CN107304264A - A kind of polyethylene composition and polyethylene film and preparation method thereof - Google Patents
A kind of polyethylene composition and polyethylene film and preparation method thereof Download PDFInfo
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- 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
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- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- 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
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- C08J2323/08—Copolymers of ethene
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- 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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- 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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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
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Abstract
The present invention relates to polyethylene film field, a kind of polyethylene composition and polyethylene film and preparation method thereof are specifically provided.The polyethylene composition contains the product prepared in accordance with the following methods：Ethene and alhpa olefin are subjected to the first polymerisation in the presence of a catalyst, then the first polymeric reaction product and ethene and alhpa olefin are subjected to the second polymerisation, the condition of first polymerisation and the second polymerisation makes the weight average molecular weight Mw of the second obtained polymeric reaction product be the g/mol of 80,000 g/mol 200,000, and Mw/Mn >=4.5, Mz/Mw >=4.5, Mz+1/Mw >=7.5.When using Flat film strength prepared by the polyethylene composition into polyethylene film, stretching ratio is big, rate of film build is high, and film forming is very good, and also has more excellent mechanical property and optical property by the film that the polyethylene composition is made.
Description
Technical field
The present invention relates to polyethylene field, and in particular to a kind of polyethylene composition, a kind of polyethylene composition
The preparation method of thing, the polyethylene composition prepared by this method, a kind of polyethylene film, one kind
The preparation method of polyethylene film and the polyethylene film prepared by this method.
Background technology
Biaxially-oriented polyethylene (Biaxially Oriented Polyethylene, BOPE) film is that have
The thin-film material that polyethylene (PE) resin of special molecular structure is molded through stretch processes.In BOPE
In the molding process of film, after the processing of film drawn, PE macromolecular chains and crystalline texture occur
It is height-oriented, so as to significantly improve the tensile strength of film, tension fracture elongation rate is reduced, and
Stretch crystallization effect in biaxial orientation process reduces the crystallite dimension in film, so that film
Mist degree is lower, transparent more preferable, glossiness is higher.Therefore, BOPE films can be widely used in packaging
It is bag, again packaging bag, Vacuum Heat sealer, low temperature packaging film, composite membrane, medical and sanitary products, agricultural big
In terms of canopy film, mulch film, and the poly- second manufactured with existing extrusioning blowing process and extrusion casting technique
Alkene film article is compared, with mechanical strength is high, puncture resistant and shock resistance is good, excellent optical performance,
The advantages such as environmental protection and energy saving.
The biaxial tension processing method of plastic sheeting has Flat film strength and envelope pulling method at present.Flat film is drawn
The method of stretching has been applied in polypropylene (PP), polyamide (PA), polyethylene terephthalate (PET)
In processing Deng thin-film material, technique is more ripe.Compared with envelope pulling method, the drawing of Flat film strength
Stretching multiplying power big (cross directional stretch multiplying power is up to more than 10 times), shaping speed, (highest rolling speed is reachable soon
Hundreds of ms/min), production efficiency it is high, and mechanical strength, optical property and the thickness of obtained film
More preferably, but film forming is influenceed significantly uniformity by process condition fluctuations, film stretch process difficulty
Greatly, there is higher requirement for film raw material.Being limited to use existing Biaxially-oriented polyethylene raw material more
Envelope pulling method prepares BOPE films, and these existing polyethylene raw materials are used into Flat film strength system
During standby BOPE films, there is film forming poor (draw speed and stretching ratio are very low), film and easily occur
The defect of rupture, i.e. be not suitable for preparing film using Flat film strength substantially.Therefore, in order to abundant
Using the above-mentioned advantage of Flat film strength, need a kind of good film-forming property of exploitation badly at present and film is not easy brokenly
What is split is applied to the polyethylene raw material that Flat film strength prepares BOPE films.
The content of the invention
The invention aims to overcome to prepare existing polyethylene raw material using Flat film strength to gather
Have that film forming is poor, film is easily broken during vinyl film, that is, be not suitable for preparing using Flat film strength thin
The defect of film, and provide a kind of new polyethylene composition, a kind of preparation method of polyethylene composition,
The polyethylene composition that is prepared by this method, a kind of polyethylene film, a kind of system of polyethylene film
Preparation Method and the polyethylene film prepared by this method.
Specifically, the invention provides a kind of polyethylene composition, the polyethylene composition contain according to
The product that lower section method is prepared：Ethene and alhpa olefin are subjected to the first polymerisation in the presence of a catalyst,
Then the first polymeric reaction product and ethene and alhpa olefin are subjected to the second polymerisation, first polymerization
The condition of reaction and the second polymerisation makes the weight average molecular weight Mw of the second obtained polymeric reaction product
For the g/mol of 80,000 g/mol-20 ten thousand, and Mw/Mn >=4.5, Mz/Mw >=4.5, Mz+1/Mw >=7.5.
Present invention also offers a kind of preparation method of polyethylene composition, this method is included ethene and α
Alkene carries out the first polymerisation in the presence of a catalyst, then by the first polymeric reaction product and ethene and
Alhpa olefin carries out the second polymerisation, and the condition of first polymerisation and the second polymerisation makes to obtain
The weight average molecular weight Mw of the second polymeric reaction product be the g/mol of 80,000 g/mol-20 ten thousand, and Mw/Mn
>=4.5, Mz/Mw >=4.5, Mz+1/Mw >=7.5.
Present invention also offers the polyethylene composition prepared by the above method.
Present invention also offers a kind of polyethylene film, the polyethylene film at least includes one layer by above-mentioned
The polyethylene layer that polyethylene composition is prepared.
Present invention also offers a kind of preparation method of polyethylene film, this method is included above-mentioned polyethylene
Composition carries out extrusion curtain coating, then obtained curtain coating slab is stretched.
In addition, present invention also offers the polyethylene film prepared by the above method.
The present inventor has found after further investigation, reacts what is obtained using two benches series polymerizations
Weight average molecular weight Mw be the g/mol of 80,000 g/mol-20 ten thousand and Mw/Mn >=4.5, Mz/Mw >=4.5,
The polyethylene composition of Mz+1/Mw >=7.5, has stretching times when preparing film using biaxial tension method
The advantage that rate is big, rate of film build is high, disclosure satisfy that high requirement of the Flat film strength to polyethylene raw material,
And the film prepared by the polyethylene composition is also with more excellent mechanical property and optics
Performance, such as tensile strength are high, puncture resistance and shock resistance are good, mist degree is low, glossiness is high,
Great prospects for commercial application.
