CN106633323B - A kind of polyethylene composition and durable membrane - Google Patents

A kind of polyethylene composition and durable membrane Download PDF

Info

Publication number
CN106633323B
CN106633323B CN201510712914.5A CN201510712914A CN106633323B CN 106633323 B CN106633323 B CN 106633323B CN 201510712914 A CN201510712914 A CN 201510712914A CN 106633323 B CN106633323 B CN 106633323B
Authority
CN
China
Prior art keywords
component
polyethylene composition
temperature
polyethylene
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510712914.5A
Other languages
Chinese (zh)
Other versions
CN106633323A (en
Inventor
施红伟
高达利
殷建军
乔金樑
张师军
郭梅芳
于鲁强
黄红红
李汝贤
王良诗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201510712914.5A priority Critical patent/CN106633323B/en
Publication of CN106633323A publication Critical patent/CN106633323A/en
Application granted granted Critical
Publication of CN106633323B publication Critical patent/CN106633323B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B29C55/143—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively firstly parallel to the direction of feed and then transversely thereto
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The present invention provides a kind of polyethylene composition and durable membranes.The polyethylene composition contains linear low density polyethylene and anti-aging auxiliary agent as made of ethylene and alhpa olefin copolymerization, wherein, the weight average molecular weight Mw of the polyethylene composition is 100,000 g/mol-18, ten thousand g/mol, and Mw/Mn is 4.0-8.0, Mz/Mw is 4.0-6.0, Mz+1/Mw 4.5-12.5.When the polyethylene composition is prepared polyethylene film using Flat film strength, stretching ratio is big, rate of film build is high, and film forming is very good, and also has excellent endurance quality.

