CN106554548A - A kind of polyethylene composition and antistatic film - Google Patents
A kind of polyethylene composition and antistatic film Download PDFInfo
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- CN106554548A CN106554548A CN201510628245.3A CN201510628245A CN106554548A CN 106554548 A CN106554548 A CN 106554548A CN 201510628245 A CN201510628245 A CN 201510628245A CN 106554548 A CN106554548 A CN 106554548A
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
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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
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- 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
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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
- 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
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention provides a kind of polyethylene composition and antistatic film.The polyethylene composition contains conductive filler, component A, component B and component C；LLDPE of component A for ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be melt index MI under 2.16kgAFor 0.01-2g/10min, density pAFor 0.880-0.936g/cm3；LLDPE of component B for ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be melt index MI under 2.16kgBFor 2.1-9.9g/10min, density pBFor 0.910-0.930g/cm3；LLDPE of component C for ethylene/alpha-olefin copolymerization, its temperature be 190 DEG C, load be melt index MI under 2.16kgCFor 10-80g/10min, density pCFor 0.880-0.930g/cm3.When the polyethylene composition prepares polyethylene film using Flat film strength, stretching ratio is big, rate of film build is high, and the film for obtaining has preferable antistatic behaviour.
Description
Technical field
The present invention relates to a kind of polyethylene composition and antistatic film.
Background technology
Biaxially-oriented polyethylene (Biaxially Oriented Polyethylene, BOPE) film is that have
The thin-film material of polyethylene (PE) the resin Jing stretch processes shaping of special molecular structure.BOPE
Film is cast the polyethylene film of technique productions in physics than the extrusioning blowing process and extrusion of prior art
Aspect of performance has greatly improved, with mechanical strength is high, puncture resistance and shock resistance is good, light
The advantages such as function admirable, heat sealability and the good, energy-conserving and environment-protective of moisture resistance are learned, and particularly 50% are reduced in thickness
In the case of key performance remain to reach the performance of other polyethylene films.Therefore, BOPE films can quilt
Be widely used in packaging bag, packaging bag, Vacuum Heat sealer, low temperature packaging film, composite membrane, medical and health again
The aspects such as articles for use, plastic film for agricultural use.
The processing method for being presently available for producing Biaxial tension polyethylene film has Flat film strength and envelope
Pulling method, the former technique are more ripe, and having stretching ratio, big (cross directional stretch multiplying power is up to 10
More than times), the advantage such as shaping speed fast (highest rolling speed is up to hundreds of ms/min), production efficiency height,
And the mechanical strength and optical property of the film for obtaining preferably and thickness evenness more preferably.However, adopting
When preparing film with Flat film strength, film forming is affected also more significantly by process condition fluctuations, film
Stretch process difficulty is big, for film raw material has higher requirement.Therefore flat film stretching polyethylene film
For polyethylene raw material has higher requirement.Existing Biaxially-oriented polyethylene raw material is relatively applied to pipe substantially
Bubble pulling method prepares BOPE films, and existing these polyethylene raw materials are prepared using Flat film strength
During BOPE films, there is film forming poor (draw speed and stretching ratio are very low), film and easily occur breaking
The defect split, i.e. be not suitable for substantially preparing film using Flat film strength.
Polyethylene is insulating materials, with nonpolar molecule structure, the strand being made up of covalent bond, both
Can not ionize and also be difficult to transmit free electron, after powered because friction makes electron exchange if be difficult to disappear
Lose, when using as film packing material, a large amount of electrostatic can be produced in its processing and application process
And cause a variety of drawbacks even to endanger.For example, when using film packaging powder commodity, usually because
The electrostatic precipitation in heat sealing face causes sealing strength significantly to decline, commodity meeting in storage, transportation
Cause to pack serious damage；Film printing processing when, because of the electrostatic precipitation effects of film
, there is inking uneven " electrostatic ink speck " etc., causes printed patterns defect in printing ink transfer；High-speed packaging
In production line packaging process, electrostatic can be impacted to the cutting of film, conveying, folding etc.；Especially
It is developing rapidly with IT industries, various sensitive electronic elements, instrument and meter etc. are also a large amount of to be adopted
Plastic film packaging, film can produce accumulation of static electricity because of electromagnetic induction and friction so that packaging commodity
Destroyed because of the electrion which produces.Therefore, antistatic film also gets more and more people's extensive concerning,
Need a kind of antistatic behaviour of exploitation and good film-forming property badly and film be not easy to occur rupture suitable for flat film
Pulling method prepares the polyethylene raw material of BOPE films.
The content of the invention
The invention aims to overcome be prepared existing polyethylene raw material using Flat film strength poly-
Have during ethene antistatic film that film forming is poor, film is easily broken, that is, be not suitable for adopting Flat film strength
The defect of antistatic film is prepared, and provides a kind of new polyethylene composition and by the polyethylene composition
Made by antistatic film.
Specifically, the present invention provide polyethylene composition contain conductive filler, component A, component B and
Component C；LLDPE of component A for ethylene/alpha-olefin copolymerization, which in temperature is
190 DEG C, load be 2.16kg under melt index MIAFor 0.01-2g/10min, density pAFor
0.880-0.936g/cm3；LLDPE of component B for ethylene/alpha-olefin copolymerization, its
Temperature be 190 DEG C, load be melt index MI under 2.16kgBFor 2.1-9.9g/10min, density pB
For 0.910-0.930g/cm3；LLDPE of component C for ethylene/alpha-olefin copolymerization,
Its temperature be 190 DEG C, load be melt index MI under 2.16kgCFor 10-80g/10min, density
ρCFor 0.880-0.930g/cm3。
The antistatic film that the present invention is provided is at least including one layer by gathering that above-mentioned polyethylene composition is formed
Pvdf layer.
The present inventor is had found after further investigation, by above-mentioned with particular melt index and density
Component A, component B and component C and conductive filler use cooperatively obtained from polyethylene composition
When polyethylene film is prepared using Flat film strength, have the advantages that stretching ratio is big, rate of film build is high,
High requirement of the Flat film strength to polyethylene raw material is disclosure satisfy that, existing Flat film strength production is adapted to
The economy demand of line, and the polyethylene film for obtaining also has excellent antistatic property, great work
Industry application prospect.
A preferred embodiment of the invention, component A described in the polyethylene composition
Mass fraction WAFor 25-90 weight portions, the mass fraction W of component BBFor 0.1-10 weight portions,
The mass fraction W of component CCFor 10-75 weight portions, and with component A, component B and group
The gross weight for dividing C is 100 weight portion meters, when the content of the conductive filler is 0.1-10 weight portions, energy
Enough so that polyethylene composition flat embrane method film biaxial tension processing in have bigger stretching ratio and
Higher rate of extension.
Another kind of preferred embodiment of the invention, when component A and the molecular weight of component B
Profile exponent meets Mw/Mn≤ 4.5, and the molecular weight distributing index satisfaction of component C
Mw/MnWhen≤8.0, the polyethylene composition on the basis of with preferable film forming and antistatic behaviour,
Also there is higher mechanical strength by the film that the polyethylene composition is prepared.