A preferred embodiment of the invention, drenches when the polyethylene composition is heated up by analytic type
The temperature rising elution curve that washing-grading method is measured includes high temperature and elutes peak and low temperature elution peak, and the high temperature drenches
The peak temperature for washing peak is 90-110 DEG C, and the peak temperature at the low temperature elution peak is 50-90 DEG C, with institute
On the basis of the gross area for stating high temperature elution peak and low temperature elution peak, the area at high temperature elution peak≤
80%, during the area at low temperature elution peak >=20%, the polyethylene composition is with preferable film forming
On the basis of, the film prepared by the polyethylene composition also have more excellent mechanical property and
Optical property.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that this place is retouched
The embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, this
A little scopes or value should be understood to comprising the value close to these scopes or value.For number range, respectively
Between the endpoint value of individual scope, between the endpoint value of each scope and single point value, and individually point
Can be combined with each other between value and obtain one or more new number ranges, these number ranges should by regarding
For specific disclosure herein.
The polyethylene composition that the present invention is provided contains the product prepared in accordance with the following methods：By ethene
The first polymerisation is carried out in the presence of a catalyst with alhpa olefin, then by the first polymeric reaction product and second
Alkene and alhpa olefin carry out the second polymerisation, and the condition of first polymerisation and the second polymerisation makes
The weight average molecular weight Mw of the second obtained polymeric reaction product is the g/mol of 80,000 g/mol-20 ten thousand, and
Mw/Mn >=4.5, Mz/Mw >=4.5, Mz+1/Mw >=7.5.Preferably, second polymerisation
The weight average molecular weight Mw of product is the g/mol of 100,000 g/mol-15 ten thousand, and Mw/Mn is 4.5-9.0,
Mz/Mw is 4.5-7.0, and Mz+1/Mw is 7.5-13.5.In the present invention, Mw, Mn, Mz,
Mz+1 is measured using high-temperature gel permeation chromatography instrument (GPC).
According to the present invention, in order that obtained polyethylene composition has more preferable filming performance and by this
The film that polyethylene composition is made has more preferable mechanical property and optical property, it is preferable that described
The weight average molecular weight Mw of one polymeric reaction product is the g/mol of 80,000 g/mol-50 ten thousand, and Mw/Mn is
2.5-8.5, Mz/Mw are 2.0-6.5, and Mz+1/Mw is 4.5-12.0；It is highly preferred that described first is poly-
The weight average molecular weight Mw for closing reaction product is the g/mol of 80,000 g/mol-30 ten thousand, and Mw/Mn is 3.0-7.0,
Mz/Mw is 2.5-5.5, and Mz+1/Mw is 4.5-9.5.
The polyethylene composition provided according to the present invention, the polyethylene composition is by analytic type temperature rising elution
The temperature rising elution curve that classification (TREF) method is measured is in addition to room temperature DDGS peak, in addition to high temperature
Peak and low temperature elution peak are eluted, and the peak temperature at high temperature elution peak is preferably 90-110 DEG C, it is more excellent
Elect 95-100 DEG C as；The peak temperature at the low temperature elution peak is preferably 50-90 DEG C, more preferably 60-90
℃.It should be noted that temperature belongs to low temperature elution peak for 90 DEG C of peak in the temperature rising elution curve
Category.Wherein, the area at room temperature DDGS peak is typically not greater than 5%.In addition, the high temperature elution peak
Area cross the optical property of biaxially oriented film that conference causes to be prepared by the polyethylene composition
Be deteriorated, and low temperature elution peak area it is excessive, can cause by the polyethylene composition prepare it is two-way
The mechanical property of oriented film is deteriorated.Therefore, in order that obtaining the polyethylene composition with good
On the basis of filming performance, while the optical property and mechanical property of gained film can also be better balanced
Can, it is preferable that on the basis of the gross area for eluting peak and low temperature elution peak by the high temperature, the high temperature drenches
Area≤80% at peak is washed, the low temperature elutes area >=20% at peak；It is highly preferred that with the high temperature
On the basis of the gross area for eluting peak and low temperature elution peak, the high temperature elutes area≤70% at peak, described
Low temperature elutes area >=30% at peak；Most preferably, peak is eluted with the high temperature and low temperature elutes the total of peak
On the basis of area, the area at the high temperature elution peak is 10-60%, and the area at the low temperature elution peak is
40-90%.
According to the present invention, particularly preferably, the polyethylene composition temperature be 190 DEG C, load be
Melt index under 2.16kg is 0.1-20g/10min, most preferably 0.5-10g/10min.Using two
Stage series polymerizations are obtained on the basis of above-mentioned polyethylene composition, the polyethylene composition is overall
Melt index is controlled in above-mentioned preferred scope, and the polyethylene composition enabled to has very excellent
Different film forming, and obtained polyethylene film has higher tensile strength and optical property.At this
In invention, the melt index is measured according to method specified in GB/T3682-2000, wherein,
It is 190 DEG C that test condition, which includes temperature, and load is 2.16kg.
As a rule, if the melting temperature of polyethylene composition is too high, follow-up curtain coating processing can be caused
During slab curing rate it is too fast, be unfavorable for be cast slab it is smooth；And if polyethylene composition
Melting temperature is too low, then can cause subsequently to be cast in process that slab curing rate is excessively slow, be unfavorable for plus
The raising of work efficiency rate.Therefore, in order that the polyethylene composition with good filming performance with
And on the basis of excellent mechanical property and optical property, also it is cast processability and higher with preferable
Processing efficiency, it is preferable that the polyethylene composition is measured by differential scanning calorimetry (DSC)
Melting peak temperature is 100-130 DEG C, more preferably 110-130 DEG C.
The present invention to derived from first polymeric reaction product and the second polymeric reaction product from alhpa olefin
The content of construction unit is not particularly limited, and both can be with identical, can also be different, and respectively with
Ethylene unit unit and derived from alpha alkene in first polymeric reaction product and the second polymeric reaction product
Construction unit total content on the basis of, can be each from the content of the construction unit of alhpa olefin derived from both
From independently being 0.2-20mol%, preferably 2-10mol%.In the present invention, the ethylene unit list
Member refers to the construction unit formed by vinyl polymerization；The construction unit of the derived from alpha alkene refers to by α
The construction unit that olefinic polymerization is formed.In the present invention, the knot of ethylene unit unit and derived from alpha alkene
The content of structure unit is used13C NMR spectrums (NMR) method is determined.
