CN108724877A - Multilayer polymer film and preparation method thereof - Google Patents

Multilayer polymer film and preparation method thereof Download PDF

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Publication number
CN108724877A
CN108724877A CN201710278384.7A CN201710278384A CN108724877A CN 108724877 A CN108724877 A CN 108724877A CN 201710278384 A CN201710278384 A CN 201710278384A CN 108724877 A CN108724877 A CN 108724877A
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layer
polyolefin
polymer film
multilayer polymer
compatible
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CN108724877B (en
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李洪飞
苑会林
贺建芸
孙晓东
郭杰
许贺
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer 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
    • 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
    • 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
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2007/00—Flat articles, e.g. films or sheets
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/552—Fatigue strength
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/73—Hydrophobic
    • 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
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging
    • 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
    • C08J2333/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2333/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—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 only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C08J2433/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Abstract

The present invention provides a kind of multilayer polymer films and preparation method thereof, it includes at least one layer of polarity engineering plastic bed of material, at least one layer of nonpolar polyolefin hydrocarbon layers, and the compatible modified layer between adjacent the polarity engineering plastic bed of material and nonpolar polyolefin hydrocarbon layers, the compatible modified layer include polarity engineering plastics and the polyolefin of modification by copolymerization.The present invention uses non-polar polyolefin polymer with common polarity engineering plastics for basic material, it solves the problems, such as the poor compatibility of polarity engineering plastics and non-polar polyolefin polymer by the method for adding compatible modified layer, improves the interface compatibility of multilayer polymer film.Multilayer polymer film prepared by the present invention not only has higher mechanical strength and weatherability compared with traditional polyolefin films, but also compared with polarity engineering plastics film, also has better corrosion resistance and water resistance.

Description

Multilayer polymer film and preparation method thereof
Technical field
The present invention relates to multilayer polymer film fields, more particularly, to a kind of multilayer polymer film and its preparation Method.
Background technology
It is well known that plastic film is widely used to food packaging, agricultural greenhouse, fishery cultivating, industrial packaging, open air The multiple fields such as facility.Traditional polyolefins plastics (such as polyethylene, polypropylene) film article is with cost is relatively low, is easy to The advantages of molding, but universal mechanical property, weatherability is not good enough.And (such as such as the polymer material using higher intensity and weatherability Polyethylene terephthalate (PET), nylon (PA), polymethyl methacrylate (PMMA) etc.), cost of material significantly carries Height, and the short slabs such as water resistance, corrosion resistance, surface property limit application.
In order to balance this to contradiction, the method molding composite plastic film of multiple polymers layering coextrusion can be used, make Two kinds of polymer various aspects of performance is learnt from other's strong points to offset one's weaknesses.But the stronger engineering plastics of polarity and nonpolar compatible polyolefin are poor, The laminated film interlayer molded is easily peelable and can not use, therefore limits the selectable range and THIN COMPOSITE of core layer polymer The performances such as the mechanical strength of film and weatherability.
Invention content
The problem of in view of background technology, the purpose of the present invention is to provide a kind of multilayer polymer film and its systems Preparation Method, this method can improve the compatibility of polarity engineering plastics and non-polar polyolefin polymer, and by multi-layer co-extruded Method one-pass molding prepare a kind of multiple layer polymer having both polarity engineering plastics film and polyolefin film reapective features Film, excellent combination property have many advantages, such as that big mechanical strength, good weatherability, water-fast corrosion resistance are strong.
To achieve the goals above, in a first aspect, the present invention provides a kind of multilayer polymer films comprising at least One layer of polarity engineering plastic bed of material, at least one layer of nonpolar polyolefin hydrocarbon layers, and between the adjacent polarity engineering plastic bed of material and non-pole Property polyolefin layer between compatible modified layer, the compatible modified layer includes the polyene of polarity engineering plastics and modification by copolymerization Hydrocarbon.
Further, the multilayer polymer film includes with five-layer structure, five-layer structure：Polyolefin layer-is compatible to be changed Property layer-polarity engineering plastic bed of material-compatible modified layer-polyolefin layer.