Description

A kind of polyethylene composition and durable membrane
Technical field
The present invention relates to a kind of polyethylene composition and durable membranes.
Background technique
Biaxially-oriented polyethylene (Biaxially Oriented Polyethylene, BOPE) film is that have special point Polyethylene (PE) resin of minor structure is through the molding thin-film material of stretch processes.In the molding process of BOPE film In, after the processing of film drawn, PE macromolecular chain and crystalline texture generation are height-oriented, to significantly improve the stretching of film Intensity reduces tension fracture elongation rate, and makes that the mist degree of film is lower, glossiness is higher and transparent more preferable.In addition, with The extrusioning blowing process of the prior art is compared with the polyethylene film product for squeezing out casting technique preparation, and BOPE film has mechanics The advantages such as intensity is high, puncture resistant and shock resistance are good, excellent optical performance, environmental protection and energy saving.Therefore, BOPE film can be wide It is general to be used for packaging bag, again packaging bag, Vacuum Heat sealer, low temperature packaging film, composite membrane, medical and sanitary products, plastic film for agricultural use etc..
The biaxial tension processing method of currently used plastic film has Flat film strength and envelope pulling method.Flat membrane stretches Method has been applied in the processing of the thin-film materials such as polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET) In, technique is more mature.Compared with envelope pulling method, the stretching ratio of Flat film strength is big, and (cross directional stretch multiplying power is up to 10 times More than), shaping speed fast (highest rolling speed is up to hundreds of ms/min), high production efficiency, and the mechanics of obtained film More preferably, but film forming is influenced significantly by process condition fluctuations for intensity, optical property and the thickness uniformity, film stretch plus Work difficulty is big, has higher requirement for film raw material.Existing Biaxially-oriented polyethylene raw material is only applicable to pipe substantially When steeping pulling method and prepare BOPE film, and these existing polyethylene raw materials being prepared BOPE film using Flat film strength, deposit The defect of rupture is easy to appear in film forming poor (tensile speed and stretching ratio are very low), film, that is, is not suitable for substantially using flat Film stretching method prepares film.Therefore, it in order to make full use of the above-mentioned advantage of Flat film strength, needs to develop a kind of film forming at present The polyethylene raw material for being suitable for Flat film strength and preparing BOPE film that good and film is not easy to occur rupturing.
Biaxial tension polyethylene film is when as agricultural film especially greenhouse film, because it has high intensity The characteristic of high transparency has apparent advantage.But since the thickness of Biaxial tension polyethylene film is thinner than conventional blown film, Its durability may be subjected to a degree of influence.Therefore high-durability for Biaxial tension polyethylene film importance more It is significant.
Summary of the invention
The purpose of the invention is to overcome existing polyethylene raw material preparing polyethylene film using Flat film strength When there are film formings that poor, film is easily broken (not being suitable for preparing film using Flat film strength) and durability is insufficient lacks It falls into, and a kind of new polyethylene composition and the durable membrane made of the polyethylene composition is provided.
Specifically, polyethylene composition provided by the invention contains the linea low density as made of ethylene and alhpa olefin copolymerization Polyethylene and anti-aging auxiliary agent, wherein the weight average molecular weight Mw of the polyethylene composition is 100,000 g/mol-18, ten thousand g/ Mol, and Mw/Mn is 4.0-8.0, Mz/Mw 4.0-6.0, Mz+1/Mw 4.5-12.5.
Durable membrane provided by the invention includes at least one layer of polyethylene layer formed by above-mentioned polyethylene composition.
The present inventor by further investigation after find, using biaxial tension method prepare film during, such as The molecular weight distribution of fruit polyethylene composition is narrow, then possibly can not carry out biaxial tension processing；And if polyethylene composition Molecular weight distribution it is wide, then the problem of may cause the in uneven thickness of film and be unable to satisfy subsequent requirement.And this It invents the polyethylene composition provided to control weight average molecular weight Mw in 100,000 g/mol-18, ten thousand g/mol, while Mw/Mn being controlled In 4.0-8.0, Mz/Mw control uses two-way drawing in 4.5-12.5, by the polyethylene composition in 4.0-6.0, Mz+1/Mw control The method of stretching has the advantages that stretching ratio is big, rate of film build is high, can satisfy Flat film strength to polyethylene raw material when preparing film High requirement.Further, since the film that the presence of anti-aging auxiliary agent can also make in polyethylene composition is with excellent Durability, great prospects for commercial application.
A preferred embodiment of the invention, when the polyethylene composition is by analytic type temperature rising elution staging The temperature rising elution curve measured includes high temperature elution peak and low temperature elution peak, and the temperature at high temperature elution peak is 90-105 DEG C, the temperature at low temperature elution peak is 50-90 DEG C, on the basis of the gross area that the high temperature elutes peak and low temperature elution peak, The area at high temperature elution peak is not higher than 60%, when the area at low temperature elution peak is not less than 40%, the polyethylene composition With preferable film forming and on the basis of durability, the film being prepared by the polyethylene composition also has more excellent object Different optical property and mechanical property, as mist degree is lower, glossiness is higher, intensity and puncture-resistant ability are preferable.
According to another preferred method of implementation of the present invention, when the molecular weight distribution of the component A, component B and component C refer to Number is all satisfied Mw/MnWhen≤4.5, the polyethylene composition is with preferable film forming and on the basis of durability, by the polyethylene The film that composition is prepared intensity also with higher and puncture resistance.
According to another preferred method of implementation of the present invention, as component A, component B and component C in the polyethylene composition Density pA、ρBAnd ρCBetween relationship meet -0.04≤ρA-ρB≤ 0.02 and -0.04≤ρA-ρCWhen≤0.02, the polyethylene For composition with preferable film forming and on the basis of durability, the film being prepared by the polyethylene composition also has drawing Stretch the advantage that intensity and punctured resistance are high and mist degree is low.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the structural schematic diagram for being used to prepare the multiple reactor shunting means of polyethylene composition.
Description of symbols
1- first reactor；2- second reactor；3- third reactor；4- solid-liquid (gas) separator；5- homogenization silo； 6- melt pelletization system.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
Polyethylene composition provided by the invention contain as ethylene and alhpa olefin copolymerization made of linear low density polyethylene with And anti-aging auxiliary agent, wherein the weight average molecular weight Mw of the polyethylene composition is 100,000 g/mol-18, ten thousand g/mol, preferably 100000 g/mol-15, ten thousand g/mol；And Mw/Mn is 4.0-8.0, Mz/Mw 4.0-6.0, Mz+1/Mw 4.5-12.5.In this hair In bright, Mw, Mn, Mz, Mz+1 are all made of high-temperature gel permeation chromatography instrument (GPC) and are measured.
The polyethylene composition provided according to the present invention, the polyethylene composition are classified by analytic type temperature rising elution (TREF) the temperature rising elution curve that method measures includes high temperature elution peak and low temperature elution peak, and the temperature at high temperature elution peak is excellent It is selected as 90-105 DEG C, more preferably 95-100 DEG C；The temperature at low temperature elution peak is preferably 50-90 DEG C, more preferably 60-90 ℃.In addition, the area at high temperature elution peak is excessive to will lead to the biaxially oriented film being prepared by the polyethylene composition Optical property be deteriorated, and low temperature elution peak area it is excessive, will lead to the two-way drawing being prepared by the polyethylene composition The mechanical property for stretching film is deteriorated.Therefore, in order to enable the polyethylene composition is with good filming performance and durable On the basis of performance, also while there is preferable optical property and mechanical property, it is preferable that peak and low temperature are eluted with the high temperature On the basis of the gross area for eluting peak, the area at high temperature elution peak is not higher than 60%, and the area at low temperature elution peak is not low In 40%；It is highly preferred that on the basis of the gross area that the high temperature elutes peak and low temperature elution peak, the face at high temperature elution peak Product is not higher than 50%, and the area at low temperature elution peak is not less than 50%；Most preferably, peak and low temperature leaching are eluted with the high temperature It washes on the basis of the gross area at peak, the area at high temperature elution peak is 5-45%, and the area at low temperature elution peak is 55- 95%.
Usually, if the melting temperature of polyethylene composition is excessively high, it will lead to and cast in subsequent curtain coating process Piece curing rate is too fast, is unfavorable for being cast the smooth of slab；And if the melting temperature of polyethylene composition is too low, it will lead to Slab curing rate is slower in subsequent curtain coating process, has both been unfavorable for the raising of processing efficiency, also results in film strength mistake It is low.Therefore, in order to enable the polyethylene composition also has with good filming performance and on the basis of endurance quality Preferable curtain coating processability and higher mechanical strength, it is preferable that the polyethylene composition is by differential scanning calorimetry (DSC) melting peak temperature measured is 100-130 DEG C, more preferably 105-128 DEG C.
The present invention is not limited particularly from the content of the structural unit of alhpa olefin derived from the linear low density polyethylene It is fixed, for example, being with the total content of the structural unit of ethylene unit unit and derived from alpha alkene in the linear low density polyethylene Benchmark, the content of the structural unit of the derived from alpha alkene can be 0.5-20mol%, preferably 2.0-10mol%.At this In invention, the ethylene unit unit refers to the structural unit formed by vinyl polymerization；The structural unit of the derived from alpha alkene Refer to the structural unit formed by alpha-olefin polymerization.
A preferred embodiment of the invention, the linear low density polyethylene have component A, component B and component C；Melt index MI of the component A in the case where temperature is 190 DEG C, load is 2.16kgAFor 0.01-2g/10min, density pAFor 0.880-0.936g/cm3；Melt index MI of the component B in the case where temperature is 190 DEG C, load is 2.16kgBFor 2.1- 14.9g/10min density pBFor 0.910-0.930g/cm3；The component C is molten in the case where temperature is 190 DEG C, load is 2.16kg Melt index M ICFor 15-150g/10min, density pCFor 0.880-0.930g/cm3。
The polyethylene composition provided according to the present invention, it is preferable that the component A is temperature is 190 DEG C, load is Melt index MI under 2.16kgAFor 0.01-1.5g/10min, the component B is in the case where temperature is 190 DEG C, load is 2.16kg Melt index MIBFor 3-10g/10min, melt index MI of the component C in the case where temperature is 190 DEG C, load is 2.16kgC For 15-100g/10min.It is highly preferred that melt index MI of the component A in the case where temperature is 190 DEG C, load is 2.16kgAFor The melt index MI of 0.01-1g/10min, the component B in the case where temperature is 190 DEG C, load is 2.16kgBFor 3-5g/10min, Melt index MI of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor 20-60g/10min.
In the present invention, the melt index is measured according to method specified in GB/T3682-2000, wherein Test condition includes that temperature is 190 DEG C, load 2.16kg.
The polyethylene composition provided according to the present invention, it is preferable that the density p of the component AAFor 0.910-0.930g/ cm3, the density p of the component BBFor 0.913-0.928g/cm3, the density p of the component CCFor 0.905-0.928g/cm3.More Preferably, the density p of the component AAFor 0.915-0.926g/cm3, the density p of the component BBFor 0.913-0.924g/ cm3, the density p of the component CCFor 0.910-0.926g/cm3.It is particularly preferred that component A, group in the polyethylene composition Divide the density p of B and component CA、ρBAnd ρCBetween relationship meet -0.04≤ρA-ρB≤ 0.02, and -0.04≤ρA-ρC≤ 0.02, The polyethylene composition enabled in this way also has very with preferable filming performance and on the basis of endurance quality High tensile strength and punctured resistance and lower mist degree.