Another kind of preferred embodiment of the invention, when component A, group in the polyethylene composition
The density p of part B and component CA、ρBAnd ρCBetween relation meet -0.04≤ρA-ρB≤ 0.02 and -0.04
≤ρA-ρCWhen≤0.02, the polyethylene composition on the basis of with preferable film forming and antistatic behaviour,
Also there is higher tensile strength by the film that the polyethylene composition is prepared.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute the part of specification, with
Detailed description below is used for explaining 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 polyethylene composition.
Description of reference numerals
1- first reactors；2- second reactors；The 3rd reactors of 3-；4- solid-liquids (gas) separator；
5- homogenization silos；6- melt pelletization systems.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The polyethylene composition that the present invention is provided contains conductive filler, component A, component B and component C；
LLDPE of component A for ethylene/alpha-olefin copolymerization, which is 190 DEG C, carries in temperature
Lotus is melt index MI under 2.16kgAFor 0.01-2g/10min, density pAFor 0.880-0.936g/cm3；
LLDPE of component B for ethylene/alpha-olefin copolymerization, which is 190 DEG C, carries in temperature
Lotus is melt index MI under 2.16kgBFor 2.1-9.9g/10min, density pBFor 0.910-0.930g/cm3；
LLDPE of component C for ethylene/alpha-olefin copolymerization, which is 190 DEG C, carries in temperature
Lotus is melt index MI under 2.16kgCFor 10-80g/10min, density pCFor 0.880-0.930g/cm3。
According to the present invention provide polyethylene composition, it is preferable that component A temperature be 190 DEG C,
Load is melt index MI under 2.16kgAFor 0.01-1.5g/10min, component B in temperature is
190 DEG C, load be 2.16kg under melt index MIBFor 3-8g/10min, component C is in temperature
It is melt index MI under 2.16kg for 190 DEG C, loadCFor 10-60g/10min.It is highly preferred that institute
State component A temperature be 190 DEG C, load be melt index MI under 2.16kgAFor 0.01-1g/10min,
Component B temperature be 190 DEG C, load be melt index MI under 2.16kgBFor 3-5g/10min,
Component C temperature be 190 DEG C, load be melt index MI under 2.16kgCFor
15-40g/10min。
According to the polyethylene composition that the present invention is provided, it is preferable that the density p of component AAFor
0.910-0.930g/cm3, the density p of component BBFor 0.913-0.928g/cm3, component C
Density pCFor 0.905-0.928g/cm3.It is highly preferred that the density p of component AAFor
0.915-0.926g/cm3, the density p of component BBFor 0.913-0.924g/cm3, component C
Density pCFor 0.910-0.926g/cm3.It is particularly preferred that component A, group in the polyethylene composition
The density p of part B and component CA、ρBAnd ρCBetween relation meet -0.04≤ρA-ρB≤ 0.02, and -0.04
≤ρA-ρC≤ 0.02, the polyethylene composition for so enabling to is with preferable filming performance and anti-
On the basis of antistatic property, also with very high tensile strength.
Component A, component B and component C are the linear low density polyethylene of ethylene/alpha-olefin copolymerization
Alkene, wherein, linear structure only contains short-chain branch structure in referring to strand, and does not contain long branched chain structure
And cross-linked structure, which is determined by polymerized monomer and polymerization process condition, specially those skilled in the art
Known, therefore not to repeat here.
In the present invention, the melt index is surveyed according to method specified in GB/T3682-2000
It is fixed, wherein, test condition includes temperature for 190 DEG C, and load is 2.16kg.The density is according to GB/T
1033.2-2010 specified in method be measured using density gradient column method.
According to the polyethylene composition that the present invention is provided, in order that the polyethylene composition for arriving has more preferably
Filming performance and antistatic property, it is preferable that in the polyethylene composition, component A
Mass fraction WAFor 25-90 weight portions, the mass fraction W of component BBFor 0.1-10 weight portions,
The mass fraction W of component CCFor 10-75 weight portions, and with component A, component B and group
The gross weight for dividing C is 100 weight portion meters, and the content of the conductive filler is 0.1-10 weight portions.It is more excellent
Selection of land, in the polyethylene composition, the mass fraction W of component AAFor 30-80 weight portions,
The mass fraction W of component BBFor 0.5-8 weight portions, the mass fraction W of component CCFor
20-70 weight portions, and count by 100 weight portions of the gross weight of component A, component B and component C,
The content of the conductive filler is 0.5-3 weight portions.Further, the mass fraction of component A
WAWith the mass fraction W of component CCWith melt index MI of component AARelation preferred meet 5.2
×lgMIA+11.6≥WA/WC≥0.9×lgMIA+ 2.1, more preferably meet 2.9 × lgMIA+6.8≥
WA/WC≥1.1×lgMIA+ 2.7, so enable to the polyethylene composition double in flat embrane method film
There is in stretch process the rate of extension of bigger stretching ratio and Geng Gao.
According to the polyethylene composition that the present invention is provided, particularly preferably, the polyethylene composition is in temperature
Spend for 190 DEG C, load be 2.16kg under melt index be 0.1-20g/10min, most preferably
0.5-10g/10min.By component A with above-mentioned particular melt index and density, component B and component
On the basis of C is used cooperatively, by the polyethylene composition overall melt index control above-mentioned preferred
In the range of, the polyethylene composition for enabling to is while have very excellent film forming, stretching strong
Degree and antistatic behaviour.
The present invention is not particularly limited to the content of component B, with the total of the polyethylene composition
On the basis of weight, mass percentage content M of component BBIt is preferred that≤35 weight %, more preferably
MB≤ 25 weight %.
According to the polyethylene composition that the present invention is provided, it is preferable that component A and component B point
Son amount profile exponent meets Mw/Mn≤ 4.5, and the molecular weight distributing index satisfaction of component C
Mw/Mn≤8.0；It is highly preferred that component A and component B molecular weight distributing index meet 2.0≤
Mw/Mn≤ 4.2, and the molecular weight distributing index of component C meets 3.5≤Mw/Mn≤6.0.Specifically
Ground, in order to obtain component A with above-mentioned molecular weight distribution, component B and component C, component A
Obtained using metallocene catalyst polymerisation with component B, and component C adopts ziegler-natta catalyzed
Agent polymerization is obtained.Wherein, the species of the metallocene catalyst and Ziegler-Natta catalyst can be
The conventional selection of this area, the metallocene catalyst is generally by metallocene compound and organo-aluminum compound
And optional electron donor is constituted, the Ziegler-Natta catalyst generally by magnesium titanium compound and has
Machine aluminium compound and optional electron donor composition, are specifically known to the skilled person, and here is not
Repeat.The present inventor is had found after further investigation, will be obtained using metallocene catalyst polymerisation
To component A and component B with above-mentioned melt index and density, adopt Ziegler-Natta catalyst
Component C and conductive filler with above-mentioned melt index and density that polymerization is obtained is used cooperatively, and is obtained
Film on the basis of with good filming performance and antistatic property, it is also strong with very high stretching
Degree, is highly suitable for packaging material.