The species of alhpa olefin used in first polymerisation and the second polymerisation can also may be used with identical
With difference, it is possible to be each independently C3-C20At least one of alkene.From the ready availability angle of raw material
Degree sets out, and the alhpa olefin used in first polymerisation and the second polymerisation is preferably propylene, 1- fourths
Alkene, 2- butylene, 3-methyl-1-butene, 4- methyl isophthalic acids-butylene, 1- amylenes, 3- Methyl-1-pentenes, 4- first
Base -1- amylenes, 3,3- dimethyl -1- amylenes, 3,4- dimethyl -1- amylenes, 4,4- dimethyl -1- amylenes, 1-
Hexene, 4- methyl isophthalic acids-hexene, 5- methyl isophthalic acids-hexene, 1- heptene, 2- heptene, 1- octenes, 1- decene,
In 1- 12 (carbon) alkene, 1- 14 (carbon) alkene, 1- 16 (carbon) alkene, (carbon) alkene of 1- 18 and 1- 20 (carbon) alkene
At least one, more preferably at least one of 1- butylene, 1- hexenes and 1- octenes.
The polyethylene composition provided according to the present invention, 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 the conventional selection of this area with consumption, for example, the lubricant can be selected from polyethylene glycol
(PEG) series lubricant agent, fluoropolymer series lubricant agent, organic silicon lubricant, aliphatic alcohols lubrication
Agent, fatty acid lubricant, fatty acid ester type emollients, stearic amide series lubricant agent, aliphatic acid gold
At least one in category soaps lubricant, alkane and oxidation of alkanes series lubricant agent and micro-and nano-particles series lubricant agent
Kind.Specifically, the PEG series lubricant agents for example can be that the PEG that molecular weight is 500-50000 divides
Son, it can also can change by end-blocking, grafting, crosslinking Treatment by other chemical modifications or physics
Property.The fluoropolymer series lubricant agent for example can be polytetrafluoroethylene (PTFE), Kynoar, poly- hexafluoro
At least one of propylene etc., or other unimodal or multimodal fluoropolymers and crystallization or half
The fluoropolymer of crystallization.The organo-silicic oil can be it is existing it is various using carbon, silicon atom as point
Sub- main chain, the oligomer or oligomer using organic groups such as methyl, phenyl, alkoxy, vinyl is sides
The compound of chain.The fatty alcohol type emollients for example can be soft fat alcohol, tallow alcohol, tallow
At least one of 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 for example can be butyl stearate, stearic acid list glyceride, palm fibre
At least one of 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
At least one of (EBS) etc..The fatty acid metal soaps lubricant for example can for lead stearate,
At least one of calcium stearate, magnesium stearate, synthesis calcium acetate etc..Alkane and the oxidation of alkanes class
Lubricant for example can be atoleine, solid paraffin, Tissuemat E, polypropylene wax, ethylene oxide wax
At least one of Deng.The micro-and nano-particles series lubricant agent for example can be that powdered rubber and/or silica gel are micro-
Grain.In addition, being counted using the gross weight of second polymeric reaction product as 100 parts by weight, the lubricant
Content can be 0.05-5 parts by weight, preferably 0.5-3 parts by weight.
In addition, can also contain in the polyethylene composition existing various in polyvinyl resin, poly- second
Other usually used auxiliary agents in alkene film, and the polyethylene that other described auxiliary agents will not be provided the present invention
Stretching film forming, mechanical property and the optical property of composition have adverse effect on.Other described auxiliary agents
Including but not limited to：It is antioxidant, halogen-absorber, heat stabilizer, slipping agent, antistatic additive, anti-sticking
At least one of agent, antifoggant, age resister, weathering stabilizers, colouring agent, filler etc..In addition,
The consumption of other auxiliary agents can be the conventional selection of this area, to the equal energy of this those skilled in the art
Know, therefore not to repeat here.
The polyethylene composition that the present invention is provided can only contain the second polymeric reaction product, can also be by
Dimerization reaction product and lubricant and other auxiliary agents are constituted, can also by the second polymeric reaction product,
Lubricant, other auxiliary agents and existing polyethylene composition.Wherein, with the total of the polyethylene composition
On the basis of weight, the content of second polymeric reaction product is not less than 80 weight %, is preferably not less than
90 weight %, more desirably not less than 95 weight %.
The preparation method for the polyethylene composition that the present invention is provided includes with alhpa olefin depositing ethene in catalyst
In the first polymerisation of lower progress, the first polymeric reaction product and ethene and alhpa olefin are then carried out second
Polymerisation, the condition of first polymerisation and the second polymerisation makes the second obtained polymerisation
The weight average molecular weight Mw of product is the g/mol of 80,000 g/mol-20 ten thousand, and Mw/Mn >=4.5, Mz/Mw
>=4.5, Mz+1/Mw >=7.5.Preferably, the weight average molecular weight Mw of second polymeric reaction product
For the g/mol of 100,000 g/mol-15 ten thousand, and Mw/Mn is 4.5-9.0, and Mz/Mw is 4.5-7.0, Mz+1/Mw
For 7.5-13.5.
According to the present invention, in order that obtained polyethylene composition has more preferable filming performance and by this
The film that polyethylene composition is made has more preferable mechanical property and optical property, it is preferable that described
The weight average molecular weight Mw of one polymeric reaction product is the g/mol of 80,000 g/mol-50 ten thousand, and Mw/Mn is
2.5-8.5, Mz/Mw are 2.0-6.5, and Mz+1/Mw is 4.5-12.0；It is highly preferred that described first is poly-
The weight average molecular weight Mw for closing reaction product is the g/mol of 80,000 g/mol-30 ten thousand, and Mw/Mn is 3.0-7.0,
Mz/Mw is 2.5-5.5, and Mz+1/Mw is 4.5-9.5.
According to the present invention, in specific course of reaction, two reactors are attached in the form of series connection,
The polymerization technique of different reactor can be with identical, can also be different, technological operation can with independent operating,
Can be with coordinated operation, by adjusting the reaction condition in different reactor (such as temperature, pressure, raw material group
Into etc.), control different reactor is interior to form different polymer, so as to control the polymer finally given
The performance of product.
The present invention does not have to the consumption of each material in first polymerisation and the second polymerization process
Especially limit, for example, the consumption of ethene and alhpa olefin can cause in above-mentioned polymerization process twice
To the first polymeric reaction product and the second polymeric reaction product derived from containing from the construction unit of alhpa olefin
Amount is each independently 0.2-20mol%, is preferably each independently 2-10mol%.In addition, generally coming
Say, hydrogen can be passed through in the first polymerisation and the second polymerization process with telo merization product
Melt index, this those skilled in the art can be known, therefore not to repeat here.