The component A, component B and component C are the linear low density polyethylene of ethylene/alpha-olefin copolymerization, wherein linear Structure refers in strand only containing short-chain branch structure, and does not contain long branched chain structure and cross-linked structure, by polymerized monomer and Polymerization process condition is determined, is specifically known to the skilled person, and therefore not to repeat here.
The polyethylene composition provided according to the present invention, in order to enable the polyethylene composition arrived is with good filming Can also have preferable mechanical property and optical property, it is preferable that in the polyethylene composition on the basis of endurance quality In, the mass fraction W of the component AAFor 25-90 parts by weight, the mass fraction W of the component BBIt is described for 0.1-10 parts by weight The mass fraction W of component CCFor 10-75 parts by weight；It is highly preferred that in the polyethylene composition, the quality of the component A Number WAFor 30-80 parts by weight, the mass fraction WB of the component B is 0.5-8 parts by weight, the mass fraction W of the component CCFor 20-70 parts by weight；It is highly preferred that in the polyethylene composition, the mass fraction W of the component AAFor 55-80 parts by weight, The mass fraction W of the component BBFor 2-8 parts by weight, the mass fraction W of the component CCFor 20-55 parts by weight.Further, The mass fraction W of the component AAWith the mass fraction W of component CCWith the melt index MI of component AARelationship preferably satisfy 5.2 ×1gMIA+11.6≥WA/WC≥0.9×1gMIA+ 2.1, more preferably 2.9 × 1gMI of satisfactionA+6.8≥WA/WC≥1.1×1gMIA+ 2.7, enable to the polyethylene composition that there is bigger stretching ratio in flat membrane method film biaxial tension processing in this way With higher rate of extension.
The polyethylene composition provided according to the present invention, particularly preferably, the polyethylene composition is 190 in temperature DEG C, the melt index under load is 2.16kg be 0.1-20g/10min, more preferably 0.5-10g/10min, most preferably 0.5- 3g/10min；Density of the polyethylene composition in the case where temperature is 190 DEG C, load is 2.16kg is 0.880-0.940g/ cm3, preferably 0.910-0.930g/cm3.In the component A, component B and component C that will have above-mentioned particular melt index and density On the basis of being used cooperatively with anti-aging auxiliary agent, by the melt index control of the polyethylene composition entirety above-mentioned preferred In range, the polyethylene composition that enables to while there is very excellent film forming, durability, tensile strength and anti-wear Pierce intensity and lower mist degree.
The polyethylene composition provided according to the present invention, it is preferable that the molecular weight of the component A, component B and component C point Cloth index is all satisfied Mw/Mn≤ 4.5, more preferably 2.0≤M of satisfactionw/Mn≤4.2.Specifically, in order to obtain with above-mentioned molecular weight Component A, the component B and component C of distribution, the component A, component B and component C are all made of metallocene catalyst polymerisation and obtain.Its In, the type of the metallocene catalyst can be the conventional selection of this field, usually by metallocene compound and organo-aluminium Compound and optional electron donor composition, are specifically known to the skilled person, therefore not to repeat here.Hair of the invention Bright people has found after further investigation, the group with above-mentioned melt index and density that will be obtained using metallocene catalyst polymerisation Point A, component B and component C are used cooperatively with anti-aging auxiliary agent, and obtained film is with good filming performance and endurance quality On the basis of, also there is very high puncture energy, be highly suitable for packaging material.
Alhpa olefin in the component A, component B and component C is each independently C3-C20At least one of alkene.From original Expect that ready availability angle is set out, the alhpa olefin in the component A, component B and component C is preferably propylene, 1- butylene, 2- butylene, 3- Methyl-1-butylene, 4- methyl-1-butylene, 1- amylene, 3- Methyl-1-pentene, 4-methyl-1-pentene, 3,3- dimethyl-1- penta Alkene, 3,4- dimethyl-1- amylene, 4,4- dimethyl-1- amylene, 1- hexene, 4- methyl-1-hexene, 5- methyl-1-hexene, 1- Heptene, 2- heptene, 1- octene, 1- decene, 1- 12 (carbon) alkene, 1- 14 (carbon) alkene, 1- 16 (carbon) alkene, 1- 18 (carbon) alkene At least one of with 1- 20 (carbon) alkene, more preferably at least one of 1- butylene, 1- hexene and 1- octene.
The anti-aging auxiliary agent can be the existing various substances that can be improved polyethylene composition anti-aging property, example It such as, can be at least one of UV absorbers, energy quencher and radical scavenger.With the component A, component B Total weight with component C is 100 parts by weight meters, and the content of the anti-aging auxiliary agent can be 0.01-5 parts by weight.These are anti-ageing Changing auxiliary agent can be commercially available.For example, the UV absorbers can be in trade name UV-531, UV-326 etc. It is at least one.By the total weight of the component A, component B and component C be 100 parts by weight in terms of, the content of the UV absorbers It can be 0.01-1 parts by weight, preferably 0.1-0.3 parts by weight.The energy quencher can be organic nickel compound, such as: double (3,5- di-tert-butyl-4-hydroxyl benzyl phosphonic acids mono ethyl ester) nickel (trade name Irgastab 2002), 2,2- thiobis (uncle 4- Octyl phenol oxygroup) nickel-n-butylamine complex compound (trade name UV-1084), 2,2- thiobis (4- t-octyl phenol oxygroup) nickel (AM- 101), dioctyl aminodithioformic acid nickel (AM-108), N, at least one in N- nickel dibutyl dithiocarbamate (NBC) Kind.Organic nickel complex is because of heavy metal ion toxicity problem, with the total weight of the component A, component B and component C for 100 weight Part meter, the dosage of organic nickel compound energy quencher should control between 0.01-0.04 parts by weight.The free radical capture Agent can be hindered amine light stabilizer, such as: Tinuvin123, Tinuvin622, Tinuvin791, GW-480, GW-540, At least one of GW-544, Chimassorb944 etc..With the total weight of the component A, component B and component C for 100 weight Part meter, the content of the radical scavenger can be 0.01-1 parts by weight, preferably 0.05-0.3 parts by weight.
The polyethylene composition provided according to the present invention, it is preferable that the polyethylene composition also contains lubricant, in this way The extrusion processability energy of the polyethylene composition can be improved.The type and dosage of the lubricant all can be this field Conventional selection, for example, the lubricant can be selected from polyethylene glycol (PEG) series lubricant agent, fluoropolymer series lubricant agent, organic Silicon series lubricant agent, fatty alcohol type emollients, fatty acid lubricant, fatty acid ester type emollients, stearic amide series lubricant agent, Fatty acid metal soaps lubricant, alkane and at least one of oxidation of alkanes series lubricant agent and micro-and nano-particles series lubricant agent. Specifically, the PEG series lubricant agent for example can be the PEG molecule that molecular weight is 500-50000, can be by blocking, connecing Branch, crosslinking Treatment, can also pass through other chemical modifications or physical modification.The fluoropolymer series lubricant agent for example can be At least one of polytetrafluoroethylene (PTFE), Kynoar, polyhexafluoropropylene etc., or other are unimodal or multimodal fluorine-containing poly- Close object and crystallization or hemicrystalline fluoropolymer.The organo-silicic oil can be existing various with carbon, silicon atom For molecular backbone, using the oligomer of the organic groups such as methyl, phenyl, alkoxy, vinyl or oligomer as the compound of side chain. The fatty alcohol type emollients can be for example at least one of soft fat alcohol, tallow alcohol, tallow fatty alcohol etc..The rouge Fat acids lubricant for example can be with stearic acid and/or 12- hydroxy stearic acid.The fatty acid ester type emollients for example can be hard At least one of resin acid butyl ester, stearic acid list glycerolipid, cetyl palmitate, tearyl base ester etc..It is described Stearic amide series lubricant agent for example can be stearic amide, oleamide, erucyl amide, n, n- ethylene bis stearic acid amide At least one of (EBS) etc..The fatty acid metal soaps lubricant for example can be lead stearate, calcium stearate, tristearin At least one of sour magnesium, synthesis calcium acetate etc..The alkane and oxidation of alkanes series lubricant agent can be for example atoleine, consolidate At least one of body paraffin, polyethylene wax, polypropylene wax, ethylene oxide wax etc..The micro-and nano-particles series lubricant agent is for example It can be powdered rubber and/or aerosil particles.In addition, with the total weight of the component A, component B and component C for 100 parts by weight Meter, the content of the lubricant can be 0.05-5 parts by weight, preferably 0.1-3 parts by weight, more preferably 0.1-0.5 weight Part.
In addition, can also contain in the polyethylene composition existing various in polyvinyl resin, polyethylene film Other usually used auxiliary agents, and other described auxiliary agents will not stretching film forming to polyethylene composition provided by the invention, Durability, mechanical property and optical property have adverse effect on.Other described auxiliary agents include but is not limited to: antioxidant, smooth At least one of agent, antistatic agent, antitack agent etc..In addition, the dosage of other auxiliary agents all can be this field routine Selection, can know this those skilled in the art, therefore not to repeat here.
The polyethylene composition can be prepared according to existing various methods, for example, first prepare respectively component A, Component B and component C, the lubricant then contained by the component A, component B and component C and anti-aging auxiliary agent and selectively and Other auxiliary agents carry out mechanical mixture in mechanical mixing equipment according to the proportion, are then added in melt blending equipment and melt altogether It is mixed.Wherein, the mechanical mixing equipment can be for example high-speed mixer, kneader etc..The melt blending equipment for example may be used Think double screw extruder, single screw extrusion machine, open mill, mixer etc..
A preferred embodiment of the invention, the polyethylene composition multiple reactor as shown in Figure 1 simultaneously Be prepared in coupling device, the multiple reactor shunting means include first reactor 1, second reactor 2, third reactor 3, Solid-liquid (gas) separator 4, homogenization silo 5 and melt pelletization system 6, wherein the first reactor 1,2 and of second reactor Third reactor 3 is connected in parallel, and the number of solid-liquid (gas) separator 4 is three, anti-with first reactor 1, second respectively Answer device 2 to be connected to third reactor 3, the component A that is prepared by first reactor 1, the component B prepared by second reactor 2 and The component C prepared by third reactor 3 is mutually separated in solid-liquid (gas) separator 4 different respectively, then will be through phase Component A, component B and component C after separation be delivered in homogenization silo 5 in proportion and with anti-aging auxiliary agent and other additives It is mixed together uniformly, is sent into melt pelletization system 6 carries out extruding pelletization later.Wherein, the polymerization in each reactor can be Batchwise polymerization is also possible to continuous polymerization.When using multiple reactor parallel polymerization, W hereinafterA、WBAnd WCExist for each component Yield in unit time in respective reaction device.
Durable membrane provided by the invention includes at least one layer of polyethylene layer formed by above-mentioned polyethylene composition.
The durable membrane can have single layer structure, it is possible to have multilayered structure.When the durable membrane is When multilayered structure, at least sandwich layer (the usually maximum layer of thickness) is the polyethylene layer formed by the polyethylene composition.Example Such as, the durable membrane can have the composite construction of upper epidermis, sandwich layer and layer, and at least described sandwich layer is by described The polyethylene layer that polyethylene composition is formed.Usually, the thickness of the durable membrane can be 10-200 μm, preferably 10-100μm.In addition, when the durable membrane has the composite construction of upper epidermis, sandwich layer and layer, the upper epidermis The 1-25% of durable membrane's thickness, preferably 1-10%, more preferably 1- are each independently with the thickness of layer 5%.
