPP), the total thickness of the CPP film Degree is 40 microns, and the ratio between plasma treated layer, sandwich layer and hot sealing layer thickness are 1: 3: 1.
Embodiment 4
A kind of aluminum-plastic composite membrane is by molten with cast polypropylene film (CPP), the three-layer co-extruded cast polypropylene film Melt extruder three extrusion heads be cast by the way of three-layer co-extruded gained, it successively include corona processing layer, sandwich layer and Hot sealing layer.Corona processing layer is mainly made of atactic copolymerized polypropene, maleic anhydride modified polypropylene and polyolefin elastomer, Substantially composition ratio is 75%:10%:15%；Sandwich layer mainly by homopolypropylene, organic modification nano silica and Polyolefin elastomer is made, and substantially composition ratio is 65%:5%:30%；And hot sealing layer is mainly gathered by random or block copolymerization Propylene, polyolefin elastomer and thermostable silicone slipping agent are made, and substantially composition ratio is 80%:18%:2%.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane, with cast polypropylene film (CPP), the corona processing layer refers to Using high-frequency high voltage to the processing of CPP surface corona, it is allowed to surface molecular and oxidation and polarization occurs, enhance film surface Adhesive force.
The key step of organic modification are as follows:
(1) preparation of nano silica:
Using sol-gel method, tetraethyl orthosilicate, ethyl alcohol, deionized water are configured to solution by volume at 1: 2: 2, 1h is stirred at 75 DEG C, it is uniformly mixed, adds cetylamine, the volume ratio of tetraethyl orthosilicate and cetylamine is 3: 2, continue to stir 1h, for control solution pH value 6 or so, room temperature, which is aged, is made milk white gel.Gel obtained is put into 650 DEG C Muffle furnace high temperature roast 1.5h, can be prepared by nano silica powder.
(2) activation of nano silica:
Dry silica is placed in 250 DEG C of high-temperature activation 5h in sand-bath under the protection of nitrogen, obtains activation nanometer Silica；
(3) organic modification of nano silica:
Octanol is added in activation nano silica, under the catalysis of p-methyl benzenesulfonic acid, 120 DEG C of heating stirring 1h, then It flows back after 1h, with washes of absolute alcohol product 3 times, drying obtains organic modification nano silica.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane with cast polypropylene film (CPP), contains in the CPP sandwich layer The nanoscale organized improved silica of high heat conductance has fast thermal conduction rate and high flexibility.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane is with cast polypropylene film (CPP), in the corona processing layer Maleic anhydride modified polypropylene has high reactivity, improves the caking property of CPP film and aluminium foil.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane is with cast polypropylene film (CPP), it is smooth in the hot sealing layer Agent is the silicone master batch using atactic copolymerized polypropene as carrier, more resistant to high temperature, so that its stable friction factor, seals layer surface Confficient of static friction is 0.12~0.2, and dynamic friction coefficient is 0.1~0.2.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane is with cast polypropylene film (CPP), it is poly- in the CPP film Olefin elastomer is propylene-based elastomeric, based elastomers, ethylene-acrylic acid copolymer, rubber modified polypropylene polymer One of which or two kinds.
Preferably, a kind of above-mentioned aluminum-plastic composite membrane cast polypropylene film (CPP), the total thickness of the CPP film Degree is 40 microns, and the ratio between plasma treated layer, sandwich layer and hot sealing layer thickness are 1: 3: 1.
Aluminium foil with a thickness of 40 microns, nylon with a thickness of 25 microns, aluminium foil two sides after Passivation Treatment, dark face It is compound by coating outer layer adhesive and nylon progress dry type, then pass through melt extruder and squeeze out inner layer resin adhesive to aluminium foil CPP film heat in bright face, with embodiment 1,2,3 and 4 is compound, so that 113 microns of aluminum-plastic composite membrane be made.