In addition, first polymerisation and the species of the alhpa olefin used in the second polymerisation can with identical,
Can also be different, it is possible to be each independently C3-C20At least one of alkene, specific species is
It is described herein above, therefore not to repeat here.
First polymerisation needs to carry out in the presence of a catalyst, and the catalyst for example can be
Ziegler-Natta catalyst.The Ziegler-Natta catalyst is generally by magnesium titanium compound and organic calorize
Compound and optional electron donor composition, are specifically known to the skilled person, therefore not to repeat here.
The present invention is not particularly limited to the condition of first polymerisation and the second polymerisation.
For example, the temperature of first polymerisation can be 50-130 DEG C, preferably 50-95 DEG C, pressure can
Think 0.5-5MPa, be preferably 0.5-2.5MPa.The temperature of second polymerisation can be 50-130
DEG C, be preferably 50-95 DEG C, pressure can for 0.5-5MPa, be preferably 0.5-2.5MPa.In the present invention
In, the pressure refers both to gauge pressure.
In addition, after above-mentioned second polymeric reaction product is obtained, can also be optionally added into lubricant,
At least one of other auxiliary agents and existing polyethylene etc., correspondingly, the polyethylene composition of gained
The second polymeric reaction product can only be contained, can also by the second polymeric reaction product and lubricant and its
His auxiliary agent composition, can also be by the second polymeric reaction product, lubricant, other auxiliary agents and existing poly-
Ethene is constituted.Wherein, the consumption of each material can make in obtained polyethylene composition, with the poly- second
On the basis of the gross weight of ene compositions, the content of second polymeric reaction product is not less than 80 weight %,
Preferably not less than 90 weight %, more desirably not less than 95 weight %.In addition, the lubricant and its
He has been described herein above the species of auxiliary agent, and therefore not to repeat here.
Present invention also offers the polyethylene composition prepared by the above method.
Present invention also offers a kind of polyethylene film, the polyethylene film at least includes one layer by above-mentioned
The polyethylene layer of polyethylene composition formation.
The polyethylene film can have single layer structure, it is possible to have sandwich construction.When the poly- second
When alkene film is sandwich construction, at least main stor(e)y (being usually the maximum layer of thickness) is by the polyethylene group
The polyethylene layer of compound formation.For example, the polyethylene film can have upper epidermis, sandwich layer and following table
The composite construction of layer, and at least described sandwich layer is the polyethylene layer formed by the polyethylene composition.It is logical
For often, the thickness of the polyethylene film can be 10-200 μm, preferably 10-100 μm.In addition,
When the polyethylene film has the composite construction of upper epidermis, sandwich layer and layer, the upper epidermis and
The thickness of layer is each independently the 1-25% of the polyethylene film thickness, preferably 0.5-5 μm.
Present invention also offers a kind of preparation method of polyethylene film, this method is included above-mentioned polyethylene
Composition carries out extrusion curtain coating, then obtained curtain coating slab is stretched.
The stretching can be simple tension, or biaxial tension, preferably bidirectional stretching is more excellent
Elect flat film biaxial tension as.Specifically, the process of polyethylene film is being prepared using flat film biaxial tension method
In, first above-mentioned polyethylene composition is added in extrusion casting apparatus and carries out extrusion curtain coating, is then incited somebody to action
To curtain coating slab carry out drawing and forming in film biaxial tension equipment.During curtain coating is extruded,
The structure for the film that slab die head can be obtained as needed is selected, for example, working as needs to be had
During the film of single layer structure, single layer die can be used；(have when needing to obtain the film with sandwich construction
Have the film of upper epidermis, sandwich layer and layer three-decker) when, die head can be combined using sandwich construction,
And at least one layer of (sandwich layer) is with being equipped with above-mentioned polyethylene composition in the compound die head of the sandwich construction
Extruder hopper is connected, and at least one layer (sandwich layer) in the film so enabled to is by above-mentioned poly-
The polyethylene layer of vinyl composition formation.In extrusion, extrusion temperature can be 160-260 DEG C,
The temperature for being cast chilling roller can be 15-85 DEG C.In addition, the biaxial tension can be using synchronous farad
Stretching process (carries out film longitudinal direction (MD) and laterally (TD) stretching) simultaneously, it would however also be possible to employ point
Footwork drawing process (first carries out film longitudinal stretching, then carries out film cross directional stretch).The synchronization
Method stretching concrete technology be：The curtain coating slab is after being fully warmed-up, while carrying out vertical and horizontal side
To stretching, wherein, preheating temperature can be 110-145 DEG C, and draft temperature can be 100-140 DEG C, indulge
To (MD) stretching ratio >=4 times, be preferably 4-8 times, transverse direction (TD) stretching ratio >=5 times, excellent
Elect 5-15 times, cross directional stretch speed >=80%/s as.The concrete technology of method of fractional steps stretching is：It is described
Slab is cast after being fully warmed-up, longitudinal stretching is first carried out, cross directional stretch is carried out afterwards, wherein, preheating
Temperature can be 70-138 DEG C, and draft temperature can be 75-135 DEG C, longitudinal direction (MD) stretching ratio >=4
Again, it is preferably 4-8 times, horizontal (TD) stretching ratio >=5 times, preferably 5-15 times, cross directional stretch
Speed >=80%/s.In addition, can be handled after film drawing and forming without setting, it can also be moved back
Fiery setting processing.When carrying out annealing setting processing, film setting treatment temperature can be 110-145 DEG C.
Finally, film can also carry out surface corona processing, cutting edge and winding processing, finally give institute of the present invention
The film stated.
The biaxially oriented film prepared using flat film biaxial tension method have higher mechanical strength and
Preferable optical property.The biaxially oriented film performance can be met：Longitudinal direction (MD) tensile strength >=
55MPa, is preferably >=60MPa；Laterally (TD) tensile strength >=80MPa, is preferably >=90MPa；
Puncture strength >=2.5N, is preferably >=3N；Mist degree≤6%, is preferably≤4.5%；Tension failure extends
Rate≤400%, is preferably≤350%.In the present invention, the longitudinal tensile strength and cross directional stretch are strong
Degree is measured according to method specified in GB/T 1040.3-2006.The puncture strength is according to GB/T
Method is measured specified in 10004-2008, wherein, the thickness of film sample is 25 ± 5 μm.Institute
Mist degree is stated to be measured according to method specified in GB/T 2410-2008, wherein, the thickness of film sample
Spend for 25 ± 5 μm.The tension fracture elongation rate enters according to method specified in GB/T 1040.3-2006
Row is determined.