In addition, the durable membrane can be monodirectional tension film, or biaxially oriented film, it is preferably bidirectional Oriented film, the biaxially oriented film being more preferably prepared by flat membrane biaxial tension method.
It is known to the skilled person using the process that flat membrane biaxial tension method prepares biaxially oriented film.Specifically, First above-mentioned polyethylene composition is added in casting apparatus and squeeze out curtain coating slab, it is then that obtained slab is double in film Drawing and forming is carried out into stretcher.During squeezing out curtain coating, slab die head can according to need the knot of the film of acquisition Structure is selected, for example, can use single layer die when needing to obtain the film with single layer structure；When needs are had It, can be multiple using multilayered structure when having film (film with upper epidermis, sandwich layer and layer three-decker) of multilayered structure Head is molded, and at least one layer of (sandwich layer) and the extruder that above-mentioned polyethylene composition is housed in the compound die head of the multilayered structure Hopper is connected to, and at least one layer (sandwich layer) in the film enabled in this way is the poly- second formed by above-mentioned polyethylene composition Alkene layer.In extrusion process, extrusion temperature can be 160-260 DEG C, and the temperature for being cast chilling roller can be 15-85 DEG C.In addition, The biaxial tension (can carry out film longitudinal (MD) simultaneously and laterally (TD) is stretched) using Synchronos method drawing process, can also (first to carry out film longitudinal stretching using method of fractional steps drawing process, then carry out film cross directional stretch).The Synchronos method stretches Specifically comprises the processes of: the slab carries out the stretching of vertical and horizontal direction after being fully warmed-up, wherein preheating temperature can Think 75-165 DEG C, draft temperature can be 75-160 DEG C, longitudinal stretching ratio >=4 times (MD), laterally stretching ratio >=5 (TD) Times, cross directional stretch rate >=50%/s.What the method for fractional steps stretched specifically comprises the processes of: the slab is advanced after being fully warmed-up Row longitudinal stretching carries out cross directional stretch later, wherein preheating temperature can be 65-158 DEG C, and draft temperature can be 65-155 DEG C, longitudinal stretching ratio >=4 times (MD), lateral stretching ratio >=5 times (TD), cross directional stretch rate >=50%/s.In addition, film It can be handled without setting after drawing and forming, annealing setting processing can also be carried out.When carrying out annealing setting processing, film The treatment temperature that shapes can be 80-165 DEG C.Finally, film can also carry out surface corona processing, cutting edge and winding processing, most Durable membrane of the present invention is obtained eventually.
Durable membrane provided by the invention has preferable film forming and stretching ratio is big, rate of extension is high.It is adopting During preparing the biaxially oriented film with Flat film strength, as described above, the longitudinal direction (MD) of the durable membrane is drawn Stretch multiplying power >=4 times；Laterally stretching ratio >=5 times (TD).Stretching ratio is bigger, then the mechanical strength of durable membrane is higher.Institute Transverse direction (TD) rate of extension >=50%/s, the preferably 60-100%/s for stating durable membrane can guarantee that industrialization connects in this way Continuous production.
Durable membrane's mechanical strength with higher provided by the invention and preferable optical property.The biaxial tension Film performance can meet: longitudinal (MD) tensile strength >=55MPa, preferably >=60MPa；Laterally (TD) tensile strength >=65MPa, Preferably >=70MPa.Puncture strength >=2.5N of the biaxially oriented film, preferably >=3.5N.The biaxially oriented film Tension fracture elongation rate≤350%, preferably≤300%.Mist degree≤8%, preferably≤5%.In the present invention, described vertical It is measured to tensile strength and transverse tensile strength according to method specified in GB/T 1040.3-2006.The puncture strength Be measured according to method specified in GB/T 10004-2008, wherein film sample with a thickness of 25 ± 5 μm.The stretching Elongation at break is measured according to method specified in GB/T 1040.3-2006.
The production cost of durable membrane provided by the invention is low, processing technology is simple, versatility is good, has widened polyethylene The application field of film.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples:
Film biaxial tension equipment is purchased from Germany Br ü ckner company, model Karo IV.
The polyethylene composition and film performance are tested in accordance with the following methods:
(1) molecular weight and molecualr weight distribution index (Mw, Mw/Mn, Mz, Mz+1): use Britain Polymer The 220 type gel permeation chromatograph combination IR5 type infrared detector of PL-GPC of Laboratories company is measured, chromatography Column is 3 series connection 10 μm of MIXED-B columns of Plgel, and solvent and mobile phase are 1,2,4- trichloro-benzenes, and column temperature is 150 DEG C, and flow velocity is 1.0mL/min carries out universal calibration using the EasiCal PS-1 Narrow distribution polystyrene standard specimen of PL company.
(2) analytic type temperature rising elution is tested: manufacturing 300 type liter of TREF using Spain Polymer Char S.A. company Temperature elution analyzer is measured, the specific steps are as follows: 80mg polyethylene composition is put into container, injects 40mL solvent (1,2,4- trichloro-benzenes, antioxidant BHT additional amount are 0.03 weight %), is warming up to 160 DEG C under nitrogen protection, then exists Constant temperature 60 minutes under the mixing speed of 200rpm then move into 2mL solution in analytical column, fast cooling (rate of temperature fall 40 DEG C/min) to 95 DEG C, constant temperature 45 minutes, then temperature is slowly dropped to 35 DEG C with the rate of 0.1 DEG C/min, then protected at 35 DEG C It holds 30 minutes, then elutes analytical column with the rate heating of 1.0 DEG C/min and with the flow rate pump of 0.5mL/min, leachates are with red External detector measures concentration, obtains the sample concentration dissolved under different temperatures, temperature rising elution curve is obtained after normalization.
(3) DSC survey melting temperature: is carried out using Perkin-Elmer DSC-7 differential scanning calorimeter under nitrogen protection Examination obtains, wherein using indium correction temperature and hot-fluid, amount of samples 5mg.Sample is heated up with the rate of 10 DEG C/min first To 180 DEG C, then keeps 5min to eliminate thermal history at such a temperature, be then cooled to 0 DEG C with the rate of 10 DEG C/min, and 0 It is warming up to 180 DEG C again with the rate of 10 DEG C/min again after keeping 1min at DEG C, heats up from first time heating, cooling and again and remembers The heat flow curve of record measures melting temperature.
(4) content of the structural unit of derived from alpha alkene: BRUKER AVANCE III 400Hz nuclear magnetic resoance spectrum is used Instrument, by13The measurement of C NMR spectrum (NMR) method, wherein it is popped one's head in using 10mm, 125 DEG C of test temperature, 90 pulses, waltz16 It uncouples, sampling time AQ is 5s, and delay time D1 is 10s.Sample preparation: sample is dissolved in deuterated neighbour with the concentration of 10%w/v In dichloro-benzenes, and dissolved by heating in 130-140 DEG C of oil bath.
(5) it melt index (MI): is measured according to method specified in GB/T 3682-2000, wherein test temperature It is 190 DEG C, load 2.16kg.
(6) it density: is measured according to method specified in GB/T 1033.2-2010 and using density gradient column method.
Embodiment 1
The present embodiment is for illustrating polyethylene composition provided by the invention and durable membrane.
Polyethylene composition provided in this embodiment is made of component A, component B, component C, anti-aging auxiliary agent and lubricant. The component A, component B and component C are the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, and are all made of phase Same catalyst system (metallocene catalyst) and polymerization technique preparation, the hydrogen that difference is added when being to prepare different component Amount and the type and molar content of alhpa olefin comonomer are different, the specific steps are as follows:
By ethylene, alhpa olefin, hydrogen and nitrogen, (ethylene, alhpa olefin, hydrogen and nitrogen are polymer grade, after removing water, oxygen Use, similarly hereinafter) it is added in gas fluidized bed reactor, catalyst system is then added, and (metallocene catalyst system is The carried metallocene catalyst being prepared by CN102453124A embodiment 1, similarly hereinafter), it is later 84 DEG C, pressure in temperature To polymerize under conditions of 2.0MPa, component A, component B and component C are respectively obtained.Wherein, the melting of component A, component B and component C The control of index realizes that density controls the type and additional amount for passing through and adjusting alhpa olefin by adjusting the additional amount of hydrogen It realizes.Alhpa olefin used is 1- hexene during preparing component A, and preparing alhpa olefin used during component B is 1- hexene, system Alhpa olefin used is 1- butylene during standby component C.
Through detecting, the performance of component A prepared by the above method, component B and component C are as follows:
The melt index MI of component AA=1.5g/10min, density pA=0.913g/cm3, molecular weight distributing index Mw/Mn= 3.4, molar content=7.5mol% of alhpa olefin comonomer；
The melt index MI of component BB=2.1g/10min, density pB=0.913g/cm3, molecular weight distributing index Mw/Mn= 3.2, molar content=7.5mol% of alhpa olefin comonomer；
The melt index MI of component CC=15g/10min, density pC=0.905g/cm3, molecular weight distributing index Mw/Mn= 3.5, molar content=9.1mol% of alhpa olefin comonomer.
Anti-aging auxiliary agent is Chimassorb 944, is produced by BASF Corp. of Germany.
Lubricant is the PEG lubricant produced by Switzerland's Clariant Corporation, molecular weight 10000.
(1) preparation of polyethylene composition:
Above-mentioned each component is weighed and mixed according to the ratio, wherein the mass fraction W of component AAFor 80 parts by weight, component The mass fraction W of BBFor 10 parts by weight, the mass fraction W of component CCFor 20 parts by weight, WA/WC=4 (meet 5.2 × 1gMIA+ 11.6≥WA/WC≥0.9×1gMIA+ 2.1, also meet 2.9 × 1gMIA+6.8≥WA/WC≥1.1×1gMIA+2.7)；With above-mentioned The quality sum of component A, component B and component C are 100 parts by weight meters, and the additional amount of anti-aging auxiliary agent is 0.3 parts by weight, lubrication The additional amount of agent is 0.1 parts by weight.It adds mixture in high speed agitator and is uniformly mixed later, then the material that will be mixed It is added in the feeder of the double screw extruder of W&P company manufacture, material enters in twin-screw via feeder, process The temperature of middle screw rod is maintained in the range of 180 ± 10 DEG C, through screw rod melting mixing uniformly, squeeze out, be granulated and dry, gathered Vinyl composition pellet, is detected its melt index MI=2.4g/10min, and specific nature is as shown in Table 1 and Table 2.
(2) preparation of durable membrane:
Polyethylene composition pellet made from above-mentioned steps (1) is dried, is added to Labtech company, Sweden later Model LCR400 multilayer extrusion casting machine sandwich layer extruder and upper and lower surface layer extruder in carry out melting extrusion simultaneously It is cast slab, wherein it also needs to be added inorganic antitack agent (silica, similarly hereinafter) in the upper and lower surface layer extruder, and upper, The weight ratio of the antitack agent and polyethylene composition pellet that are added in layer extruder is 0.02: 1, in curtain coating slab process In, curtain coating chilling roll temperature is set as 25 DEG C, polyethylene thickness slab is made, is made of upper epidermis, sandwich layer and layer.
Above-mentioned polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, is drawn using first longitudinal direction (MD) The two-way step drawing technological forming that laterally (TD) is stretched after stretching, each step process condition are as follows: MD preheating temperature is 100 DEG C, MD Draft temperature is 110 DEG C, and MD stretching ratio is 4 times；TD preheating temperature is 100 DEG C, and TD draft temperature is 115 DEG C, and TD is stretched again Rate is 5 times, and film TD rate of extension is 60%/s；Film setting temperature is 120 DEG C, obtains the film that average thickness is 25 μm, It is made of upper epidermis, sandwich layer and layer, and each layer raw material is the polyethylene composition of the present embodiment, and upper epidermis and following table Also contain antitack agent in layer, the thickness of upper epidermis and layer is 0.5 μm.
Embodiment 2
The present embodiment is for illustrating polyethylene composition provided by the invention and durable membrane.
