CN107312229B - A kind of polyethylene film and preparation method thereof - Google Patents

A kind of polyethylene film and preparation method thereof Download PDF

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Publication number
CN107312229B
CN107312229B CN201610265201.3A CN201610265201A CN107312229B CN 107312229 B CN107312229 B CN 107312229B CN 201610265201 A CN201610265201 A CN 201610265201A CN 107312229 B CN107312229 B CN 107312229B
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polyethylene
10min
melt index
temperature
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CN107312229A (en
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高达利
张师军
施红伟
李汝贤
郭梅芳
邹浩
李�杰
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Sinopec Beijing Research Institute of Chemical Industry
China Petrochemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petrochemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D7/00—Producing flat articles, e.g. films or sheets
    • B29D7/01—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
    • 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
    • B32B27/32—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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/242—All polymers belonging to those covered by group B32B27/32
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal 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
    • B32B2307/40—Properties of the layers or laminate having particular optical 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
    • B32B2307/54—Yield strength; Tensile 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • B32B2323/046—LDPE, i.e. low density polyethylene
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The present invention relates to polymer arts, a kind of polyethylene film and preparation method thereof is provided.The polyethylene film includes the polyethylene skin of polyethylene core at least side surface for being attached to the polyethylene core, the polyethylene core is formed by the first polyethylene composition containing component A, component B and component C, and the polyethylene skin is formed by the second polyethylene composition containing component D；The component A, component B, component C and component D are the linear low density polyethylene of ethylene/alpha-olefin copolymerization, and melt index of the these types of component in the case where temperature is 190 DEG C, load is 2.16kg is respectively 0.01-3.5g/10min, 3.6-9.9g/10min, 10-80g/10min and 0.5-50g/10min, density is respectively 0.915-0.936g/cm3、0.915‑0.930g/cm3、0.915‑0.930g/cm3And 0.880-0.910g/cm3.The polyethylene film has excellent mechanical property, optical property and heat-seal strength, great prospects for commercial application.

Description

A kind of polyethylene film and preparation method thereof
Technical field
It is prepared the present invention relates to a kind of polyethylene film, a kind of preparation method of polyethylene film and by this method Polyethylene film.
Background technique
Biaxially-oriented polyethylene (Biaxially Oriented Polyethylene, BOPE) film is that have special point Polyethylene (PE) resin of minor structure is through the molding thin-film material of stretch processes.In the molding process of BOPE film In, after the processing of film drawn, PE macromolecular chain and crystalline texture generation are height-oriented, to significantly improve the stretching of film Intensity reduces tension fracture elongation rate, and makes that the mist degree of film is lower, glossiness is higher and transparent more preferable.In addition, with The extrusioning blowing process of the prior art is compared with the polyethylene film product for squeezing out casting technique preparation, and BOPE film has mechanics The advantages such as intensity is high, puncture resistant and shock resistance are good, excellent optical performance, environmental protection and energy saving.Therefore, BOPE film can be wide It is general to be used for packaging bag, again packaging bag, Vacuum Heat sealer, low temperature packaging film, composite membrane, medical and sanitary products, plastic film for agricultural use etc..
The biaxial tension processing method of currently used plastic film has Flat film strength and envelope pulling method.Flat membrane stretches Method has been applied in the processing of the thin-film materials such as polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET) In, technique is more mature.Compared with envelope pulling method, the stretching ratio of Flat film strength is big, and (cross directional stretch multiplying power is up to 10 times More than), shaping speed fast (highest rolling speed is up to hundreds of ms/min), high production efficiency, and the mechanics of obtained film More preferably, but film forming is influenced significantly by process condition fluctuations for intensity, optical property and the thickness uniformity, film stretch plus Work difficulty is big, has higher requirement for film raw material.Existing Biaxially-oriented polyethylene raw material is only applicable to pipe substantially When steeping pulling method and prepare BOPE film, and these existing polyethylene raw materials being prepared BOPE film using Flat film strength, deposit In the mechanics for the film that film forming poor (tensile speed and stretching ratio are very low), film are easy to appear the defect of rupture, and obtain Performance and optical property are poor.
Summary of the invention
The purpose of the invention is to overcome the mechanical property of existing polyethylene film and the poor defect of optical property, And it is thin to provide a kind of polyethylene film, a kind of polyethylene with higher mechanical property, optical property and heat-seal strength The preparation method of film and the polyethylene film being prepared by this method.
Specifically, polyethylene film provided by the invention includes polyethylene core and is attached to the polyethylene core extremely The polyethylene skin of a few side surface, the polyethylene core is by the first polyethylene composition containing component A, component B and component C Object is formed, and the polyethylene skin is formed by the second polyethylene composition containing component D；The component A is ethylene/alpha-olefin The linear low density polyethylene of copolymerization, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgAFor 0.01- 3.5g/10min, density pAFor 0.915-0.936g/cm3；The component B is the linear low density polyethylene of ethylene/alpha-olefin copolymerization Alkene, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgBFor 3.6-9.9g/10min, density pBFor 0.915- 0.930g/cm3；The component C is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, temperature is 190 DEG C, load is Melt index MI under 2.16kgCFor 10-80g/10min, density pCFor 0.915-0.930g/cm3；The component D is ethylene/alpha The linear low density polyethylene of olefin-copolymerization, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgDFor 0.5- 50g/10min, density pDFor 0.880-0.910g/cm3。
The preparation method of polyethylene film provided by the invention includes that will gather containing the first of component A, component B and component C Vinyl composition and the second polyethylene composition containing component D are sent into the extrusion casting apparatus with multi-layer co-extruded structure Curtain coating is squeezed out, later again stretches obtained curtain coating slab, obtains including polyethylene core and be attached to the polyethylene The polyethylene film of at least polyethylene skin of a side surface of sandwich layer, the polyethylene core is by first polyethylene composition Object is formed, and the polyethylene skin is formed by second polyethylene composition；The component A is the line of ethylene/alpha-olefin copolymerization Property low density polyethylene (LDPE), the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgAFor 0.01-3.5g/10min, Density pAFor 0.915-0.936g/cm3；The component B is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, in temperature Melt index MI under being 2.16kg for 190 DEG C, loadBFor 3.6-9.9g/10min, density pBFor 0.915-0.930g/cm3； The component C is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, in the case where temperature is 190 DEG C, load is 2.16kg Melt index MICFor 10-80g/10min, density pCFor 0.915-0.930g/cm3；The component D is ethylene/alpha-olefin copolymerization Linear low density polyethylene, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgDFor 0.5-50g/10min, Density pDFor 0.880-0.910g/cm3。
In addition, the present invention also provides polyethylene films prepared by the above method.
The present inventor has found after further investigation, when by the above-mentioned component containing particular melt index and density A, the second polyethylene of the first polyethylene composition of component B and component C and the component D containing particular melt index and density For composition with the use of when film is made, obtained polyethylene film has the advantages that stretching ratio is big, rate of film build is high, can The polyethylene film mechanical property with higher that meets Flat film strength to the high requirement of polyethylene raw material, and obtain and Optical property and preferable heat-seal strength are highly suitable for packaging material, great prospects for commercial application.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the structural schematic diagram for being used to prepare the multiple reactor shunting means of the first polyethylene composition.