Present invention also offers the polyethylene film prepared by the above method.
The production cost of the polyethylene composition that the present invention is provided is low, processing technology is simple, versatility good,
Suitable for preparing various BOPE film products, such as packaging film, composite membrane, plastic film for agricultural use, Obstruct membrane, Asia
Light film, imitative paper membrane etc., have widened the application field of polyethylene film, have improved the performance of product.
The present invention will be described in detail by way of examples below.
In the following Examples and Comparative Examples：
Film biaxial tension equipment is purchased from Br ü ckner companies of Germany, model Karo IV.
The performance of the polyethylene composition is tested in accordance with the following methods：
(1) molecular weight and molecualr weight distribution index (Mw、Mw/Mn、Mz、Mz+1)：Using English
The type gel permeation chromatograph combination IR5 of PL-GPC 220 of Polymer Laboratories companies of state production
Type infrared detector is measured, and chromatographic column is 3 series connection 10 μm of MIXED-B posts of Plgel, solvent
And mobile phase is 1,2,4- trichloro-benzenes, column temperature is 150 DEG C, and flow velocity is 1.0mL/min, using PL companies
EasiCal PS-1 Narrow distribution polystyrenes standard specimen carry out universal calibration；
(2) analytic type temperature rising elution is tested：Manufactured using Polymer Char S.A. companies of Spain
The type temperature rising elution analyzers of TREF 300 are measured, and are comprised the following steps that：By 80mg polyethylene compositions
Thing is put into container, and (1,2,4- trichloro-benzenes, antioxidant BHT addition is 0.03 to injection 40mL solvents
Weight %), 160 DEG C are warming up under nitrogen protection, then the constant temperature 60 under 200rpm mixing speed
Minute, then 2mL solution is moved into analytical column, fast cooling (rate of temperature fall is 40 DEG C/min)
To 95 DEG C, constant temperature 45 minutes, then temperature is slowly dropped to 35 DEG C with 0.1 DEG C/min speed, then
Kept at 35 DEG C 30 minutes, then with 1.0 DEG C/min speed heating and with 0.5mL/min pump
Flow velocity elutes analytical column, and leachates determine concentration with infrared detector, obtain the sample dissolved under different temperatures
Temperature rising elution curve is obtained after product concentration, normalization.
(3) melting temperature is tested：Using Perkin-Elmer DSC-7 differential scanning calorimeters in nitrogen
The lower progress DSC tests of protection are obtained, wherein, temperature and hot-fluid are corrected using indium, amount of samples is 5mg.
Sample is warming up to 180 DEG C with 10 DEG C/min speed first, then keeps 5min to disappear at such a temperature
Except thermal history, 0 DEG C then is cooled to 10 DEG C/min speed, and kept at 0 DEG C after 1min again
180 DEG C are warming up to again with 10 DEG C/min speed, are heated up from first time heating, cooling and again and are recorded
Heat flow curve determine melting temperature.
(4) content of the construction unit of derived from alpha alkene：Using BRUKER AVANCE III 400Hz
Nuclear magnetic resonance spectrometer, by13C NMR spectrums (NMR) method is determined, wherein, visited using 10mm
Head, 125 DEG C of test temperature, 90 pulses, waltz16 uncouples, and sampling time AQ is 5s, during delay
Between D1 be 10s.Sample preparation：Sample is dissolved in deuterated o-dichlorohenzene with 10%w/v concentration, and
Dissolved by heating in 130-140 DEG C of oil bath.
(5) 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.
(6) density：According to method specified in GB/T 1033.2-2010 and using density gradient column method
It is measured.
Embodiment 1
The embodiment is used for the polyethylene composition and polyethylene film and its preparation for illustrating that the present invention is provided.
(1) preparation of polyethylene composition：
Using two fluidized-bed reactors, (internal diameter is polyethylene composition described in the present embodiment
300mm, height is 1000mm, similarly hereinafter) preparation of tandem process direct polymerization, wherein polymer reactor
1 product and the product of polymer reactor 2 are ethylene/alpha-olefin copolymerization LLDPE
(LLDPE).Specifically, circulating air 1 carries out the first polymerisation in polymer reactor 1, and will
First polymeric reaction product introduces polymer reactor 2, while circulating air 2 is introduced into polymer reactor 2
Carry out the second polymerisation.Wherein, the alhpa olefin employed in reactor is 1- butylene, polymerisation
The catalyst that device 1 is used for Ziegler-Natta catalyst, (serve as reasons by the Ziegler-Natta catalyst
The Ziegler-Natta catalyst that CN101838351A embodiments 1 are prepared, consumption is 0.2g/hr,
Similarly hereinafter), polymer reactor 2 is added without catalyst.Concrete operations condition is as follows：
85 DEG C of 1 reaction temperature of polymer reactor, reaction pressure 1.9MPa, the composition of circulating air 1 is ethene
35% (mol), fourth second ratio is 0.45 (mol/mol), and hydrogen second ratio is 0.1 (mol/mol), circulating air gas
Fast 1.0m/s；85 DEG C of 2 reaction temperature of polymer reactor, reaction pressure 1.9MPa, circulating air 2 is constituted
For ethene 35% (mol), fourth second ratio is 0.5 (mol/mol), and hydrogen second ratio is 0.3 (mol/mol), is followed
Ring gas gas velocity 1.0m/s；The productivity ratio for controlling two reactor interpolymers is 4.0, i.e. first reactor
Polymer weight W1/ (second reactor polymer weight-first reactor polymer weight) W2 is 4.0.
Wherein, the specific nature of the first polymeric reaction product and the second polymeric reaction product is shown in Table 1.
Lubricant is added into above-mentioned second polymeric reaction product and carries out mixing homogenizing.Wherein, lubricant is selected
The PEG series lubricant agents (number-average molecular weight is 10000) of Switzerland's Clariant Corporation production are taken as, relative to
Second polymeric reaction product of 100 parts by weight, the addition of lubricant is 0.1 parts by weight.Afterwards, will
Mixture after homogenized is added in the feeder of the double screw extruder of W＆P companies, material via
Feeder enters in twin-screw, and the temperature of screw rod is maintained between 180-240 DEG C in process, through spiral shell
Bar melting mixing is uniform, extruding pelletization and dry, and obtains polyethylene composition pellet, its property is shown in Table 2.