Polyethylene composition provided in this embodiment is made of component A, component B, component C, anti-aging auxiliary agent and lubricant. The component A, component B and component C are the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, and are all made of phase Same catalyst system (metallocene catalyst) and polymerization technique preparation, the hydrogen that difference is added when being to prepare different component Amount and the type and molar content of alhpa olefin comonomer are different, the specific steps are as follows:
Ethylene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, catalyst system is then added, it It polymerize under conditions of temperature is 88 DEG C, pressure is 1.8MPa afterwards, respectively obtains component A, component B and component C.Wherein, component A, the control of the melt index of component B and component C is realized by adjusting the additional amount of hydrogen, and the control of density is by adjusting α The type and additional amount of alkene and realize.Alhpa olefin used is 1- butylene during preparing component A, during preparing component B Alhpa olefin used is 1- butylene, and alhpa olefin used is 1- hexene during preparing component C.
Through detecting, the performance of component A prepared by the above method, component B and component C are as follows:
The melt index MI of component AA=0.01g/10min, density pA=0.930g/cm3, molecular weight distributing index Mw/Mn =3.0, molar content=1.6mol% of alhpa olefin comonomer；
The melt index MI of component BB=10.0g/10min, density pB=0.930g/cm3, molecular weight distributing index Mw/Mn =2.8, molar content=1.9mol% of alhpa olefin comonomer；
The melt index MI of component CC=60g/10min, density pC=0.922g/cm3, molecular weight distributing index Mw/Mn= 2.9, molar content=3.8mol% of alhpa olefin comonomer.
Anti-aging auxiliary agent is Tinuvin622, is produced by BASF Corp. of Germany.
Lubricant is the PEG lubricant produced by Switzerland's Clariant Corporation, molecular weight 10000.
(1) preparation of polyethylene composition:
Above-mentioned each component is weighed and mixed according to the ratio, wherein the mass fraction W of component AAFor 55 parts by weight, component The mass fraction W of BBFor 5 parts by weight, the mass fraction W of component CCFor 55 parts by weight, WA/WC=1 (meets 5.2 × 1gMIA+11.6 ≥WA/WC≥0.9×1gMIA+ 2.1, also meet 2.9 × 1gMIA+6.8≥WA/WC≥1.1×1gMIA+2.7)；With said components A, the quality sum of component B and component C are 100 parts by weight meters, and the additional amount of anti-aging auxiliary agent is 0.2 parts by weight, lubricant Additional amount is 0.1 parts by weight.It adds mixture in high speed agitator and is uniformly mixed later, then the material mixed is added In the feeder of the double screw extruder manufactured to W&P company, material enters in twin-screw via feeder, spiral shell in process The temperature of bar is maintained in the range of 230 ± 10 DEG C, through screw rod melting mixing uniformly, squeeze out, be granulated and dry, obtain polyethylene Composition pellet, is detected its melt index MI=0.9g/10min, and specific nature is as shown in Table 1 and Table 2.
(2) preparation of durable membrane:
Polyethylene composition pellet made from above-mentioned steps (1) is dried, is added to Labtech company, Sweden later Model LCR400 multilayer extrusion casting machine sandwich layer extruder and upper and lower surface layer extruder in carry out melting extrusion simultaneously It is cast slab, wherein also need that inorganic antitack agent is added in the upper and lower surface layer extruder, and add in the extruder of upper and lower surface layer The weight ratio of the antitack agent and polyethylene composition pellet that enter is 0.02: 1, during being cast slab, will be cast chilling roller Temperature is set as 85 DEG C, and polyethylene thickness slab is made, is made of upper epidermis, sandwich layer and layer.
Above-mentioned polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, is drawn using first longitudinal direction (MD) The two-way step drawing technological forming that laterally (TD) is stretched after stretching, each step process condition are as follows: MD preheating temperature is 130 DEG C, MD Draft temperature is 126 DEG C, and MD stretching ratio is 4 times；TD preheating temperature is 130 DEG C, and TD draft temperature is 128 DEG C, and TD is stretched again Rate is 6 times, and film TD rate of extension is 100%/s；Film setting temperature is 130 DEG C, obtains the film that average thickness is 25 μm, It is made of upper epidermis, sandwich layer and layer, and each layer raw material is the polyethylene composition of the present embodiment, and upper epidermis and following table Also contain antitack agent in layer, the thickness of upper epidermis and layer is 1 μm.
Embodiment 3
The present embodiment is for illustrating polyethylene composition provided by the invention and durable membrane.
Polyethylene composition provided in this embodiment polymerize to obtain using multiple reactor shunting means shown in FIG. 1, wherein The polymerization preparation of first reactor 1 component A, the polymerization preparation of second reactor 2 component B, the polymerization preparation component C of third reactor 3, group Dividing A, component B and component C is the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, these three components are all made of phase Same catalyst system (metallocene catalyst) and polymerization technique preparation, the hydrogen that difference is added when being to prepare different component Amount, the type of alhpa olefin comonomer and molar content and the yield in unit time of each reactor are different, and specific steps are such as Under:
Alhpa olefin, n-hexane and hydrogen are added in polymer reactor, and polymer reactor is heated to preset polymerization Vinyl monomer and catalyst system are added in polymer reactor by temperature simultaneously later, and temperature is 140 DEG C, pressure is Polyase 13 0 minute under conditions of 2.5MPa respectively obtains component A, component B and component C.Wherein, component A, component B and component C The control of melt index realizes that the control of density passes through the type and addition that adjust alhpa olefin by adjusting the additional amount of hydrogen It measures and realizes.Alhpa olefin used is 1- octene during preparing component A, and preparing alhpa olefin used during component B is 1- fourth Alkene, alhpa olefin used is 1- butylene during preparing component C.
During the preparation process by the yield in unit time W of component A in first reactor 1A, component B in second reactor 2 Yield in unit time WBWith the yield in unit time W of component C in third reactor 3CWeight ratio maintain WA∶WB∶WC=75: 2: 35, wherein WA/WC=2.1 (meet 5.2 × 1gMIA+11.6≥WA/WC≥0.9×1gMIA+ 2.1, also meet 2.9 × 1gMIA+ 6.8≥WA/WC≥1.1×1gMIA+2.7)。
Through detecting, the performance of component A prepared by the above method, component B and component C are as follows:
The melt index MI of component AA=0.1g/10min, density pA=0.920g/cm3, molecular weight distributing index Mw/Mn= 3.1, molar content=2.1mol% of alhpa olefin comonomer；
The melt index MI of component BB=5.0g/10min, density pB=0.920g/cm3, molecular weight distributing index Mw/Mn= 3.5, molar content=5.1mol% of alhpa olefin comonomer；
The melt index MI of component CC=25g/10min, density pC=0.920g/cm3, molecular weight distributing index Mw/Mn= 3.2, molar content=5.1mol% of alhpa olefin comonomer.
Anti-aging auxiliary agent is GW-540, is produced by BASF Corp. of Germany.
Lubricant is the PEG lubricant produced by Switzerland's Clariant Corporation, molecular weight 10000.
(1) preparation of polyethylene composition:
Component A obtained above, component B and component C are respectively delivered to different solid-liquids in yield in unit time ratio It is mutually separated and is transported in the homogenization silo 5 with stirring in turn in (gas) separator 4, is then added according to the ratio anti-aging Auxiliary agent and lubricant carry out mixing homogenizing.Wherein, with the quality sum of said components A, component B and component C for 100 parts by weight Meter, the additional amount of anti-aging auxiliary agent are 0.3 parts by weight, and the additional amount of lubricant is 0.5 parts by weight.Later by homogenized feed bin 5 The mixture of homogenizing is added in the feeder of the double screw extruder of W&P company manufacture, and material enters double spiral shells via feeder In bar, the temperature of screw rod is maintained in the range of 200 ± 10 DEG C in process, and, extrusion uniform through screw rod melting mixing is granulated And dry, polyethylene composition pellet is obtained, its melt index MI=0.6g/10min, specific nature such as 1 He of table are detected Shown in table 2.
(2) preparation of durable membrane:
Polyethylene composition pellet made from above-mentioned steps (1) is dried, is added to Labtech company, Sweden later Model LCR400 multilayer extrusion casting machine in carry out melting extrusion and be cast slab and will be flowed during being cast slab Prolong chilling roll temperature and be set as 35 DEG C, polyethylene thickness slab is made, which is single layer structure.
Above-mentioned polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, is drawn using first longitudinal direction (MD) The two-way step drawing technological forming that laterally (TD) is stretched after stretching, each step process condition are as follows: MD preheating temperature is 116 DEG C, MD Draft temperature is 118 DEG C, and MD stretching ratio is 4 times；TD preheating temperature is 120 DEG C, and TD draft temperature is 120 DEG C, and TD is stretched again Rate is 5 times, and film TD rate of extension is 100%/s；Film setting temperature is 122 DEG C, obtains the single layer that average thickness is 25 μm Film.
Embodiment 4
The present embodiment is for illustrating polyethylene composition provided by the invention and durable membrane.
Prepare polyethylene composition and durable membrane according to the method for embodiment 1, unlike, anti-aging auxiliary agent by The production of Tianjin Xin Lifeng company, trade mark UV-531, and with the quality sum of component A, component B and component C for 100 parts by weight Meter, the additional amount of anti-aging auxiliary agent are 0.3 parts by weight, obtain the film that average thickness is 25 μm, by upper epidermis, sandwich layer and under Surface layer is constituted, and each layer raw material is the polyethylene composition of the present embodiment, and also contains antitack agent in upper epidermis and layer, on The thickness of surface layer and layer is 0.5 μm.
Embodiment 5
The present embodiment is for illustrating polyethylene composition provided by the invention and durable membrane.
Polyethylene composition and durable membrane are prepared according to the method for embodiment 1, unlike, durable membrane's Drawing process in preparation process is synchronous bidirectional stretching, and preheating temperature is 105 DEG C, and draft temperature is 110 DEG C, the drawing of MD and TD Stretching multiplying power is 4 times, rate of extension 60%/s, and obtaining average thickness is 25 μm of film, wherein upper epidermis and layer Thickness is 0.5 μm.
Embodiment 6
The present embodiment is for illustrating polyethylene composition provided by the invention and durable membrane.
Polyethylene composition and polyethylene film are prepared according to the method for embodiment 1, unlike, in the component A Preparation process in, alhpa olefin is 1- hexene, and the performance of obtained component A is as follows: the melt index MI of component AA=1.5g/ 10min, density pA=0.928g/cm3, molecular weight distributing index Mw/Mn=3.0, the molar content of alhpa olefin comonomer= 1.9mol%.That is, the density p of component A, component B and component CA、ρBAnd ρCBetween relationship be unsatisfactory for -0.04≤ρA-ρB≤0.02 And -0.04≤ρA-ρC≤ 0.02, obtaining average thickness is 25 μm of film, wherein upper epidermis and the thickness of layer are 0.5 μm。
Comparative example 1
This comparative example is used to illustrate polyethylene raw material and the durable membrane of reference.
(1) polyethylene raw material:
Polyethylene raw material used in this comparative example is the film-grade linear low density polyethylene of U.S. DOW chemical company production Alkene, trade mark ELITE 5400G, catalyst are metallocene catalyst, melt index MI=1.0g/10min, density p=0.916g/ cm3, molecular weight distributing index Mw/Mn=3.2.
(2) preparation of durable membrane:
Durable membrane is prepared according to the method for embodiment 3, unlike, by the polyethylene composition pellet with identical The polyethylene raw material of this comparative example step (1) of parts by weight substitutes, and is repeatedly attempted the case where stretching rupture of membranes, no farad occur It is stretched into film.In addition, repeatedly being attempted still to occur after the TD rate of extension in durable membrane's preparation process is down to 50%/s The case where stretching rupture of membranes, can not stretch film forming.
Comparative example 2
This comparative example is used to illustrate polyethylene raw material and the durable membrane of reference.
(1) polyethylene raw material:
Polyethylene raw material used in this comparative example is identical as comparative example 1.
(2) preparation of durable membrane:
The durable membrane of this comparative example uses the upper blowing method film blowing device extrusion and blow molding of DR.COLLIN company, Germany It obtains, the specific method is as follows: the polyethylene raw material that above-mentioned steps (1) is chosen is added to the material of upper blowing method film blowing device extruder In bucket, melt membrane tube is made after the abundant fusion plastification of extruder, by the annular die extrusion of head in raw material, after it is empty through compression Air-blowing is swollen (blow-up ratio is 2.5 times), and durable membrane is made after vane is cooling, and it is 25 μm that wherein film, which is average thickness, Single layer structure.
Comparative example 3
This comparative example is used to illustrate polyethylene composition and the durable membrane of reference.
The polyethylene composition that this comparative example provides is made of component 1, component 2 and lubricant.The component 1 and component 2 It is the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, and is all made of identical catalyst system (metallocene is urged Agent) and polymerization technique preparation, the kind of amounts of hydrogen and alhpa olefin comonomer that difference is added when being to prepare different component Class and molar content are different, the specific steps are as follows:
Ethylene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, catalyst system is then added, it It polymerize 60 minutes under conditions of temperature is 84 DEG C, pressure is 2.0MPa afterwards, respectively obtains component 1 and component 2.Wherein, component 1 Control with the melt index of component 2 realizes that the control of density passes through the kind for adjusting alhpa olefin by adjusting the additional amount of hydrogen Class and additional amount and realize.Alhpa olefin used is 1- hexene during preparing component 2, prepares α alkene used during component 2 Hydrocarbon is 1- butylene.
Through detecting, the performance of component 1 and component 2 prepared by the above method is as follows:
The melt index MI of component 11=5.0g/10min, density p1=0.913g/cm3, molecular weight distributing index Mw/Mn= 3.2, molar content=7.5mol% of alhpa olefin comonomer；
The melt index MI of component 22=15g/10min, density p2=0.905g/cm3, molecular weight distributing index Mw/Mn= 3.5, molar content=9.8mol% of alhpa olefin comonomer.
Lubricant is the PEG lubricant of Switzerland's Clariant Corporation production, molecular weight 10000.
(1) preparation of polyethylene composition:
Above-mentioned each component is weighed and mixed according to the ratio, wherein the mass fraction W of component 11For 80 parts by weight, component 2 mass fraction W2For 20 parts by weight, W1/W2=4；Then lubricant is added, and (quality sum with said components 1 and component 2 is 100 parts by weight meters, the additional amount of lubricant are 0.1 parts by weight), it adds mixture in high speed agitator and is mixed later It is even, then by the material mixed be added to W&P company manufacture double screw extruder feeder in, material via feeder into Enter in twin-screw, the temperature of screw rod is maintained in the range of 180 ± 10 DEG C in process, uniform, crowded through screw rod melting mixing Out, it is granulated and dries, obtain polyethylene composition pellet, specific nature is as shown in Table 1 and Table 2.
(2) preparation of durable membrane:
The preparation of durable membrane is carried out according to the method for embodiment 1, the results showed that, by repeatedly attempting, biaxial tension The maximum tension multiplying power of film is only 2 times (TD) × 2 times (MD), and film TD highest stretching ratio is only 10%/s, that is, is stretched again Rate and rate of extension are too low, and stretching film forming is poor, do not have practicability.
Comparative example 4
This comparative example is used to illustrate polyethylene composition and the durable membrane of reference.
The polyethylene composition that this comparative example provides is made of component 1, component 2 and lubricant.The component 1 and component 2 It is the linear low density polyethylene (LLDPE) of ethylene/alpha-olefin copolymerization, and is all made of identical catalyst system (metallocene is urged Agent) and polymerization technique preparation, the kind of amounts of hydrogen and alhpa olefin comonomer that difference is added when being to prepare different component Class and molar content are different, the specific steps are as follows:
Ethylene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, catalyst system is then added, it It polymerize 60 minutes under conditions of temperature is 84 DEG C, pressure is 2.0MPa afterwards, respectively obtains component 1 and component 2.Wherein, component 1 Control with the melt index of component 2 realizes that the control of density passes through the kind for adjusting alhpa olefin by adjusting the additional amount of hydrogen Class and additional amount and realize.Alhpa olefin used is 1- butylene during preparing component 1, prepares α alkene used during component 2 Hydrocarbon is 1- hexene.
Through detecting, the performance of component 1 and component 2 prepared by the above method is as follows:
The melt index MI of component 11=0.01g/10min, density p1=0.930g/cm3, molecular weight distributing index Mw/Mn =2.8, molar content=1.8mol% of alhpa olefin comonomer；
The melt index MI of component 22=5.0g/10min, density p2=0.922g/cm3, molecular weight distributing index Mw/Mn= 2.7, molar content=4.1mol% of alhpa olefin comonomer.
Lubricant is the PEG lubricant of Switzerland's Clariant Corporation production, molecular weight 10000.
(1) preparation of polyethylene composition:
Above-mentioned each component is weighed and mixed according to the ratio, wherein the mass fraction W of component 11For 55 parts by weight, component 2 mass fraction W2For 55 parts by weight, W1/W2=1；Then lubricant is added, and (quality sum with said components 1 and component 2 is 100 parts by weight meters, the additional amount of lubricant are 3 parts by weight), it adds mixture in high speed agitator and is uniformly mixed later, The material mixed is added to again in the feeder of double screw extruder of W&P company manufacture, material enters via feeder In twin-screw, the temperature of screw rod is maintained in the range of 230 ± 10 DEG C in process, extrusion uniform through screw rod melting mixing, It is granulated and dries, obtain polyethylene composition pellet, specific nature is as shown in Table 1 and Table 2.
(2) preparation of durable membrane:
The preparation of durable membrane is carried out according to the method for embodiment 2, the results showed that, by repeatedly attempting, biaxial tension The maximum tension multiplying power of film is only 2 times (TD) × 2 times (MD), and film TD highest stretching ratio is only 10%/s, that is, is stretched again Rate and rate of extension are too low, and stretching film forming is poor, do not have practicability.
Comparative example 5
This comparative example is used to illustrate polyethylene composition and the durable membrane of reference.
(1) preparation of polyethylene composition:
The polyethylene composition that this comparative example provides polymerize to obtain using multiple reactor shunting means, wherein first reactor Polymerization preparation component 1, second reactor polymerization preparation component 2, component 1 and component 2 are the linear low close of ethylene/alpha-olefin copolymerization It spends polyethylene (LLDPE), both components are all made of identical catalyst system (metallocene catalyst) and polymerization technique preparation, Amounts of hydrogen, the type of alhpa olefin comonomer and the molar content and each reaction that difference is added when being to prepare different component The yield in unit time of device is different.Specific step is as follows:
Alhpa olefin, n-hexane and hydrogen are added in polymer reactor, and polymer reactor is heated to preset polymerization Vinyl monomer and catalyst system are added in polymer reactor by temperature simultaneously later, and temperature is 140 DEG C, pressure is Polyase 13 0 minute under conditions of 2.5MPa, respectively obtains component 1 and component 2.Wherein, the control of the melt index of component 1 and component 2 System realizes that the control of density is realized by the type and additional amount for adjusting alhpa olefin by adjusting the additional amount of hydrogen.Preparation Alhpa olefin used is 1- octene during component 1, and preparing alhpa olefin used during component 2 is 1- butylene.
During the preparation process by the yield in unit time W of component 1 in first reactor1With component 2 in second reactor Yield in unit time W2Weight ratio maintain W1∶W2=20: 80.
Through detecting, the performance of component 1 and component 2 prepared by the above method is as follows:
The melt index MI of component 11=0.1g/10min, density p1=0.920g/cm3, molecular weight distributing index Mw/Mn= 3.1, molar content=2.1mol% of alhpa olefin comonomer；
The melt index MI of component 22=25g/10min, density p2=0.920g/cm3, molecular weight distributing index Mw/Mn= 3.5, molar content=5.1mol% of alhpa olefin comonomer.
Each component obtained above is transported in solid-liquid (gas) separator in yield in unit time ratio and is mutually separated And be transported in the homogenization silo with stirring in turn, lubricant is then added according to the ratio and carries out mixing homogenizing.Wherein, lubricant For Honeywell Inc., the U.S. production polyethylene wax, by the quality sum of said components 1 and component 2 be 100 parts by weight in terms of, profit The additional amount of lubrication prescription is 1 parts by weight.The twin-screw that the mixture that homogenized feed bin is homogenized is added to the manufacture of W&P company is squeezed later Out in the feeder of machine, material enters in twin-screw via feeder, and the temperature of screw rod is maintained at 200 ± 30 DEG C in process In the range of, through screw rod melting mixing uniformly, squeeze out, be granulated and dry, obtain polyethylene composition pellet, specific nature is such as Shown in Tables 1 and 2.
(2) preparation of durable membrane:
The preparation of durable membrane is carried out according to the method for embodiment 3, the results showed that, by repeatedly attempting, biaxial tension The maximum tension multiplying power of film is only 2 times (TD) × 2 times (MD), and film TD highest stretching ratio is only 10%/s, that is, is stretched again Rate and rate of extension are too low, and stretching film forming is poor, do not have practicability.
Test case
Test case is used to illustrate the test of durable membrane and reference durable membrane's performance.
(1) it Film Haze: is measured according to method specified in GB/T 2410-2008, wherein film sample thickness It is 25 ± 5 μm, acquired results are as shown in table 3.
(2) film modulus, tensile strength and tension fracture elongation rate: according to method specified in GB/T 1040.3-2006 It is measured, acquired results are as shown in table 3.
(3) it membrane puncture intensity: is measured according to method specified in GB/T10004-2008, wherein film sample With a thickness of 25 ± 5 μm, acquired results are as shown in table 3.
(4) ageing-resistant performance: according to method specified in GB/T-16422 " xenon lamp aging test method " to the resistance to of film Ageing properties are tested, test index: tensile strength and elongation at break, parameter: tensile strength retention rate and fracture Elongation retention rate, acquired results are as shown in table 3.
Table 1
Table 2
Note: in table 2, high temperature elutes peak area ratio and low temperature elution peak area ratio elutes peak and low temperature leaching with high temperature It washes on the basis of the gross area at peak.
It can be concluded that, polyethylene composition provided by the invention is used to prepare in embodiment 1-3 two-way from the result in table 3 Stretch PE film, with the film of the prior art compared with have form a film multiplying power it is big, rate of extension is fast, durability is good, mechanical strength is high, The advantages of good in optical property, the performance of prepared film are able to satisfy longitudinal direction (MD) tensile strength >=55MPa, and laterally (TD) is stretched Intensity >=65MPa, puncture strength >=2.5N, tension fracture elongation rate≤350%, mist degree≤8%.From embodiment 1 and embodiment 5 Comparison as can be seen that in the polyethylene composition component A, component B and component C density pA、ρBAnd ρCBetween relationship Meet -0.04≤ρA-ρB≤ 0.02 and -0.04≤ρA-ρCWhen≤0.02, the polyethylene composition with preferable film forming and On the basis of durability, the film tensile strength also with higher and punctured resistances that be prepared by the polyethylene composition And lower mist degree.It can be seen that the commercially available poly- second using prior art preparation from the comparison of embodiment 1 and comparative example 1-2 Alkene raw material can not stretch film forming, thus be not suitable for being processed using Flat film strength, and compared with envelope pulling method, use Flat film strength formed film mechanical strength and puncture strength is higher and Film Haze is lower.In addition, from embodiment 1-3 with The comparison of comparative example 3-5 has more as can be seen that using polyethylene composition provided by the invention as the raw material for preparing film Good filming performance and endurance quality, more prospects for commercial application.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally The thought of invention, it should also be regarded as the disclosure of the present invention.