Description of symbols
1- first reactor；2- second reactor；3- third reactor；4- solid-liquid (gas) separator；5- homogenization silo； 6- melt pelletization system.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
Polyethylene film provided by the invention includes polyethylene core and at least side for being attached to the polyethylene core The polyethylene skin on surface, the polyethylene core is by the first polyethylene composition shape containing component A, component B and component C At the polyethylene skin is formed by the second polyethylene composition containing component D；The component A is ethylene/alpha-olefin copolymerization Linear low density polyethylene, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgAFor 0.01-3.5g/ 10min, density pAFor 0.915-0.936g/cm3；The component B is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, Melt index MI in the case where temperature is 190 DEG C, load is 2.16kgBFor 3.6-9.9g/10min, density pBFor 0.915- 0.930g/cm3；The component C is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, temperature is 190 DEG C, load is Melt index MI under 2.16kgCFor 10-80g/10min, density pCFor 0.915-0.930g/cm3；The component D is ethylene/alpha The linear low density polyethylene of olefin-copolymerization, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgDFor 0.5- 50g/10min, density pDFor 0.880-0.910g/cm3。
The polyethylene film provided according to the present invention, it is preferable that the component A temperature be 190 DEG C, load 2.16kg Under melt index MIAFor 0.01-3g/10min, melting of the component B in the case where temperature is 190 DEG C, load is 2.16kg refers to Number MIBFor 4-8g/10min, melt index MI of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor 10-60g/ The melt index MI of 10min, the component D in the case where temperature is 190 DEG C, load is 2.16kgDFor 0.5-30g/10min.It is more excellent Selection of land, melt index MI of the component A in the case where temperature is 190 DEG C, load is 2.16kgAFor 0.01-2g/10min, described group Divide melt index MI of the B in the case where temperature is 190 DEG C, load is 2.16kgBFor 4-5g/10min, the component C is 190 in temperature DEG C, load be 2.16kg under melt index MICFor 15-40g/10min, the component D is temperature is 190 DEG C, load is Melt index MI under 2.16kgDFor 1-20g/10min.
In the present invention, the melt index is measured according to method specified in GB/T3682-2000, wherein Test condition includes that temperature is 190 DEG C, load 2.16kg.
The polyethylene film provided according to the present invention, it is preferable that the density p of the component AAFor 0.915-0.930g/cm3, The density p of the component BBFor 0.915-0.928g/cm3, the density p of the component CCFor 0.915-0.928g/cm3, described group Divide the density p of DDFor 0.880-0.905g/cm3, the polyethylene film enabled in this way is with preferable filming performance On the basis of, also there is higher tensile strength, optical property and heat-seal strength.
The component A, component B, component C and component D are the linear low density polyethylene of ethylene/alpha-olefin copolymerization, In, linear structure refers to only containing short-chain branch structure in strand, and does not contain long branched chain structure and cross-linked structure, by polymerizeing Monomer and polymerization process condition are determined, are specifically known to the skilled person, and therefore not to repeat here.
The polyethylene film provided according to the present invention, in order to enable the polyethylene film arrived has higher mechanical strength, Preferably, in first polyethylene composition, the mass fraction W of the component AAFor 25-90 parts by weight, the component B Mass fraction WBFor 0.1-10 parts by weight, the mass fraction W of the component CCFor 10-75 parts by weight；It is highly preferred that described In first polyethylene composition, the mass fraction W of the component AAFor 30-80 parts by weight, the mass fraction W of the component BBFor 0.5-8 parts by weight, the mass fraction W of the component CCFor 20-70 parts by weight.Further, the mass fraction W of the component AA With the mass fraction W of component CCWith the melt index MI of component AARelationship preferably satisfy 4.6 × lgMIA+10.4≥WA/WC≥ 0.34×lgMIA+ 1, it enables to have during preparing polyethylene film using flat membrane biaxial tension method so bigger Stretching ratio and higher rate of extension.
The polyethylene film provided according to the present invention, particularly preferably, first polyethylene composition is 190 in temperature DEG C, the melt index under load is 2.16kg be 0.1-20g/10min, most preferably 0.5-10g/10min.By said components A, on the basis of component B and component C is used cooperatively, the melt index of the first polyethylene composition entirety is controlled above-mentioned It is preferred that range in, the first polyethylene composition for enabling to has very excellent film forming, and obtained poly- second Alkene film has higher tensile strength, optical property and heat-seal strength.
The polyethylene film provided according to the present invention, the component A, component B, component C and component D can use existing Various methods are prepared, for example, can be prepared using Ziegler-Natta catalyst, can also use metallocene catalysis Agent is prepared.Wherein, the type of the Ziegler-Natta catalyst and metallocene catalyst can be the conventional choosing of this field It selects, for example, the Ziegler-Natta catalyst is usually by magnesium titanium compound and organo-aluminum compound and optional electron Body composition, the metallocene catalyst is usually by metallocene compound and organo-aluminum compound and optional electron donor group At being specifically known to the skilled person, therefore not to repeat here.
The present invention does not limit the content of alhpa olefin comonomer in the component A, component B, component C and component D particularly It is fixed, for example, the molar content of alhpa olefin comonomer can be each independently in the component A, component B, component C and component D 0.2-15mol%, preferably 1.5-10mol%.In the present invention, the molar content of alhpa olefin comonomer refers to is gathered by alhpa olefin The mole for the structural unit that conjunction is formed accounts for the ratio of the mole of total monomer structural unit.In addition, the component A, component B, Alhpa olefin in component C and component D is each independently C3-C20At least one of alkene.The angle ready availability from raw material goes out It sends out, the alhpa olefin in the component A, component B, component C and component D is preferably propylene, 1- butylene, 2- butylene, 3- methyl-1-fourth Alkene, 4- methyl-1-butylene, 1- amylene, 3- Methyl-1-pentene, 4-methyl-1-pentene, 3,3- dimethyl-1- amylene, 3,4- bis- Methyl-1-pentene, 4,4- dimethyl-1- amylene, 1- hexene, 4- methyl-1-hexene, 5- methyl-1-hexene, 1- heptene, 2- heptan Alkene, 1- octene, 1- decene, 1- 12 (carbon) alkene, 1- 14 (carbon) alkene, 1- 16 (carbon) alkene, (carbon) alkene of 1- 18 and 1- 20 At least one of at least one of (carbon) alkene, more preferably 1- butylene, 1- hexene and 1- octene.
In addition, can also be containing existing various poly- in first polyethylene composition and the second polyethylene composition Other usually used auxiliary agents in vinyl and polyethylene film, and other described auxiliary agents will not be to poly- second provided by the invention Stretching film forming, mechanical property, optical property and the heat-seal strength of alkene film have adverse effect on.Other described auxiliary agents Including but not limited to: at least one of antioxidant, lubricant, slipping agent, antistatic agent, antitack agent etc..In addition, it is described other The dosage of auxiliary agent all can be this field conventional selection, this those skilled in the art can be known, therefore not to repeat here.
First polyethylene composition can be prepared according to existing various methods, for example, first preparing group respectively Divide A, component B and component C, other auxiliary agents then contained by the component A, component B and component C and selectively are according to the proportion Mechanical mixture is carried out in mechanical mixing equipment, is then added in melt blending equipment and is carried out melt blending.Wherein, the machinery Mixing apparatus can be for example high-speed mixer, kneader etc..The melt blending equipment for example can for double screw extruder, Single screw extrusion machine, open mill, mixer etc..
A preferred embodiment of the invention, first polyethylene composition is in more reactions as shown in Figure 1 It is prepared in device shunting means, the multiple reactor shunting means includes first reactor 1, second reactor 2, third reaction Device 3, solid-liquid (gas) separator 4, homogenization silo 5 and melt pelletization system 6, wherein the first reactor 1, second reactor 2 and third reactor 3 be connected in parallel, the number of solid-liquid (gas) separator 4 is three, respectively with first reactor 1, the Two reactors 2 are connected to third reactor 3, the component A prepared by first reactor 1, the component B prepared by second reactor 2 And the component C prepared by third reactor 3 is mutually separated in different solid-liquid (gas) separators 4 respectively, it then will be through Component A, component B and component C after mutually separating are delivered in homogenization silo 5 in proportion and mix together with other optional additives It closes uniformly, is sent into melt pelletization system 6 carries out extruding pelletization later.Wherein, it is poly- to can be interval for the polymerization in each reactor It closes, is also possible to continuous polymerization.When using multiple reactor parallel polymerization, W hereinafterA、WBAnd WCIt is each component corresponding anti- Answer the yield in unit time in device.