(2) preparation of polyethylene film：
Polyethylene composition pellet made from above-mentioned steps (1) is dried, Sweden is added to afterwards
Melting extrusion is carried out in the model LCR400 of Labtech companies multilayer extrusion casting machine and casting is cast
Piece, wherein, polyethylene composition pellet is added separately to sandwich layer extruder and upper and lower top layer is extruded
In machine, also need to add inorganic antitack agent (silica, similarly hereinafter) in the upper and lower top layer extruder,
And the weight of the antitack agent added in upper and lower top layer extruder and the polyethylene composition pellet each added
It is 0.02 to measure ratio:1, during curtain coating slab, curtain coating chilling roll temperature is set as 85 DEG C, is made
Polyethylene thickness slab, it is made up of upper epidermis, sandwich layer and layer.
The thick slab of above-mentioned polyethylene is put into the stretching clamp of film biaxial tension equipment, using first indulging
The two-way step drawing technological forming that laterally (TD) is stretched after being stretched to (MD), each step process condition
It is as follows：MD preheating temperatures are 100 DEG C, and MD draft temperatures are 110 DEG C, and MD stretching ratios are 4 times,
TD preheating temperatures are 100 DEG C, and TD draft temperatures are 115 DEG C, and TD stretching ratios are 5 times, film
TD rates of extension are 150%/s, and film setting temperature is 120 DEG C, and it is 25 μm to obtain average thickness
Film, it is made up of upper epidermis, sandwich layer and layer, and the thickness of upper epidermis and layer is 1.5 μm.
Embodiment 2
The embodiment is used for the polyethylene composition and polyethylene film and its preparation for illustrating that the present invention is provided.
(1) preparation of polyethylene composition：
Polyethylene composition described in the present embodiment is directly gathered using two fluidized-bed reactor tandem process
Close and prepare, the product of the wherein product of polymer reactor 1 and polymer reactor 2 is that ethylene/alpha-olefin is total to
Poly- LLDPE (LLDPE).Specifically, circulating air 1 is carried out in polymer reactor 1
First polymerisation, and the first polymeric reaction product is introduced into polymer reactor 2, while by circulating air 2
It is introduced into polymer reactor 2 and carries out the second polymerisation.Wherein, the alhpa olefin employed in reactor is equal
For 1- hexenes, the catalyst that polymer reactor 1 is used is Ziegler-Natta catalyst, polymerisation
Device 2 is added without catalyst.Comprise the following steps that：
80 DEG C of 1 reaction temperature of polymer reactor, reaction pressure 1.9MPa, the composition of circulating air 1 is ethene
35% (mol), own second ratio is 0.08 (mol/mol), and hydrogen second ratio is 0.01 (mol/mol), circulating air
Gas velocity 1.0m/s；88 DEG C of 2 reaction temperature of polymer reactor, reaction pressure 1.9MPa, 2 groups of circulating air
As ethene 35% (mol), own second ratio is 0.13 (mol/mol), and hydrogen second ratio is 0.5 (mol/mol),
Circulating air gas velocity 1.0m/s；The productivity ratio for controlling two reactor interpolymers is 1.0, i.e., the first reaction
Device polymer weight W1/ (second reactor polymer weight-first reactor polymer weight) W2 is
1.0.Wherein, the specific nature of the first polymeric reaction product and the second polymeric reaction product is shown in Table 1.
Lubricant is added into above-mentioned second polymeric reaction product and carries out mixing homogenizing.Wherein, lubricant is selected
The PEG series lubricant agents (number-average molecular weight is 10000) of Switzerland's Clariant Corporation production are taken as, relative to
Second polymeric reaction product of 100 parts by weight, the addition of lubricant is 3 parts by weight.Afterwards, will be through
Mixture after homogenizing is added in the feeder of the double screw extruder of W＆P companies, material via feed
Glassware enters in twin-screw, and the temperature of screw rod is maintained between 180-240 DEG C in process, through screw rod
Melting mixing is uniform, extruding pelletization and dry, and obtains polyethylene composition pellet, its property is shown in Table 2.
(2) preparation of polyethylene film：
Polyethylene composition pellet made from above-mentioned steps (1) is dried, Sweden is added to afterwards
Melting extrusion is carried out in the model LCR400 of Labtech companies multilayer extrusion casting machine and casting is cast
Piece, wherein, polyethylene composition pellet is added separately to sandwich layer extruder and upper and lower top layer is extruded
In machine, also need to add inorganic antitack agent in the upper and lower top layer extruder, and upper and lower top layer is extruded
The weight ratio of the antitack agent added in machine and the polyethylene composition pellet each added is 0.02:1,
Be cast during slab, curtain coating chilling roll temperature be set as 25 DEG C, the thick slab of polyethylene is made, its by
Upper epidermis, sandwich layer and layer are constituted.
The thick slab of above-mentioned polyethylene is put into the stretching clamp of film biaxial tension equipment, using first indulging
The two-way step drawing technological forming that laterally (TD) is stretched after being stretched to (MD), each step process condition
It is as follows：MD preheating temperatures are 100 DEG C, and MD draft temperatures are 110 DEG C, and MD stretching ratios are 4 times,
TD preheating temperatures are 100 DEG C, and TD draft temperatures are 115 DEG C, and TD stretching ratios are 6 times, film
TD rates of extension are 100%/s, and film setting temperature is 120 DEG C, and it is 25 μm to obtain average thickness
Film, it is made up of upper epidermis, sandwich layer and layer, and the thickness of upper epidermis and layer is 1.5 μm.
Comparative example 1
The comparative example is used for polyethylene composition and polyethylene film and its preparation for illustrating reference.
Choose a kind of commercially available polyethylene raw material and carry out polyethylene film using flat embrane method stretch processes
Preparation, and the stretching film forming and film performance of raw material are compared with the present invention.
(1) polyethylene raw material：
Choose the film-grade LLDPE of Yanshan Petrochemical company of SINOPEC production, the trade mark
For 7042, it uses Z-N (Ziegler-Natta) catalyst preparation to obtain, melt index
MI=2.0g/10min, density p=0.920g/cm3, its specific nature is shown in Tables 1 and 2.
(2) preparation of polyethylene film：
Method according to embodiment 1 prepares polyethylene film, unlike, by the polyethylene composition
Pellet is substituted using the polyethylene raw material of this comparative example step (1), broken through repeatedly attempting appearance stretching
The situation of film, it is impossible to stretch film forming.In addition, by the TD rates of extension in polyethylene film preparation process
It is down to after 50%/s, the situation through repeatedly attempting still to occur stretching rupture of membranes, it is impossible to stretch film forming.