CPP film in embodiment 1,2,3 and 4 is passed through 60 DEG C of high temperature resistant processing respectively and tests its heat cover table over 1 day Coefficient of friction variation in face tests its longitudinal tensile strength and elongation at break with universal testing machine.It is as shown in the table for test result:
Table 1
The performance of the table 1 of CPP can be seen that from above-described embodiment 1,2 and 3, the tensile strength of the CPP in embodiment 1 and disconnected It is all bigger than CPP in embodiment 2 to split elongation, and in Examples 1 and 2 CPP hot sealing layer surface dynamic friction coefficient by nothing before and after high temperature Variation, this is related with the modification for the nano silica that organises；CPP heat cover is by dynamic after high-temperature process in embodiment 1 Coefficient of friction variation is much smaller compared to CPP in embodiment 3, and the tensile strength of the two and elongation at break are substantially similar, say The addition of bright silicone slipping agent influences CPP heat cover vulnerable to high temperature.The tensile strength of CPP, elongation at break in embodiment 1 It is similar to Example 4 by high temperature variation with hot sealing layer surface dynamic friction coefficient, in conjunction with CPP property in embodiment 2 and 3, explanation Plasma and sided corona treatment do not generate certain influence to the mechanical property of CPP, hot sealing layer performance.
Aluminum-plastic composite membrane obtained by CPP in embodiment 1,2,3 and 4 respectively in aluminum plastic film scouring depth molding machine and single-station The scouring depth (the scouring depth pressure of 0.5MPa, the scouring depth time of 5s) and heat-sealing (0.35MPa under same test parameter are carried out on heat sealing machine Heat-sealing pressure, 200 DEG C of upper and lower mould temperature and 210, the heat-sealing time of 4s) test.Aluminum plastic film is sealed by universal testing machine Intensity and the peel strength of AL//CPP are tested.
Aluminum-plastic composite membrane test result made from embodiment 1,2,3 and 4 is as shown in table 2:
Using CPP film of the invention in embodiment 1 be made aluminum-plastic composite membrane is made compared to CPP film in embodiment 2 Aluminum-plastic composite membrane, find the aluminum-plastic composite membrane of embodiment 1 more resistant to scouring depth molding, under lower heat-sealing temperature just it is available compared with High heat seal strength, this is added with the nano modification silica of high-termal conductivity so that the heat conductivity and toughness of CPP enhance It is related；Using CPP film of the invention in embodiment 1 be made aluminum-plastic composite membrane compared to aluminium made from CPP film in embodiment 3 Composite membrane is moulded, it is found that the aluminum-plastic composite membrane of embodiment 1 is formed more resistant to scouring depth, this is related with the use of thermostable silicone master batch；Make With CPP film of the invention in embodiment 1 be made aluminum-plastic composite membrane is plastic-aluminum combined compared to made from CPP film in embodiment 4 Film finds that the peel strength of the AL//CPP of aluminum-plastic composite membrane in embodiment 1 is much larger, this corona compared with corona treatment It is smaller, more efficient related to handle CPP surface breakdown.
In conclusion the plasma treated layer of the CPP film of the application and the adhesion strength of aluminium foil enhance, sandwich layer heat is passed Lead high, intensity and flexibility increase, hot sealing layer skin-friction coefficient is stablized, make made of aluminum-plastic composite membrane have more resistant to scouring depth at Type is easier to low-temperature heat-sealing, more resistant to performances such as electrolyte.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art Member, without departing from the inventive concept of the premise, can also make several improvements and modifications, these improvements and modifications also should be regarded as In protection scope of the present invention.

Claims (10)

1. a kind of aluminum-plastic composite membrane cast polypropylene film, which is characterized in that pass through three extrusion heads of melt extruder It is cast gained by the way of three-layer co-extruded, successively includes plasma treated layer, sandwich layer and hot sealing layer.
2. a kind of aluminum-plastic composite membrane cast polypropylene film as described in claim 1, which is characterized in that the plastic-aluminum is multiple Close film cast polypropylene film overall thickness be 30~80 microns, and every layer of plasma treated layer, sandwich layer and hot sealing layer it Between thickness ratio be 1: 3: 1.
3. a kind of aluminum-plastic composite membrane cast polypropylene film as described in claim 1, which is characterized in that corona treatment Layer is made of atactic copolymerized polypropene, maleic anhydride modified polypropylene and polyolefin elastomer, and composition ratio is 65~80%: 10 ~15%: 10~15%.
4. a kind of aluminum-plastic composite membrane cast polypropylene film as described in claim 1, which is characterized in that hot sealing layer is by random Or block copolymerization polypropylene, polyolefin elastomer and slipping agent are made, composition ratio is 70~80%: 15~25%: 1~5%.