According to the present invention, as described above, the polyethylene film includes polyethylene core and is attached to the polyvinyl plastic core The polyethylene skin of an at least side surface for layer, that is, the polyethylene film can have the three of upper epidermis, sandwich layer and layer Layer structure, it is possible to have the double-layer structure of upper epidermis and sandwich layer.The polyethylene core and the thickness of polyethylene skin can be with It is suitably selected according to the use condition of the polyethylene film, if the condition used requires the polyethylene film to have Biggish mechanical strength and lower to optical performance requirements, then the polyethylene core and the thickness of polyethylene skin can be compared with It is thick；If the condition that uses requires the polyethylene film to have preferable translucency and lower to mechanical strength requirement, The polyethylene core and the thickness of polyethylene skin can be relatively thin.Under normal conditions, the poly- second of the polyethylene core side The thickness on alkene surface layer can be the 2-35% of the polyethylene film thickness.Further, when the polyethylene film is with upper When the composite construction on surface layer, sandwich layer and layer, it is thick that the thickness of the upper epidermis and layer is each independently the film The 2-25% of degree；When the polyethylene film has the composite construction of upper epidermis and sandwich layer, the upper epidermis with a thickness of institute State the 2-35% of film thickness.In addition, the overall thickness of the polyethylene film can be 10-200 μm, preferably 10-100 μm.
The preparation method of polyethylene film provided by the invention includes that will gather containing the first of component A, component B and component C Vinyl composition and the second polyethylene composition containing component D are sent into the extrusion casting apparatus with multi-layer co-extruded structure Curtain coating is squeezed out, later again stretches obtained curtain coating slab, obtains including polyethylene core and be attached to the polyethylene The polyethylene film of at least polyethylene skin of a side surface of sandwich layer, the polyethylene core is by first polyethylene composition Object is formed, and the polyethylene skin is formed by second polyethylene composition；The component A is the line of ethylene/alpha-olefin copolymerization Property low density polyethylene (LDPE), the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgAFor 0.01-3.5g/10min, Density pAFor 0.915-0.936g/cm3；The component B is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, in temperature Melt index MI under being 2.16kg for 190 DEG C, loadBFor 3.6-9.9g/10min, density pBFor 0.915-0.930g/cm3； The component C is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, in the case where temperature is 190 DEG C, load is 2.16kg Melt index MICFor 10-80g/10min, density pCFor 0.915-0.930g/cm3；The component D is ethylene/alpha-olefin copolymerization Linear low density polyethylene, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgDFor 0.5-50g/10min, Density pDFor 0.880-0.910g/cm3。
According to the present invention, the more excellent polyethylene film of performance in order to obtain, under preferable case, this method further include First polyethylene composition and the second polyethylene composition are sent into before squeezing out casting apparatus, by the first polyethylene composition and Second polyethylene composition is dried.The drying side that the method and condition of the drying can be known to the skilled person Method and condition, for example, can be vacuum drying, forced air drying etc., drying temperature can be 60-100 DEG C.Drying equipment is usually Drying equipment including heating, drying warm air blowoff or vacuum system, for example, can for continuous dryer, vacuum drying oven and Hot-air oven etc..
It should be noted that squeezing out casting apparatus generally includes multiple extruders, it can be to different in multiple extruders Material is heated, and the material after different extruder heating can be multiple by the same multilayer for including at least two layers Mold head squeeze out curtain coating, thus obtain include multilayer curtain coating slab；Wherein, the material in each extruder is from the multilayer Wherein one layer of extrusion of compound die head.Therefore, those skilled in the art should be readily understood that, when needing to obtain polyethylene When the polyethylene film of the side surface attachment polyethylene skin of sandwich layer, two different extruders can be used described first Polyethylene composition and the melting of the second polyethylene composition, and it includes that two layers of die head squeezes that molten product is passed through same simultaneously It is cast out, the two membranes obtained after extrusion are stacked together, then polyethylene film of the invention is just obtained after drawn；Work as needs When obtaining the both side surface of polyethylene core and being attached with the polyethylene film of polyethylene skin, different it can be squeezed using three Raw material melting (wherein, is added the first polyethylene composition, the second poly- second is added in the extruder of surface layer by machine out in main extruder Ene compositions), and molten product is squeezed out and is cast, then polyethylene film of the invention can be obtained after drawn.
According to the present invention, the curtain coating extruder used that squeezes out can be single screw extrusion machine, or twin-screw Extruder.In addition, the condition for squeezing out curtain coating can be existing conventional selection, this those skilled in the art can be known It knows, therefore not to repeat here.
In addition, the stretching can be simple tension, or biaxial tension, preferably bidirectional stretching, more preferably Flat membrane biaxial tension.It is known to the skilled person using the process that flat membrane biaxial tension method prepares biaxially oriented film.Tool Body, first above-mentioned polyethylene composition is added in extrusion casting apparatus and carries out extrusion curtain coating, then casts obtained curtain coating Piece carries out drawing and forming in film biaxial tension equipment.In addition, the biaxial tension can be using Synchronos method drawing process (i.e. Film longitudinal (MD) is carried out simultaneously and laterally (TD) is stretched), film (it is longitudinal can also first to be carried out using method of fractional steps drawing process It stretches, then carries out film cross directional stretch).What the Synchronos method stretched specifically comprises the processes of: the curtain coating slab after being fully warmed-up, The stretching of vertical and horizontal direction is carried out simultaneously, wherein preheating temperature can be 75-165 DEG C, and draft temperature can be 75-160 DEG C, longitudinal stretching ratio >=4 times (MD), lateral stretching ratio >=5 times (TD), cross directional stretch rate >=50%/s.The substep What method stretched specifically comprises the processes of: the curtain coating slab first carries out longitudinal stretching, carries out cross directional stretch later after being fully warmed-up, Wherein, preheating temperature can be 65-158 DEG C, and draft temperature can be 65-155 DEG C, longitudinal stretching ratio >=4 times (MD), laterally (TD) stretching ratio >=5 times, cross directional stretch rate >=50%/s.In addition, can be handled without setting after film drawing and forming, It can also carry out annealing setting processing.When carrying out annealing setting processing, film setting treatment temperature can be 80-165 DEG C.Most Afterwards, film can also carry out surface corona processing, cutting edge and winding processing, finally obtain polyethylene film of the present invention.
Polyethylene film provided by the invention has preferable film forming and stretching ratio is big, rate of extension is high.It is adopting During preparing the biaxially oriented film with Flat film strength, as described above, longitudinal direction (MD) stretching ratio of the film >=4 times, lateral stretching ratio >=5 times (TD).Stretching ratio is bigger, then the mechanical strength of film is higher.The transverse direction of the film (TD) rate of extension >=50%/s, preferably 60-150%/s can guarantee to industrialize continuous production in this way.
Polyethylene film mechanical strength, optical property and heat-seal strength with higher provided by the invention, specifically It can meet: longitudinal (MD) tensile strength >=50MPa, preferably >=55MPa；Laterally (TD) tensile strength >=50MPa, preferably >= 55MPa；Tension fracture elongation rate≤350%, preferably≤300%；Puncture strength >=2.5N, preferably >=3.5N；Mist degree≤ 6%, preferably≤3%；Heat-seal strength >=2.5N, preferably >=3.5N.In the present invention, the longitudinal tensile strength and cross It is measured to tensile strength according to method specified in GB/T 1040.3-2006.The tension fracture elongation rate is according to GB/T Method specified in 1040.3-2006 is measured.The puncture strength according to method specified in GB/T10004-2008 into Row measurement, wherein film sample with a thickness of 25 ± 5 μm.The mist degree according to method specified in GB/T 2410-2008 into Row measurement, wherein film sample with a thickness of 25 ± 5 μm.The heat-seal strength is according to side specified in QBT2358-1998 Method is measured, wherein heat-sealing temperature is 120 DEG C, and heat-sealing pressure is 0.18MPa.
In addition, the present invention also provides polyethylene films prepared by the above method.
In addition, the production cost of polyethylene film provided by the invention is low, processing technology is simple, versatility is good, widen The application field of polyethylene film.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples:
Film biaxial tension equipment is purchased from Germany Br ü ckner company, model Karo IV.
The performance of each component is tested in accordance with the following methods in polyethylene composition:
(1) it melt index (MI): is measured according to method specified in GB/T 3682-2000, wherein test temperature It is 190 DEG C, load 2.16kg；
(2) it density: is measured according to method specified in GB/T 1033.2-2010 and using density gradient column method.
Embodiment 1
The present embodiment is for illustrating polyethylene film provided by the invention and preparation method thereof.
(1) preparation of polyethylene composition:
First polyethylene composition provided in this embodiment is made of component A, component B and component C, the second polyethylene composition Object is made of component D.Wherein, component A, component B, component C and component D are the linear low density polyethylene of ethylene/alpha-olefin copolymerization Alkene (LLDPE), and it is all made of identical catalyst system (Ziegler-Natta catalyst) and polymerization technique preparation, difference is The type and molar content of the amounts of hydrogen and alhpa olefin comonomer that are added when preparing different component are different.Specific step It is rapid as follows:
By ethylene, alhpa olefin, hydrogen and nitrogen, (ethylene, alhpa olefin, hydrogen and nitrogen are polymer grade, after removing water, oxygen Use, similarly hereinafter) it is added in gas fluidized bed reactor, the ziegler-natta catalyst systems (Ziegler-is then added Natta catalyst systems are the ziegler-natta catalyst systems being prepared by CN101838351A embodiment 1, similarly hereinafter), it It polymerize under conditions of temperature is 84-88 DEG C, pressure is 1.8-2.0MPa afterwards, respectively obtains component A, component B, component C and group Divide D.Wherein, the control of the melt index of component A, component B, component C and component D is realized by adjusting the additional amount of hydrogen, The control of density is realized by the type and additional amount for adjusting alhpa olefin.Prepare alhpa olefin used during component A be 1- oneself Alkene, alhpa olefin used is 1- butylene during preparing component B, and preparing alhpa olefin used during component C is 1- butylene, preparation Alhpa olefin used is 1- hexene during component D.
Through detecting, the performance of each component prepared by the above method is as follows:
The melt index MI of component AA=2.0g/10min, density pA=0.915g/cm3, mole of alhpa olefin comonomer Content=8.0mol%；
The melt index MI of component BB=4.0g/10min, density pB=0.915g/cm3, mole of alhpa olefin comonomer Content=8.0mol%；
The melt index MI of component CC=15g/10min, density pC=0.915g/cm3, alhpa olefin comonomer mole contains Amount=9.8mol%；
The melt index MI of component DD=5.0g/10min, density pD=0.900g/cm3, mole of alhpa olefin comonomer Content=10.3mol%.
Said components A, component B and component C are weighed and mixed according to the ratio, wherein the mass fraction W of component AAFor 80 parts by weight, the mass fraction W of component BBFor 10 parts by weight, the mass fraction W of component CCFor 20 parts by weight, WA/WC=4 (meet 4.6×lgMIA+10.4≥WA/WC≥0.34×lgMIA+1)；It adds mixture in high speed agitator and is uniformly mixed later, The material mixed is added to again in the feeder of double screw extruder of W&P company manufacture, material enters via feeder In twin-screw, the temperature of screw rod is maintained between 160-210 DEG C in process, and, extrusion uniform through screw rod melting mixing is granulated And dry, the first polyethylene composition pellet is obtained, its melt index MI=3.4g/10min is detected.In addition, using above-mentioned Identical method prepares the second polyethylene composition pellet, unlike, component A, component B and component C are all made of component D and replace Generation.
(2) preparation of polyethylene film:
First polyethylene composition pellet made from above-mentioned steps (1) and the second polyethylene composition pellet are done It is dry, it is added to progress melting extrusion cocurrent in the multilayer extrusion casting machine of the model LCR400 of Labtech company, Sweden later Prolong slab, wherein the first polyethylene composition pellet is added to sandwich layer extruder, and the second polyethylene composition pellet is added Enter into upper and lower surface layer extruder, also need that inorganic antitack agent (silica, similarly hereinafter) is added in the upper and lower surface layer extruder, And the weight ratio for the antitack agent and the second polyethylene composition pellet being added in the extruder of upper and lower surface layer is 0.02:1, In Be cast slab during, will curtain coating chilling roll temperature be set as 25 DEG C, polyethylene thickness slab is made, by upper epidermis, sandwich layer and Layer is constituted.
Above-mentioned polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, is drawn using first longitudinal direction (MD) The two-way step drawing technological forming that laterally (TD) is stretched after stretching, each step process condition are as follows: MD preheating temperature is 100 DEG C, MD Draft temperature is 110 DEG C, and MD stretching ratio is 4 times, and TD preheating temperature is 100 DEG C, and TD draft temperature is 115 DEG C, TD stretching times Rate is 5 times, and film TD rate of extension is 150%/s, and film setting temperature is 120 DEG C, obtains the film that average thickness is 25 μm, It is made of upper epidermis, sandwich layer and layer, and core layer raw material is first polyethylene composition of the present embodiment, upper epidermis and following table Layer raw material is second polyethylene composition of the present embodiment, and the thickness of upper epidermis and layer is 1.5 μm.
Embodiment 2
The present embodiment is for illustrating polyethylene film provided by the invention and preparation method thereof.
(1) preparation of polyethylene composition:
First polyethylene composition provided in this embodiment is made of component A, component B and component C, the second polyethylene composition Object is made of component D.Wherein, component A, component B, component C and component D are the linear low density polyethylene of ethylene/alpha-olefin copolymerization Alkene (LLDPE), and it is all made of identical catalyst system (ziegler-natta catalyst systems) and polymerization technique preparation, difference The type and molar content of the amounts of hydrogen and alhpa olefin comonomer that are added when being to prepare different component are different.Tool Steps are as follows for body:
Ethylene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, ziegler-nata is then added and urges Agent system polymerize under conditions of temperature is 84-88 DEG C, pressure is 1.8-2.0MPa later, respectively obtains component A, component B, component C and component D.Wherein, the control of the melt index of component A, component B, component C and component D is by adjusting adding for hydrogen Enter amount and realize, the control of density is realized by the type and additional amount for adjusting alhpa olefin.α used during preparation component A Alkene is 1- butylene, and alhpa olefin used is 1- butylene during preparing component B, prepares alhpa olefin used during component C and is 1- hexene, alhpa olefin used is 1- hexene during preparing component D.
Through detecting, the performance of each component prepared by the above method is as follows:
The melt index MI of component AA=0.01g/10min, density pA=0.930g/cm3, mole of alhpa olefin comonomer Content=2.1mol%；
The melt index MI of component BB=9.0g/10min, density pB=0.930g/cm3, mole of alhpa olefin comonomer Content=2.8mol%；
The melt index MI of component CC=40g/10min, density pC=0.922g/cm3, alhpa olefin comonomer mole contains Amount=4.0mol%；
The melt index MI of component DD=1.0g/10min, density pD=0.910g/cm3, mole of alhpa olefin comonomer Content=9.0mol%.
Said components A, component B and component C are weighed and mixed according to the ratio, wherein the mass fraction W of component AAFor 55 parts by weight, the mass fraction W of component BBFor 5 parts by weight, the mass fraction W of component CCFor 55 parts by weight, WA/WC=1 (meets 4.6×lgMIA+10.4≥WA/WC≥0.34×lgMIA+1)；It adds mixture in high speed agitator and is uniformly mixed later, The material mixed is added to again in the feeder of double screw extruder of W&P company manufacture, material enters via feeder In twin-screw, the temperature of screw rod is maintained between 180-240 DEG C in process, and, extrusion uniform through screw rod melting mixing is granulated And dry, the first polyethylene composition pellet is obtained, its melt index MI=0.7g/10min is detected.In addition, using above-mentioned Identical method prepares the second polyethylene composition pellet, unlike, component A, component B and component C are all made of component D and replace Generation.
(2) preparation of polyethylene film:
First polyethylene composition pellet made from above-mentioned steps (1) and the second polyethylene composition pellet are done It is dry, it is added to progress melting extrusion cocurrent in the multilayer extrusion casting machine of the model LCR400 of Labtech company, Sweden later Prolong slab, wherein the first polyethylene composition pellet is added to sandwich layer extruder, and the second polyethylene composition pellet is added Enter into upper and lower surface layer extruder, also need that inorganic antitack agent (silica, similarly hereinafter) is added in the upper and lower surface layer extruder, And the weight ratio for the antitack agent and the second polyethylene composition pellet being added in the extruder of upper and lower surface layer is 0.02:1, In Be cast slab during, will curtain coating chilling roll temperature be set as 85 DEG C, polyethylene thickness slab is made, by upper epidermis, sandwich layer and Layer is constituted.
Above-mentioned polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, is drawn using first longitudinal direction (MD) The two-way step drawing technological forming that laterally (TD) is stretched after stretching, each step process condition are as follows: MD preheating temperature is 130 DEG C, MD Draft temperature is 132 DEG C, and MD stretching ratio is 4 times, and TD preheating temperature is 130 DEG C, and TD draft temperature is 132 DEG C, TD stretching times Rate is 6 times, and film TD rate of extension is 100%/s, and film setting temperature is 135 DEG C, obtains the film that average thickness is 25 μm, It is made of upper epidermis, sandwich layer and layer, and core layer raw material is first polyethylene composition of the present embodiment, upper epidermis and following table Layer raw material is second polyethylene composition of the present embodiment, and also contains antitack agent in upper epidermis and layer, and upper epidermis is under The thickness on surface layer is 1 μm.
Embodiment 3
The present embodiment is for illustrating polyethylene film provided by the invention and preparation method thereof.
(1) preparation of polyethylene composition:
First polyethylene composition provided in this embodiment is made of component A, component B and component C, the second polyethylene composition Object is made of component D.Wherein, first polyethylene composition polymerize to obtain using multiple reactor shunting means shown in FIG. 1, The wherein polymerization of first reactor 1 preparation component A, the polymerization preparation of second reactor 2 component B, the polymerization preparation component of third reactor 3 C.Component A, component B, component C and component D are the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, and adopt It is prepared with identical catalyst system (metallocene catalyst system) and polymerization technique, difference is to prepare added when different component The type and molar content and the yield in unit time of each reactor of the amounts of hydrogen, alhpa olefin comonomer that enter are different.Tool Steps are as follows for body:
Alhpa olefin, n-hexane and hydrogen are added in polymer reactor, and polymer reactor is heated to preset polymerization Temperature, by vinyl monomer and metallocene catalyst system, (metallocene catalyst system is by CN102453124A reality later The carried metallocene catalyst that example 1 is prepared is applied, similarly hereinafter) while being added in polymer reactor, and be 140 in temperature DEG C, pressure be 2.5MPa under conditions of polyase 13 0 minute, respectively obtain component A, component B, component C and component D.Wherein, component A, the control of the melt index of component B, component C and component D realizes that the control of density passes through by adjusting the additional amount of hydrogen Adjust alhpa olefin type and additional amount and realize.Alhpa olefin used is 1- octene during preparing component A, preparation component B's Used in the process of alhpa olefin be 1- butylene, alhpa olefin used is 1- butylene during preparing component C, during preparing component D Alhpa olefin used is 1- octene.
During the preparation process by the yield in unit time W of component A in first reactor 1A, component B in second reactor 2 Yield in unit time WBWith the yield in unit time W of component C in third reactor 3CWeight ratio maintain WA: WB: WC=75:2: 35, wherein WA/WC=2.1 (meet 4.6 × lgMIA+10.4≥WA/WC≥0.34×lgMIA+1)。
Through detecting, the performance of each component prepared by the above method is as follows:
The melt index MI of component AA=0.1g/10min, density pA=0.920g/cm3, mole of alhpa olefin comonomer Content=2.1mol%；
The melt index MI of component BB=5.0g/10min, density pB=0.920g/cm3, mole of alhpa olefin comonomer Content=5.1mol%；
The melt index MI of component CC=25g/10min, density pC=0.920g/cm3, alhpa olefin comonomer mole contains Amount=5.1mol%；
The melt index MI of component DD=25g/10min, density pD=0.905g/cm3, alhpa olefin comonomer mole contains Amount=8.0mol%.
Component A obtained above, component B and component C are respectively delivered to different solid-liquids in yield in unit time ratio It is mutually separated and is transported in the homogenization silo 5 with stirring in turn in (gas) separator 4 and carry out mixing homogenizing.It later will be through The mixture that homogenization silo 5 is homogenized is added in the feeder of the double screw extruder of W&P company manufacture, and material is via feeder Into in twin-screw, the temperature of screw rod is maintained between 170-230 DEG C in process, extrusion uniform through screw rod melting mixing, It is granulated and dries, obtain the first polyethylene composition pellet, detected its melt index MI=0.6g/10min.In addition, using Above-mentioned identical method prepares the second polyethylene composition pellet, unlike, component A, component B and component C are all made of component D Substitution.
(2) preparation of polyethylene film:
First polyethylene composition pellet made from above-mentioned steps (1) and the second polyethylene composition pellet are done It is dry, it is added to progress melting extrusion cocurrent in the multilayer extrusion casting machine of the model LCR400 of Labtech company, Sweden later Prolong slab, wherein the first polyethylene composition pellet is added to sandwich layer extruder, and the second polyethylene composition pellet is added Enter into upper epidermis extruder, also needs to be added inorganic antitack agent (silica, similarly hereinafter) in the upper epidermis extruder, and on The weight ratio of the antitack agent and the second polyethylene composition pellet that are added in the extruder of surface layer is 0.02:1, in curtain coating slab process In, curtain coating chilling roll temperature is set as 35 DEG C, polyethylene thickness slab is made, is made of upper epidermis and sandwich layer.
Above-mentioned polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, is drawn using first longitudinal direction (MD) The two-way step drawing technological forming that laterally (TD) is stretched after stretching, each step process condition are as follows: MD preheating temperature is 110 DEG C, MD Draft temperature is 110 DEG C, and MD stretching ratio is 4 times, and TD preheating temperature is 115 DEG C, and TD draft temperature is 115 DEG C, TD stretching times Rate is 5 times, and film TD rate of extension is 100%/s, and film setting temperature is 122 DEG C, obtains the film that average thickness is 25 μm, It is made of upper epidermis and sandwich layer, and core layer raw material is first polyethylene composition of the present embodiment, and upper epidermis raw material is this implementation Second polyethylene composition of example, and also contain antitack agent in upper epidermis, the thickness of upper epidermis is 2 μm.
Embodiment 4
The present embodiment is for illustrating polyethylene film provided by the invention and preparation method thereof.
Polyethylene film is prepared according to the method for embodiment 1, unlike, in the process for preparing the first polyethylene composition In, the dosage W of component AAFor 80 parts by weight, the dosage W of component BBFor 25 parts by weight, the mass fraction W of component CCFor 5 parts by weight, WA/WC=16 (are unsatisfactory for 4.6 × lgMIA+10.4≥WA/WC≥0.34×lgMIA+ 1), by repeatedly attempting, biaxial tension The maximum tension multiplying power of film is 4 times (TD) × 4 times (MD), obtains polyethylene film.
Comparative example 1
This comparative example is for illustrating polyethylene film of reference and preparation method thereof.