Comparative example 2
The comparative example is used for polyethylene composition and polyethylene film and its preparation for illustrating reference.
The preparation that a kind of commercially available polyethylene raw material carries out polyethylene film using extrusioning blowing process is chosen,
And be compared film performance with the present invention.
(1) polyethylene raw material：
Polyethylene raw material used in this comparative example is identical with comparative example 1.
(2) preparation of polyethylene film：
The polyethylene film of this comparative example uses the upper blowing method film blowing device of DR.COLLIN companies of Germany
Extrusion and blow molding is obtained, and specific method is as follows：The polyethylene raw material that above-mentioned steps (1) are chosen adds
Enter into the hopper of upper blowing method film blowing device extruder, after the abundant fusion plastification of the extruded machine of raw material, by machine
Melt membrane tube is made in the annular die extrusion of head, afterwards compressed air inflation (blow-up ratio is 2.5 times),
And polyethylene film is made after being cooled down through vane, wherein film is the single layer structure that average thickness is 25 μm.
Comparative example 3
The comparative example is used for polyethylene composition and polyethylene film and its preparation for illustrating reference.
(1) preparation of polyethylene composition：
The first polymeric reaction product, the second polymeric reaction product and poly- second are prepared according to the method for embodiment 1
Ene compositions pellet, unlike, in the preparation process of the first polymeric reaction product, in circulating air 1
Hydrogen second ratio mole is 0.2.Wherein, the specifics of the first polymeric reaction product and the second polymeric reaction product
Matter is shown in Table 1, and the specific nature of polyethylene composition pellet is shown in Table 2.
(2) preparation of polyethylene film：
The preparation of polyethylene film is carried out according to the method for embodiment 1, difference is, extrudate flow delay is thin
The top layer of film and core layer raw material are substituted using the polyethylene composition pellet of above-mentioned steps (1), as a result
Show, by repeatedly trial, the maximum tension multiplying power of biaxially oriented film is only 2 times of (TD) × 2 times
(MD), film TD highests stretching ratio is only 10%/s, i.e. stretching ratio and rate of extension mistake
Low, stretching film forming is poor, does not possess practicality.
Comparative example 4
The comparative example is used for polyethylene composition and polyethylene film and its preparation for illustrating reference.
The comparative example prepares polyethylene composition using parallel connection technology, comprises the following steps that：
(1) preparation of polyethylene composition：
The first polymeric reaction product, the second polymeric reaction product and poly- second are prepared according to the method for embodiment 2
Ene compositions pellet, unlike, in the preparation process of the first polymeric reaction product, in circulating air 1
Hydrogen second ratio mole is 0.3.Wherein, the specifics of the first polymeric reaction product and the second polymeric reaction product
Matter is shown in Table 1, and the specific nature of polyethylene composition pellet is shown in Table 2.
(2) preparation of polyethylene film：
Method according to embodiment 1 prepares polyethylene film, unlike, by the polyethylene composition
Pellet is substituted using the polyethylene composition pellet of this comparative example step (1), is as a result shown, through excessive
Secondary to attempt, the maximum tension multiplying power of biaxially oriented film is only 2 times of (TD) × 2 times (MD), 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.
Table 1
Table 2
Test case
Test case is used for the test for illustrating polyethylene film and reference polyethylene film performance.
(1) mist degree：It is measured according to method specified in GB/T 2410-2008, wherein, film
Sample thickness is 25 ± 5 μm, and acquired results are as shown in table 3；
(2) tensile strength, modulus and tension fracture elongation rate：Advised according in GB/T 1040.3-2006
Fixed method is measured, and acquired results are as shown in table 3；
(3) puncture strength：It is measured according to method specified in GB/T10004-2008, wherein,
Film sample thickness is 25 ± 5 μm, and acquired results are as shown in table 3.
Table 3
It can be drawn from the result of table 3 to draw a conclusion：
(1) polyethylene composition that embodiment 1-2 is provided using the present invention prepares polyethylene film, with
Using existing polyethylene raw material prepare polyethylene film compare have that film forming multiplying power is big, rate of extension fast,
Mechanical strength is high, the advantage of good in optical property, and the performance of prepared film can meet longitudinal direction (MD)
Tensile strength >=55MPa, horizontal (TD) tensile strength >=80MPa, puncture strength >=2.5N, mist degree≤
4.5%, tension fracture elongation rate≤350%.
(2) it be can be seen that from the contrast of embodiment 1 and comparative example 1 and comparative example 2 using existing skill
Commercial polyethylene raw material prepared by art can not stretch film forming, thus not be suitable for flat embrane method stretch processes
Processing.And compared with the flat embrane method Biaxial tension polyethylene film that the present invention is provided, commercial polyethylene
Raw material is relatively low using the mechanical strength and puncture strength of the inflation film of extrusion film-blowing process manufacture, and film
Mist degree is higher, and its performance result more of the present invention has larger gap.
(3) contrast from embodiment 1 and comparative example 3 and comparative example 4 can be seen that when the poly- second
When ene compositions do not possess the Nomenclature Composition and Structure of Complexes for the polyethylene composition that the present invention is provided, stretching film forming is not
It is good, do not have practicality for existing flat embrane method stretch processes film preparation.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited to above-mentioned reality
The detail in mode is applied, can be to technical side of the invention in the range of the technology design of the present invention
Case carries out a variety of simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means.In order to avoid need not
The repetition wanted, the present invention no longer separately illustrates to various possible combinations.
In addition, various embodiments of the present invention can be combined randomly, as long as its
Without prejudice to the thought of the present invention, it should equally be considered as content disclosed in this invention.
Claims (15)
1. a kind of polyethylene composition, it is characterised in that the polyethylene composition contains according to following
The product that method is prepared：Ethene and alhpa olefin are subjected to the first polymerisation in the presence of a catalyst,
Then the first polymeric reaction product and ethene and alhpa olefin are subjected to the second polymerisation, first polymerization
The condition of reaction and the second polymerisation makes the weight average molecular weight Mw of the second obtained polymeric reaction product
For the g/mol of 80,000 g/mol-20 ten thousand, and Mw/Mn >=4.5, Mz/Mw >=4.5, Mz+1/Mw >=7.5.