Claims (32)

1. a kind of polyethylene composition, the polyethylene composition contains the linea low density as made of ethylene and alhpa olefin copolymerization Polyethylene and anti-aging auxiliary agent, which is characterized in that the weight average molecular weight Mw of the polyethylene composition is 100,000 g/mol-18 Ten thousand g/mol, and Mw/Mn is 4.0-8.0, Mz/Mw 4.0-6.0, Mz+1/Mw 4.5-12.5；
The linear low density polyethylene contains component A, component B and component C；The component A is temperature is 190 DEG C, load is Melt index MI under 2.16kgAFor 0.01-2g/10min, density pAFor 0.880-0.936g/cm3；The component B is in temperature Melt index MI under being 2.16kg for 190 DEG C, loadBFor 2.1-14.9g/10min, density pBFor 0.910-0.930g/cm3； Melt index MI of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor 15-150g/10min, density pCFor 0.880-0.930g/cm3；
In the polyethylene composition, the mass fraction W of the component AAFor 25-90 parts by weight, the mass parts of the component B Number WBFor 0.1-10 parts by weight, the mass fraction W of the component CCFor 10-75 parts by weight.
2. polyethylene composition according to claim 1, wherein the polyethylene composition is by analytic type temperature rising elution point The temperature rising elution curve that grade method measures includes high temperature elution peak and low temperature elution peak, and the temperature at high temperature elution peak is 90- 105 DEG C, the temperature at low temperature elution peak is 50-90 DEG C；The gross area at peak and low temperature elution peak is eluted as base using the high temperature Standard, the area at high temperature elution peak are not higher than 60%, and the area at low temperature elution peak is not less than 40%.
3. polyethylene composition according to claim 2, wherein the temperature at high temperature elution peak is 95-100 DEG C, institute The temperature for stating low temperature elution peak is 60-90 DEG C；On the basis of the gross area that the high temperature elutes peak and low temperature elution peak, the height The area at temperature elution peak is not higher than 50%, and the area at low temperature elution peak is not less than 50%.
4. polyethylene composition according to claim 1, wherein the polyethylene composition is surveyed by differential scanning calorimetry The melting temperature obtained is 100-130 DEG C.
5. polyethylene composition according to claim 4, wherein the polyethylene composition is surveyed by differential scanning calorimetry The melting temperature obtained is 105-128 DEG C.
6. polyethylene composition according to claim 1, wherein from alhpa olefin derived from the linear low density polyethylene Structural unit content be 0.5-20mol%.
7. polyethylene composition according to claim 6, wherein from alhpa olefin derived from the linear low density polyethylene Structural unit content be 2-10mol%.
8. polyethylene composition according to claim 1, wherein the component A is temperature is 190 DEG C, load is Melt index MI under 2.16kgAFor 0.01-1.5g/10min, the component B is in the case where temperature is 190 DEG C, load is 2.16kg Melt index MIBFor 3-10g/10min, melt index MI of the component C in the case where temperature is 190 DEG C, load is 2.16kgC For 15-100g/10min.
9. polyethylene composition according to claim 8, wherein the component A is temperature is 190 DEG C, load is Melt index MI under 2.16kgAFor 0.01-1g/10min, the component B is in the case where temperature is 190 DEG C, load is 2.16kg Melt index MIBFor 3-5g/10min, melt index MI of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor 20-60g/10min。
10. polyethylene composition according to claim 1, wherein the density p of the component AAFor 0.910-0.930g/ cm3, the density p of the component BBFor 0.913-0.928g/cm3, the density p of the component CCFor 0.905-0.928g/cm3。
11. polyethylene composition according to claim 10, wherein the density p of the component AAFor 0.915-0.926g/ cm3, the density p B of the component B is 0.913-0.924g/cm3, the density p of the component CCFor 0.910-0.926g/cm3。
12. polyethylene composition described in 0 or 11 according to claim 1, wherein component A, component in the polyethylene composition The density p of B and component CA, ρ B and ρCBetween relationship meet -0.04≤ρA-ρB≤ 0.02 and -0.04≤ρA-ρC≤0.02。
13. polyethylene composition according to claim 1, wherein in the polyethylene composition, the component A's Mass fraction WAFor 30-80 parts by weight, the mass fraction W of the component BBFor 0.5-8 parts by weight, the mass fraction of the component C WCFor 20-70 parts by weight.
14. polyethylene composition according to claim 13, wherein the mass fraction W of the component AAWith the matter of component C Measure number WCWith the melt index MI of component AARelationship meet 5.2 × lgMIA+11.6≥WA/WC≥0.9×lgMIA+2.1。
15. polyethylene composition according to claim 14, wherein the mass fraction W of the component AAWith the matter of component C Measure number WCWith the melt index MI of component AARelationship meet 2.9 × lgMIA+6.8≥WA/WC≥1.1×lgMIA+2.7。
16. polyethylene composition according to claim 1, wherein the polyethylene composition is 190 DEG C, carries in temperature Melt index under lotus is 2.16kg is 0.1-20g/10min.
17. polyethylene composition according to claim 16, wherein the polyethylene composition is 190 DEG C, carries in temperature Melt index under lotus is 2.16kg is 0.5-10g/10min.
18. polyethylene composition according to claim 1, wherein the molecular weight of the component A, component B and component C point Cloth index is all satisfied Mw/Mn≤4.5。
19. polyethylene composition according to claim 18, wherein the molecular weight of the component A, component B and component C point Cloth index is all satisfied 2.0≤Mw/Mn≤4.2。
20. polyethylene composition according to claim 19, wherein the component A, component B and component C are all made of luxuriant gold Metal catalyst polymerize to obtain.
21. polyethylene composition according to claim 1, wherein the alhpa olefin in the component A, component B and component C is each From independently being C3-C20At least one of alkene.
22. polyethylene composition according to claim 21, wherein the alhpa olefin in the component A, component B and component C It is each independently propylene, 1- butylene, 2- butylene, 3-methyl-1-butene, 4- methyl-1-butylene, 1- amylene, 3- methyl-1-pentene Alkene, 4-methyl-1-pentene, 3,3- dimethyl -1- amylene, 3,4- dimethyl -1- amylene, 4,4- dimethyl -1- amylene, 1- oneself Alkene, 4- methyl-1-hexene, 5- methyl-1-hexene, 1- heptene, 2- heptene, 1- octene, 1- decene, 1- dodecylene, 1- 14 At least one of carbene, cetene, 1- octadecene and 1- eicosylene.
23. polyethylene composition according to claim 22, wherein the alhpa olefin in the component A, component B and component C It is each independently at least one of 1- butylene, 1- hexene and 1- octene.
24. polyethylene composition according to claim 1, wherein with the total weight of the component A, component B and component C For 100 parts by weight meters, the content of the anti-aging auxiliary agent is 0.01-5 parts by weight.
25. polyethylene composition according to claim 24, wherein the anti-aging auxiliary agent is UV absorbers, energy Measure at least one of quencher and light stabilizer.
26. a kind of durable membrane, the durable membrane includes at least one layer as described in any one of claim 1-25 Polyethylene composition formed polyethylene layer.
27. durable membrane according to claim 26, wherein the durable membrane have upper epidermis, sandwich layer and under The composite construction on surface layer, and at least described sandwich layer is the polyethylene layer formed by the polyethylene composition.
28. durable membrane according to claim 27, wherein when the durable membrane have upper epidermis, sandwich layer and When the composite construction of layer, the thickness of the upper epidermis and layer is each independently the 1- of durable membrane's thickness 25%.
29. durable membrane according to claim 27, wherein the durable membrane is by flat membrane biaxial tension legal system It is standby to obtain biaxially oriented film.
30. durable membrane according to claim 29, wherein preparing the two-way drawing using flat membrane biaxial tension method During stretching film, longitudinal stretching multiplying power >=4 times, cross directional stretch multiplying power >=5 times；Institute is being prepared using flat membrane biaxial tension method During stating biaxially oriented film, cross directional stretch rate >=50%/s.
31. the durable membrane according to any one of claim 26-30, wherein the thickness of the durable membrane It is 10-200 μm.
32. durable membrane according to claim 31, wherein the antifog drop films with a thickness of 10-100 μm.
CN201510712914.5A 2015-10-28 2015-10-28 A kind of polyethylene composition and durable membrane Active CN106633323B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510712914.5A CN106633323B (en) 2015-10-28 2015-10-28 A kind of polyethylene composition and durable membrane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510712914.5A CN106633323B (en) 2015-10-28 2015-10-28 A kind of polyethylene composition and durable membrane