The present invention does not have to the content of alhpa olefin comonomer in component A, component B and component C
Especially limit, for example, in component A, component B and component C, alhpa olefin comonomer rubs
You can be each independently 0.2-15mol%, preferably 1.5-10mol% at content.In the present invention, α
The molar content of olefin comonomer refers to that the mole of the construction unit formed by alpha-olefin polymerization accounts for total list
The ratio of the mole of body construction unit.Additionally, the α in component A, component B and component C
Alkene is each independently C3-C20At least one in alkene.From the ready availability angle of raw material, institute
The alhpa olefin stated in component A, component B and component C is preferably propylene, 1- butylene, 2- butylene, 3- first
Base -1- butylene, 4- methyl isophthalic acids-butylene, 1- amylenes, 3- Methyl-1-pentenes, 4-methyl-1-pentene, 3,3- bis-
Methyl-1-pentene, 3,4- dimethyl -1- amylenes, 4,4- dimethyl -1- amylenes, 1- hexenes, 4- methyl isophthalic acids-oneself
Alkene, 5- methyl isophthalic acids-hexene, 1- heptene, 2- heptene, 1- octenes, 1- decene, 1- 12 (carbon) alkene, 1- ten
At least one in four (carbon) alkene, 1- 16 (carbon) alkene, 18 (carbon) alkene of 1- and 1- 20 (carbon) alkene, it is more excellent
Elect at least one in 1- butylene, 1- hexenes and 1- octenes as.
According to the polyethylene composition that the present invention is provided, the conductive filler can be the conventional choosing of this area
Select, for example, can be carbon black, graphite, CNT, carbon fiber, conductive metal particles, conductive gold
At least one in category fiber and metal oxide.Wherein, the carbon black includes acetylene carbon black, superconduction charcoal
Black, the special at least one led in carbon black etc..The graphite includes native graphite, expansible graphite, expansion
At least one in graphite, Graphene etc..The CNT includes long time without surface modification or Jing tables
The modified SWCN in face and/or multi-walled carbon nano-tubes.Wherein, the modified method in the surface is this
Known in art personnel, therefore not to repeat here.In the conductive metal particles and conductive metallic fiber
Conducting metal is each independently silver, aluminium, copper, iron, nickel, stainless steel and lead plating, nickel plating, silver-plated
Glass marble, glass fibre, at least one in mica sheet etc..The metal oxide include titanium oxide,
At least one in zinc oxide, tin oxide, indium oxide, cadmium oxide etc..Additionally, with component A,
The gross weight of component B and component C is 100 weight portion meters, and the content of the conductive filler can be 0.1-10
Weight portion, preferably 0.5-3 weight portions.
According to the polyethylene composition that the present invention is provided, it is preferable that the polyethylene composition is also containing profit
Lubrication prescription, can so improve the extrusion processing characteristics of the polyethylene composition.The species of the lubricant
Can be that the conventional of this area selects with consumption, for example, the lubricant can be selected from polyethylene glycol
(PEG) series lubricant agent, fluoropolymer series lubricant agent, silicone lubricant, aliphatic alcohols lubrication
Agent, fatty acid lubricant, fatty acid ester type emollients, stearic amide series lubricant agent, aliphatic acid gold
In category soaps lubricant, alkane and oxidation of alkanes series lubricant agent and micro-and nano-particles series lubricant agent at least one
Kind.Specifically, the PEG series lubricant agents can for example be that molecular weight divides for the PEG of 500-50000
Son, which can be through end-blocking, grafting, crosslinking Treatment, it is also possible to change through other chemical modifications or physics
Property.The fluoropolymer series lubricant agent can for example be polytetrafluoroethylene (PTFE), Kynoar, poly- hexafluoro
At least one in propylene etc., or the fluoropolymer of other unimodal or multimodals and crystallization or half
The fluoropolymer of crystallization.The organo-silicic oil can for it is existing it is various with carbon, silicon atom for divide
Sub- main chain, the oligomer or oligomer with organic groups such as methyl, phenyl, alkoxyl, vinyl is as side
The compound of chain.The fatty alcohol type emollients can for example be soft fat alcohol, tallow alcohol, tallow
At least one in fat alcohol etc..The fatty acid lubricant for example can be hard with stearic acid and/or 12- hydroxyls
Resin acid.The fatty acid ester type emollients can for example be butyl stearate, stearic acid list glyceride, palm fibre
At least one in palmitic acid acid cetyl ester, tearyl base ester etc..The stearic amide class profit
Lubrication prescription for example can be stearic amide, oleamide, erucyl amide, n, n- ethylene bis stearic acid amides
Etc. (EBS) at least one in.The fatty acid metal soaps lubricant for example can for lead stearate,
At least one in calcium stearate, magnesium stearate, synthesis calcium acetate etc..The alkane and oxidation of alkanes class
Lubricant can for example be atoleine, solid paraffin, Tissuemat E, polypropylene wax, ethylene oxide wax
At least one in.The micro-and nano-particles series lubricant agent can for example be that powdered rubber and/or silica gel are micro-
Grain.Additionally, counting by 100 weight portions of the gross mass of component A, component B and component C, institute
The content for stating lubricant can be 0.05-5 weight portions, preferably 0.5-3 weight portions.
Additionally, can also contain in the polyethylene composition existing various in polyvinyl resin, poly- second
Other auxiliary agents being usually used in alkene film, and the polyethylene that described other auxiliary agents will not be provided to the present invention
The stretching film forming of composition, antistatic behaviour and mechanical property have adverse effect on.Described other are helped
Agent is included but is not limited to：At least one in antioxidant, slipping agent, antistatic additive, antitack agent etc..This
Outward, the consumption of other auxiliary agents can be the conventional selection of this area, to this those skilled in the art
Can know, therefore not to repeat here.
The polyethylene composition can be prepared according to existing various methods, for example, first made respectively
Then component A, component B, component C, conduction are filled out by standby component A, component B and component C
Material and the selective lubricant for containing and other auxiliary agents carry out machine in mechanical mixing equipment according to proportioning
Tool mixes, and carries out melt blending in being subsequently adding melt blending equipment.Wherein, the mechanical mixing equipment
Can for example be homogenizer, kneader etc..The melt blending equipment for example can be squeezed for twin-screw
Go out machine, single screw extrusion machine, mill, banbury etc..
A preferred embodiment of the invention, the polyethylene composition is as shown in Figure 1 more
Prepare in reactor shunting means, the multiple reactor shunting means include first reactor 1,
Two reactors 2, the 3rd reactor 3, solid-liquid (gas) separator 4, homogenization silo 5 and melt pelletization
System 6, wherein, the first reactor 1, second reactor 2 and the 3rd reactor 3 are connected in parallel,
The number of solid-liquid (gas) separator 4 is three, respectively with first reactor 1, second reactor
2 connect with the 3rd reactor 3, component A that prepared by first reactor 1, are made by second reactor 2
Standby component B and component C that prepared by the 3rd reactor 3 are respectively different at solid-liquid (gas)
It is separated in separator 4, then component A Jing after being separated, component B and component C is pressed
The lubricant contained during ratio is delivered to homogenization silo 5 and with conductive filler and selectivity and other additions
Agent is mixed together uniformly, carries out extruding pelletization in sending into melt pelletization system 6 afterwards.Wherein, it is each to react
Polymerization in device can be batchwise polymerization, or continuous polymerization.When using multiple reactor parallel polymerization
When, W hereinafterA、WBAnd WCFor yield in unit time of each component in respective reaction device.