(1) polyethylene raw material:
Polyethylene raw material used in this comparative example is that the film-grade of Sinopec Group Yanshan Petrochemical company production is linearly low Density polyethylene, trade mark DFDA-7042, melt index MI=2.0g/10min, density p=0.920g/cm3。
(2) preparation of polyethylene film:
Prepare polyethylene film according to the method for embodiment 1, unlike, will the first polyethylene composition pellet with Second polyethylene composition pellet uses the polyethylene raw material of this comparative example step (1) of identical weight part to substitute, and is repeatedly tasted There is the case where stretching rupture of membranes in examination, can not stretch film forming.In addition, the TD rate of extension in polyethylene film preparation process is dropped To 50%/s, is repeatedly attempted the case where stretching rupture of membranes still occur, film forming can not be stretched.
Comparative example 2
This comparative example is for illustrating polyethylene film of reference and preparation method thereof.
(1) polyethylene raw material:
Polyethylene raw material used in this comparative example is identical as comparative example 1.
(2) preparation of polyethylene film:
The polyethylene film of this comparative example uses the upper blowing method film blowing device extrusion and blow molding of DR.COLLIN company, Germany It obtains, the specific method is as follows: the polyethylene raw material that above-mentioned steps (1) is chosen is added to the material of upper blowing method film blowing device extruder In bucket, melt membrane tube is made after the abundant fusion plastification of extruder, by the annular die extrusion of head in raw material, after it is empty through compression Air-blowing is swollen (blow-up ratio is 2.5 times), and polyethylene film is made after vane is cooling, and it is 25 μm that wherein film, which is average thickness, Single layer structure.
Comparative example 3
This comparative example is used to illustrate the polyethylene film of reference.
(1) preparation of polyethylene composition:
The polyethylene composition that this comparative example provides is by component 1 (the component B of embodiment 1) and (group of embodiment 1 of component 2 Divide C) composition, that is, the method for preparation method and embodiment 1 the first polyethylene composition of disclosed preparation of the polyethylene composition It is identical, unlike, it is added without component A.Specifically, component 1 and component 2 are that the linea low density of ethylene/alpha-olefin copolymerization is poly- Ethylene (LLDPE), and it is all made of identical catalyst system (ziegler-natta catalyst systems) and polymerization technique preparation, area The type and molar content of the amounts of hydrogen and alhpa olefin comonomer that are added when not being to prepare different component are different. Specific step is as follows:
Ethylene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, ziegler-nata is then added and urges Agent system polymerize under conditions of temperature is 84-88 DEG C, pressure is 1.8-2.0MPa later, respectively obtains component 1 and component 2.Wherein, the control of the melt index of component 1 and component 2 realizes that the control of density passes through by adjusting the additional amount of hydrogen Adjust alhpa olefin type and additional amount and realize.Alhpa olefin used is 1- butylene during preparing component 1, preparation component 2 Used in the process of alhpa olefin be 1- butylene.
Through detecting, the performance of component 1 and component 2 prepared by the above method is as follows:
The melt index MI of component 11=4.0g/10min, density p1=0.915g/cm3, mole of alhpa olefin comonomer Content=8.0mol%；
The melt index MI of component 22=15g/10min, density p2=0.915g/cm3, alhpa olefin comonomer mole contains Amount=9.8mol%.
Each component obtained above is weighed and mixed according to the ratio, wherein the mass fraction W of component 11For 80 weight Part, the mass fraction W of component 22It for 30 parts by weight, adds mixture in high speed agitator and is uniformly mixed later, then will mix The material got togather is added in the feeder of the double screw extruder of W&P company manufacture, and material enters twin-screw via feeder In, the temperature of screw rod is maintained between 160-210 DEG C in process, through screw rod melting mixing uniformly, squeeze out, be granulated and dry It is dry, polyethylene composition pellet is obtained, its melt index MI=6.2g/10min is detected.
(2) preparation of polyethylene film:
Carry out the preparation of polyethylene film according to the method for embodiment 1, difference is, the surface layer of extrudate flow retarder film and Core layer raw material is all made of the polyethylene composition pellet substitution of above-mentioned steps (1), the results showed that, by repeatedly attempting, two-way drawing The maximum tension multiplying power for stretching film is only 2 times (TD) × 2 times (MD), and film TD highest stretching ratio is only 10%/s, that is, is stretched Multiplying power and rate of extension are too low, and stretching film forming is poor, do not have practicability.
Comparative example 4
This comparative example is for illustrating polyethylene film of reference and preparation method thereof.
(1) preparation of polyethylene composition:
The first polyethylene composition that this comparative example provides is by component 1 (the component A of embodiment 2) and (embodiment 2 of component 2 Component B) composition, that is, the preparation method of first polyethylene composition and embodiment 2 is disclosed prepares the first polyethylene composition The method of object is identical, unlike, it is added without component C.Second polyethylene composition is by component 3 (the component D of embodiment 2) group At, that is, the method phase of the preparation method of second polyethylene composition and the second polyethylene composition of disclosed preparation of embodiment 2 Together.Wherein, component 1, component 2 and component 3 are the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, and adopt It is prepared with identical catalyst system (ziegler-natta catalyst systems) and polymerization technique, difference is to prepare different component When the type and molar content of the amounts of hydrogen and alhpa olefin comonomer that are added it is different.Specific step is as follows:
Ethylene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, ziegler-nata is then added and urges Agent system polymerize under conditions of temperature is 84-88 DEG C, pressure is 1.8-2.0MPa later, respectively obtains component 1, component 2 With component 3.Wherein, the control of the melt index of component 1, component 2 and component 3 is realized by adjusting the additional amount of hydrogen, close The control of degree is realized by the type and additional amount for adjusting alhpa olefin.Alhpa olefin used is 1- butylene during preparing component 1, Alhpa olefin used is 1- butylene during preparing component 2, and preparing alhpa olefin used during component 3 is 1- hexene.
Through detecting, the performance of each component prepared by the above method is as follows:
The melt index MI of component 11=0.01g/10min, density p1=0.930g/cm3, mole of alhpa olefin comonomer Content=2.1mol%；
The melt index MI of component 22=9.0g/10min, density p2=0.930g/cm3, mole of alhpa olefin comonomer Content=2.8mol%；
The melt index MI of component 33=1.0g/10min, density p3=0.910g/cm3, mole of alhpa olefin comonomer Content=9.0mol%.
Said components 1 and component 2 are weighed and mixed according to the ratio, wherein the mass fraction W of component 11For 55 weight Part, the mass fraction W of component 22It for 65 parts by weight, adds mixture in high speed agitator and is uniformly mixed later, then will mix The material got togather is added in the feeder of the double screw extruder of W&P company manufacture, and material enters twin-screw via feeder In, the temperature of screw rod is maintained between 180-240 DEG C in process, through screw rod melting mixing uniformly, squeeze out, be granulated and dry It is dry, the first polyethylene composition pellet is obtained, its melt index MI=0.22g/10min is detected.In addition, using above-mentioned identical Method prepare the second polyethylene composition pellet, unlike, component 1 and component 2 are all made of the substitution of component 3.
(2) preparation of polyethylene film:
The preparation of polyethylene film is carried out according to the method for embodiment 2, the results showed that, by repeatedly attempting, biaxial tension The maximum tension multiplying power of film is only 2 times (TD) × 2 times (MD), and film TD highest stretching ratio is only 10%/s, that is, is stretched again Rate and rate of extension are too low, and stretching film forming is poor, do not have practicability.
Comparative example 5
This comparative example is for illustrating polyethylene film of reference and preparation method thereof.
(1) preparation of polyethylene composition:
The first polyethylene composition that this comparative example provides is by component 1 (the component A of embodiment 3) and (embodiment 3 of component 2 Component C) composition, that is, the preparation method of first polyethylene composition and embodiment 3 is disclosed prepares the first polyethylene composition The method of object is identical, unused to be, is added without component B.Second polyethylene composition is by component 3 (the component D of embodiment 3) group At, that is, the method phase of the preparation method of second polyethylene composition and the second polyethylene composition of disclosed preparation of embodiment 3 Together.Specifically, the first polyethylene composition polymerize to obtain using multiple reactor shunting means shown in FIG. 1, wherein the first reaction Device polymerization preparation component 1, second reactor polymerization preparation component 2.Component 1, component 2 and component 3 are ethylene/alpha-olefin copolymerization Linear low density polyethylene (LLDPE), these three components be all made of identical catalyst system (metallocene catalyst system) and Polymerization technique preparation, amounts of hydrogen that difference is added when being to prepare different component, the type of alhpa olefin comonomer and mole contains Amount and the yield in unit time of each reactor are different.Specific step is as follows:
Alhpa olefin, n-hexane and hydrogen are added in polymer reactor, and polymer reactor is heated to preset polymerization Vinyl monomer and catalyst system are added in polymer reactor by temperature simultaneously later, and temperature is 140 DEG C, pressure is Polyase 13 0 minute under conditions of 2.5MPa respectively obtains component 1, component 2 and component 3.Wherein, component 1, component 2 and component 3 The control of melt index realizes that the control of density passes through the type and addition that adjust alhpa olefin by adjusting the additional amount of hydrogen It measures and realizes.Alhpa olefin used is 1- octene during preparing component 1, and preparing alhpa olefin used during component 2 is 1- fourth Alkene, alhpa olefin used is 1- octene during preparing component 3.
During the preparation process by the yield in unit time W of component 1 in first reactor1With component 2 in second reactor Yield in unit time W2Weight ratio maintain W1: W2=35:75.
Through detecting, the performance of each component prepared by the above method is as follows:
The melt index MI of component 11=0.1g/10min, density p1=0.920g/cm3, mole of alhpa olefin comonomer Content=2.1mol%；
The melt index MI of component 22=25g/10min, density p2=0.920g/cm3, alhpa olefin comonomer mole contains Amount=5.1mol%；
The melt index MI of component 33=25g/10min, density p3=0.905g/cm3, alhpa olefin comonomer mole contains Amount=8.0mol%.
Component 1 obtained above and component 2 are transported in solid-liquid (gas) separator in yield in unit time ratio and carried out Mutually separation is simultaneously transported in the homogenization silo with stirring in turn and carries out mixing homogenizing, the mixing for being later homogenized homogenized feed bin Object is added in the feeder of the double screw extruder of W&P company manufacture, and material enters in twin-screw via feeder, processed The temperature of screw rod is maintained between 170-230 DEG C in journey, through screw rod melting mixing uniformly, squeeze out, be granulated and dry, obtain first Polyethylene composition pellet is detected its melt index MI=8.2g/10min.In addition, using above-mentioned identical method preparation the Dimerized vinyl composition pellet, unlike, component 1 and component 2 are all made of the substitution of component 3.
(2) preparation of polyethylene film:
The preparation of polyethylene film is carried out according to the method for embodiment 3, the results showed that, by repeatedly attempting, biaxial tension The maximum tension multiplying power of film is only 2 times (TD) × 2 times (MD), and film TD highest stretching ratio is only 10%/s, that is, is stretched again Rate and rate of extension are too low, and stretching film forming is poor, do not have practicability.
Comparative example 6
This comparative example is for illustrating polyethylene film of reference and preparation method thereof.
(1) preparation of polyethylene composition:
The first polyethylene composition and the second polyethylene composition are prepared according to the method for embodiment 4, unlike, it is making The melt index MI of the component D made during standby component D by the dosage of adjusting hydrogen and alhpa olefinD=60.0g/ 10min, density pD=0.930g/cm3, molar content=3.0mol% of alhpa olefin comonomer.That is, the second of this comparative example is poly- Vinyl composition is different from the present invention.
(2) preparation of polyethylene film:
The preparation of polyethylene film is carried out according to the method for embodiment 4, the results showed that, the heat-seal strength of gained film compared with It is low, do not have practicability.
Test case
Test case is used to illustrate the test of polyethylene film and reference polyethylene film performance.
(1) it mist degree: is measured according to method specified in GB/T 2410-2008, wherein film sample is with a thickness of 25 ± 5 μm, acquired results are as shown in table 1；
(2) tensile strength and tension fracture elongation rate: being measured according to method specified in GB/T 1040.3-2006, Acquired results are as shown in table 1；
(3) it puncture strength: is measured according to method specified in GB/T10004-2008, wherein film sample thickness It is 25 ± 5 μm, acquired results are as shown in table 1；
(4) it heat-seal strength: is measured according to method specified in QBT2358-1998Q, wherein heat-sealing temperature is 120 DEG C, heat-sealing pressure is 0.18MPa, and acquired results are as shown in table 1.
Table 1
From embodiment 1 and comparative example 1-2, embodiment 1 and comparative example 3, embodiment 2 and comparative example 4, embodiment 3 and comparison The comparison of example 5 and embodiment 4 and comparative example 6 can be seen that polyethylene film provided by the invention big, drawing with film forming multiplying power The advantage that rate is fast, mechanical strength is high, good in optical property, heat-seal strength are high is stretched, the performance of prepared film is able to satisfy vertical To (MD) tensile strength >=50MPa, lateral (TD) tensile strength >=50MPa, tension fracture elongation rate≤350%, puncture strength >=2.5N, heat-seal strength >=4.5N.In addition, can be seen that from the comparison of embodiment 1 and embodiment 4 to prepare polyethylene thin During film, when controlling the dosage of each substance in currently preferred range, obtained polyethylene film has more Excellent comprehensive performance.It can be seen that the commercially available poly- second using prior art preparation from the comparison of embodiment 1 and comparative example 1-2 Alkene raw material can not stretch film forming, thus be not suitable for being processed using Flat film strength, and the inflation film with the prior art It compares, and film higher using the mechanical strength, puncture strength and heat-seal strength of the film of Flat film strength machine-shaping Mist degree is lower.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (33)

1. a kind of polyethylene film, which is characterized in that the polyethylene film includes polyethylene core and is attached to the poly- second The polyethylene skin of an at least side surface for alkene sandwich layer, the polyethylene core is by first containing component A, component B and component C Polyethylene composition is formed, and the polyethylene skin is formed by the second polyethylene composition containing component D；The component A is The linear low density polyethylene of ethylene/alpha-olefin copolymerization, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgA For 0.01-3.5g/10min, density pAFor 0.915-0.936g/cm3；The component B is the linear low close of ethylene/alpha-olefin copolymerization Spend polyethylene, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgBFor 3.6-9.9g/10min, density pBFor 0.915-0.930g/cm3；The component C be ethylene/alpha-olefin copolymerization linear low density polyethylene, temperature be 190 DEG C, Load is the melt index MI under 2.16kgCFor 10-80g/10min, density pCFor 0.915-0.930g/cm3；The component D is The linear low density polyethylene of ethylene/alpha-olefin copolymerization, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgD For 0.5-50g/10min, density pDFor 0.880-0.910g/cm3。
2. polyethylene film according to claim 1, wherein the component A temperature be 190 DEG C, load 2.16kg Under melt index MIAFor 0.01-3g/10min, melting of the component B in the case where temperature is 190 DEG C, load is 2.16kg refers to Number MIBFor 4-8g/10min, melt index MI of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor 10-60g/ The melt index MI of 10min, the component D in the case where temperature is 190 DEG C, load is 2.16kgDFor 0.5-30g/10min.
3. polyethylene film according to claim 2, wherein the component A temperature be 190 DEG C, load 2.16kg Under melt index MIAFor 0.01-2g/10min, melting of the component B in the case where temperature is 190 DEG C, load is 2.16kg refers to Number MIBFor 4-5g/10min, melt index MI of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor 15-40g/ The melt index MI of 10min, the component D in the case where temperature is 190 DEG C, load is 2.16kgDFor 1-20g/10min.
4. polyethylene film according to claim 1, wherein in first polyethylene composition, the component A's Mass fraction WAFor 25-90 parts by weight, the mass fraction W of the component BBFor 0.1-10 parts by weight, the mass parts of the component C Number WCFor 10-75 parts by weight.
5. polyethylene film according to claim 4, wherein in first polyethylene composition, the component A's Mass fraction WAFor 30-80 parts by weight, the mass fraction W of the component BBFor 0.5-8 parts by weight, the mass fraction of the component C WCFor 20-70 parts by weight.
6. polyethylene film according to claim 4, wherein the mass fraction W of the component AAWith the mass parts of component C Number WCWith the melt index MI of component AARelationship meet 4.6 × lgMIA+10.4≥WA/WC≥0.34×lgMIA+1。
7. polyethylene film described in any one of -6 according to claim 1, wherein first polyethylene composition is in temperature Melt index under degree is 190 DEG C, load is 2.16kg is 0.1-20g/10min.
8. polyethylene film according to claim 7, wherein first polyethylene composition is 190 DEG C, carries in temperature Melt index under lotus is 2.16kg is 0.5-10g/10min.
9. polyethylene film described in any one of -6 according to claim 1, wherein the component A, component B, component C and The molar content of alhpa olefin comonomer is each independently 0.2-15mol% in component D.
10. polyethylene film according to claim 9, wherein alhpa olefin in the component A, component B, component C and component D The molar content of comonomer is each independently 1.5-10mol%.
11. polyethylene film according to claim 9, wherein the α alkene in the component A, component B, component C and component D Hydrocarbon is each independently C3-C20At least one of alkene.
12. polyethylene film according to claim 11, wherein the α in the component A, component B, component C and component D Alkene is each independently propylene, 1- butylene, 2- butylene, 3-methyl-1-butene, 4- methyl-1-butylene, 1- amylene, 3- methyl- 1- amylene, 4-methyl-1-pentene, 3,3- dimethyl -1- amylene, 3,4- dimethyl -1- amylene, 4,4- dimethyl -1- amylene, 1- Hexene, 4- methyl-1-hexene, 5- methyl-1-hexene, 1- heptene, 2- heptene, 1- octene, 1- decene, 1- dodecylene, 1- ten At least one of four carbenes, cetene, 1- octadecene and 1- eicosylene.
13. polyethylene film according to claim 12, wherein the α in the component A, component B, component C and component D Alkene is each independently at least one of 1- butylene, 1- hexene and 1- octene.
14. polyethylene film described in any one of -6 according to claim 1, wherein gather the polyethylene core side The 2-35% with a thickness of the polyethylene film thickness on ethylene surface layer.
15. polyethylene film according to claim 14, wherein the polyethylene film with a thickness of 10-200 μm.
16. polyethylene film according to claim 15, wherein the polyethylene film with a thickness of 10-100 μm.
17. a kind of preparation method of polyethylene film, which is characterized in that this method includes that will contain component A, component B and component C The first polyethylene composition and the second polyethylene composition containing component D be sent into the extrudate flow with multi-layer co-extruded structure Curtain coating is squeezed out in rolling equipment, later again stretches obtained curtain coating slab, obtains including polyethylene core and be attached to institute The polyethylene film of at least polyethylene skin of a side surface of polyethylene core is stated, the polyethylene core is gathered by described first Vinyl composition is formed, and the polyethylene skin is formed by second polyethylene composition；The component A is ethylene/alpha-olefin The linear low density polyethylene of copolymerization, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgAFor 0.01- 3.5g/10min, density pAFor 0.915-0.936g/cm3；The component B is the linear low density polyethylene of ethylene/alpha-olefin copolymerization Alkene, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgBFor 3.6-9.9g/10min, density pBFor 0.915- 0.930g/cm3；The component C is the linear low density polyethylene of ethylene/alpha-olefin copolymerization, temperature is 190 DEG C, load is Melt index MI under 2.16kgCFor 10-80g/10min, density pCFor 0.915-0.930g/cm3；The component D is ethylene/alpha The linear low density polyethylene of olefin-copolymerization, the melt index MI in the case where temperature is 190 DEG C, load is 2.16kgDFor 0.5- 50g/10min, density pDFor 0.880-0.910g/cm3。
18. according to the method for claim 17, wherein the component A is in the case where temperature is 190 DEG C, load is 2.16kg Melt index MIAFor 0.01-3g/10min, melt index MI of the component B in the case where temperature is 190 DEG C, load is 2.16kgB For 4-8g/10min, melt index MI of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor 10-60g/ The melt index MI of 10min, the component D in the case where temperature is 190 DEG C, load is 2.16kgDFor 0.5-30g/10min.
19. according to the method for claim 18, wherein the component A is in the case where temperature is 190 DEG C, load is 2.16kg Melt index MIAFor 0.01-2g/10min, melt index MI of the component B in the case where temperature is 190 DEG C, load is 2.16kgB For 4-5g/10min, melt index MI of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor 15-40g/ The melt index MI of 10min, the component D in the case where temperature is 190 DEG C, load is 2.16kgDFor 1-20g/10min.
20. according to the method for claim 17, wherein in first polyethylene composition, the quality of the component A Number WAFor 25-90 parts by weight, the mass fraction W of the component BBFor 0.1-10 parts by weight, the mass fraction W of the component CC For 10-75 parts by weight.
21. according to the method for claim 20, wherein in first polyethylene composition, the quality of the component A Number WAFor 30-80 parts by weight, the mass fraction W of the component BBFor 0.5-8 parts by weight, the mass fraction W of the component CCFor 20-70 parts by weight.
22. according to the method for claim 20, wherein the mass fraction W of the component AAWith the mass fraction W of component CC With the melt index MI of component AARelationship meet 4.6 × lgMIA+10.4≥WA/WC≥0.34×lgMIA+1。
23. method described in any one of 7-22 according to claim 1, wherein first polyethylene composition is in temperature Melt index under being 2.16kg for 190 DEG C, load is 0.1-20g/10min.
24. according to the method for claim 23, wherein first polyethylene composition is temperature is 190 DEG C, load is Melt index under 2.16kg is 0.5-10g/10min.
25. method described in any one of 7-22 according to claim 1, wherein the component A, component B, component C and component The molar content of alhpa olefin comonomer is each independently 0.2-15mol% in D.
26. according to the method for claim 25, wherein alhpa olefin is copolymerized in the component A, component B, component C and component D The molar content of monomer is each independently 1.5-10mol%.
27. according to the method for claim 26, wherein the alhpa olefin in the component A, component B, component C and component D is each From independently being C3-C20At least one of alkene.
28. according to the method for claim 27, wherein the alhpa olefin in the component A, component B, component C and component D is each From independently being propylene, 1- butylene, 2- butylene, 3-methyl-1-butene, 4- methyl-1-butylene, 1- amylene, 3- methyl-1-pentene Alkene, 4-methyl-1-pentene, 3,3- dimethyl -1- amylene, 3,4- dimethyl -1- amylene, 4,4- dimethyl -1- amylene, 1- oneself Alkene, 4- methyl-1-hexene, 5- methyl-1-hexene, 1- heptene, 2- heptene, 1- octene, 1- decene, 1- dodecylene, 1- 14 At least one of carbene, cetene, 1- octadecene and 1- eicosylene.
29. according to the method for claim 28, wherein the alhpa olefin in the component A, component B, component C and component D is each From independently being at least one of 1- butylene, 1- hexene and 1- octene.
30. method described in any one of 7-22 according to claim 1, wherein first polyethylene composition and second The dosage and extrusion curtain coating of polyethylene composition and the condition stretched make the polyethylene skin of the polyethylene core side The 2-35% with a thickness of the polyethylene film thickness.
31. according to the method for claim 30, wherein first polyethylene composition and the second polyethylene composition Dosage and squeeze out curtain coating and stretch condition make the polyethylene film with a thickness of 10-200 μm.
32. according to the method for claim 31, wherein first polyethylene composition and the second polyethylene composition Dosage and squeeze out curtain coating and stretch condition make the polyethylene film with a thickness of 10-100 μm.
33. the polyethylene film that the method as described in any one of claim 17-32 is prepared.
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CN111114061B (en) * 2018-10-31 2021-05-11 中国石油化工股份有限公司 Tear-resistant polyethylene film and preparation method thereof
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