Further, the multilayer polymer film includes with seven-layer structure, seven-layer structure：Functionalized surface layer-is poly- Compatible modified layer-polyolefin layer-functionalized surface the layer of the compatible modified layer of olefin layer-- polarity engineering plastic bed of material-, the functionalization Superficial layer includes at least one kind in hydrophilic modifying layer, uvioresistant layer, antistatic layer, extinction layer.
Further, the multilayer polymer film includes with nine layers of structure, nine layers of structure：Functionalized surface layer-phase Hold the compatible modified layer-polarity engineering plastic bed of material-compatible modified layer-work(of compatible modified layer-polyolefin layer-of modified layer-polyolefin layer- Superficial layer can be changed, the functionalized surface layer includes at least in hydrophilic modifying layer, uvioresistant layer, antistatic layer, extinction layer It is a kind of.
To achieve the goals above, in second aspect, the present invention provides a kind of preparation method of multilayer polymer film, It is used to prepare the multilayer polymer film described according to a first aspect of the present invention comprising step：(1) polyene is mixed in proportion Hydrocarbon, initiator and compatible modifier carry out modification by copolymerization, obtain the polyolefin particles of modification by copolymerization；(2) polarity is mixed in proportion The polyolefin particles of engineering plastics and modification by copolymerization obtain the compatible modified materials for being molded compatible modified layer；(3) change compatible Property material, polyolefin, polarity engineering plastics are separately added into the different extruders in multi-layer co-extruded former, are extruded into simultaneously Type obtains multilayer polymer film.
Further, the polyolefin includes at least one in polyethylene, polypropylene, polybutene, ethylene propylene copolymer Kind；The polarity engineering plastics include at least nylon, polyethylene terephthalate, polybutylene terephthalate (PBT), gather One in methyl methacrylate, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, makrolon or its recycling resin Kind；The initiator includes at least dibenzoyl peroxide, di-t-butyl peroxide, di-t-butyl peroxide, potassium peroxydisulfate, mistake Aoxidize one kind in two diisopropyl carbonates, hydrogen peroxide, azodiisobutyronitrile or azobisisoheptonitrile；The compatible modifier Including at least maleic anhydride, bismaleimide, glycidyl methacrylate, vinyl silanes, maleic anhydride-propylene One kind in acid, polyethylene methacrylic acid ethylene oxidic ester.
Further, in step (1), the weight ratio of the polyolefin, initiator and compatible modifier is 100：0.1- 0.5：1-4.
Further, in step (2), chain extender and polarity engineering plastics and the polyolefin blend of modification by copolymerization, institute is added Chain extender is stated including at least one butanediol of Isosorbide-5-Nitrae, 1,6 one hexylene glycols, glycerine, trimethylolpropane, diethylene glycol (DEG), triethylene glycol, new penta Glycol, sorbierite, diethylaminoethanol, ethylenediamine, N, N- dihydroxy (diisopropyl) aniline, quinhydrones one or two (mono- ethoxys of β) It is a kind of in ether, styrene-acrylonitrile-glycidyl methacrylate terpolymer.
Further, in step (2), the compatible modified materials further carry out extruding pelletization.
Further, in step (3), the multi-layer co-extruded former is that coextrusion blowing or coextrusion curtain coating are set It is standby.
Beneficial effects of the present invention are as follows：
The present invention uses non-polar polyolefin polymer with common polarity engineering plastics for basic material, compatible by adding The method of modified layer solves the problems, such as the poor compatibility of polarity engineering plastics and non-polar polyolefin polymer, improves multilayer The interface compatibility of thin polymer film.
Multilayer polymer film prepared by the present invention not only has higher mechanical strength compared with traditional polyolefin films And weatherability, and compared with polarity engineering plastics film, also there is better corrosion resistance and water resistance.
The polarity engineering plastics film or engineering plastic containing polarized that polarity engineering plastics used in the present invention can be recycling The multilayer plastic film material of material, it is environmentally protective, and greatly reduce cost of material.
Modification and forming method used in the present invention is without increasing special equipment, and easy to implement and operation, existing one As produce in property film molding equipment.
