CN107312229A - 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
CN107312229A
CN107312229A CN201610265201.3A CN201610265201A CN107312229A CN 107312229 A CN107312229 A CN 107312229A CN 201610265201 A CN201610265201 A CN 201610265201A CN 107312229 A CN107312229 A CN 107312229A
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component
polyethylene
10min
temperature
melt index
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CN107312229B (en
Inventor
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 Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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

Abstract

The present invention relates to polymer arts, there is provided a kind of polyethylene film and preparation method thereof.The polyethylene film includes polyethylene core and is attached to the polyethylene skin of an at least side surface for 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 LLDPE of ethylene/alpha-olefin copolymerization, and this several component temperature be 190 DEG C, load be that melt index under 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/cm3With 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
The present invention relates to a kind of polyethylene film, a kind of preparation method of polyethylene film and by this method The polyethylene film prepared.
Background technology
Biaxially-oriented polyethylene (Biaxially Oriented Polyethylene, BOPE) film is that have The thin-film material that polyethylene (PE) resin of special molecular structure is molded through stretch processes.In BOPE In the molding process of film, after the processing of film drawn, PE macromolecular chains and crystalline texture occur It is height-oriented, so as to significantly improve the tensile strength of film, tension fracture elongation rate is reduced, and make Film mist degree is lower, glossiness is higher and it is transparent more preferably.In addition, being blown with the extrusion of prior art The polyethylene film product that modeling technique is prepared with extrusion casting technique is compared, and BOPE films have mechanics strong The advantages such as degree is high, puncture resistant and shock resistance is good, excellent optical performance, environmental protection and energy saving.Therefore, BOPE films can be widely used in packaging bag, again packaging bag, Vacuum Heat sealer, low temperature packaging film, multiple In terms of conjunction film, medical and sanitary products, plastic film for agricultural use.
The biaxial tension processing method of the plastic sheeting used at present has Flat film strength and envelope pulling method. Flat film strength has been applied in polypropylene (PP), polyamide (PA), polyethylene terephthalate Etc. (PET) in the processing of thin-film material, technique is more ripe.Compared with envelope pulling method, flat film is drawn Stretch fast (the highest winding of stretching ratio big (cross directional stretch multiplying power is up to more than 10 times), shaping speed of method Speed is up to hundreds of ms/min), production efficiency it is high and the mechanical strength of obtained film, optical Can be with thickness evenness more preferably, but film forming is influenceed significantly by process condition fluctuations, film stretching Difficulty of processing is big, there is higher requirement for film raw material.Existing Biaxially-oriented polyethylene raw material base This is only applicable to envelope pulling method and prepares BOPE films, and these existing polyethylene raw materials are used Flat film strength prepare BOPE films when, exist film forming poor (draw speed and stretching ratio are very low), Easily there is the defect ruptured in film, and the mechanical property and optical property of obtained film are poor.
The content of the invention
The invention aims to overcome the mechanical property and optical property of existing polyethylene film compared with The defect of difference, and provide a kind of with the poly- of higher mechanical property, optical property and heat-seal strength Vinyl film, a kind of preparation method of polyethylene film and the polyethylene prepared by this method are thin Film.
Specifically, the polyethylene film that the present invention is provided includes polyethylene core and is attached to the polyethylene The polyethylene skin of an at least side surface for sandwich layer, the polyethylene core is by containing component A, component B Formed with component C the first polyethylene composition, the polyethylene skin is by second containing component D Polyethylene composition is formed；The component A is the LLDPE of ethylene/alpha-olefin copolymerization, its Temperature be 190 DEG C, load be 2.16kg under melt index MIAFor 0.01-3.5g/10min, density ρAFor 0.915-0.936g/cm3；The component B is the LLDPE of ethylene/alpha-olefin copolymerization, Its temperature be 190 DEG C, load be 2.16kg under melt index MIBIt is close for 3.6-9.9g/10min Spend ρBFor 0.915-0.930g/cm3；The component C is the linear low density polyethylene of ethylene/alpha-olefin copolymerization Alkene, its temperature be 190 DEG C, load be 2.16kg under melt index MICFor 10-80g/10min, Density pCFor 0.915-0.930g/cm3；The component D gathers for the linea low density of ethylene/alpha-olefin copolymerization Ethene, its temperature be 190 DEG C, load be 2.16kg under melt index MIDFor 0.5-50g/10min, Density pDFor 0.880-0.910g/cm3。
The preparation method for the polyethylene film that the present invention is provided includes that component A, component B and component will be contained C the first polyethylene composition and the second polyethylene composition feeding containing component D are common with multilayer Squeeze and curtain coating is extruded in the extrusion casting apparatus of structure, obtained curtain coating slab is stretched again afterwards, obtained To the polyethylene skin including polyethylene core He at least side surface for being attached to the polyethylene core Polyethylene film, the polyethylene core formed by first polyethylene composition, the polyethylene Top layer is formed by second polyethylene composition；The component A is linear low for ethylene/alpha-olefin copolymerization Density polyethylene, its temperature be 190 DEG C, load be 2.16kg under melt index MIAFor 0.01-3.5g/10min, density pAFor 0.915-0.936g/cm3；The component B is common for ethylene/alpha-olefin Poly- LLDPE, its temperature be 190 DEG C, load be 2.16kg under melt index MIBFor 3.6-9.9g/10min, density pBFor 0.915-0.930g/cm3；The component C is ethylene/alpha The LLDPE of olefin-copolymerization, its temperature be 190 DEG C, load be 2.16kg under melting Index M ICFor 10-80g/10min, density pCFor 0.915-0.930g/cm3；The component D is ethene The LLDPE of/alhpa olefin copolymerization, its temperature be 190 DEG C, load be molten under 2.16kg Melt index M IDFor 0.5-50g/10min, density pDFor 0.880-0.910g/cm3。
In addition, present invention also offers the polyethylene film prepared by the above method.
The present inventor has found after further investigation, when will be above-mentioned containing particular melt index and close Component A, the component B of degree and component C the first polyethylene composition and contain particular melt index During with the component D of density the second polyethylene composition with the use of film is made, obtained polyethylene is thin Film has the advantages that stretching ratio is big, rate of film build is high, disclosure satisfy that Flat film strength to polyethylene raw material High requirement, and obtained polyethylene film have higher mechanical property and optical property and compared with Good heat-seal strength, is highly suitable for packaging material, great prospects for commercial application.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with Following embodiment is used to explain the present invention together, but is not construed as limiting the invention. In accompanying drawing：
Fig. 1 is the structural representation for preparing the multiple reactor shunting means of the first polyethylene composition.
Description of reference numerals
1- first reactors；2- second reactors；The reactors of 3- the 3rd；4- solid-liquids (gas) separator； 5- homogenization silos；6- melt pelletization systems.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place is retouched The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, this A little scopes or value should be understood to comprising the value close to these scopes or value.For number range, respectively Between the endpoint value of individual scope, between the endpoint value of each scope and single point value, and individually point Can be combined with each other between value and obtain one or more new number ranges, these number ranges should by regarding For specific disclosure herein.