5. a kind of aluminum-plastic composite membrane cast polypropylene film as claimed in claim 4, which is characterized in that the hot sealing layer In slipping agent be silicone master batch using polypropylene as carrier, the confficient of static friction for sealing layer surface is 0.12~0.2, dynamic friction Coefficient is 0.1~0.2, and the component of slipping agent is atactic copolymerized polypropene and silicone, and the mass ratio of the two is 1: 1.1.
6. a kind of aluminum-plastic composite membrane cast polypropylene film as described in claim 1, which is characterized in that sandwich layer is by homopolymerization Polypropylene, organic modification nano silica and polyolefin elastomer are made, and composition ratio is 65~75%: 5~10%: 15 ~30%.
7. a kind of aluminum-plastic composite membrane cast polypropylene film as claimed in claim 6, which is characterized in that organic modification is received The key step of rice silica are as follows:
(1) preparation of nano silica:
Using sol-gel method, tetraethyl orthosilicate, ethyl alcohol, deionized water are configured to solution by volume at 1: 2: 2,75 1h is stirred at DEG C, is uniformly mixed it, is added cetylamine, the volume ratio of tetraethyl orthosilicate and cetylamine is 3: 2, after Continuous stirring 1h, for control solution pH value 6, room temperature, which is aged, is made milk white gel；Gel obtained is put into 650 DEG C of Muffle furnace High temperature roasts 1.5h, can be prepared by nano silica powder；
(2) activation of nano silica:
Dry silica is placed in 250 DEG C of high-temperature activation 5h in sand-bath under the protection of nitrogen, obtains activation nano-silica SiClx；
(3) organic modification of nano silica:
Octanol is added in activation nano silica, under the catalysis of p-methyl benzenesulfonic acid, 120 DEG C of heating stirring 1h, then flow back After 1h, with washes of absolute alcohol product 3 times, drying obtains organic modification nano silica；
The mass ratio for activating nano silica and octanol is 1: 5；
Activate the mass ratio 25: 1 of nano silica and toluenesulfonic acid.
8. a kind of preparation method of aluminum-plastic composite membrane cast polypropylene film, which is characterized in that the specific steps are that:
(1) that outer layer adhesive is applied to the acid passivation on double surfaces of liquid containing chromium passivating in the way of intaglio plate roller coating is processed Aluminium foil dark face, it is compound with BON biaxially oriented nylon film dry type after drying tunnel is dried.Aluminium foil passivation temperature is 200~220 DEG C, It is 80~150 DEG C that heat, which dries temperature, and compound hot pressing temperature is 100~150 DEG C；
(2) using melt extruder the extrusion coated bright face of aluminium foil to composite nylon of inner layer resin adhesive, extrusion temperature It is 160~240 DEG C, so that aluminum-plastic composite membrane be made.
9. a kind of preparation method of aluminum-plastic composite membrane cast polypropylene film as claimed in claim 8, which is characterized in that institute The outer layer adhesive stated is polyurethane resin and polyisocyanate curing agent.
10. a kind of preparation method of aluminum-plastic composite membrane cast polypropylene film as claimed in claim 8, which is characterized in that The inner layer resin adhesive is acid-modified polyolefin resin and epoxy curing agent.
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CN115991908A (en) * 2021-10-20 2023-04-21 中国石油化工股份有限公司 Polypropylene composite film and preparation method and application thereof
CN115991909A (en) * 2021-10-20 2023-04-21 中国石油化工股份有限公司 Polypropylene composite film and preparation method and application thereof
CN114142170A (en) * 2021-10-22 2022-03-04 浙江华正能源材料有限公司 Puncture-resistant electrolyte-resistant cast polypropylene film, aluminum plastic film and application thereof
CN114603959A (en) * 2022-03-28 2022-06-10 河南鸿鹄新材料有限公司 Low-temperature heat-sealing CPP film
CN115257136A (en) * 2022-08-08 2022-11-01 常州斯威克光伏新材料有限公司 Preparation method of aluminum-plastic composite film for improving aluminum leakage of molten adhesive
CN115139615A (en) * 2022-08-25 2022-10-04 河北泰达包装材料有限公司 Flexible package modified CPP film and production method thereof

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