2. polyethylene composition according to claim 1, wherein, the second polymerisation production
The weight average molecular weight Mw of thing is the g/mol of 100,000 g/mol-15 ten thousand, and Mw/Mn is 4.5-9.0, Mz/Mw
For 4.5-7.0, Mz+1/Mw is 7.5-13.5.
3. polyethylene composition according to claim 1, wherein, the first polymerisation production
The weight average molecular weight Mw of thing is the g/mol of 80,000 g/mol-50 ten thousand, and Mw/Mn is 2.5-8.5, Mz/Mw
For 2.0-6.5, Mz+1/Mw is 4.5-12.0；Preferably, first polymeric reaction product is divided equally again
Son amount Mw is the g/mol of 80,000 g/mol-30 ten thousand, and Mw/Mn is 3.0-7.0, and Mz/Mw is 2.5-5.5,
Mz+1/Mw is 4.5-9.5.
4. the polyethylene composition according to any one in claim 1-3, wherein, it is described poly-
The temperature rising elution curve that vinyl composition is measured by analytic type temperature rising elution staging includes high temperature and elutes peak
Peak is eluted with low temperature, and the peak temperature at high temperature elution peak is 90-110 DEG C, the low temperature elutes peak
Peak temperature be 50-90 DEG C；On the basis of the gross area for eluting peak and low temperature elution peak by the high temperature,
The high temperature elutes area≤80% at peak, and the low temperature elutes area >=20% at peak；
Preferably, the peak temperature at the high temperature elution peak is 95-100 DEG C, and the low temperature elutes the peak at peak
It is 60-90 DEG C to be worth temperature；It is described on the basis of the gross area for eluting peak and low temperature elution peak by the high temperature
High temperature elutes area≤70% at peak, and the low temperature elutes area >=30% at peak.
5. the polyethylene composition according to any one in claim 1-3, wherein, it is described poly-
Vinyl composition temperature be 190 DEG C, load be that melt index under 2.16kg is 0.1-20g/10min,
Preferably 0.5-10g/10min.
6. the polyethylene composition according to any one in claim 1-3, wherein, it is described poly-
The melting temperature that vinyl composition is measured by differential scanning calorimetry is 100-130 DEG C, preferably 110-130
℃。
7. the polyethylene composition according to any one in claim 1-3, wherein, described
Alhpa olefin used in one polymerisation and the second polymerisation is each independently C3-C20In alkene at least
One kind, preferably propylene, 1- butylene, 2- butylene, 3-methyl-1-butene, 4- methyl isophthalic acids-butylene, 1- penta
Alkene, 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, 1- dodecylenes, tetradecene, cetene, 1- vaccenic acids and 1-
At least one of at least one of eicosylene, more preferably 1- butylene, 1- hexenes and 1- octenes.
8. a kind of preparation method of polyethylene composition, this method is included ethene and alhpa olefin in catalysis
The first polymerisation is carried out in the presence of agent, then the first polymeric reaction product and ethene and alhpa olefin is carried out
Second polymerisation, the condition of first polymerisation and the second polymerisation makes obtain second to polymerize
The weight average molecular weight Mw of reaction product is the g/mol of 80,000 g/mol-20 ten thousand, and Mw/Mn >=4.5,
Mz/Mw >=4.5, Mz+1/Mw >=7.5；
Preferably, the weight average molecular weight Mw of second polymeric reaction product is 100,000 g/mol-15 ten thousand
G/mol, and Mw/Mn is 4.5-9.0, Mz/Mw is 4.5-7.0, and Mz+1/Mw is 7.5-13.5；
Preferably, the weight average molecular weight Mw of first polymeric reaction product is 80,000 g/mol-50 ten thousand
G/mol, and Mw/Mn is 2.5-8.5, Mz/Mw is 2.0-6.5, and Mz+1/Mw is 4.5-12.0；
Preferably, the weight average molecular weight Mw of first polymeric reaction product is 80,000 g/mol-30 ten thousand
G/mol, and Mw/Mn is 3.0-7.0, Mz/Mw is 2.5-5.5, and Mz+1/Mw is 4.5-9.5.
9. method according to claim 8, wherein, the temperature of first polymerisation is 50-130
DEG C, pressure is 0.5-5MPa；The temperature of second polymerisation is 50-130 DEG C, and pressure is
0.5-5MPa。
10. method according to claim 8 or claim 9, wherein, first polymerisation and second
Alhpa olefin used in polymerisation is each independently C3-C20At least one of 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 of one kind, more preferably 1- butylene, 1- hexenes and 1- octenes.
11. the polyethylene composition prepared as the method described in any one in claim 8-10.
12. a kind of polyethylene film, the polyethylene film at least include one layer by claim 1-7 and
The polyethylene layer that polyethylene composition in 11 described in any one is prepared.
13. a kind of preparation method of polyethylene film, this method is included in claim 1-7 and 11
Polyethylene composition described in any one carries out extrusion curtain coating, then obtained curtain coating slab is drawn
Stretch.
14. method according to claim 13, wherein, the method for the stretching is biaxial tension,
And longitudinal stretching multiplying power >=4 times, preferably 4-8 times, preferably cross directional stretch multiplying power >=5 times, 5-15
Times；Cross directional stretch speed >=80%/s.
15. the polyethylene film prepared as the method described in claim 13 or 14.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020132923A1 (en) * | 2018-12-26 | 2020-07-02 | 东莞正新包装制品有限公司 | Pe mulch film |
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| CN101688032A (en) * | 2007-05-09 | 2010-03-31 | 陶氏环球技术公司 | Ethylene-based polymer compositions, methods of making the same, and articles prepared therefrom |
| CN102971346A (en) * | 2010-07-01 | 2013-03-13 | Lg化学株式会社 | Olefin-based polymer and method for preparing same |
| CN105524337A (en) * | 2014-10-27 | 2016-04-27 | 中国石油化工股份有限公司 | Polyethylene composition and film thereof |
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| CN101688032A (en) * | 2007-05-09 | 2010-03-31 | 陶氏环球技术公司 | Ethylene-based polymer compositions, methods of making the same, and articles prepared therefrom |
| CN102971346A (en) * | 2010-07-01 | 2013-03-13 | Lg化学株式会社 | Olefin-based polymer and method for preparing same |
| CN105524337A (en) * | 2014-10-27 | 2016-04-27 | 中国石油化工股份有限公司 | Polyethylene composition and film thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020132923A1 (en) * | 2018-12-26 | 2020-07-02 | 东莞正新包装制品有限公司 | Pe mulch film |
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