The multilayer polymer film of the present invention can be widely applied to food packaging, agricultural greenhouse, fishery cultivating, industry packet The multiple fields such as dress, outdoor facilities.
By the way that the detailed description of exemplary embodiment of the present invention, other feature of the invention and its advantage will below It becomes apparent.
Specific implementation mode
To keep the above objects, features, and advantages of invention more obvious and easy to understand, below to the specific implementation of the present invention Mode is described in detail.
Many details are elaborated in the following description to facilitate a thorough understanding of the present invention, still the present invention may be used also To be implemented different from other manner described here using other, those skilled in the art can be without prejudice to intension of the present invention In the case of do similar popularization, therefore the present invention is not limited by following public specific embodiment.
Illustrate multilayer polymer film according to a first aspect of the present invention first.
Multilayer polymer film according to a first aspect of the present invention includes at least one layer of polarity engineering plastic bed of material, at least one layer of Nonpolar polyolefin hydrocarbon layers, and the compatible modified layer between adjacent the polarity engineering plastic bed of material and nonpolar polyolefin hydrocarbon layers, The compatible modified layer includes polarity engineering plastics and the polyolefin of modification by copolymerization.
In one embodiment, the multilayer polymer film includes with three-decker, three-decker：Polyolefin layer-phase Hold modified layer-polarity engineering plastic bed of material.
In one embodiment, the multilayer polymer film includes with four-layer structure, four-layer structure：Polyolefin layer-phase Hold the modified layer-polarity engineering plastic bed of material-functionalized surface layer, the functionalized surface layer includes at least hydrophilic modifying layer, anti-purple One kind in outside line layer, antistatic layer, extinction layer.Functionalized surface layer is different, the function of serving from it is also different, in reality In, it is selected according to actual needs.
In one embodiment, the multilayer polymer film includes with five-layer structure, five-layer structure：Polyolefin layer-phase Hold modified layer-polarity engineering plastic bed of material-compatible modified layer-polyolefin layer.In another embodiment, the multilayer polymer film With five-layer structure, five-layer structure includes：The polarity engineering plastic bed of material-compatible modified layer-polarity of compatible modified layer-polyolefin layer- The engineering plastic bed of material.
In one embodiment, the multilayer polymer film includes with six layer structure, six layer structure：Polyolefin layer-phase Hold the compatible modified layer-polyolefin layer-functionalized surface layer of modified layer-polarity engineering plastic bed of material-, the functionalized surface layer is at least Including one kind in hydrophilic modifying layer, uvioresistant layer, antistatic layer, extinction layer.
In one embodiment, the multilayer polymer film includes with seven-layer structure, seven-layer structure：Functionalized surface Compatible modified layer-polyolefin layer-functionalized surface the layer of the compatible modified layer of layer-polyolefin layer-- polarity engineering plastic bed of material-, the work( Superficial layer can be changed including at least one kind in hydrophilic modifying layer, uvioresistant layer, antistatic layer, extinction layer.
In one embodiment, the multilayer polymer film includes with nine layers of structure, nine layers of structure：Polyolefin layer-phase Holding modified layer-polarity engineering plastic bed of material-compatible modified layer of compatible modified layer-polyolefin layer--, the polarity engineering plastic bed of material-is compatible changes Property layer-polyolefin layer.
In another embodiment, the multilayer polymer film includes with nine layers of structure, nine layers of structure：Functionalized surface Layer-compatible modified layer-polarity engineering plastic bed of material-compatible the modification of compatible modified layer-polyolefin layer-of compatible modified layer-polyolefin layer- Layer-functionalized surface layer, the functionalized surface layer include at least hydrophilic modifying layer, uvioresistant layer, antistatic layer, extinction layer In one kind.
The multilayer polymer film, the number of plies is unlimited, and functionalized surface layer is unlimited.In practical applications, according to specifics It can be selected with function, as long as the design for meeting the present invention is all within the scope of the present invention.
Secondly the preparation method of the multilayer polymer film of explanation according to a second aspect of the present invention.