The polyethylene film that the present invention is provided includes polyethylene core and is attached to the polyethylene core At least polyethylene skin of a side surface, the polyethylene core is by containing component A, component B and component C the first polyethylene composition is formed, and the polyethylene skin is by the second polyethylene group containing component D Compound is formed；The component A is the LLDPE of ethylene/alpha-olefin copolymerization, and it is in temperature 190 DEG C, load be 2.16kg under melt index MIAFor 0.01-3.5g/10min, density pAFor 0.915-0.936g/cm3；The component B is the LLDPE of ethylene/alpha-olefin copolymerization, its Temperature be 190 DEG C, load be 2.16kg under melt index MIBFor 3.6-9.9g/10min, density pB For 0.915-0.930g/cm3；The component C is the LLDPE of ethylene/alpha-olefin copolymerization, Its temperature be 190 DEG C, load be 2.16kg under melt index MICFor 10-80g/10min, density ρCFor 0.915-0.930g/cm3；The component D is the LLDPE of ethylene/alpha-olefin copolymerization, Its temperature be 190 DEG C, load be 2.16kg under melt index MIDFor 0.5-50g/10min, density ρDFor 0.880-0.910g/cm3。
According to the polyethylene film that provides of the present invention, it is preferable that the component A temperature be 190 DEG C, Load is the melt index MI under 2.16kgAIt is in temperature for 0.01-3g/10min, the component B 190 DEG C, load be 2.16kg under melt index MIBFor 4-8g/10min, the component C is in temperature It is the melt index MI under 2.16kg for 190 DEG C, loadCExist for 10-60g/10min, the component D Temperature is 190 DEG C, load is melt index MI under 2.16kgDFor 0.5-30g/10min.It is highly preferred that The component A temperature be 190 DEG C, load be 2.16kg under melt index MIAFor 0.01-2g/10min, the component B temperature be 190 DEG C, load be 2.16kg under melt index MIBFor 4-5g/10min, the component C temperature be 190 DEG C, load be that melting under 2.16kg refers to Number MICFor 15-40g/10min, the component D temperature be 190 DEG C, load be molten under 2.16kg Melt index M IDFor 1-20g/10min.
In the present invention, the melt index is surveyed according to method specified in GB/T3682-2000 It is fixed, wherein, it is 190 DEG C that test condition, which includes temperature, and load is 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 component C's Density pCFor 0.915-0.928g/cm3, the density p of the component DDFor 0.880-0.905g/cm3, this The polyethylene film that sample is enabled to is on the basis of with preferable filming performance, also with higher Tensile strength, optical property and heat-seal strength.
The component A, component B, component C and component D are the linear low of ethylene/alpha-olefin copolymerization Density polyethylene, wherein, linear structure refers to only contain short-chain branch structure in strand, and does not contain length Branched structure and cross-linked structure, it is determined by polymerized monomer and polymerization process condition, specially this area Known in technical staff, therefore not to repeat here.
The polyethylene film provided according to the present invention, in order that obtained polyethylene film has higher power Learn intensity, it is preferable that in first polyethylene composition, the mass fraction W of the component AA For 25-90 parts by weight, the mass fraction W of the component BBFor 0.1-10 parts by weight, the component C Mass fraction WCFor 10-75 parts by weight；It is highly preferred that 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, it is described Component A mass fraction WAWith component C mass fraction WCWith component A melt index MIA Relation preferred meet 4.6 × lgMIA+10.4≥WA/WC≥0.34×lgMIA+ 1, so enable to With bigger stretching ratio and more during polyethylene film is prepared using flat film biaxial tension method High rate of extension.
The polyethylene film provided according to the present invention, particularly preferably, first polyethylene composition exists Temperature is 190 DEG C, load is that melt index under 2.16kg is 0.1-20g/10min, is most preferably 0.5-10g/10min.On the basis of said components A, component B and component C are used cooperatively, by institute State the overall melt index of the first polyethylene composition to control in above-mentioned preferred scope, enable to The first polyethylene composition there is very excellent film forming, and obtained polyethylene film has more High 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 It can be prepared using existing various methods, it is for instance possible to use Ziegler-Natta catalyst system It is standby to obtain, it would however also be possible to employ metallocene catalyst is prepared.Wherein, the ziegler-natta catalyzed The species of agent and metallocene catalyst can be the conventional selection of this area, for example, the Ziegler-receive Tower catalyst is generally made up of magnesium titanium compound and organo-aluminum compound and optional electron donor, described Metallocene catalyst is generally by metallocene compound and organo-aluminum compound and optional electron donor group Into being specifically known to the skilled person, therefore not to repeat here.
The present invention is to alhpa olefin comonomer in the component A, component B, component C and component D Content is not particularly limited, for example, α in the component A, component B, component C and component D The molar content of olefin comonomer can be each independently 0.2-15mol%, be preferably 1.5-10mol%.In the present invention, the molar content of alhpa olefin comonomer refers to by alpha-olefin polymerization shape Into construction unit mole account for total monomer construction unit mole ratio.In addition, the component Alhpa olefin in A, component B, component C and component D is each independently C3-C20In alkene at least It is a kind of.From the ready availability angle of raw material, the component A, component B, component C and component D Alhpa olefin be preferably propylene, 1- butylene, 2- butylene, 3-methyl-1-butene, 4- methyl isophthalic acids-butylene, 1- Amylene, 3- Methyl-1-pentenes, 4-methyl-1-pentene, 3,3- dimethyl -1- amylenes, 3,4- dimethyl -1- penta Alkene, 4,4- dimethyl -1- amylenes, 1- hexenes, 4- methyl isophthalic acids-hexene, 5- methyl isophthalic acids-hexene, 1- heptene, 2- heptene, 1- octenes, 1- decene, 1- 12 (carbon) alkene, 1- 14 (carbon) alkene, 1- 16 (carbon) alkene, 1- ten At least one of eight (carbon) alkene and 1- 20 (carbon) alkene, more preferably 1- butylene, 1- hexenes and 1- octenes At least one of.
In addition, can also contain in first polyethylene composition and the second polyethylene composition existing Various usually used other auxiliary agents in polyvinyl resin and polyethylene film, and other described auxiliary agents are not Stretching film forming, mechanical property, optical property and the heat-sealing for the polyethylene film that the present invention can be provided Intensity is closed to have adverse effect on.Other described auxiliary agents include but is not limited to：It is antioxidant, lubricant, refreshing At least one of lubrication prescription, antistatic additive, antitack agent etc..In addition, the consumption of other auxiliary agents Think the conventional selection of this area, 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 dividing Do not prepare component A, component B and component C, then by the component A, component B and component C with And other auxiliary agents that selectivity contains carry out mechanical mixture, Ran Houjia according to proportioning in mechanical mixing equipment Enter and melt blending is carried out in melt blending equipment.Wherein, the mechanical mixing equipment for example can be at a high speed Mixer, kneader etc..The melt blending equipment can for example squeeze for double screw extruder, single screw rod Go out machine, mill, banbury etc..
A preferred embodiment of the invention, first polyethylene composition is as shown in Figure 1 Multiple reactor shunting means in prepare, the multiple reactor shunting means include first reactor 1, Second reactor 2, the 3rd reactor 3, solid-liquid (gas) separator 4, homogenization silo 5 and melting are made Grain system 6, wherein, the first reactor 1, second reactor 2 and the 3rd reactor 3 are in parallel even Connect, the number of solid-liquid (gas) separator 4 is three, anti-with first reactor 1, second respectively Device 2 is answered to be connected with the 3rd reactor 3, the component A that is prepared by first reactor 1, by second reactor The 2 component B prepared the and component C that is prepared by the 3rd reactor 3 are respectively in different solid-liquids (gas) It is separated, is then pressed the component A after phase separation, component B and component C in separator 4 Ratio is delivered in homogenization silo 5 and is mixed together uniformly with other optional additives, sends into afterwards molten Melt and extruding pelletization is carried out in granulating system 6.Wherein, the polymerization in each reactor can be batchwise polymerization, It can also be continuous polymerization.When using multiple reactor parallel polymerization, W hereinafterA、WBAnd WC For yield in unit time of each component in respective reaction device.
According to the present invention, as described above, the polyethylene film includes polyethylene core and is attached to described The polyethylene skin of an at least side surface for polyethylene core, i.e. the polyethylene film can have upper The three-decker on top layer, sandwich layer and layer, it is possible to have the double-layer structure of upper epidermis and sandwich layer.Institute State polyethylene core and polyethylene skin thickness can according to the use condition of the polyethylene film come Appropriate selection, if the condition used requires that the polyethylene film has larger mechanical strength and right Optical performance requirements are relatively low, then the polyethylene core and the thickness of polyethylene skin can be thicker；If institute State the condition that uses require the polyethylene film have preferable translucency and to mechanical strength requirement compared with Low, then the polyethylene core and the thickness of polyethylene skin can be with relatively thin.Under normal circumstances, it is described poly- The thickness of the polyethylene skin of ethene sandwich layer side can be the 2-35% of the polyethylene film thickness.Enter One step, it is described when the polyethylene film has the composite construction of upper epidermis, sandwich layer and layer Upper epidermis and the thickness of layer are each independently the 2-25% of the film thickness；When the polyethylene When film has the composite construction of upper epidermis and sandwich layer, the thickness of the upper epidermis is the film thickness 2-35%.In addition, the gross thickness of the polyethylene film can be 10-200 μm, preferably 10-100 μm.
The preparation method for the polyethylene film that the present invention is provided includes that component A, component B and component will be contained C the first polyethylene composition and the second polyethylene composition feeding containing component D are common with multilayer Squeeze and curtain coating is extruded in the extrusion casting apparatus of structure, obtained curtain coating slab is stretched again afterwards, obtained To the polyethylene skin including polyethylene core He at least side surface for being attached to the polyethylene core Polyethylene film, the polyethylene core formed by first polyethylene composition, the polyethylene Top layer is formed by second polyethylene composition；The component A is linear low for ethylene/alpha-olefin copolymerization Density polyethylene, its temperature be 190 DEG C, load be 2.16kg under melt index MIAFor 0.01-3.5g/10min, density pAFor 0.915-0.936g/cm3；The component B is common for ethylene/alpha-olefin Poly- LLDPE, its temperature be 190 DEG C, load be 2.16kg under melt index MIBFor 3.6-9.9g/10min, density pBFor 0.915-0.930g/cm3；The component C is ethylene/alpha The LLDPE of olefin-copolymerization, its temperature be 190 DEG C, load be 2.16kg under melting Index M ICFor 10-80g/10min, density pCFor 0.915-0.930g/cm3；The component D is ethene The LLDPE of/alhpa olefin copolymerization, its temperature be 190 DEG C, load be molten under 2.16kg Melt index M IDFor 0.5-50g/10min, density pDFor 0.880-0.910g/cm3。
According to the present invention, in order to obtain under performance more excellent polyethylene film, preferable case, the party Method be additionally included in by the first polyethylene composition and the second polyethylene composition feeding extrusion casting apparatus it Before, the first polyethylene composition and the second polyethylene composition are dried.The method of the drying and Drying means and condition that condition can be known to the skilled person, for example, can for vacuum drying, Forced air drying etc., drying temperature can be 60-100 DEG C.Drying equipment is usually to include heating, dry heat The drying equipment of air purging or vacuum system, for example, can be continuous dryer, vacuum drying oven and heat Wind baking oven etc..
It should be noted that generally include in multiple extruders, multiple extruders can be with for extrusion casting apparatus Different materials is heated, and the material after different extruder heating can be by same The MULTILAYER COMPOSITE die head extrudate flow at least including two layers prolongs, so as to obtain including the curtain coating slab of multilayer；Its In, the material in each extruder is extruded from wherein one layer of the MULTILAYER COMPOSITE die head.Therefore, originally Art personnel should be readily understood that, when needing to obtain the side surface attachment of polyethylene core During the polyethylene film of polyethylene skin, two different extruders can be used by first polyethylene Composition and the melting of second polyethylene composition, and by molten product simultaneously by same including two layers The two membranes obtained after die head extrusion curtain coating, extrusion are stacked together, then the present invention is just obtained after drawn Polyethylene film；The poly- of polyethylene skin is attached with when needing the both side surface for obtaining polyethylene core During vinyl film, raw materials melt (wherein, can be added in main extruder using three different extruders Enter in the first polyethylene composition, top layer extruder and add the second polyethylene composition), and will melting Product extrusion curtain coating, then the polyethylene film of the present invention is just can obtain after drawn.
According to the present invention, extrusion curtain coating extruder used can be single screw extrusion machine, can also For double screw extruder.In addition, the condition of the extrusion curtain coating can be existing conventional selection, to this Those skilled in the art can know that therefore not to repeat here.
In addition, the stretching can be simple tension, or biaxial tension, preferably bidirectional stretching, More preferably flat film biaxial tension.Flat film biaxial tension method is used to prepare the process of biaxially oriented film for this Known in art personnel.Specifically, first above-mentioned polyethylene composition is added in extrusion casting apparatus Extrusion curtain coating is carried out, is then drawn into obtained curtain coating slab in film biaxial tension equipment Type.In addition, the biaxial tension (can carry out film longitudinal direction simultaneously using Synchronos method drawing process (MD) and laterally (TD) is stretched), it would however also be possible to employ method of fractional steps drawing process (first carries out film Longitudinal stretching, then carry out film cross directional stretch).The concrete technology of Synchronos method stretching is：The stream Prolong slab after being fully warmed-up, while vertical and horizontal direction stretching is carried out, wherein, preheating temperature can be with For 75-165 DEG C, draft temperature can be 75-160 DEG C, and longitudinal direction (MD) stretching ratio >=4 times are horizontal To (TD) stretching ratio >=5 times, cross directional stretch speed >=50%/s.It is specific that the method for fractional steps is stretched Technique is：The curtain coating slab first carries out longitudinal stretching, cross directional stretch is carried out afterwards after being fully warmed-up, Wherein, preheating temperature can be 65-158 DEG C, and draft temperature can be 65-155 DEG C, longitudinal direction (MD) Stretching ratio >=4 times, horizontal (TD) stretching ratio >=5 times, cross directional stretch speed >=50%/s.This Outside, it can be handled after film drawing and forming without setting, annealing setting processing can also be carried out.When entering During row annealing setting processing, film setting treatment temperature can be 80-165 DEG C.Finally, film can be with Surface corona processing, cutting edge and winding processing are carried out, polyethylene film of the present invention is finally given.
The polyethylene film that the present invention is provided has that preferable film forming and stretching ratio be big, rate of extension It is high.During the biaxially oriented film is prepared using Flat film strength, as described above, described thin Longitudinal direction (MD) stretching ratio >=4 times of film, horizontal (TD) stretching ratio >=5 times.Stretching ratio Bigger, then the mechanical strength of film is higher.Transverse direction (TD) rate of extension >=50%/s of the film, Preferably 60-150%/s, so ensure that the continuous production of industrialization.
The polyethylene film that the present invention is provided has higher mechanical strength, optical property and heat sealing strong Degree, can specifically meet：Longitudinal direction (MD) tensile strength >=50MPa, is preferably >=55MPa；Laterally (TD) tensile strength >=50MPa, is preferably >=55MPa；Tension fracture elongation rate≤350%, it is excellent Elect≤300% as；Puncture strength >=2.5N, preferably >=3.5N；Mist degree≤6%, is preferably≤3%；Heat Sealing strength >=2.5N, is preferably >=3.5N.In the present invention, the longitudinal tensile strength and laterally drawing Intensity is stretched to be measured according to method specified in GB/T 1040.3-2006.The tension fracture elongation rate It is measured according to method specified in GB/T 1040.3-2006.The puncture strength is according to GB/T Method is measured specified in 10004-2008, wherein, the thickness of film sample is 25 ± 5 μm.Institute Mist degree is stated to be measured according to method specified in GB/T 2410-2008, wherein, the thickness of film sample Spend for 25 ± 5 μm.The heat-seal strength is measured according to method specified in QBT2358-1998, Wherein, heat-sealing temperature is 120 DEG C, and heat-sealing pressure is 0.18MPa.
In addition, present invention also offers the polyethylene film prepared by the above method.
In addition, the production cost for the polyethylene film that the present invention is provided is low, processing technology is simple, versatility It 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 Br ü ckner companies of Germany, model Karo IV.
The performance of each component is tested in accordance with the following methods in polyethylene composition：
(1) melt index (MI)：It is measured according to method specified in GB/T 3682-2000, Wherein, test temperature is 190 DEG C, and load is 2.16kg；
(2) density：According to method specified in GB/T 1033.2-2010 and using density gradient column method It is measured.
Embodiment 1
The present embodiment is used to illustrate polyethylene film of the invention provided and preparation method thereof.
(1) preparation of polyethylene composition：
The first polyethylene composition that the present embodiment is provided is made up of component A, component B and component C, Second polyethylene composition is made up of component D.Wherein, component A, component B, component C and component D It is the LLDPE (LLDPE) of ethylene/alpha-olefin copolymerization, and is catalyzed using identical Prepared by agent system (Ziegler-Natta catalyst) and polymerization technique, when difference is to prepare different component The amounts of hydrogen and the species and molar content of alhpa olefin comonomer added is different.Specific steps It is as follows：
By ethene, alhpa olefin, hydrogen and nitrogen (ethene, alhpa olefin, hydrogen and nitrogen are polymer grade, Used after removing water, oxygen, similarly hereinafter) it is added in gas fluidized bed reactor, then add Ziegler (ziegler-natta catalyst systems are by CN101838351A embodiments to-natta catalyst systems 1 ziegler-natta catalyst systems prepared, similarly hereinafter), it is afterwards 84-88 DEG C, pressure in temperature To polymerize under conditions of 1.8-2.0MPa, component A, component B, component C and component D are respectively obtained. Wherein, the control of component A, component B, component C and component D melt index is by adjusting hydrogen Addition and realize, the control of density is realized by adjusting the species and addition of alhpa olefin.Preparation group Alhpa olefin used is 1- hexenes during dividing A, and alhpa olefin used is 1- during preparing component B Butylene, alhpa olefin used is 1- butylene during preparing component C, prepares institute during component D It is 1- hexenes with alhpa olefin.
After testing, the performance of each component prepared by the above method is as follows：
Component A melt index MIA=2.0g/10min, density pA=0.915g/cm3, alhpa olefin copolymerization Molar content=8.0mol% of monomer；
Component B melt index MIB=4.0g/10min, density pB=0.915g/cm3, alhpa olefin copolymerization Molar content=8.0mol% of monomer；
Component C melt index MIC=15g/10min, density pC=0.915g/cm3, alhpa olefin copolymerization list Molar content=9.8mol% of body；
Component D melt index MID=5.0g/10min, density pD=0.900g/cm3, alhpa olefin copolymerization Molar content=10.3mol% of monomer.
Said components A, component B and component C are weighed and mixed, wherein component A by proportioning Mass fraction WAFor 80 parts by weight, component B mass fraction WBFor 10 parts by weight, component C Mass fraction WCFor 20 parts by weight, WA/WC=4 (meet 4.6 × lgMIA+10.4≥WA/WC≥ 0.34×lgMIA+1)；Add mixture in high speed agitator and be well mixed afterwards, then will mix Material be added to W＆P companies manufacture double screw extruder feeder in, material is via feeder Into in twin-screw, the temperature of screw rod is maintained between 160-210 DEG C in process, is melted through screw rod It is well mixed, extrudes, granulates and dry, obtain the first polyethylene composition pellet, it is melted after testing Index M I=3.4g/10min.In addition, preparing the second polyethylene composition grain using above-mentioned identical method Material, unlike, component A, component B and component C are substituted using component D.
(2) preparation of polyethylene film：
By the first polyethylene composition pellet made from above-mentioned steps (1) and the second polyethylene composition grain Material is dried, and the model LCR400 of Labtech companies of Sweden multilayer extrusion stream is added to afterwards Prolong and melting extrusion is carried out in machine and slab is cast, wherein, the first polyethylene composition pellet is added to core Layer extruder, and the second polyethylene composition pellet is added in upper and lower top layer extruder, it is described it is upper, Also need to add inorganic antitack agent (silica, similarly hereinafter), and upper and lower top layer in layer extruder The antitack agent and the weight ratio of the second polyethylene composition pellet added in extruder is 0.02:1, in stream Prolong during slab, curtain coating chilling roll temperature is set as 25 DEG C, the thick slab of polyethylene is made, it is by upper Top layer, sandwich layer and layer are constituted.
The thick slab of above-mentioned polyethylene is put into the stretching clamp of film biaxial tension equipment, using first indulging The two-way step drawing technological forming that laterally (TD) is stretched after being stretched to (MD), each step process condition It is as follows：MD preheating temperatures are 100 DEG C, and MD draft temperatures are 110 DEG C, and MD stretching ratios are 4 times, TD preheating temperatures are 100 DEG C, and TD draft temperatures are 115 DEG C, and TD stretching ratios are 5 times, film TD rates of extension are 150%/s, and film setting temperature is 120 DEG C, and it is 25 μm to obtain average thickness Film, it is made up of upper epidermis, sandwich layer and layer, and core layer raw material is first polyethylene of the present embodiment Composition, upper epidermis and layer raw material are second polyethylene composition of the present embodiment, and upper epidermis is with The thickness on top layer is 1.5 μm.
Embodiment 2
The present embodiment is used to illustrate polyethylene film of the invention provided and preparation method thereof.
(1) preparation of polyethylene composition：
The first polyethylene composition that the present embodiment is provided is made up of component A, component B and component C, Second polyethylene composition is made up of component D.Wherein, component A, component B, component C and component D It is the LLDPE (LLDPE) of ethylene/alpha-olefin copolymerization, and is catalyzed using identical Prepared by agent system (ziegler-natta catalyst systems) and polymerization technique, difference is to prepare different groups The amounts of hydrogen and the species and molar content of alhpa olefin comonomer that timesharing is added are different.Specifically Step is as follows：
Ethene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, then added neat Ge Le-natta catalyst systems, is afterwards 84-88 DEG C, under conditions of pressure is 1.8-2.0MPa in temperature Polymerization, respectively obtains component A, component B, component C and component D.Wherein, component A, component B, The control of component C and component D melt index realized by adjusting the addition of hydrogen, density Control is realized by adjusting the species and addition of alhpa olefin.Prepare α used during component A Alkene is 1- butylene, and alhpa olefin used is 1- butylene during preparing component B, prepares component C's Used in the process of alhpa olefin be 1- hexenes, alhpa olefin used is 1- hexenes during preparing component D.
After testing, the performance of each component prepared by the above method is as follows：
Component A melt index MIA=0.01g/10min, density pA=0.930g/cm3, alhpa olefin copolymerization Molar content=2.1mol% of monomer；
Component B melt index MIB=9.0g/10min, density pB=0.930g/cm3, alhpa olefin copolymerization Molar content=2.8mol% of monomer；
Component C melt index MIC=40g/10min, density pC=0.922g/cm3, alhpa olefin copolymerization list Molar content=4.0mol% of body；
Component D melt index MID=1.0g/10min, density pD=0.910g/cm3, alhpa olefin copolymerization Molar content=9.0mol% of monomer.
Said components A, component B and component C are weighed and mixed, wherein component A by proportioning Mass fraction WAFor 55 parts by weight, component B mass fraction WBFor 5 parts by weight, component C Mass fraction WCFor 55 parts by weight, WA/WC=1 (meets 4.6 × lgMIA+10.4≥WA/WC≥ 0.34×lgMIA+1)；Add mixture in high speed agitator and be well mixed afterwards, then will mix Material be added to W＆P companies manufacture double screw extruder feeder in, material is via feeder Into in twin-screw, the temperature of screw rod is maintained between 180-240 DEG C in process, is melted through screw rod It is well mixed, extrudes, granulates and dry, obtain the first polyethylene composition pellet, it is melted after testing Index M I=0.7g/10min.In addition, preparing the second polyethylene composition grain using above-mentioned identical method Material, unlike, component A, component B and component C are substituted using component D.
(2) preparation of polyethylene film：
By the first polyethylene composition pellet made from above-mentioned steps (1) and the second polyethylene composition grain Material is dried, and the model LCR400 of Labtech companies of Sweden multilayer extrusion stream is added to afterwards Prolong and melting extrusion is carried out in machine and slab is cast, wherein, the first polyethylene composition pellet is added to core Layer extruder, and the second polyethylene composition pellet is added in upper and lower top layer extruder, it is described it is upper, Also need to add inorganic antitack agent (silica, similarly hereinafter), and upper and lower top layer in layer extruder The antitack agent and the weight ratio of the second polyethylene composition pellet added in extruder is 0.02:1, in stream Prolong during slab, curtain coating chilling roll temperature is set as 85 DEG C, the thick slab of polyethylene is made, it is by upper Top layer, sandwich layer and layer are constituted.
The thick slab of above-mentioned polyethylene is put into the stretching clamp of film biaxial tension equipment, using first indulging The two-way step drawing technological forming that laterally (TD) is stretched after being stretched to (MD), each step process condition It is as follows：MD preheating temperatures are 130 DEG C, and MD draft temperatures are 132 DEG C, and MD stretching ratios are 4 times, TD preheating temperatures are 130 DEG C, and TD draft temperatures are 132 DEG C, and TD stretching ratios are 6 times, film TD rates of extension are 100%/s, and film setting temperature is 135 DEG C, and it is 25 μm to obtain average thickness Film, it is made up of upper epidermis, sandwich layer and layer, and core layer raw material is first polyethylene of the present embodiment Composition, upper epidermis and layer raw material be the present embodiment the second polyethylene composition, and upper epidermis and Also contain antitack agent in layer, the thickness of upper epidermis and layer is 1 μm.
Embodiment 3
The present embodiment is used to illustrate polyethylene film of the invention provided and preparation method thereof.
(1) preparation of polyethylene composition：
The first polyethylene composition that the present embodiment is provided is made up of component A, component B and component C, Second polyethylene composition is made up of component D.Wherein, first polyethylene composition uses Fig. 1 Shown multiple reactor shunting means polymerization is obtained, and the wherein polymerization of first reactor 1 prepares component A, the The polymerization of two reactors 2 prepares component B, the polymerization of the 3rd reactor 3 and prepares component C.Component A, component B, component C and component D are the LLDPE (LLDPE) of ethylene/alpha-olefin copolymerization, And prepared using identical catalyst system (metallocene catalyst system) and polymerization technique, difference exists The amounts of hydrogen, the species of alhpa olefin comonomer and the molar content that are added when different component is prepared and The yield in unit time of each reactor is different.Comprise the following steps that：
Alhpa olefin, n-hexane and hydrogen are added in polymer reactor, and polymer reactor is heated to Default polymerization temperature, afterwards by vinyl monomer and the metallocene catalyst system (metallocene catalyst System is the carried metallocene catalyst prepared by CN102453124A embodiments 1, similarly hereinafter) Be added to simultaneously in polymer reactor, and temperature be 140 DEG C, pressure be to gather under conditions of 2.5MPa Close 30 minutes, respectively obtain component A, component B, component C and component D.Wherein, component A, The control of component B, component C and component D melt index realized by adjusting the addition of hydrogen, The control of density is realized by adjusting the species and addition of alhpa olefin.Prepare institute during component A It is 1- octenes with alhpa olefin, alhpa olefin used is 1- butylene during preparing component B, prepares component C During alhpa olefin used be 1- butylene, alhpa olefin used is 1- octenes during preparing component D.
By the yield in unit time W of component A in first reactor 1 in preparation processA, second reaction Component B yield in unit time W in device 2BWith the yield in unit time of component C in the 3rd reactor 3 WCWeight 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)。
After testing, the performance of each component prepared by the above method is as follows：
Component A melt index MIA=0.1g/10min, density pA=0.920g/cm3, alhpa olefin copolymerization Molar content=2.1mol% of monomer；
Component B melt index MIB=5.0g/10min, density pB=0.920g/cm3, alhpa olefin copolymerization Molar content=5.1mol% of monomer；
Component C melt index MIC=25g/10min, density pC=0.920g/cm3, alhpa olefin copolymerization list Molar content=5.1mol% of body；
Component D melt index MID=25g/10min, density pD=0.905g/cm3, alhpa olefin copolymerization list Molar content=8.0mol% of body.
Component A obtained above, component B and component C are conveyed respectively in yield in unit time ratio It is separated and and then is transported to the homogenization material stirred into different solid-liquid (gas) separators 4 Mixing homogenizing is carried out in storehouse 5.The mixture that homogenized feed bin 5 is homogenized afterwards is added to W＆P companies In the feeder of the double screw extruder of manufacture, material enters in twin-screw via feeder, process The temperature of middle screw rod is maintained between 170-230 DEG C, through screw rod melting mixing is uniform, extrusion, is granulated simultaneously Drying, obtains the first polyethylene composition pellet, after testing its melt index MI=0.6g/10min.This Outside, the second polyethylene composition pellet is prepared using above-mentioned identical method, unlike, component A, Component B and component C are substituted using component D.
(2) preparation of polyethylene film：
By the first polyethylene composition pellet made from above-mentioned steps (1) and the second polyethylene composition grain Material is dried, and the model LCR400 of Labtech companies of Sweden multilayer extrusion stream is added to afterwards Prolong and melting extrusion is carried out in machine and slab is cast, wherein, the first polyethylene composition pellet is added to core Layer extruder, and the second polyethylene composition pellet is added in upper epidermis extruder, the upper epidermis Also need to add inorganic antitack agent (silica, similarly hereinafter) in extruder, and add in upper epidermis extruder The antitack agent and the weight ratio of the second polyethylene composition pellet entered is 0.02:1, during curtain coating slab, Curtain coating chilling roll temperature is set as 35 DEG C, the thick slab of polyethylene is made, it is made up of upper epidermis and sandwich layer.
The thick slab of above-mentioned polyethylene is put into the stretching clamp of film biaxial tension equipment, using first indulging The two-way step drawing technological forming that laterally (TD) is stretched after being stretched to (MD), each step process condition It is as follows：MD preheating temperatures are 110 DEG C, and MD draft temperatures are 110 DEG C, and MD stretching ratios are 4 times, TD preheating temperatures are 115 DEG C, and TD draft temperatures are 115 DEG C, and TD stretching ratios are 5 times, film TD rates of extension are 100%/s, and film setting temperature is 122 DEG C, and it is 25 μm to obtain average thickness Film, it is made up of upper epidermis and sandwich layer, and core layer raw material is first polyethylene composition of the present embodiment, Upper epidermis raw material is second polyethylene composition of the present embodiment, and also contains antitack agent in upper epidermis, on The thickness on top layer is 2 μm.
Embodiment 4
The present embodiment is used to illustrate polyethylene film of the invention provided and preparation method thereof.
Method according to embodiment 1 prepares polyethylene film, unlike, preparing the first polyethylene group During compound, component A consumption WAFor 80 parts by weight, component B consumption WBFor 25 weights Measure part, component C mass fraction WCFor 5 parts by weight, WA/WC=16 (are unsatisfactory for 4.6 × lgMIA+10.4 ≥WA/WC≥0.34×lgMIA+ 1), by repeatedly trial, the maximum tension times of its biaxially oriented film Rate is 4 times of (TD) × 4 times (MD), obtains polyethylene film.
Comparative example 1
This comparative example is used to illustrate polyethylene film of reference and preparation method thereof.
(1) polyethylene raw material：
Polyethylene raw material used in this comparative example is the film that Yanshan Petrochemical company of SINOPEC produces Level LLDPE, trade mark DFDA-7042, melt index MI=2.0g/10min, density ρ=0.920g/cm3。
(2) preparation of polyethylene film：
Method according to embodiment 1 prepares polyethylene film, unlike, by the first polyethylene group Compound pellet and the second polyethylene composition pellet use this comparative example step (1) of identical weight part Polyethylene raw material is substituted, the situation through repeatedly attempting to occur stretching rupture of membranes, it is impossible to stretch film forming.In addition, TD rates of extension in polyethylene film preparation process are down to after 50%/s, still gone out through repeatedly trial Now stretch the situation of rupture of membranes, it is impossible to stretch film forming.
Comparative example 2
This comparative example is used to illustrate polyethylene film of reference and preparation method thereof.
(1) polyethylene raw material：
Polyethylene raw material used in this comparative example is identical with comparative example 1.
(2) preparation of polyethylene film：
The polyethylene film of this comparative example uses the upper blowing method film blowing device of DR.COLLIN companies of Germany Extrusion and blow molding is obtained, and specific method is as follows：The polyethylene raw material that above-mentioned steps (1) are chosen adds Enter into the hopper of upper blowing method film blowing device extruder, after the abundant fusion plastification of the extruded machine of raw material, by machine Melt membrane tube is made in the annular die extrusion of head, afterwards compressed air inflation (blow-up ratio is 2.5 times), And polyethylene film is made after being cooled down through vane, wherein film is the single layer structure that average thickness is 25 μm.
Comparative example 3
This comparative example is used for the polyethylene film for illustrating reference.
(1) preparation of polyethylene composition：
The polyethylene composition that this comparative example is provided is by component 1 (the component B of embodiment 1) and component 2 (the component C of embodiment 1) is constituted, i.e. the preparation method of the polyethylene composition is public with embodiment 1 The method for the polyethylene composition of preparation first opened is identical, unlike, it is added without component A.Specifically, Component 1 and component 2 are the LLDPE (LLDPE) of ethylene/alpha-olefin copolymerization, and Prepared using identical catalyst system (ziegler-natta catalyst systems) and polymerization technique, difference It is to prepare the amounts of hydrogen added during different component and the species and molar content of alhpa olefin comonomer It is different.Comprise the following steps that：
Ethene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, then added neat Ge Le-natta catalyst systems, is afterwards 84-88 DEG C, under conditions of pressure is 1.8-2.0MPa in temperature Polymerization, respectively obtains component 1 and component 2.Wherein, the control of the melt index of component 1 and component 2 Realized by adjusting the addition of hydrogen, the control of density is by adjusting the species and addition of alhpa olefin And realize.Alhpa olefin used is 1- butylene during preparing component 1, prepares institute during component 2 It is 1- butylene with alhpa olefin.
After testing, the component 1 and the performance of 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, alhpa olefin copolymerization list Molar content=8.0mol% of body；
The melt index MI of component 22=15g/10min, density p2=0.915g/cm3, alhpa olefin copolymerization list Molar content=9.8mol% of body.
Each component obtained above is weighed and mixed by proportioning, wherein the mass fraction of component 1 W1For 80 parts by weight, the mass fraction W of component 22For 30 parts by weight, add mixture to afterwards It is well mixed in high speed agitator, then the material mixed is added to the twin-screw that W＆P companies manufacture In the feeder of extruder, material enters in twin-screw via feeder, the temperature of screw rod in process Be maintained between 160-210 DEG C, through screw rod melting mixing it is uniform, extrude, granulate and dry, gathered Vinyl composition pellet, after testing its melt index MI=6.2g/10min.
(2) preparation of polyethylene film：
The preparation of polyethylene film is carried out according to the method for embodiment 1, difference is, extrudate flow delay is thin The top layer of film and core layer raw material are substituted using the polyethylene composition pellet of above-mentioned steps (1), as a result Show, by repeatedly trial, the maximum tension multiplying power of biaxially oriented film is only 2 times of (TD) × 2 times (MD), film TD highests stretching ratio is only 10%/s, i.e. stretching ratio and rate of extension mistake Low, stretching film forming is poor, does not possess practicality.
Comparative example 4
This comparative example is used to illustrate polyethylene film of reference and preparation method thereof.
(1) preparation of polyethylene composition：
The first polyethylene composition that this comparative example is provided is by component 1 (the component A of embodiment 2) and group Divide 2 (the component B of embodiment 2) compositions, i.e. the preparation method and reality of first polyethylene composition Apply the disclosed method for preparing the first polyethylene composition of example 2 identical, unlike, it is added without component C. Second polyethylene composition is made up of component 3 (the component D of embodiment 2), i.e. second polyethylene The preparation method of composition is identical with the disclosed method for preparing the second polyethylene composition of embodiment 2.Its In, component 1, component 2 and component 3 are the LLDPE of ethylene/alpha-olefin copolymerization (LLDPE), and using identical catalyst system (ziegler-natta catalyst systems) and polymerization Prepared by technique, difference is to prepare the amounts of hydrogen added during different component and alhpa olefin comonomer Species and molar content are different.Comprise the following steps that：
Ethene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, then added neat Ge Le-natta catalyst systems, is afterwards 84-88 DEG C, under conditions of pressure is 1.8-2.0MPa in temperature Polymerization, respectively obtains component 1, component 2 and component 3.Wherein, component 1, component 2 and component 3 The control of melt index realize that the control of density is by adjusting α alkene by adjusting the addition of hydrogen The species and addition of hydrocarbon and realize.Alhpa olefin used is 1- butylene during preparing component 1, is prepared Alhpa olefin used is 1- butylene during component 2, and alhpa olefin used is during preparing component 3 1- hexenes.
After testing, 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, alhpa olefin copolymerization Molar content=2.1mol% of monomer；
The melt index MI of component 22=9.0g/10min, density p2=0.930g/cm3, alhpa olefin copolymerization list Molar content=2.8mol% of body；
The melt index MI of component 33=1.0g/10min, density p3=0.910g/cm3, alhpa olefin copolymerization list Molar content=9.0mol% of body.
Said components 1 and component 2 are weighed and mixed by proportioning, wherein the mass fraction of component 1 W1For 55 parts by weight, the mass fraction W of component 22For 65 parts by weight, add mixture to afterwards It is well mixed in high speed agitator, then the material mixed is added to the twin-screw that W＆P companies manufacture In the feeder of extruder, material enters in twin-screw via feeder, the temperature of screw rod in process Be maintained between 180-240 DEG C, through screw rod melting mixing it is uniform, extrude, granulate and dry, obtain the One polyethylene composition pellet, after testing its melt index MI=0.22g/10min.In addition, using above-mentioned Identical method prepares the second polyethylene composition pellet, unlike, component 1 and component 2 are used Component 3 is substituted.
(2) preparation of polyethylene film：
The preparation of polyethylene film is carried out according to the method for embodiment 2, is as a result shown, by repeatedly trial, The maximum tension multiplying power of biaxially oriented film is only 2 times of (TD) × 2 times (MD), film TD highests Stretching ratio is only 10%/s, i.e. stretching ratio and rate of extension are too low, and stretching film forming is poor, Do not possess practicality.
Comparative example 5
This comparative example is used to illustrate polyethylene film of reference and preparation method thereof.
(1) preparation of polyethylene composition：
The first polyethylene composition that this comparative example is provided is by component 1 (the component A of embodiment 3) and group Divide 2 (the component C of embodiment 3) compositions, i.e. the preparation method and reality of first polyethylene composition Apply the disclosed method for preparing the first polyethylene composition of example 3 identical, it is no to be, it is added without component B. Second polyethylene composition is made up of component 3 (the component D of embodiment 3), i.e. second polyethylene The preparation method of composition is identical with the disclosed method for preparing the second polyethylene composition of embodiment 3.Tool Body, the first polyethylene composition is obtained using the multiple reactor shunting means polymerization shown in Fig. 1, wherein First reactor polymerization prepares component 1, second reactor polymerization and prepares component 2.Component 1, component 2 With the LLDPE (LLDPE) that component 3 is ethylene/alpha-olefin copolymerization, these three components are equal Prepared using identical catalyst system (metallocene catalyst system) and polymerization technique, difference is to make The amounts of hydrogen, the species of alhpa olefin comonomer and the molar content that are added during standby different component and each anti- Answer the yield in unit time of device different.Comprise the following steps that：
Alhpa olefin, n-hexane and hydrogen are added in polymer reactor, and polymer reactor is heated to Vinyl monomer and catalyst system, are added in polymer reactor by default polymerization temperature simultaneously afterwards, And temperature be 140 DEG C, pressure be polyase 13 0 minute under conditions of 2.5MPa, respectively obtain component 1, Component 2 and component 3.Wherein, the control of the melt index of component 1, component 2 and component 3 is by adjusting Save the addition of hydrogen and realize, the control of density is realized by adjusting the species and addition of alhpa olefin. Alhpa olefin used is 1- octenes during preparing component 1, prepares alhpa olefin used during component 2 For 1- butylene, alhpa olefin used is 1- octenes during preparing component 3.
By the yield in unit time W of component in first reactor 1 in preparation process1With second reactor The yield in unit time W of middle component 22Weight ratio maintain W1：W2=35：75.
After testing, 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, alhpa olefin copolymerization list Molar content=2.1mol% of body；
The melt index MI of component 22=25g/10min, density p2=0.920g/cm3, alhpa olefin copolymerization list Molar content=5.1mol% of body；
The melt index MI of component 33=25g/10min, density p3=0.905g/cm3, alhpa olefin copolymerization list Molar content=8.0mol% of body.
Component 1 obtained above and component 2 are transported to solid-liquid (gas) point in yield in unit time ratio From be separated in device and and then be transported to stirring homogenization silo in carry out mixing homogenizing, afterwards The mixture that homogenized feed bin is homogenized is added to the feeder of the double screw extruder of W＆P companies manufacture In, material enters in twin-screw via feeder, and the temperature of screw rod is maintained at 170-230 in process Between DEG C, through screw rod melting mixing it is uniform, extrude, granulate and dry, obtain the first polyethylene composition Pellet, after testing its melt index MI=8.2g/10min.In addition, being prepared using above-mentioned identical method Second polyethylene composition pellet, unlike, component 1 and component 2 are substituted using component 3.
(2) preparation of polyethylene film：
The preparation of polyethylene film is carried out according to the method for embodiment 3, is as a result shown, by repeatedly trial, The maximum tension multiplying power of biaxially oriented film is only 2 times of (TD) × 2 times (MD), film TD highests Stretching ratio is only 10%/s, i.e. stretching ratio and rate of extension are too low, and stretching film forming is poor, Do not possess practicality.
Comparative example 6
This comparative example is used to illustrate polyethylene film of reference and preparation method thereof.
(1) preparation of polyethylene composition：
Method according to embodiment 4 prepares the first polyethylene composition and the second polyethylene composition, different , the component D obtained during component D is prepared by adjusting the consumption of hydrogen and alhpa olefin to make Melt index MID=60.0g/10min, density pD=0.930g/cm3, mole of alhpa olefin comonomer Content=3.0mol%.That is, second polyethylene composition of this comparative example 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, is as a result shown, the heat of gained film Sealing strength is relatively low, without practicality.
Test case
Test case is used for the test for illustrating polyethylene film and reference polyethylene film performance.
(1) mist degree：It is measured according to method specified in GB/T 2410-2008, wherein, film Sample thickness is 25 ± 5 μm, and acquired results are as shown in table 1；
(2) tensile strength and tension fracture elongation rate：According to side specified in GB/T 1040.3-2006 Method is measured, and acquired results are as shown in table 1；
(3) puncture strength：It is measured according to method specified in GB/T10004-2008, wherein, Film sample thickness is 25 ± 5 μm, and acquired results are as shown in table 1；
(4) heat-seal strength：It is measured according to method specified in QBT2358-1998Q, wherein, Heat-sealing temperature is 120 DEG C, and 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, The contrast of embodiment 3 and comparative example 5 and embodiment 4 and comparative example 6 can be seen that offer of the present invention Polyethylene film have that film forming multiplying power is big, rate of extension is fast, mechanical strength is high, good in optical property, heat The high advantage of sealing strength, the performance of prepared film can meet longitudinal direction (MD) tensile strength >=50MPa, horizontal (TD) tensile strength >=50MPa, tension fracture elongation rate≤350%, puncture strength >=2.5N, heat-seal strength >=4.5N.In addition, the contrast from embodiment 1 and embodiment 4 can be seen that During polyethylene film is prepared, controlled when by the consumption of each material in currently preferred scope When, obtained polyethylene film has more excellent combination property.From embodiment 1 and comparative example 1-2's Contrast can not stretch film forming as can be seen that using the commercial polyethylene raw material of prior art preparation, thus not It is adapted to be processed using Flat film strength, and compared with the inflation film of prior art, using flat film Mechanical strength, puncture strength and the heat-seal strength of the film of pulling method machine-shaping be higher and film mist Degree is relatively low.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited to above-mentioned reality The detail in mode is applied, can be to technical side of the invention in the range of the technology design of the present invention Case carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned embodiment is special Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not The repetition wanted, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as its Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.

Claims (15)

1. a kind of polyethylene film, it is characterised in that the polyethylene film include polyethylene core and Be attached to the polyethylene skin of an at least side surface for the polyethylene core, the polyethylene core by containing The first polyethylene composition for having component A, component B and component C is formed, the polyethylene skin by The second polyethylene composition containing component D is formed；The component A is the line of ethylene/alpha-olefin copolymerization Property low density polyethylene (LDPE), its temperature be 190 DEG C, load be 2.16kg under melt index MIAFor 0.01-3.5g/10min, density pAFor 0.915-0.936g/cm3；The component B is common for ethylene/alpha-olefin Poly- LLDPE, its temperature be 190 DEG C, load be 2.16kg under melt index MIBFor 3.6-9.9g/10min, density pBFor 0.915-0.930g/cm3；The component C is ethylene/alpha The LLDPE of olefin-copolymerization, its temperature be 190 DEG C, load be 2.16kg under melting Index M ICFor 10-80g/10min, density pCFor 0.915-0.930g/cm3；The component D is ethene The LLDPE of/alhpa olefin copolymerization, its temperature be 190 DEG C, load be molten under 2.16kg Melt index M IDFor 0.5-50g/10min, density pDFor 0.880-0.910g/cm3。
2. polyethylene film according to claim 1, wherein, the component A is in temperature 190 DEG C, load be 2.16kg under melt index MIAFor 0.01-3g/10min, the component B is in temperature Degree is 190 DEG C, load is melt index MI under 2.16kgBExist for 4-8g/10min, the component C Temperature is 190 DEG C, load is melt index MI under 2.16kgCFor 10-60g/10min, the component D temperature be 190 DEG C, load be 2.16kg under melt index MIDFor 0.5-30g/10min；It is preferred that Ground, the component A temperature be 190 DEG C, load be 2.16kg under melt index MIAFor 0.01-2g/10min, the component B temperature be 190 DEG C, load be 2.16kg under melt index MIBFor 4-5g/10min, the component C temperature be 190 DEG C, load be that melting under 2.16kg refers to Number MICFor 15-40g/10min, the component D temperature be 190 DEG C, load be molten under 2.16kg Melt index M IDFor 1-20g/10min.
3. polyethylene film according to claim 1, wherein, in first polyethylene composition In thing, the mass fraction W of the component AAFor 25-90 parts by weight, the mass fraction of the component B WBFor 0.1-10 parts by weight, the mass fraction W of the component CCFor 10-75 parts by weight；Preferably, 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.
4. polyethylene film according to claim 3, wherein, the mass fraction of the component A WAWith component C mass fraction WCWith component A melt index MIARelation meet 4.6 × lgMIA+10.4≥WA/WC≥0.34×lgMIA+1。
5. the polyethylene film according to any one in claim 1-4, wherein, described first Polyethylene composition temperature be 190 DEG C, load be that melt index under 2.16kg is 0.1-20g/10min, Preferably 0.5-10g/10min.
6. the polyethylene composition according to any one in claim 1-4, wherein, described group The molar content of alhpa olefin comonomer is independently of one another in point A, component B, component C and component D For 0.2-15mol%, preferably 1.5-10mol%；
Preferably, the alhpa olefin in the component A, component B, component C and component D is each independent Ground is C3-C20At least one of alkene, preferably propylene, 1- butylene, 2- butylene, 3- methyl isophthalic acids-fourth Alkene, 4- methyl isophthalic acids-butylene, 1- amylenes, 3- Methyl-1-pentenes, 4-methyl-1-pentene, 3,3- dimethyl -1- Amylene, 3,4- dimethyl -1- amylenes, 4,4- dimethyl -1- amylenes, 1- hexenes, 4- methyl isophthalic acids-hexene, 5- Methyl isophthalic acid-hexene, 1- heptene, 2- heptene, 1- octenes, 1- decene, 1- dodecylenes, tetradecene, At least one of cetene, 1- vaccenic acids and 1- eicosylenes, more preferably 1- butylene, 1- At least one of hexene and 1- octenes.
7. the polyethylene film according to any one in claim 1-4, wherein, the poly- second The thickness of the polyethylene skin of alkene sandwich layer side is the 2-35% of the polyethylene film thickness；
Preferably, the thickness of the polyethylene film is 10-200 μm, preferably 10-100 μm.
8. a kind of preparation method of polyethylene film, it is characterised in that this method includes that component will be contained A, component B and component C the first polyethylene composition and the second polyethylene composition containing component D Thing feeding extrudes curtain coating in the extrusion casting apparatus with multi-layer co-extruded structure, afterwards again by obtained curtain coating Slab is stretched, and is obtained including polyethylene core and is attached at least side table of the polyethylene core The polyethylene film of the polyethylene skin in face, the polyethylene core is by the first polyethylene composition shape Into the polyethylene skin is formed by second polyethylene composition；The component A is ethylene/alpha The LLDPE of olefin-copolymerization, its temperature be 190 DEG C, load be 2.16kg under melting Index M IAFor 0.01-3.5g/10min, density pAFor 0.915-0.936g/cm3；The component B is second The LLDPE of alkene/alhpa olefin copolymerization, it is 190 DEG C, under load is 2.16kg in temperature Melt index MIBFor 3.6-9.9g/10min, density pBFor 0.915-0.930g/cm3；The component C For the LLDPE of ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be 2.16kg Under melt index MICFor 10-80g/10min, density pCFor 0.915-0.930g/cm3；The component D is the LLDPE of ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be 2.16kg Under melt index MIDFor 0.5-50g/10min, density pDFor 0.880-0.910g/cm3。
9. method according to claim 8, wherein, the component A temperature be 190 DEG C, Load is the melt index MI under 2.16kgAIt is in temperature for 0.01-3g/10min, the component B 190 DEG C, load be 2.16kg under melt index MIBFor 4-8g/10min, the component C is in temperature It is the melt index MI under 2.16kg for 190 DEG C, loadCExist for 10-60g/10min, the component D Temperature is 190 DEG C, load is melt index MI under 2.16kgDFor 0.5-30g/10min；Preferably, The component A temperature be 190 DEG C, load be 2.16kg under melt index MIAFor 0.01-2g/10min, the component B temperature be 190 DEG C, load be 2.16kg under melt index MIBFor 4-5g/10min, the component C temperature be 190 DEG C, load be that melting under 2.16kg refers to Number MICFor 15-40g/10min, the component D temperature be 190 DEG C, load be molten under 2.16kg Melt index M IDFor 1-20g/10min.
10. method according to claim 8, wherein, in first polyethylene composition, The mass fraction W of the component AAFor 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 CCFor 10-75 parts by weight；Preferably, in institute State in the first polyethylene composition, the mass fraction W of the component AAIt is described for 30-80 parts by weight Component B mass fraction WBFor 0.5-8 parts by weight, the mass fraction W of the component CCFor 20-70 Parts by weight.
11. method according to claim 10, wherein, the mass fraction W of the component AA With component C mass fraction WCWith component A melt index MIARelation meet 4.6 × lgMIA+10.4≥WA/WC≥0.34×lgMIA+1。
12. the method according to any one in claim 8-11, wherein, the first poly- second Ene compositions temperature be 190 DEG C, load be that melt index under 2.16kg is 0.1-20g/10min, it is excellent Elect 0.5-10g/10min as.
13. the method according to any one in claim 8-11, wherein, the component A, group The molar content of alhpa olefin comonomer in B, component C and component D is divided to be each independently 0.2-15mol%, preferably 1.5-10mol%；
Preferably, the alhpa olefin in the component A, component B, component C and component D is each independent Ground is C3-C20At least one of alkene, preferably propylene, 1- butylene, 2- butylene, 3- methyl isophthalic acids-fourth Alkene, 4- methyl isophthalic acids-butylene, 1- amylenes, 3- Methyl-1-pentenes, 4-methyl-1-pentene, 3,3- dimethyl -1- Amylene, 3,4- dimethyl -1- amylenes, 4,4- dimethyl -1- amylenes, 1- hexenes, 4- methyl isophthalic acids-hexene, 5- Methyl isophthalic acid-hexene, 1- heptene, 2- heptene, 1- octenes, 1- decene, 1- dodecylenes, tetradecene, At least one of cetene, 1- vaccenic acids and 1- eicosylenes, more preferably 1- butylene, 1- At least one of hexene and 1- octenes.
14. the method according to any one in claim 8-11, wherein, the first poly- second The consumption and extrusion curtain coating and the condition of stretching of ene compositions and the second polyethylene composition cause described The thickness of the polyethylene skin of polyethylene core side is the 2-35% of the polyethylene film thickness, preferably So that the thickness of the polyethylene film is 10-200 μm, more preferably 10-100 μm.
15. the polyethylene film prepared as the method described in any one in claim 8-14.
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CN111100350A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Polyethylene composition, method of making the same, and packaging articles
CN111100363A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Polyethylene composition and film thereof
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CN103946022A (en) * 2011-12-02 2014-07-23 埃克森美孚化学专利公司 Multilayer film and method of making same
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CN111100366A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Polyethylene composition, preparation method thereof and film packaging product
CN111100350A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Polyethylene composition, method of making the same, and packaging articles
CN111100363A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Polyethylene composition and film thereof
CN111100351A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Polyethylene composition, preparation method thereof and plastic-absorbing packaging product
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CN111114061A (en) * 2018-10-31 2020-05-08 中国石油化工股份有限公司 Tear-resistant polyethylene film and preparation method thereof
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