The antistatic film that the present invention is provided is at least including one layer by gathering that above-mentioned polyethylene composition is formed
Pvdf layer.
The antistatic film can have single layer structure, it is possible to have sandwich construction.When described anti-quiet
When conductive film is sandwich construction, at least top layer is the polyethylene layer formed by the polyethylene composition.Example
Such as, the antistatic film can have the composite construction of upper epidermis, sandwich layer and layer, and at least institute
It is the polyethylene layer formed by the polyethylene composition to state upper epidermis or layer.As a rule, it is described
The thickness of antistatic film can be 10-200 μm, preferably 10-100 μm.Additionally, when described anti-quiet
When conductive film has the composite construction of upper epidermis, sandwich layer and layer, the thickness of the upper epidermis and layer
Degree is each independently the 1-25% of the antistatic film thickness.
Additionally, antistatic film can be monodirectional tension film, or biaxially oriented film, preferably
For biaxially oriented film, the biaxially oriented film for more preferably being prepared by flat film biaxial tension method.
The process that biaxially oriented film is prepared using flat film biaxial tension method is known to the skilled person.
Specifically, first above-mentioned polyethylene composition is added in casting apparatus carries out extrusion curtain coating slab, then
The slab for obtaining is carried out into drawing and forming in film biaxial tension equipment.During extrusion curtain coating,
The structure of the film that slab die head can be obtained as needed is selected, and for example, has list when needing to obtain
During the film of Rotating fields, single layer die can be adopted；(have when film of the acquisition with sandwich construction is needed
Have the film of upper epidermis, sandwich layer and layer three-decker) when, die head can be combined using sandwich construction,
And in the compound die head of the sandwich construction at least one of which (upper epidermis or layer) with above-mentioned poly- second is housed
The extruder hopper connection of ene compositions, at least one of which (upper epidermis in the film for so enabling to
Or layer) it is the polyethylene layer formed by above-mentioned polyethylene composition.In extrusion, extrusion temperature
Degree can be 160-260 DEG C, and the temperature for being cast chilling roller can be 15-85 DEG C.Additionally, the two-way drawing
Stretching can be using Synchronos method drawing process (i.e. while carrying out film longitudinal direction (MD) and laterally (TD) drawing
Stretch), it would however also be possible to employ method of fractional steps drawing process (first carries out film longitudinal stretching, then carries out film horizontal stroke
To stretching).The concrete technology of Synchronos method stretching is：The slab is Jing after being fully warmed-up, while entering
Row vertical and horizontal direction stretches, wherein, preheating temperature can be 75-165 DEG C, and draft temperature can be
75-160 DEG C, longitudinal direction (MD) stretching ratio >=4 times, horizontal (TD) stretching ratio >=5 times, laterally
Rate of extension >=50%/s.The concrete technology of method of fractional steps stretching is：The slab Jing after being fully warmed-up,
Longitudinal stretching is first carried out, cross directional stretch is carried out afterwards, wherein, preheating temperature can be 65-158 DEG C, draw
It can be 65-155 DEG C to stretch temperature, longitudinal direction (MD) stretching ratio >=4 times, laterally (TD) stretching times
Rate >=5 times, cross directional stretch speed >=50%/s.Additionally, can not carry out at setting after film drawing and forming
Reason, it is also possible to carry out setting process of annealing.When annealing setting process is carried out, film setting treatment temperature
It can be 80-165 DEG C.Finally, film can also carry out surface corona process, cutting edge and winding process,
Finally give antistatic film of the present invention.
The antistatic film that the present invention is provided has preferable antistatic behaviour and film forming and stretching ratio
Greatly, rate of extension is high.During the biaxially oriented film is prepared using Flat film strength, as above
It is described, longitudinal direction (MD) stretching ratio >=4 times of the antistatic film, laterally (TD) stretching times
Rate >=5 times.Stretching ratio is bigger, then the mechanical strength of antistatic film is higher.The antistatic film
Horizontal (TD) rate of extension >=50%/s, preferably 60-100%/s, so ensure that industrialization
It is continuous to produce.
The antistatic film that the present invention is provided have higher mechanical strength and preferable optical property and
More excellent antistatic property.The biaxially oriented film performance can meet：Longitudinal direction (MD) stretching is strong
Degree >=40MPa, preferably >=50MPa；Horizontal (TD) tensile strength >=40MPa, preferably >=
50MPa.Tension fracture elongation rate≤350% of the biaxially oriented film, preferably≤300%.This
Outward, the surface resistivity of the antistatic film is 103-1010Ω, preferably 103-107Ω.In the present invention
In, the longitudinal tensile strength, transverse tensile strength and tension fracture elongation rate are according to GB/T
Specified in 1040.3-2006, method is measured.The surface resistivity is according to GB/T 1410-2006
Specified in method be measured.
The low production cost of the antistatic film that the present invention is provided, processing technology are simple, versatility is good, open up
The wide application of polyethylene film.
Hereinafter will be described the present invention by embodiment.
In the following Examples and Comparative Examples：
Film biaxial tension equipment is purchased from Br ü ckner companies of Germany, model Karo IV.
The polyethylene composition and film performance are tested in accordance with the following methods：
(1) molecular weight distributing index (Mw/Mn)：Using Polymer Laboratories companies of Britain
220 type gel permeation chromatographs of PL-GPC be measured with reference to IR5 type infrared detectors, chromatographic column
For 3 series connection 10 μm of MIXED-B posts of Plgel, solvent and mobile phase are 1,2,4- trichloro-benzenes, and column temperature is
150 DEG C, flow velocity is 1.0mL/min, using the EasiCal PS-1 Narrow distribution polystyrene marks of PL companies
Sample carries out universal calibration；
(2) 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；
(3) 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 for the polyethylene composition and antistatic film for illustrating present invention offer.
Fill out containing component A, component B, component C, conduction in the polyethylene composition that the present embodiment is provided
Material and lubricant.Component A, component B and component C are the linear low close of ethylene/alpha-olefin copolymerization
Degree polyethylene (LLDPE), wherein, component A and component B prepare (institute using metallocene catalyst
It is the loaded metallocene prepared by CN102453124A embodiments 1 to state metallocene catalyst system
Catalyst, similarly hereinafter), component C prepares the (Ziegler-receive using Ziegler-Natta catalyst
Tower catalyst system is the Ziegler-Natta catalyst prepared by CN101838351A embodiments 1
System, similarly hereinafter).The performance of component A, component B, component C, conductive filler and lubricant is as follows：
Melt index MI of component AA=1.5g/10min, density pA=0.913g/cm3, molecular weight distribution
Index Mw/Mn=3.4, the molar content=7.5mol% of alhpa olefin comonomer；
Melt index MI of component BB=2.1g/10min, density pB=0.913g/cm3, molecular weight distribution
Index Mw/Mn=3.2, the molar content=7.5mol% of alhpa olefin comonomer；
Melt index MI of component CC=15g/10min, density pC=0.905g/cm3, molecular weight distribution refers to
Number Mw/Mn=4.6, the molar content=10.1mol% of alhpa olefin comonomer；
Conductive filler is multi-walled carbon nano-tubes (MWNTs), is produced by Cheaptubes companies of the U.S., directly
Footpath is 20-30nm, and length is 20-30 μm；
Lubricant is the PEG lubricants produced by Switzerland's Clariant Corporation, and molecular weight is 10000.
(1) preparation of polyethylene composition：
Above-mentioned each component is weighed by proportioning and mixed, wherein the mass fraction W of component AAFor 80
Weight portion, the mass fraction W of component BBFor 10 weight portions, the mass fraction W of component CCFor 20
Weight portion, WA/WC=4 (meet 5.2 × lgMIA+11.6≥WA/WC≥0.9×lgMIA+ 2.1, it is also full
2.9 × lgMI of footA+6.8≥WA/WC≥1.1×lgMIA+ 2.7), with component A, component B and component C
Gross mass be 100 weight portion meters, the addition of conductive filler is 3 weight portions, the addition of lubricant
For 0.1 weight portion.It is well mixed in adding mixture to high speed agitator afterwards, then will mixes
Material is added in the feeder of the double screw extruder of W＆P companies manufacture, and material enters via feeder
Enter in twin-screw, in process, the temperature of screw rod is maintained between 160-210 DEG C, the melting of Jing screw rods is mixed
Close it is uniform, extrude, granulate and dry, obtain polyethylene composition pellet, after testing its melt index
MI=2.4g/10min.
(2) preparation of antistatic film：
Polyethylene composition pellet obtained in above-mentioned steps (1) is dried, Sweden is added to afterwards
The sandwich layer extruder of the multilayer extrusion casting machine of model LCR400 of Labtech companies and upper and lower
Melting extrusion is carried out in the extruder of top layer and slab is cast, wherein, in the upper and lower top layer extruder also
Need to add inorganic antitack agent (silica, similarly hereinafter), and add in upper and lower top layer extruder it is anti-
Stick is 0.02 with the weight ratio of polyethylene composition pellet:1, during curtain coating slab, will curtain coating
Chilling roll temperature is set as 25 DEG C, makes polyethylene thickness slab, and which is by upper epidermis, sandwich layer and layer structure
Into.
Above-mentioned polyethylene thickness slab is put in the stretching clamp of film biaxial tension equipment, is adopted and is first indulged
The two-way step drawing technological forming that laterally (TD) is stretched to after (MD) stretching, 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 60%/s；Film setting temperature is 120 DEG C, and it is 25 μm thin to obtain average thickness
Film, which is made up of upper epidermis, sandwich layer and layer, and each layer raw material is the polyethylene composition of the present embodiment
The thickness for also containing antitack agent, upper epidermis and layer in thing, and upper epidermis and layer is 0.5 μm.
Embodiment 2
The present embodiment is used for the polyethylene composition and antistatic film for illustrating present invention offer.
Fill out containing component A, component B, component C, conduction in the polyethylene composition that the present embodiment is provided
Material and lubricant.Component A, component B and component C are the linea low density of ethylene/alpha-olefin copolymerization
Polyethylene (LLDPE), wherein, component A and component B are prepared using metallocene catalyst, group
C is divided to prepare using Ziegler-Natta catalyst.Component A, component B, component C, conduction are filled out
The performance of material and lubricant is as follows：
Melt index MI of component AA=0.01g/10min, density pA=0.930g/cm3, molecular weight distribution
Index Mw/Mn=3.0, the molar content=1.6mol% of alhpa olefin comonomer；
Melt index MI of component BB=9.0g/10min, density pB=0.930g/cm3, molecular weight distribution
Index Mw/Mn=2.8, the molar content=1.9mol% of alhpa olefin comonomer；
Melt index MI of component CC=40g/10min, density pC=0.922g/cm3, molecular weight distribution refers to
Number Mw/Mn=4.4, the molar content=4.0mol% of alhpa olefin comonomer；
Conductive filler is Graphene, purchased from Xiamen Knano Graphene Technology Corporation Limited；
Lubricant is the PEG lubricants produced by Switzerland's Clariant Corporation, and molecular weight is 10000.
(1) preparation of polyethylene composition：
Above-mentioned each component is weighed by proportioning and mixed, wherein the mass fraction W of component AAFor 55
Weight portion, the mass fraction W of component BBFor 5 weight portions, the mass fraction W of component CCFor 55
Weight portion, WA/WC=1 (meets 5.2 × lgMIA+11.6≥WA/WC≥0.9×lgMIA+ 2.1, it is also full
2.9 × lgMI of footA+6.8≥WA/WC≥1.1×lgMIA+ 2.7), with component A, component B and component C
Gross mass be 100 weight portion meters, the addition of conductive filler is 3 weight portions, the addition of lubricant
For 0.1 weight portion.It is well mixed in adding mixture to high speed agitator afterwards, then will mixes
Material is added in the feeder of the double screw extruder of W＆P companies manufacture, and material enters via feeder
Enter in twin-screw, in process, the temperature of screw rod is maintained between 180-240 DEG C, the melting of Jing screw rods is mixed
Close it is uniform, extrude, granulate and dry, obtain polyethylene composition pellet, after testing its melt index
MI=0.7g/10min.
(2) preparation of antistatic film：
Polyethylene composition pellet obtained in above-mentioned steps (1) is dried, Sweden is added to afterwards
The sandwich layer extruder of the multilayer extrusion casting machine of model LCR400 of Labtech companies and upper and lower
Melting extrusion is carried out in the extruder of top layer and slab is cast, wherein, in the upper and lower top layer extruder also
The antitack agent added during inorganic antitack agent, and upper and lower top layer extruder need to be added and polyethylene composition
The weight ratio of pellet is 0.02:1, during curtain coating slab, curtain coating chilling roll temperature is set as into 85
DEG C, polyethylene thickness slab is made, which is made up of upper epidermis, sandwich layer and layer.
Above-mentioned polyethylene thickness slab is put in the stretching clamp of film biaxial tension equipment, is adopted and is first indulged
The two-way step drawing technological forming that laterally (TD) is stretched to after (MD) stretching, each step process condition
It is as follows：MD preheating temperatures are 130 DEG C, and MD draft temperatures are 126 DEG C, and MD stretching ratios are 4 times；
TD preheating temperatures are 130 DEG C, and TD draft temperatures are 128 DEG C, and TD stretching ratios are 6 times, film
TD rates of extension are 100%/s；Film setting temperature is 130 DEG C, and it is 25 μm to obtain average thickness
Film, which is made up of upper epidermis, sandwich layer and layer, and each layer raw material is the polyethylene group of the present embodiment
The thickness for also containing antitack agent, upper epidermis and layer in compound, and upper epidermis and layer is 1 μm.
Embodiment 3
The present embodiment is used for the polyethylene composition and antistatic film for illustrating present invention offer.
Fill out containing component A, component B, component C, conduction in the polyethylene composition that the present embodiment is provided
Material and lubricant.Component A, component B and component C are the linea low density of ethylene/alpha-olefin copolymerization
Polyethylene (LLDPE), wherein, component A and component B are prepared using metallocene catalyst, group
C is divided to prepare using Ziegler-Natta catalyst.Component A, component B, component C, conduction are filled out
The performance of material and lubricant is as follows：
Melt index MI of component AA=0.1g/10min, density pA=0.920g/cm3, molecular weight distribution
Index Mw/Mn=3.1, the molar content=2.1mol% of alhpa olefin comonomer；
Melt index MI of component BB=5.0g/10min, density pB=0.920g/cm3, molecular weight distribution
Index Mw/Mn=3.5, the molar content=5.1mol% of alhpa olefin comonomer；
Melt index MI of component CC=25g/10min, density pC=0.920g/cm3, molecular weight distribution refers to
Number Mw/Mn=4.2, the molar content=5.7mol% of alhpa olefin comonomer；
Conductive filler is titanium oxide, purchased from nine Chemical Co., Ltd. of nation of Shanghai；
Lubricant is the PEG lubricants produced by Switzerland's Clariant Corporation, and molecular weight is 10000.
(1) preparation of polyethylene composition：
Above-mentioned each component is weighed by proportioning and mixed, wherein the mass fraction W of component AAFor 75
Weight portion, the mass fraction W of component BBFor 2 weight portions, the mass fraction W of component CCFor 35
Weight portion, wherein WA/WC=2.1 (meet 5.2 × lgMIA+11.6≥WA/WC≥0.9×lgMIA+ 2.1,
Also meet 2.9 × lgMIA+6.8≥WA/WC≥1.1×lgMIA+ 2.7), with component A, component B and group
The gross mass of point C is 100 weight portion meters, and the addition of conductive filler is 3 weight portions, lubricant plus
Enter amount for 0.1 weight portion.It is well mixed in adding mixture to high speed agitator afterwards, then will mixing
Good material is added in the feeder of the double screw extruder of W＆P companies manufacture, and material is via feeding
Device is entered in twin-screw, and in process, the temperature of screw rod is maintained between 160-210 DEG C, and Jing screw rods melt
Melt and be well mixed, extrude, granulate and dry, obtain polyethylene composition pellet, its melting after testing refers to
Number MI=0.6g/10min.
(2) preparation of antistatic film：
Polyethylene composition pellet obtained in above-mentioned steps (1) is dried, Sweden is added to afterwards
Melting extrusion is carried out in the multilayer extrusion casting machine of model LCR400 of Labtech companies and casting is cast
Curtain coating chilling roll temperature, during curtain coating slab, is set as 35 DEG C by piece, makes polyethylene thickness slab,
The slab is single layer structure.
Above-mentioned polyethylene thickness slab is put in the stretching clamp of film biaxial tension equipment, is adopted and is first indulged
The two-way step drawing technological forming that laterally (TD) is stretched to after (MD) stretching, each step process condition
It is as follows：MD preheating temperatures are 116 DEG C, and MD draft temperatures are 118 DEG C, and MD stretching ratios are 4 times；
TD preheating temperatures are 120 DEG C, and TD draft temperatures are 120 DEG C, and TD stretching ratios are 5 times, film
TD rates of extension are 100%/s；Film setting temperature is 122 DEG C, and it is 25 μm to obtain average thickness
Single thin film.
Embodiment 4
The present embodiment is used for the polyethylene composition and antistatic film for illustrating present invention offer.
Method according to embodiment 1 prepares polyethylene composition and antistatic film, except for the difference that, will lead
The effective acetylene carbon black of electric filler multi-wall carbon nano-tube (is purchased from Tianjin Li Huajin Chemical Co., Ltd.s, No. CAS is
1333-86-4) substitute, and count by 100 weight portions of the gross mass of component A, component B and component C,
The addition of conductive filler be 5 weight portions, obtain the film that average thickness is 25 μm, its by upper epidermis,
Sandwich layer and layer are constituted, and each layer raw material is the polyethylene composition of the present embodiment, and upper epidermis is with
The thickness for also containing antitack agent, upper epidermis and layer in top layer is 1 μm.
Embodiment 5
The present embodiment is used for the polyethylene composition and antistatic film for illustrating present invention offer.
Method according to embodiment 1 prepares polyethylene composition and antistatic film, except for the difference that, resists quiet
Drawing process in the preparation process of conductive film is stretched for synchronous bidirectional, and preheating temperature is 100 DEG C, stretching
Temperature is 110 DEG C, and the stretching ratio of MD and TD is 4 times, and rate of extension is 60%/s, is put down
Thickness is 25 μm of film, wherein, the thickness of upper epidermis and layer is 0.5 μm.
Embodiment 6
The present embodiment is used for the polyethylene composition and antistatic film for illustrating present invention offer.
Method according to embodiment 1 prepares polyethylene composition and antistatic film, except for the difference that, described
Component A has following property：Melt index MI of component AA=1.5g/10min, density
ρA=0.928g/cm3, molecular weight distributing index Mw/Mn=3.0, molar content=1.9 of alhpa olefin comonomer
Mol%, i.e. the density p of component A, component B and component CA、ρBAnd ρCBetween relation be discontented with
- 0.04≤ρ of footA-ρB≤ 0.02 and -0.04≤ρA-ρC≤ 0.02, the film that average thickness is 25 μm is obtained,
Wherein, the thickness of upper epidermis and layer is 0.5 μm.
Comparative example 1
This comparative example is used for the polyethylene raw material and antistatic film for illustrating reference.
Polyethylene raw material：
Polyethylene raw material used by this comparative example is that the film-grade of DOW chemical companies of U.S. production is linearly low
Density polyethylene, the trade mark are ELITE 5400G, and in preparation process, catalyst used is metallocene catalysis
Agent, melt index MI=1.0g/10min, density p=0.916g/cm3, molecular weight distributing index Mw/Mn
=3.2.
The preparation of polyethylene composition and antistatic film：
Method according to embodiment 1 prepares polyethylene composition and antistatic film, except for the difference that, by institute
State this comparative example that component A in polyethylene composition, component B and component C use identical weight part
Above-mentioned polyethylene raw material substitute, Jing attempts the situation for stretching rupture of membranes occur for many times, it is impossible to stretch film forming.
Additionally, the TD rates of extension in antistatic film preparation process are down to after 50%/s, many trials of Jing
Still there is the situation of stretching rupture of membranes, it is impossible to stretch film forming.
Comparative example 2
This comparative example is used for the polyethylene raw material and film for illustrating reference.
Method according to embodiment 1 prepares polyethylene composition and film, except for the difference that, in polyethylene group
Conductive filler multi-walled carbon nano-tubes is added without in the preparation process of compound and film, obtaining average thickness is
25 μm of film, wherein, the thickness of upper epidermis and layer is 0.5 μm.
Comparative example 3
This comparative example is used for the polyethylene composition and antistatic film for illustrating reference.
The polyethylene composition that this comparative example is provided is by component 1, component 2, conductive filler and lubricant group
Into, wherein, component 1 and component 2 are the LLDPE of ethylene/alpha-olefin copolymerization
(LLDPE), component 1 is prepared using metallocene catalyst, and component 2 is urged using Z-N
Agent is prepared.The performance of component 1, component 2, conductive filler and lubricant is as follows：
Melt index MI of component 11=2.1g/10min, density p1=0.913g/cm3, molecular weight distribution refers to
Number Mw/Mn=3.2, the molar content=7.5mol% of alhpa olefin comonomer；
Melt index MI of component 22=15g/10min, density p2=0.905g/cm3, molecular weight distribution refers to
Number Mw/Mn=4.6, the molar content=10.1mol% of alhpa olefin comonomer；
Conductive filler is multi-walled carbon nano-tubes (MWNTs), is produced by Cheaptubes companies of the U.S., directly
Footpath is 20-30nm, and length is 20-30 μm；
Lubricant is the PEG lubricants produced by Switzerland's Clariant Corporation, and molecular weight is 10000.
(1) preparation of polyethylene composition：
Method according to embodiment 1 prepares polyethylene composition, and except for the difference that, the consumption of each component is different,
Specifically, the consumption of component 1 is 80 weight portions, and the consumption of component 2 is 30 weight portions, with component 1
It is 100 weight portion meters with the gross mass of component 2, the addition of conductive filler is 3 weight portions, lubricant
Addition be 0.1 weight portion, obtain polyethylene composition pellet.
(2) preparation of antistatic film：
Method according to embodiment 1 carries out the preparation of polyethylene antistatic film, as a result shows, Jing Guoduo
Secondary trial, maximum tension multiplying power only 2 times of (TD) × 2 times (MD) of biaxially oriented film, film
TD highest stretching ratios are only 10%/s, i.e. stretching ratio and rate of extension are too low, stretch film forming
Property is poor, does not possess practicality.
Comparative example 4
This comparative example is used for the polyethylene composition and antistatic film for illustrating reference.
The polyethylene composition that this comparative example is provided is by component 1, component 2, conductive filler and lubricant group
Into, wherein, component 1 and component 2 are the LLDPE of ethylene/alpha-olefin copolymerization
(LLDPE), component 1 is prepared using metallocene catalyst, and component 2 is urged using Z-N
Agent is prepared.The performance of component 1, component 2, conductive filler and lubricant is as follows：
Melt index MI of component 11=1.5g/10min, density p1=0.913g/cm3, molecular weight distribution refers to
Number Mw/Mn=3.4, the molar content=7.5mol% of alhpa olefin comonomer；
Melt index MI of component 22=15g/10min, density p2=0.905g/cm3, molecular weight distribution refers to
Number Mw/Mn=4.6, the molar content=10.1mol% of alhpa olefin comonomer；
Conductive filler is multi-walled carbon nano-tubes (MWNTs), is produced by Cheaptubes companies of the U.S., directly
Footpath is 20-30nm, and length is 20-30 μm；
Lubricant is the PEG lubricants produced by Switzerland's Clariant Corporation, and molecular weight is 10000.
(1) preparation of polyethylene composition：
Method according to embodiment 1 prepares polyethylene composition, and except for the difference that, the consumption of each component is different,
Specifically, the consumption of component 1 is 80 weight portions, and the consumption of component 2 is 30 weight portions, with component 1
It is 100 weight portion meters with the gross mass of component 2, the addition of conductive filler is 3 weight portions, lubricant
Addition be 0.1 weight portion, obtain polyethylene composition pellet.
(2) preparation of antistatic film：
Method according to embodiment 1 carries out the preparation of polyethylene antistatic film, as a result shows, Jing Guoduo
Secondary trial, maximum tension multiplying power only 2 times of (TD) × 2 times (MD) of biaxially oriented film, film
TD highest stretching ratios are only 10%/s, i.e. stretching ratio and rate of extension are too low, stretch film forming
Property is poor, does not possess practicality.
Test case
Test case is used for the test for illustrating polyethylene film and reference polyethylene film performance.
(1) film tensile strength and tension fracture elongation rate：Specify according in GB/T 1040.3-2006
Method be measured, acquired results are as shown in table 1；
(2) surface resistivity：It is measured according to method specified in GB/T 1410-2006, gained
As a result it is as shown in table 1.
Table 1
Can draw from result above, the polyethylene composition provided using the present invention has preferable film forming
Performance, and the film for obtaining has preferable antistatic property, great prospects for commercial application.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the present invention, can be to the technical side of the present invention
Case carries out various 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 specific 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 are no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of embodiments of the present invention, as long as its
Without prejudice to the thought of the present invention, which should equally be considered as content disclosed in this invention.
Claims (19)
1. a kind of polyethylene composition, it is characterised in that the polyethylene composition contain conductive filler,
Component A, component B and component C；Component A is gathered for the linea low density of ethylene/alpha-olefin copolymerization
Ethene, its temperature be 190 DEG C, load be melt index MI under 2.16kgAFor 0.01-2g/10min,
Density pAFor 0.880-0.936g/cm3；Component B is gathered for the linea low density of ethylene/alpha-olefin copolymerization
Ethene, its temperature be 190 DEG C, load be melt index MI under 2.16kgBFor 2.1-9.9g/10min,
Density pBFor 0.910-0.930g/cm3；Component C is gathered for the linea low density of ethylene/alpha-olefin copolymerization
Ethene, its temperature be 190 DEG C, load be melt index MI under 2.16kgCFor 10-80g/10min,
Density pCFor 0.880-0.930g/cm3。
2. polyethylene composition according to claim 1, wherein, component A in temperature is
190 DEG C, load be 2.16kg under melt index MIAFor 0.01-1.5g/10min, component B exists
Temperature is 190 DEG C, load is melt index MI under 2.16kgBFor 3-8g/10min, component C
Temperature be 190 DEG C, load be melt index MI under 2.16kgCFor 10-60g/10min；Preferably,
Component A temperature be 190 DEG C, load be melt index MI under 2.16kgAFor
0.01-1g/10min, component B temperature be 190 DEG C, load be melt index under 2.16kg
MIBFor 3-5g/10min, component C temperature be 190 DEG C, load be that melting under 2.16kg refers to
Number MICFor 15-40g/10min.
3. polyethylene composition according to claim 1, wherein, the density p of component AA
For 0.910-0.930g/cm3, the density p of component BBFor 0.913-0.928g/cm3, component C
Density pCFor 0.905-0.928g/cm3；Preferably, the density p of component AAFor
0.915-0.926g/cm3, the density p of component BBFor 0.913-0.924g/cm3, component C
Density pCFor 0.910-0.926g/cm3。
4. polyethylene composition according to claim 3, wherein, in the polyethylene composition
The density p of component A, component B and component CA、ρBAnd ρCBetween relation meet -0.04≤ρA-ρB
≤ 0.02, and -0.04≤ρA-ρC≤0.02。
5. the polyethylene composition according to any one in claim 1-4, wherein, described
In polyethylene composition, the mass fraction W of component AAFor 25-90 weight portions, component B
Mass fraction WBFor 0.1-10 weight portions, the mass fraction W of component CCFor 10-75 weight
Part, and count by 100 weight portions of the gross weight of component A, component B and component C, it is described to lead
The content of electric filler is 0.1-10 weight portions；
Preferably, in the polyethylene composition, the mass fraction W of component AAFor 30-80
Weight portion, the mass fraction W of component BBFor 0.5-8 weight portions, the mass parts of component C
Number WCFor 20-70 weight portions, and with the gross weight of component A, component B and component C as 100
Weight portion meter, the content of the conductive filler is 0.5-3 weight portions.
6. polyethylene composition according to claim 5, wherein, the mass parts of component A
Number WAWith the mass fraction W of component CCWith melt index MI of component AARelation meet 5.2 ×
lgMIA+11.6≥WA/WC≥0.9×lgMIA+ 2.1, preferably meet 2.9 × lgMIA+6.8≥WA/WC
≥1.1×lgMIA+2.7。
7. polyethylene composition according to claim 6, wherein, with the polyethylene composition
Gross weight on the basis of, mass percentage content M of component BB≤ 35 weight %, preferred MB≤25
Weight %.
8. the polyethylene composition according to any one in claim 1-4,6 and 7, wherein,
The 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.
9. the polyethylene composition according to any one in claim 1-4, wherein, described group
A and the molecular weight distributing index of component B is divided to meet Mw/Mn≤ 4.5, and the molecular weight of component C
Profile exponent meets Mw/Mn≤8.0；Preferably, the molecular weight distribution of component A and component B refers to
Number meets 2.0≤Mw/Mn≤ 4.2, and component C molecular weight distributing index meet 3.5≤
Mw/Mn≤6.0。
10. polyethylene composition according to claim 9, wherein, component A and component B
Obtained using metallocene catalyst polymerisation, and component C is polymerized using Ziegler-Natta catalyst
Arrive.
11. polyethylene compositions according to any one in claim 1-4, wherein, described group
The molar content of alhpa olefin comonomer in A, component B and component C is divided to be each independently
0.2-15mol%, preferably 1.5-10mol%.
12. polyethylene compositions according to claim 11, wherein, component A, component B
C is each independently with the alhpa olefin in component C3-C20At least one in alkene, preferably propylene,
1- butylene, 2- butylene, 3-methyl-1-butene, 4- methyl isophthalic acids-butylene, 1- amylenes, 3- Methyl-1-pentenes,
4-methyl-1-pentene, 3,3- dimethyl -1- amylenes, 3,4- dimethyl -1- amylenes, 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,
In 1- dodecylenes, tetradecene, cetene, 1- vaccenic acids and 1- eicosylenes at least
At least one in one kind, more preferably 1- butylene, 1- hexenes and 1- octenes.
13. polyethylene compositions according to any one in claim 1-4, wherein, it is described to lead
Electric filler be carbon black, graphite, CNT, carbon fiber, conductive metal particles, conductive metallic fiber and
At least one in metal oxide.
14. polyethylene compositions according to any one in claim 1-4, wherein, it is described poly-
Vinyl composition also contains lubricant；Preferably, with the total of component A, component B and component C
Weight is 100 weight portion benchmark, and the content of the lubricant is 0.05-5 weight portions；It is highly preferred that institute
State lubricant selected from polyethylene glycol series lubricant agent, fluoropolymer series lubricant agent, silicone lubricant,
Fatty alcohol type emollients, fatty acid lubricant, fatty acid ester type emollients, stearic amide class lubrication
Agent, fatty acid metal soaps lubricant, alkane and oxidation of alkanes series lubricant agent and micro-and nano-particles class lubrication
At least one in agent.
A kind of 15. antistatic films, the antistatic film is at least including one layer by claim 1-14
The polyethylene layer that polyethylene composition described in middle any one is formed.
16. antistatic films according to claim 15, wherein, the antistatic film has
The composite construction of upper epidermis, sandwich layer and layer, and at least described upper epidermis or layer are by described poly-
The polyethylene layer that vinyl composition is formed；Preferably, when the antistatic film has upper epidermis, sandwich layer
During with the composite construction of layer, the thickness of the upper epidermis and layer is each independently described anti-quiet
The 1-25% of conductive film thickness.
17. antistatic films according to claim 15, wherein, the antistatic film is served as reasons
The biaxially oriented film that flat film biaxial tension method is prepared；Preferably, using flat film biaxial tension method
During preparing the biaxially oriented film, longitudinal stretching multiplying power >=4 times, cross directional stretch multiplying power >=5
Times；During the biaxially oriented film is prepared using flat film biaxial tension method, cross directional stretch speed
>=50%/s.
18. antistatic films according to any one in claim 15-17, wherein, it is described anti-
The thickness of electrostatic film is 10-200 μm, preferably 10-100 μm.
19. antistatic films according to claim 17, wherein, the biaxially oriented film
Longitudinal tensile strength >=40MPa, transverse tensile strength >=40MPa；The stretching of the biaxially oriented film
Elongation at break≤350%；The surface resistivity of the biaxially oriented film is 103-1010Ω。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020012300A3 (en) * | 2018-07-11 | 2020-04-30 | Nova Chemicals (International) S.A. | Polyethylene composition and film having high stiffness, outstanding sealability and high permeability |
| CN114479226A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Antistatic polyethylene composition, polyethylene forming body and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101291959A (en) * | 2005-10-18 | 2008-10-22 | 博里利斯技术公司 | Polyethylene blend component and blends containing the same |
| CN102604194A (en) * | 2012-02-11 | 2012-07-25 | 常州市嘉鹏塑料制品有限公司 | Transparent electromagnetic shielding film |
-
2015
- 2015-09-28 CN CN201510628245.3A patent/CN106554548B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101291959A (en) * | 2005-10-18 | 2008-10-22 | 博里利斯技术公司 | Polyethylene blend component and blends containing the same |
| CN102604194A (en) * | 2012-02-11 | 2012-07-25 | 常州市嘉鹏塑料制品有限公司 | Transparent electromagnetic shielding film |
Non-Patent Citations (1)
| Title |
|---|
| 岳德茂: "《印刷科技实用手册--第三分册 印刷器材篇》", 30 April 2010, 印刷工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020012300A3 (en) * | 2018-07-11 | 2020-04-30 | Nova Chemicals (International) S.A. | Polyethylene composition and film having high stiffness, outstanding sealability and high permeability |
| JP2021532210A (en) * | 2018-07-11 | 2021-11-25 | ノヴァ ケミカルズ（アンテルナショナル）ソシエテ アノニム | Polyethylene compositions and films with high rigidity, excellent sealing and high permeability |
| JP7417582B2 (en) | 2018-07-11 | 2024-01-18 | ノヴァ ケミカルズ（アンテルナショナル）ソシエテ アノニム | Polyethylene compositions and films with high stiffness, excellent sealing properties and high permeability |
| CN114479226A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Antistatic polyethylene composition, polyethylene forming body and preparation method thereof |
| CN114479226B (en) * | 2020-10-23 | 2023-09-08 | 中国石油化工股份有限公司 | Antistatic polyethylene composition, polyethylene molded body and preparation method of antistatic polyethylene composition |
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