The preparation method of multilayer polymer film according to a second aspect of the present invention is used to prepare according to first party of the present invention The multilayer polymer film in face, including step：(1) polyolefin (can be powder or particle) is mixed in proportion, initiator and compatible Modifying agent carries out block or grafting, copolymerization and modification, obtains the polyolefin particles of modification by copolymerization；(2) polarity engineering is mixed in proportion The polyolefin particles of plastics (can be powder or particle) and modification by copolymerization, obtain the compatible modification for being molded compatible modified layer Material；(3) compatible modified materials, polyolefin (can be powder or particle), polarity engineering plastics (can be powder or particle) are added respectively Enter the different extruders in multi-layer co-extruded former, while extrusion molding, obtains multilayer polymer film.
In one embodiment, the polyolefin includes at least in polyethylene, polypropylene, polybutene, ethylene propylene copolymer One kind.
In one embodiment, the polarity engineering plastics include at least nylon (PA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT) (PBT), polymethyl methacrylate (PMMA), thermoplastic polyester elastomer (TPEE), one kind in thermoplastic polyamide elastomer (TPAE), makrolon (PC) or its recycling resin.
In one embodiment, the initiator includes at least dibenzoyl peroxide (BPO), di-t-butyl peroxide, mistake Aoxidize di-t-butyl, potassium peroxydisulfate, di-isopropyl peroxydicarbonate, two different heptan of hydrogen peroxide, azodiisobutyronitrile or azo One kind in nitrile.
In one embodiment, the compatible modifier includes at least maleic anhydride, bismaleimide, methacrylic acid contracting One kind in water glyceride, vinyl silanes, maleic acid anhydride-propenoic acid, polyethylene methacrylic acid ethylene oxidic ester.
In one embodiment, in step (1), the weight ratio of the polyolefin, initiator and compatible modifier is 100： 0.1-0.5：1-4.
In one embodiment, in step (2), the compatible modified materials further carry out extruding pelletization.Twin-screw can be used Extruder carries out extruding pelletization.
In one embodiment, in step (2), chain extender is added and polarity engineering plastics and the polyolefin of modification by copolymerization are total Mixed, the chain extender includes at least one butanediol of Isosorbide-5-Nitrae (BDO), 1,6 one hexylene glycols, glycerine, trimethylolpropane, diethylene glycol (DEG) (DEG), triethylene glycol, neopentyl glycol (NPG), sorbierite, diethylaminoethanol (DEAE), ethylenediamine (DA), N, N- dihydroxy (two Isopropyl) aniline (HPA), quinhydrones one or two (mono- ethoxys of β) ether (HQEE), styrene-acrylonitrile-methyl propenoic acid glycidyl It is a kind of in ester terpolymer (SAG).
In one embodiment, in step (3), the multi-layer co-extruded former is coextrusion blowing or coextrusion curtain coating Equipment.Can with identical or certain proportion extrusion capacity, obtain each layer thickness it is identical or be a certain proportion of multilayer polymer film.
Hereinafter, being done specifically to the preparation method of the photochemistry hydrophilic modifying thin polymer film of the present invention in conjunction with specific embodiments Explanation.
Embodiment 1
(1) raw material proportioning of compatible modified materials：
Linear low density polyethylene：100 parts, polymethyl methacrylate：100 parts, dibenzoyl peroxide：0.5 part, first Base glycidyl acrylate：2 parts.
(2) it is initiator, linear low density polyethylene particle and methyl propenoic acid glycidyl by dibenzoyl peroxide Ester high-speed mixer after being mixed 15 minutes, is added same to engaging with 1000 revs/min of rotating speed, the condition of temperature 50 C To double screw extruder, extruding pelletization obtains the linear low density polyethylene particle of graft modification；Then with polymethylacrylic acid Methyl esters is blended, and obtains compatible modified materials for being molded compatible modified layer.The temperature in each area of extruder：One 150 DEG C of area, two areas 170 DEG C, three 180 DEG C of areas, four 175 DEG C of areas；
(3) compatible modified materials, linear low density polyethylene particle, poly methyl methacrylate particle are separately added into five layers The different extruders being coextruded in blow moulding equipment, while extrusion molding, acquisition structure are the compatible modification of linear low density polyethylene- The multi-layer co-extruded film of the compatible modified layer-linear low density polyethylene of layer-polymethyl methacrylate-, the thickness ratio of each layer 1:1:1:1:1, overall thickness 0.1mm.
Embodiment 2
(1) raw material proportioning of compatible modified materials：
Polypropylene：100 parts, polyethylene terephthalate reclaimed materials：150 parts, azodiisobutyronitrile：0.1 part, Malaysia Acid anhydrides：4 parts, glycidyl methacrylate：4.5 part.
(2) by after azodiisobutyronitrile and maleic anhydride acetone solution, with PP GRANULES material in high-speed mixer Mixing, 1000 revs/min of rotating speed, the condition of temperature 50 C after being mixed 15 minutes, are added to intermeshing co rotating twin screw extrusion Machine, extruding pelletization obtain the PP GRANULES of graft modification；The temperature in each area of extruder：One 150 DEG C of area, two 170 DEG C of areas, three 180 DEG C of area, four 175 DEG C of areas, 170 DEG C of head.
(3) being blended and then by polyethylene terephthalate reclaimed materials and glycidyl methacrylate (GMA), Meshing co rotating twin screw extrusion extruding pelletization obtains modified polyethylene terephthalate reclaimed materials.Each area of extruder Temperature：One 250 DEG C of area, two 265 DEG C of areas, three 270 DEG C of areas, four 270 DEG C of areas, 265 DEG C of head.Modified poly terephthalic acid second Diol ester reclaimed materials is mixed with the PP GRANULES of graft modification, obtains compatible modified materials for being molded compatible modified layer.
(4) the polyethylene terephthalate reclaimed materials by compatible modified materials, PP GRANULES, modification is separately added into five Different extruders in layer coextrusion casting apparatus, while extrusion molding, it is poly- pair of the compatible modified layer-of polypropylene-to obtain structure The polyacrylic five-layer co-squeezing of the compatible modified layer-of ethylene terephthalate-goes out film, and the thickness of each layer is than 1:1:1:1:1, total thickness Spend 0.1mm.
Embodiment 3
(1) raw material proportioning of compatible modified materials：
Low density polyethylene (LDPE)：100 parts, nylon 6：300 parts, di-isopropyl peroxydicarbonate：0.2 part, maleic anhydride：1 Part, polyethylene wax：1 part, styrene-grafted maleic anhydride random copolymer：5 parts.
(2) by initiator di-isopropyl peroxydicarbonate, polyethylene wax and maleic anhydride are in high-speed mixer, to turn The condition of 150 DEG C of 1000 revs/min of speed and temperature after being mixed 45 minutes, then is proportionally added into low density polyethylene (LDPE) respectively Particle, 6 particle of nylon and styrene-grafted maleic anhydride random copolymer continue mixing 10 minutes, and engagement is added in last mixture Parallel dual-screw extruding machine, extruding pelletization obtain compatible modified materials；The temperature in each area of extruder：One 250 DEG C of area, two areas 270 DEG C, three 280 DEG C of areas, four 275 DEG C of areas, 260 DEG C of head.
(3) compatible modified materials, low density polyethylene (LDPE) particle, 6 particle of nylon are separately added into five-layer co-squeezing and go out casting apparatus In different extruders, while extrusion molding, acquisition structure is the compatible modified layer of low density polyethylene (LDPE)-- compatible modifications of nylon 6- The five-layer co-squeezing of layer-low density polyethylene (LDPE) goes out film, and each layer thickness is than 1:1:2:1:1, overall thickness 0.1mm.
Embodiment 4
The preparation method of compatible modified materials is identical with embodiment 2, unlike：
It is 3 by compatible modified materials, PP GRANULES, PP GRANULES and antistatic master batch (AT4082PP) weight ratio:1 Blend, modified polyethylene terephthalate particle reclaimed materials are separately added into the difference that seven-layer co-extrusion goes out in casting apparatus Extruder, acquisition structure are the compatible modification of the compatible modified layer-polyethylene terephthalate-of antistatic polypropylene-polypropylene- The seven-layer co-extrusion of layer-polypropylene-antistatic polypropylene layer goes out film, and the thickness of each layer is than 0.5:1:1:1:1:1:0.5, overall thickness 0.1mm。
Embodiment 5
The preparation method of compatible modified materials is identical with embodiment 3, unlike：
Compatible modified materials, low density polyethylene (LDPE) particle, 6 particle of nylon are separately added into nine layers of coextrusion casting apparatus Different extruders, while extrusion molding, it is that compatible modified layer-is low by the compatible modified layer of low density polyethylene (LDPE)-- nylon 6- to obtain structure Nine layers of co-extrusion film of the compatible modified layer of density polyethylene-- compatible modified layer-low density polyethylene (LDPE)s of nylon 6-, each layer thickness Than 1:1:1:1:2:1:1:1:1, overall thickness 0.15mm.
Comparative example 1
Purely linear low-density polyethylene film, thickness 0.1mm.
Comparative example 2
Pet film, thickness 0.1mm.
Comparative example 3
Other than not using compatible modified layer, other preparation processes are same as Example 1.
Performance test
1, tensile strength and the measurement of elongation at break
According to national standards《The measurement of plastic tensile performance》(GB T1040.3-2006) third portion, film and thin slice Experimental condition：Dumbbell shape batten is length 150mm, and narrow parallel width is 10mm, tensile speed 50mm/min, room temperature 25 ℃。
2, the measurement of tearing strength
Quote GB/T 16578-1996《Plastic film and thin slice tearing-resistant performance test method trousers shape method of Tearing》, stretch 200 ± 20mm/min of speed.
3, the measurement of peel strength
Film sample is width 15mm, length 200mm；Specimen length direction is pre- by the polarity engineering plastic bed of material and polyolefin layer It first peels off, carries out T-type stripping, measure Average peel force (N), test speed 300mm/min.
4, the measurement of OTR oxygen transmission rate
Quote national standard《Plastic film and thin slice gas-premeable test method》(GB/T1038-2000).
5, thermal aging test
Quote national standard《Plastics thermal aging test method》(GB/T7141-2008), in gravity convection formula thermal aging oven, 90 DEG C of temperature, ageing time tests tensile strength after 24 hours.
The performance test results are as shown in table 1.
1 the performance test results of table
The compatible modified layer used in the present invention it can be seen from the above embodiments that significantly improves polyolefin layer and engineering Bonding force between plastic layer；It is coextruded the engineering plastics prepared and polyolefin composite multi-layer thin polymer film and pure polyolefin is thin Film is compared to be compared with higher mechanical strength, than pure engineering plastics film, and aging post-tensioning intensity declines unobvious, has Better resistance to ag(e)ing；Secondly, the polarity engineering plastics used in the present invention can be polarity engineering plastics film reclaimed materials or contain The multilayer polarity engineering plastics film reclaimed materials of polarized engineering plastics belongs to waste recovery recycling, not only environmentally protective, and And reduce cost of material；In addition, the modification and forming method used in the present invention are in existing general film molding equipment It can produce, it is simple and practical, without increasing special equipment.
The multilayer polymer film of the present invention can be widely applied to food packaging, agricultural greenhouse, fishery cultivating, industry packet The multiple fields such as dress, outdoor facilities.
Although some specific embodiments of the present invention are described in detail by example, the skill of this field Art personnel it should be understood that above example merely to illustrating, the range being not intended to be limiting of the invention.The skill of this field Art personnel are it should be understood that can without departing from the scope and spirit of the present invention modify to above example.This hair Bright range is defined by the following claims.

Claims (10)

1. a kind of multilayer polymer film, which is characterized in that including at least one layer of polarity engineering plastic bed of material, at least one layer of nonpolarity Polyolefin layer, and the compatible modified layer between adjacent the polarity engineering plastic bed of material and nonpolar polyolefin hydrocarbon layers, the phase It includes polarity engineering plastics and the polyolefin of modification by copolymerization to hold modified layer.
2. multilayer polymer film according to claim 1, which is characterized in that the multilayer polymer film has five layers Structure, five-layer structure include：The compatible modified layer of the polyolefin layer-- polarity engineering plastic bed of material-compatible modified layer-polyolefin layer.
3. multilayer polymer film according to claim 1, which is characterized in that the multilayer polymer film has seven layers Structure, seven-layer structure include：The compatible modified layer of the functionalized surface layer-polyolefin layer-- polarity engineering plastic bed of material-compatible modified layer- Polyolefin layer-functionalized surface layer, the functionalized surface layer include at least hydrophilic modifying layer, uvioresistant layer, antistatic layer, One kind in extinction layer.
4. multilayer polymer film according to claim 1, which is characterized in that the multilayer polymer film has nine layers Structure, nine layers of structure include：The compatible modified layer of the compatible modified layer-polyolefin layer-of the functionalized surface layer-- polarity engineering plastic bed of material- Compatible modified layer-functionalized surface the layer of compatible modified layer-polyolefin layer-, the functionalized surface layer include at least hydrophilic modifying One kind in layer, uvioresistant layer, antistatic layer, extinction layer.
5. a kind of preparation method of multilayer polymer film, is used to prepare the multilayer as described in any one of claim 1-4 Thin polymer film, which is characterized in that including step：
(1) polyolefin, initiator and compatible modifier are mixed in proportion, are carried out modification by copolymerization, are obtained the polyolefin of modification by copolymerization Particle；
(2) polarity engineering plastics and the polyolefin particles of modification by copolymerization are mixed in proportion, are obtained for being molded compatible modified layer Compatible modified materials；
(3) the different extrusions being separately added into compatible modified materials, polyolefin, polarity engineering plastics in multi-layer co-extruded former Machine, while extrusion molding obtain multilayer polymer film.
6. the preparation method of multilayer polymer film according to claim 5, which is characterized in that
The polyolefin includes at least one kind in polyethylene, polypropylene, polybutene, ethylene propylene copolymer；
The polarity engineering plastics include at least nylon, polyethylene terephthalate, polybutylene terephthalate (PBT), gather One in methyl methacrylate, thermoplastic polyester elastomer, thermoplastic polyamide elastomer, makrolon or its recycling resin Kind；
The initiator include at least dibenzoyl peroxide, di-t-butyl peroxide, di-t-butyl peroxide, potassium peroxydisulfate, One kind in di-isopropyl peroxydicarbonate, hydrogen peroxide, azodiisobutyronitrile or azobisisoheptonitrile；
The compatible modifier includes at least maleic anhydride, bismaleimide, glycidyl methacrylate, vinyl silicon One kind in alkane, maleic acid anhydride-propenoic acid, polyethylene methacrylic acid ethylene oxidic ester.
7. the preparation method of multilayer polymer film according to claim 5, which is characterized in that described poly- in step (1) The weight ratio of alkene, initiator and compatible modifier is 100：0.1-0.5：1-4.
8. the preparation method of multilayer polymer film according to claim 5, which is characterized in that in step (2), be added and expand Chain agent includes at least one butanediol of Isosorbide-5-Nitrae, 1,6 one with polarity engineering plastics and the polyolefin blend of modification by copolymerization, the chain extender Hexylene glycol, glycerine, trimethylolpropane, diethylene glycol (DEG), triethylene glycol, neopentyl glycol, sorbierite, diethylaminoethanol, ethylenediamine, N, N- dihydroxy (diisopropyl) aniline, quinhydrones one or two (mono- ethoxys of β) ether, styrene-acrylonitrile-methyl propenoic acid glycidyl It is a kind of in ester terpolymer.
9. the preparation method of multilayer polymer film according to claim 5, which is characterized in that in step (2), the phase Hold modified materials and further carries out extruding pelletization.
10. the preparation method of multilayer polymer film according to claim 5, which is characterized in that described in step (3) Multi-layer co-extruded former is coextrusion blowing or coextrusion casting apparatus.
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