Publications (2)

Publication Number Publication Date
CN106633323A CN106633323A (en) 2017-05-10
CN106633323B true CN106633323B (en) 2019-05-31

Family

ID=58816187

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510712914.5A Active CN106633323B (en) 2015-10-28 2015-10-28 A kind of polyethylene composition and durable membrane

Country Status (1)

Country Link
CN (1) CN106633323B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11440984B2 (en) * 2017-12-26 2022-09-13 Lg Chem, Ltd. Olefin-based polymer

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104837914A (en) * 2012-10-12 2015-08-12 陶氏环球技术有限责任公司 Polyethylene composition suitable for stretch film applications, and method of producing the same

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104837914A (en) * 2012-10-12 2015-08-12 陶氏环球技术有限责任公司 Polyethylene composition suitable for stretch film applications, and method of producing the same

Also Published As

Publication number Publication date
CN106633323A (en) 2017-05-10

Similar Documents

Publication Publication Date Title
CN106633328B (en) A kind of polyethylene composition and its film
CN105623059B (en) A kind of polyethylene composition and its film
CN107304265B (en) Polyethylene composition, polyethylene film and preparation method thereof
CN105524339B (en) A kind of polyethylene film
CN105623058B (en) A kind of polyethylene film
CN105623060B (en) A kind of polyethylene composition and its film
CN106633323B (en) A kind of polyethylene composition and durable membrane
CN106633319B (en) A kind of polyethylene composition and antifog drop films
CN105623055B (en) A kind of polyethylene composition and its film
CN105524337B (en) A kind of polyethylene composition and its film
CN106633320B (en) A kind of polyethylene composition and antifog drop films
CN106633318B (en) A kind of polyethylene composition and durable membrane
CN106633325B (en) A kind of polyethylene composition and durable membrane
CN105623056B (en) A kind of polyethylene composition and its film
CN105524338B (en) A kind of polyethylene composition and its film
CN106633330B (en) A kind of polyethylene composition and its film
CN106554542B (en) A kind of polyethylene composition and its microporous barrier
CN106633324B (en) A kind of polyethylene composition and durable membrane
CN106554546B (en) A kind of polyethylene composition and antistatic film
CN106554545B (en) A kind of polyethylene composition and its microporous barrier
CN106633329B (en) A kind of polyethylene composition and its film
CN106633322B (en) A kind of polyethylene composition and antifog drop films
CN106633321B (en) A kind of polyethylene composition and antifog drop films
CN105623057B (en) A kind of polyethylene composition and its film
CN106554550B (en) A kind of polyethylene composition and its microporous barrier

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant