CN105623060B - A kind of polyethylene composition and its film - Google Patents
A kind of polyethylene composition and its film Download PDFInfo
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- CN105623060B CN105623060B CN201410584803.6A CN201410584803A CN105623060B CN 105623060 B CN105623060 B CN 105623060B CN 201410584803 A CN201410584803 A CN 201410584803A CN 105623060 B CN105623060 B CN 105623060B
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Abstract
The invention provides a kind of polyethylene composition and its film.The polyethylene composition contains component A, component C and the component B selectively contained；The LLDPE that the component A is copolymerized for ethylene/alpha-olefin, its melt index MI in the case where temperature is 190 DEG C, load is 2.16kgAFor 0.01 2g/10min, density pAFor 0.880 0.936g/cm3；The LLDPE that the component B is copolymerized for ethylene/alpha-olefin, its melt index MI in the case where temperature is 190 DEG C, load is 2.16kgBFor 2.1 9.9g/10min, density pBFor 0.910 0.930g/cm3；The LLDPE that the component C is copolymerized for ethylene/alpha-olefin, its melt index MI in the case where temperature is 190 DEG C, load is 2.16kgCFor 10 80g/10min, density pCFor 0.880 0.930g/cm3.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.
Description
Technical field
The present invention relates to a kind of polyethylene composition and its film.
Background technology
Biaxially-oriented polyethylene (Biaxially Oriented Polyethylene, BOPE) film is that have special point
The thin-film material that polyethylene (PE) resin of minor structure is molded through stretch processes.In the molding process of BOPE films
In, after the processing of film drawn, PE macromolecular chains and crystalline texture generation are height-oriented, so as to significantly improve the stretching of film
Intensity, tension fracture elongation rate is reduced, and make it that the mist degree of film is lower, glossiness is higher and transparent more preferable.In addition, with
The polyethylene film product that the extrusioning blowing process of prior art is prepared with extrusion casting technique is compared, and BOPE films have 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 films 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 the plastic sheeting used at present has Flat film strength and envelope pulling method.Flat film stretching
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 ripe.Compared with envelope pulling method, (cross directional stretch multiplying power is up to 10 times greatly for the stretching ratio of Flat film strength
More than), shaping speed fast (highest rolling speed is up to hundreds of ms/min), production efficiency it is high, and the mechanics of obtained film
More preferably, but film forming is influenceed significantly by process condition fluctuations for intensity, optical property and thickness evenness, film stretching plus
Work difficulty is big, there is 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 films, and using Flat film strength being prepared by these existing polyethylene raw materials into BOPE films, deposit
Easily there is the defects of rupture in film forming poor (draw speed and stretching ratio are very low), film, i.e. be not suitable for substantially using flat
Film stretching method prepares film.Therefore, in order to make full use of the above-mentioned advantage of Flat film strength, a kind of film forming of exploitation is needed badly at present
Property good and film be not easy the polyethylene raw material for being applied to Flat film strength and preparing BOPE films that occurs rupturing.
The content of the invention
The invention aims to overcome existing polyethylene raw material preparing polyethylene film using Flat film strength
When have that film forming is poor, film is easily broken, that is, the defects of not being suitable for preparing film using Flat film strength, and provide a kind of new
Polyethylene composition and the film made of the polyethylene composition.
Specifically, polyethylene composition provided by the invention contains component A, component C and the component B selectively contained；
The component A is the LLDPE of ethylene/alpha-olefin copolymerization, and it is in the case where temperature is 190 DEG C, load is 2.16kg
Melt index MIAFor 0.01-2g/10min, density 0.880-0.936g/cm3；The component B is ethylene/alpha-olefin copolymerization
LLDPE, its melt index MI in the case where temperature is 190 DEG C, load is 2.16kgBFor 2.1-9.9g/10min,
Density is 0.910-0.930g/cm3；The component C is the LLDPE of ethylene/alpha-olefin copolymerization, and it is in temperature
190 DEG C, load be 2.16kg under melt index MICFor 10-80g/10min, density 0.880-0.930g/cm3。
Film provided by the invention comprises at least one layer of polyethylene layer formed by above-mentioned polyethylene composition.
The present inventor has found after further investigation, by the above-mentioned component A with particular melt index and density,
When polyethylene composition obtained from component B and component C is used cooperatively prepares polyethylene film using Flat film strength, have and draw
The advantages of multiplying power is big, rate of film build is high is stretched, disclosure satisfy that high requirement of the Flat film strength to polyethylene raw material, and adapt to existing
Flat film strength production line economy demand, great prospects for commercial application.
A preferred embodiment of the invention, the mass fraction of the component A described in the polyethylene composition
WAFor 25-90 parts by weight, the mass fraction W of the component BBFor 0.1-10 parts by weight, the mass fraction W of the component CCFor 10-
During 75 parts by weight, the polyethylene composition is prepared on the basis of with preferable film forming by the polyethylene composition
Film also has relatively low mist degree.
According to another preferred embodiment of the present invention, when the component A and component B molecular weight distributing index meets
Mw/Mn≤ 4.5, and the molecular weight distributing index of the component C meets Mw/MnWhen≤8.0, the polyethylene composition with compared with
On the basis of good film forming, the film being prepared by the polyethylene composition also has higher intensity and puncture resistance.
According to another preferred embodiment of the present invention, when component A, component B and component C in the polyethylene composition
Density pA、ρBAnd ρCBetween relation meet -0.04≤ρA-ρB≤ 0.02, and -0.04≤ρA-ρCWhen≤0.02, the polyethylene
The film that composition is prepared on the basis of with preferable film forming, by the polyethylene composition also have tensile strength and
The advantages of punctured resistance height and low mist degree.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, 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 for the structural representation for the multiple reactor shunting means for preparing polyethylene composition.
Description of reference numerals
1- first reactors；2- second reactors；The reactors of 3- the 3rd；4- solid-liquids (gas) separator；5- homogenization silos；
6- melt pelletization systems.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
Polyethylene composition provided by the invention contains component A, component C and the component B selectively contained；The component
The LLDPE that A is copolymerized for ethylene/alpha-olefin, its melt index in the case where temperature is 190 DEG C, load is 2.16kg
MIAFor 0.01-2g/10min, density pAFor 0.880-0.936g/cm3；The component B is the linear low of ethylene/alpha-olefin copolymerization
Density polyethylene, its melt index MI in the case where temperature is 190 DEG C, load is 2.16kgBFor 2.1-9.9g/10min, density pB
For 0.910-0.930g/cm3；The component C is the LLDPE of ethylene/alpha-olefin copolymerization, and it is 190 in temperature
DEG C, load be 2.16kg under melt index MICFor 10-80g/10min, density pCFor 0.880-0.930g/cm3。
According to polyethylene composition provided by the invention, it is preferable that the component A temperature be 190 DEG C, load be
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 3-8g/10min, melt index MIs of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor
10-60g/10min.It is highly preferred that melt index MIs 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 MIs of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor 15-40g/10min.
In the present 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, load 2.16kg.
According to polyethylene composition provided by the 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
Part B and component C density pA、ρBAnd ρCBetween relation meet -0.04≤ρA-ρB≤ 0.02, and -0.04≤ρA-ρC≤ 0.02,
The polyethylene composition so enabled to also has very high stretching strong on the basis of with preferable filming performance
Degree and punctured resistance and relatively low mist degree.
The component A, component B and component C are the LLDPE of ethylene/alpha-olefin copolymerization, wherein, linearly
Structure refers to only contain short-chain branch structure in strand, and does not contain long branched chain structure and cross-linked structure, its by polymerized monomer and
Polymerization process condition is determined, is specifically known to the skilled person, and therefore not to repeat here.
According to polyethylene composition provided by the invention, in order that obtained polyethylene composition is with good filming
On the basis of energy, also with preferable optical property, it is preferable that in the polyethylene composition, the mass parts of the component A
Number WAFor 25-90 parts by weight, the mass fraction W of the component BBFor 0.1-10 parts by weight, the mass fraction W of the component CCFor
10-75 parts by weight；It is highly preferred that in the polyethylene composition, the mass fraction W of the component AAFor 30-80 parts by weight,
The mass fraction W of the component BBFor 0.5-8 parts by weight, the mass fraction W of the component CCFor 20-70 parts by weight.Further
Ground, the mass fraction W of the component AAWith component C mass fraction WCWith component A melt index MIARelation preferably meet
5.2×lgMIA+11.6≥WA/WC≥0.9×lgMIA+ 2.1, more preferably meet 2.9 × lgMIA+6.8≥WA/WC≥1.1×
lgMIA+ 2.7, so enable to the polyethylene composition that there is bigger drawing in flat embrane method film biaxial tension processing
Stretch multiplying power and Geng Gao rate of extension.
According to polyethylene composition provided by the 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, most preferably 0.5-10g/10min.It is above-mentioned that will have
It is on the basis of the particular melt index and component A of density, component B and component C are used cooperatively, the polyethylene composition is overall
Melt index control in above-mentioned preferable scope, the polyethylene composition that enables at the same have it is very excellent into
Film, tensile strength and punctured resistance and relatively low mist degree.
The present invention is not particularly limited to the content of the component B, using the gross weight of the polyethylene composition as base
Standard, the mass percentage content M of the component BBIt is preferred that≤35 weight %, more preferably MB≤ 25 weight %.
According to polyethylene composition provided by the invention, it is preferable that the molecular weight distributing index of the component A and component B
Meet Mw/Mn≤ 4.5, and the molecular weight distributing index of the component C meets Mw/Mn≤8.0；It is highly preferred that the component A and
Component B molecular weight distributing index meets 2.0≤Mw/Mn≤ 4.2, and the molecular weight distributing index satisfaction 3.5 of the component C≤
Mw/Mn≤6.0.Specifically, in order to obtain the component A with above-mentioned molecular weight distribution, component B and component C, the component A and group
B is divided to be obtained using metallocene catalyst polymerisation, and the component C polymerize to obtain using Ziegler-Natta catalyst.Wherein, institute
The species for stating metallocene catalyst and Ziegler-Natta catalyst can be the conventional selection of this area, the metallocene catalysis
Agent is generally made up of metallocene compound and organo-aluminum compound and optional electron donor, the ziegler-natta catalyzed
Agent is generally made up of magnesium titanium compound and organo-aluminum compound and optional electron donor, specially those skilled in the art
Known, therefore not to repeat here.The present inventor has found after further investigation, will be obtained using metallocene catalyst polymerisation
Component A with above-mentioned melt index and density and component B and using Ziegler-Natta catalyst polymerize to obtain with
The component C of above-mentioned melt index and density is used cooperatively, and obtained film also has on the basis of with good filming performance
Very high intensity and puncture energy, are highly suitable for packaging material.
The present invention is not particularly limited to the content of alhpa olefin comonomer in the component A, component B and component C, example
Such as, the molar content of alhpa olefin comonomer can be each independently 0.2- in the component A, component B and component C
15mol%, preferably 1.5-10mol%.In the present invention, the molar content of alhpa olefin comonomer refers to by alpha-olefin polymerization shape
Into construction unit mole account for total monomer construction unit mole ratio.In addition, the component A, component B and component
Alhpa olefin in C is each independently C3-C20At least one of alkene.The angle ready availability from raw material, the component A,
Alhpa olefin in component B and component C is preferably propylene, 1- butylene, 2- butylene, 3-methyl-1-butene, 4- methyl isophthalic acids-butylene, 1-
Amylene, 3- Methyl-1-pentenes, 4-methyl-1-pentene, 3,3- dimethyl -1- amylenes, 3,4- dimethyl -1- amylenes, 4,4- diformazans
Base -1- amylenes, 1- hexenes, 4- methyl isophthalic acids-hexene, 5- methyl isophthalic acids-hexene, 1- heptene, 2- heptene, 1- octenes, 1- decene, 1- ten
At least one of two (carbon) alkene, 1- 14 (carbon) alkene, 1- 16 (carbon) alkene, (carbon) alkene of 1- 18 and 1- 20 (carbon) alkene, more
Preferably at least one of 1- butylene, 1- hexenes and 1- octenes.
According to polyethylene composition provided by the invention, it is preferable that the polyethylene composition also contains lubricant, so
The extrusion processing characteristics of the polyethylene composition can be improved.The species and dosage of the lubricant can be this area
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 agents for example can be the PEG molecules that molecular weight is 500-50000, and it can pass through end-blocking, connect
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-
Compound and crystallization or hemicrystalline fluoropolymer.The organo-silicic oil can be existing various with carbon, silicon atom
For molecular backbone, the compound using the oligomer of the organic groups such as methyl, phenyl, alkoxy, vinyl or oligomer as side chain.
The fatty alcohol type emollients such as can be soft fat alcohol, tallow alcohol, at least one of tallow fatty alcohol.The fat
Fat acids lubricant for example can be with stearic acid and/or 12- hydroxy stearic acids.The fatty acid ester type emollients for example can be hard
At least one of resin acid butyl ester, stearic acid list glyceride, cetyl palmitate, tearyl base ester etc..It is described
Stearic amide series lubricant agent can be for example 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 be lead stearate, calcium stearate, tristearin
At least one of sour magnesium, synthesis calcium acetate etc..Alkane and the oxidation of alkanes series lubricant agent can be for example atoleine, consolidate
At least one of body paraffin, Tissuemat E, polypropylene wax, ethylene oxide wax etc..The micro-and nano-particles series lubricant agent is for example
Can be powdered rubber and/or aerosil particles.In addition, using the component A, component B and component C gross mass as 100 parts by weight
Meter, the content of the lubricant can be 0.05-5 parts by weight, preferably 0.5-3 parts by weight.
In addition, it can also contain in the polyethylene composition existing various in polyvinyl resin, polyethylene film
Other usually used auxiliary agents, and stretching film forming that other described auxiliary agents will not be to polyethylene composition provided by the invention,
Mechanical property and optical property have adverse effect on.Other described auxiliary agents include but is not limited to：It is antioxidant, slipping agent, anti-quiet
At least one of electric agent, antitack agent etc..In addition, the dosage of other auxiliary agents can be the conventional selection of this area, it is right
This those skilled in the art can know that 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, then by the component A, component B and component C and the lubricant selectively contained and other auxiliary agents according to
Proportioning carries out mechanical mixture in mechanical mixing equipment, then adds in melt blending equipment and carries out melt blending.Wherein, it is described
Mechanical mixing equipment is such as can be homogenizer, kneader.The melt blending equipment can for example squeeze for twin-screw
Go out machine, single screw extrusion machine, mill, banbury etc..
A preferred embodiment of the invention, the polyethylene composition in 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, the 3rd reactor 3,
Solid-liquid (gas) separator 4, homogenization silo 5 and melt pelletization system 6, wherein, the first reactor 1, the and of second reactor 2
3rd 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 with the 3rd 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 the 3rd reactor 3 is separated different in solid-liquid (gas) separator 4 respectively, then will be through phase
Component A, component B and component C after separation are delivered in homogenization silo 5 and are mixed together uniformly with other additives in proportion,
It is sent into afterwards in melt pelletization system 6 and carries out extruding pelletization.Wherein, the polymerization in each reactor can be batchwise polymerization, also may be used
To be continuous polymerization.When using multiple reactor parallel polymerization, W hereinafterA、WBAnd WCIt is each component in respective reaction device
Yield in unit time.
Film provided by the invention comprises at least one layer of polyethylene layer formed by above-mentioned polyethylene composition.
The film can have single layer structure, it is possible to have sandwich construction.When the film is sandwich construction, extremely
Few main stor(e)y (being usually the maximum layer of thickness) is the polyethylene layer formed by the polyethylene composition.For example, the film can
With the composite construction with upper epidermis, sandwich layer and layer, and at least described sandwich layer is formed by the polyethylene composition
Polyethylene layer.As a rule, the thickness of the film can be 10-200 μm, preferably 10-100 μm.In addition, work as the film
During composite construction with upper epidermis, sandwich layer and layer, the thickness of the upper epidermis and layer is each independently described
The 1-25% of film thickness.
In addition, the film can be monodirectional tension film, or biaxially oriented film, preferably bidirectional stretching are thin
Film, the biaxially oriented film being more preferably prepared by flat film biaxial tension method.
The process for preparing biaxially oriented film using flat film biaxial tension method is known to the skilled person.Specifically,
First above-mentioned polyethylene composition is added in casting apparatus and carries out extrusion curtain coating slab, it is then that obtained slab is double in film
Drawing and forming is carried out into stretcher.During curtain coating is extruded, the knot for the film that slab die head can obtain as needed
Structure is selected, for example, when needing to obtain the film with single layer structure, can use single layer die；When needs are had
When having film (film with upper epidermis, sandwich layer and layer three-decker) of sandwich construction, it can be answered using sandwich construction
Matched moulds head, and at least one layer of (sandwich layer) and the extruder equipped with above-mentioned polyethylene composition in the compound die head of the sandwich construction
Hopper connects, and at least one layer (sandwich layer) in the film so enabled to is the poly- second formed by above-mentioned polyethylene composition
Alkene layer.In extrusion, 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 use Synchronos method drawing process (carrying out film longitudinal direction (MD) and laterally (TD) stretching simultaneously), also may be used
(first to carry out film longitudinal stretching using method of fractional steps drawing process, then carry out film cross directional stretch).The Synchronos method stretching
Concrete technology be：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 direction (MD) stretching ratio >=4 times, laterally (TD) stretching ratio >=5
Times, cross directional stretch speed >=50%/s.The concrete technology of method of fractional steps stretching is：The slab is advanced after being fully warmed-up
Row longitudinal stretching, cross directional stretch is carried out afterwards, wherein, preheating temperature can be 65-158 DEG C, and draft temperature can be 65-155
DEG C, longitudinal direction (MD) stretching ratio >=4 times, horizontal (TD) stretching ratio >=5 times, cross directional stretch speed >=50%/s.It is in addition, thin
It can be handled after film stretching shaping without setting, setting processing of annealing can also be carried out.It is thin when carrying out annealing setting processing
Film setting treatment temperature can be 80-165 DEG C.Finally, film can also carry out surface corona processing, cutting edge and winding processing,
Finally give film of the present invention.
Film provided by the invention has preferable film forming and stretching ratio is big, rate of extension is high.Using flat film
During pulling method prepares the biaxially oriented film, as described above, longitudinal direction (MD) stretching ratio >=4 times of the film,
Laterally (TD) stretching ratio >=5 times.Stretching ratio is bigger, then the mechanical strength of film is higher.The transverse direction (TD) of the film is drawn
Speed >=50%/s, preferably 60-100%/s are stretched, can so ensure to industrialize continuous production.
Film provided by the invention has higher mechanical strength and preferable optical property.The biaxially oriented film
It is able to can meet：Longitudinal direction (MD) tensile strength >=55MPa, it is preferably >=60MPa；Laterally (TD) tensile strength >=65MPa, it is preferably
≥70MPa.Puncture strength >=2.5N of the biaxially oriented film, it is preferably >=3.5N.The stretching of the biaxially oriented film
Elongation at break≤350%, it is preferably≤300%.In the present invention, the longitudinal tensile strength and transverse tensile strength according to
Method is measured specified in GB/T1040.3-2006.The puncture strength is according to side specified in GB/T 10004-2008
Method is measured, wherein, the thickness of film sample is 25 ± 5 μm.The tension fracture elongation rate is according to GB/T 1040.3-
Method is measured specified in 2006.
The production cost of film provided by the invention is low, processing technology is simple, versatility is good, has widened polyethylene film
Application field.
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 German Br ü ckner companies, model Karo IV.
The polyethylene composition and film performance are tested in accordance with the following methods：
(1) molecular weight distributing index (Mw/Mn)：Using the PL-GPC 220 of Polymer Laboratories companies of Britain
Type gel permeation chromatograph combination IR5 type infrared detectors are measured, and chromatographic column is 3 series connection Plgel, 10 μm of MIXED-
B posts, solvent and mobile phase are 1,2,4- trichloro-benzenes, and column temperature is 150 DEG C, flow velocity 1.0mL/min, using PL companies
EasiCal PS-1 Narrow distribution polystyrenes standard specimen carries out universal calibration；
(2) melt index (MI)：It is measured according to method specified in GB/T 3682-2000, wherein, test temperature
For 190 DEG C, load 2.16kg；
(3) density：It is measured according to method specified in GB/T 1033.2-2010 and using density gradient column method.
Embodiment 1
The present embodiment is used to illustrate polyethylene composition and its film provided by the invention.
(1) preparation of polyethylene composition：
The polyethylene composition that the present embodiment provides is made up of component A, component B and component C, and these three components are second
The LLDPE (LLDPE) of alkene/alhpa olefin copolymerization, wherein, component A and component B are prepared into using metallocene catalyst
To (metallocene catalyst system is the carried metallocene catalyst that is prepared by CN102453124A embodiments 1, under
Together), component C is prepared that (ziegler-natta catalyst systems are served as reasons using Ziegler-Natta catalyst
The ziegler-natta catalyst systems that CN101838351A embodiments 1 are prepared, similarly hereinafter).Comprise the following steps that：
By ethene, alhpa olefin, hydrogen and nitrogen, (ethene, 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, is 84-88 DEG C, presses in temperature afterwards
Power polymerize under conditions of being 1.8-2.0MPa, respectively obtains component A, component B and component C.Wherein, component A, component B and component C
The control of melt index realized by adjusting the addition of hydrogen, the control of density by adjust alhpa olefin species and plus
Enter amount and realize.Alhpa olefin used is 1- hexenes during preparing component A, and alhpa olefin used is 1- during preparing component B
Hexene, alhpa olefin used is 1- butylene during preparing component C.
After testing, the component A, component B and the component C that are prepared by the above method performance are as follows：
Component A melt index MIA=1.5g/10min, density pA=0.913g/cm3, molecular weight distributing index Mw/Mn=
3.4, molar content=7.5mol% of alhpa olefin comonomer；
Component B melt index MIB=2.1g/10min, density pB=0.913g/cm3, molecular weight distributing index Mw/Mn=
3.2, molar content=7.5mol% of alhpa olefin comonomer；
Component C melt index MIC=15g/10min, density pC=0.905g/cm3, molecular weight distributing index Mw/Mn=
4.6, molar content=10.1mol% of alhpa olefin comonomer.
Each component obtained above is weighed and mixed by proportioning, wherein component A mass fraction WAFor 80 weight
Part, component B mass fraction WBFor 10 parts by weight, component C mass fraction WCFor 20 parts by weight, WA/WC=4 (satisfaction 5.2 ×
lgMIA+11.6≥WA/WC≥0.9×lgMIA+ 2.1, also meet 2.9 × lgMIA+6.8≥WA/WC≥1.1×lgMIA+2.7)；
Then adding lubricant, (lubricant is the PEG lubricants of Switzerland Clariant Corporation production, molecular weight 10000, and with above-mentioned
Component A, component B and component C quality sum are 100 parts by weight meters, and the addition of lubricant is 0.1 parts by weight), afterwards will be mixed
Compound is added in high speed agitator and is well mixed, then the material mixed is added to the twin-screw extrusion of W＆P companies manufacture
In the feeder of machine, material via feeder enter twin-screw in, in process the temperature of screw rod be maintained at 160-210 DEG C it
Between, through screw rod melting mixing uniformly, extrude, be granulated and dry, obtain polyethylene composition pellet, after testing its melt index MI
=2.4g/10min.
(2) preparation of polyethylene film：
Polyethylene composition pellet made from above-mentioned steps (1) is dried, is added to Labtech companies of Sweden afterwards
Model LCR400 multilayer extrusion casting machine sandwich layer extruder and upper and lower top layer extruder in carry out melting extrusion simultaneously
Slab is cast, wherein, also need to add inorganic antitack agent (silica, similarly hereinafter) in the upper and lower top layer extruder, and go up,
The weight ratio of the antitack agent added in layer extruder and polyethylene composition pellet 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, it is made up of upper epidermis, sandwich layer and layer.
Above-mentioned polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, drawn using first longitudinal direction (MD)
Laterally the two-way step drawing technological forming of (TD) stretching, each step process condition are as follows after stretching：MD preheating temperatures are 100 DEG C, MD
Draft temperature is 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, TD stretchings times
Rate is 5 times, and film TD rates of extension are 60%/s；Film setting temperature is 120 DEG C, obtains the film that average thickness is 25 μm,
It is made up 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 used to illustrate polyethylene composition and its film provided by the invention.
(1) preparation of polyethylene composition：
The polyethylene composition that the present embodiment provides is made up of component A, component B and component C, and these three components are second
The LLDPE (LLDPE) of alkene/alhpa olefin copolymerization, wherein, component A and component B are prepared into using metallocene catalyst
Arrive, component C is prepared using Ziegler-Natta catalyst.Comprise the following steps that：
Ethene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, then add catalyst system, it
It polymerize afterwards under conditions of temperature is 84-88 DEG C, pressure is 1.8-2.0MPa, respectively obtains component A, component B and component C.Its
In, the control of component A, component B and component C melt index realizes that the control of density is led to by adjusting the addition of hydrogen
Overregulate alhpa olefin species and addition and realize.Alhpa olefin used is 1- butylene during preparing component A, prepares component B
During alhpa olefin used be 1- butylene, alhpa olefin used is 1- hexenes during preparing component C.
After testing, the component A, component B and the component C that are prepared by the above method performance are as follows：
Component A melt index MIA=0.01g/10min, density pA=0.930g/cm3, molecular weight distributing index Mw/Mn
=3.0, molar content=1.6mol% of alhpa olefin comonomer；
Component B melt index MIB=9.0g/10min, density pB=0.930g/cm3, molecular weight distributing index Mw/Mn=
2.8, molar content=1.9mol% of alhpa olefin comonomer；
Component C melt index MIC=40g/10min, density pC=0.922g/cm3, molecular weight distributing index Mw/Mn=
4.4, molar content=4.0mol% of alhpa olefin comonomer.
Each component obtained above is weighed and mixed by proportioning, wherein component A mass fraction WAFor 55 weight
Part, component B mass fraction WBFor 5 parts by weight, component C mass fraction WCFor 55 parts by weight, WA/WC=1 (satisfaction 5.2 ×
lgMIA+11.6≥WA/WC≥0.9×lgMIA+ 2.1, also meet 2.9 × lgMIA+6.8≥WA/WC≥1.1×lgMIA+2.7)；
Then adding lubricant, (lubricant is the PEG lubricants of Switzerland Clariant Corporation production, molecular weight 6000, and with above-mentioned
Component A, component B and component C quality sum are 100 parts by weight meters, and the addition of lubricant is 3 parts by weight), afterwards will mixing
Thing is added in high speed agitator and is well mixed, then the material mixed is added to the double screw extruder of W＆P companies manufacture
Feeder in, material via feeder enter twin-screw in, in process the temperature of screw rod be maintained at 180-240 DEG C it
Between, through screw rod melting mixing uniformly, extrude, be granulated and dry, obtain polyethylene composition pellet, after testing its melt index MI
=0.7g/10min.
(2) preparation of polyethylene film：
Polyethylene composition pellet made from above-mentioned steps (1) is dried, is added to Labtech companies of Sweden afterwards
Model LCR400 multilayer extrusion casting machine sandwich layer extruder and upper and lower top layer extruder in carry out melting extrusion simultaneously
Slab is cast, wherein, also need to add inorganic antitack agent in the upper and lower top layer extruder, and in upper and lower top layer extruder add
The weight ratio of the antitack agent entered and polyethylene composition pellet is 0.02:1, during slab is cast, chilling roller will be cast
Temperature is set as 85 DEG C, and polyethylene thickness slab is made, and it is made up of upper epidermis, sandwich layer and layer.
Above-mentioned polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, drawn using first longitudinal direction (MD)
Laterally the two-way step drawing technological forming of (TD) stretching, each step process condition are as follows after stretching：MD preheating temperatures are 130 DEG C, MD
Draft temperature is 126 DEG C, and MD stretching ratios are 4 times；TD preheating temperatures are 130 DEG C, and TD draft temperatures are 128 DEG C, TD stretchings times
Rate is 6 times, and film TD rates of extension are 100%/s；Film setting temperature is 130 DEG C, obtains the film that average thickness is 25 μm,
It is made up 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 used to illustrate polyethylene composition and its film provided by the invention.
(1) preparation of polyethylene composition：
The polyethylene composition that the present embodiment provides polymerize to obtain using the multiple reactor shunting means shown in Fig. 1, wherein
The polymerization of first reactor 1 prepares component A, the polymerization of second reactor 2 prepares component B, the polymerization of the 3rd reactor 3 prepares component C, this
Three kinds of components are the LLDPE (LLDPE) of ethylene/alpha-olefin copolymerization, wherein, component A and component B are using cyclopentadienyl gold
Metal catalyst is prepared, and component C is prepared using Ziegler-Natta catalyst.Comprise the following steps that：
Alhpa olefin, n-hexane and hydrogen are added in polymer reactor, and polymer reactor is heated to default polymerization
Temperature, vinyl monomer and catalyst system are added in polymer reactor simultaneously afterwards, wherein component A and component B are in temperature
It polymerize under conditions of being 2.5MPa for 140 DEG C, pressure and obtains；Component C is under conditions of temperature is 240 DEG C, pressure is 14.8MPa
Polymerization obtains.Wherein, the control of component A, component B and component C melt index is realized by adjusting the addition of hydrogen, close
The control of degree is realized by adjusting species and the addition of alhpa olefin.Alhpa olefin used is 1- octenes during preparing component A,
Alhpa olefin used is 1- butylene during preparing component B, and alhpa olefin used is 1- butylene during preparing component C.
By the yield in unit time W of component A in first reactor 1 in preparation processA, component B in second reactor 2
Yield in unit time WBWith the yield in unit time W of component C in the 3rd reactor 3CWeight ratio maintain WA：WB：WC=75：2：
35, wherein WA/WC=2.1 (meet 5.2 × lgMIA+11.6≥WA/WC≥0.9×lgMIA+ 2.1, also meet 2.9 × lgMIA+
6.8≥WA/WC ≥1.1×lgMIA+2.7)。
After testing, the component A, component B and the component C that are prepared by the above method performance are as follows：
Component A melt index MIA=0.1g/10min, density pA=0.920g/cm3, molecular weight distributing index Mw/Mn=
3.1, molar content=2.1mol% of alhpa olefin comonomer；
Component B melt index MIB=5.0g/10min, density pB=0.920g/cm3, molecular weight distributing index Mw/Mn=
3.5, molar content=5.1mol% of alhpa olefin comonomer；
Component C melt index MIC=25g/10min, density pC=0.920g/cm3, molecular weight distributing index Mw/Mn=
4.2, molar content=5.7mol% of alhpa olefin comonomer.
Each component obtained above is respectively delivered to different solid-liquids (gas) separator 4 in yield in unit time ratio
It is middle be separated and and then be transported in the homogenization silo 5 with stirring, then adding lubricant by proportioning mix
Change.Wherein, lubricant is the Tissuemat E of Honeywell Inc. of U.S. production, with said components A, component B and component C quality
Sum is 100 parts by weight meters, and the addition of lubricant is 1 parts by weight.The mixture that homogenized feed bin 5 is homogenized is added to afterwards
In the feeder of the double screw extruder of W＆P companies manufacture, material enters in twin-screw via feeder, screw rod in process
Temperature be maintained between 170-230 DEG C, through screw rod melting mixing uniformly, extrude, be granulated and dry, obtain polyethylene composition
Pellet, after testing its melt index MI=0.6g/10min.
(2) preparation of polyethylene film：
Polyethylene composition pellet made from above-mentioned steps (1) is dried, is added to Labtech companies of Sweden afterwards
Model LCR400 multilayer extrusion casting machine in carry out melting extrusion and being cast slab, during slab is cast, will flow
Prolong chilling roll temperature and be set as 35 DEG C, polyethylene thickness slab is made, the slab is single layer structure.
Above-mentioned polyethylene thickness slab is put into the stretching clamp of film biaxial tension equipment, drawn using first longitudinal direction (MD)
Laterally the two-way step drawing technological forming of (TD) stretching, each step process condition are as follows after stretching：MD preheating temperatures are 116 DEG C, MD
Draft temperature is 118 DEG C, and MD stretching ratios are 4 times；TD preheating temperatures are 120 DEG C, and TD draft temperatures are 120 DEG C, TD stretchings times
Rate is 5 times, and film TD rates of extension are 100%/s；Film setting temperature is 122 DEG C, obtains the individual layer that average thickness is 25 μm
Film.
Embodiment 4
The present embodiment is used to illustrate polyethylene composition and its film provided by the invention.
Method according to embodiment 1 prepares polyethylene composition and polyethylene film, unlike, the polyethylene group
Component B in compound is substituted with the component C of identical weight part, i.e. only contain component A and component C in the polyethylene composition,
The film that average thickness is 25 μm is obtained, wherein, the thickness of upper epidermis and layer is 0.5 μm.
Embodiment 5
The present embodiment is used to illustrate polyethylene composition and its film provided by the invention.
Method according to embodiment 1 prepares polyethylene composition and polyethylene film, unlike, component A preparation
During each material dosage it is different so that component A, component B and component C density pA、ρBAnd ρCBetween relation be unsatisfactory for-
0.04≤ρA-ρB≤ 0.02 and -0.04≤ρA-ρC≤ 0.02, the film that average thickness is 25 μm is obtained, wherein, upper epidermis is with
The thickness on top layer is 0.5 μm.In the preparation process of the component A, alhpa olefin is 1- hexenes, and obtained component A performance is such as
Under：Component A melt index MIA=1.5g/10min, density pA=0.928g/cm3, molecular weight distributing index Mw/Mn=3.0, α
Molar content=1.9mol% of olefin comonomer.
Comparative example 1
This comparative example is used for the polyethylene raw material and its film for illustrating reference.
(1) polyethylene raw material：
Polyethylene raw material used in this comparative example is the film-grade linear low density polyethylene of DOW chemical companies of U.S. 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 polyethylene film：
Method according to embodiment 3 prepares polyethylene film, unlike, by the polyethylene composition pellet with identical
The polyethylene raw material of this comparative example step (1) of parts by weight substitutes, through repeatedly attempting the situation for stretching rupture of membranes, no farad occur
It is stretched into film.In addition, after the TD rates of extension in polyethylene film preparation process are down into 50%/s, still occur through repeatedly trial
The situation of rupture of membranes is stretched, film forming can not be stretched.
Comparative example 2
This comparative example is used for the polyethylene raw material and its film for illustrating reference.
(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 extrusion and blow molding of German DR.COLLIN companies
Obtain, specific method is as follows：The polyethylene raw material that above-mentioned steps (1) are chosen is added to the material of upper blowing method film blowing device extruder
In bucket, after the abundant fusion plastification of the extruded machine of raw material, melt membrane tube is made by the annular die extrusion of head, afterwards compressed sky
Air-blowing is swollen (blow-up ratio is 2.5 times), and polyethylene film is made after vane cools down, and wherein film is that average thickness is 25 μm
Single layer structure.
Comparative example 3
This comparative example is used for the polyethylene composition and its film for illustrating reference.
(1) preparation of polyethylene composition：
The polyethylene composition that this comparative example provides is made up of component 1 and component 2, and both components are ethylene/alpha-olefin
The LLDPE (LLDPE) of copolymerization, wherein, component 1 is prepared using metallocene catalyst, and component 2 is using neat
Ge Le-Natta catalyst is prepared.Comprise the following steps that：
Ethene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, then add catalyst system, it
It polymerize afterwards under conditions of temperature is 84-88 DEG C, pressure is 1.8-2.0MPa, respectively obtains component 1 and component 2.Wherein, component
1 and the control of melt index of component 2 realize that the control of density is by adjusting alhpa olefin by adjusting the addition of hydrogen
Species and addition and realize.Alhpa olefin used is 1- hexenes during preparing component 2, prepares α used during component 2
Alkene is 1- butylene.
After testing, the component 1 and the performance of component 2 being prepared by the above method are 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=
5.5, molar content=10.8mol% of alhpa olefin comonomer.
Each component obtained above is weighed and mixed by proportioning, wherein the mass fraction W of component 11For 80 weight
Part, the mass fraction W of component 22For 20 parts by weight, W1/W2=4；Then adding lubricant, (lubricant is Switzerland's Clariant
The PEG lubricants of company's production, molecular weight 10000, and counted by 100 parts by weight of the quality sum of said components 1 and component 2,
The addition of lubricant is 0.1 parts by weight), add mixture in high speed agitator and be well mixed afterwards, then will mix
Material be added to W＆P companies manufacture double screw extruder feeder in, material via feeder enter twin-screw in, add
The temperature of screw rod is maintained between 160-210 DEG C during work, through screw rod melting mixing uniformly, extrude, be granulated and dry, obtain
Polyethylene composition pellet, after testing its melt index MI=6.2g/10min.
(2) preparation of polyethylene film：
The preparation of polyethylene film is carried out according to the method for embodiment 1, the results showed that, by repeatedly attempting, biaxial tension
The maximum tension multiplying power of film is only 2 times of (TD) × 2 times (MD), and film TD highest stretching ratios are only 10%/s, i.e. stretching times
Rate and rate of extension are too low, and stretching film forming is poor, does not possess practicality.
Comparative example 4
This comparative example is used for the polyethylene composition and its film for illustrating reference.
(1) preparation of polyethylene composition：
The polyethylene composition that this comparative example provides is made up of component 1 and component 2, and both components are ethylene/alpha-olefin
The LLDPE (LLDPE) of copolymerization, wherein, component 1 is prepared using metallocene catalyst, and component 2 is using neat
Ge Le-Natta catalyst is prepared.Comprise the following steps that：
Ethene, alhpa olefin, hydrogen and nitrogen are added in gas fluidized bed reactor, then add catalyst system, it
It polymerize afterwards under conditions of temperature is 84-88 DEG C, pressure is 1.8-2.0MPa, respectively obtains component 1 and component 2.Wherein, component
1 and the control of melt index of component 2 realize that the control of density is by adjusting alhpa olefin by adjusting the addition of hydrogen
Species and addition and realize.Alhpa olefin used is 1- butylene during preparing component 1, prepares α used during component 2
Alkene is 1- hexenes.
After testing, the component 1 and the performance of component 2 being prepared by the above method are 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=
4.5, molar content=4.9mol% of alhpa olefin comonomer.
Each component obtained above is weighed and mixed by proportioning, wherein the mass fraction W of component 11For 55 weight
Part, the mass fraction W of component 22For 55 parts by weight, W1/W2=1；Then adding lubricant, (lubricant is Switzerland's Clariant
The PEG lubricants of company's production, molecular weight 6000, and counted by 100 parts by weight of the quality sum of said components 1 and component 2, moisten
The addition of lubrication prescription is 3 parts by weight), add mixture in high speed agitator and be well mixed afterwards, then the thing that will be mixed
Material is added in the feeder of the double screw extruder of W＆P companies manufacture, and material enters in twin-screw via feeder, processed
The temperature of screw rod is maintained between 180-240 DEG C in journey, through screw rod melting mixing uniformly, extrude, be granulated and dry, obtain poly- second
Ene compositions pellet, after testing its melt index MI=0.22g/10min.
(2) preparation of polyethylene film：
The preparation of polyethylene film is carried out according to the method for embodiment 2, the results showed that, by repeatedly attempting, biaxial tension
The maximum tension multiplying power of film is only 2 times of (TD) × 2 times (MD), and film TD highest stretching ratios are only 10%/s, i.e. stretching times
Rate and rate of extension are too low, and stretching film forming is poor, does not possess practicality.
Comparative example 5
This comparative example is used for the polyethylene composition and its film for illustrating 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 prepares component 1, second reactor polymerization prepares component 2, and both components are the linear low close of ethylene/alpha-olefin copolymerization
Polyethylene (LLDPE) is spent, wherein, component 1 is prepared using metallocene catalyst, and component 2 uses Ziegler-Natta catalyst
It is prepared.Comprise the following steps that：
Alhpa olefin, n-hexane and hydrogen are proportionally added into polymer reactor, and polymer reactor is heated to preset
Polymerization temperature, vinyl monomer and catalyst system are added in polymer reactor simultaneously afterwards, wherein component 1 is in temperature
140 DEG C, pressure polymerize and obtains under conditions of being 2.5MPa；Component 2 is gathered under conditions of temperature is 240 DEG C, pressure is 14.8MPa
Conjunction obtains.Wherein, the control of the melt index of component 1 and component 2 is realized by adjusting the addition of hydrogen, the control of density
Realized by adjusting species and the addition of alhpa olefin.Alhpa olefin used is 1- octenes during preparing component 1, prepares component
Alhpa olefin used is 1- butylene during 2.
By the yield in unit time W of component in first reactor 1 in preparation process1With component in second reactor 2
Yield in unit time W2Weight ratio maintain W1：W2=20：80.
After testing, the component 1 and the performance of component 2 being prepared by the above method are 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=
4.2, molar content=5.7mol% of alhpa olefin comonomer.
Each component obtained above is respectively delivered in different solid-liquids (gas) separator in yield in unit time ratio
Be separated and and then be transported to stirring homogenization silo in, then by proportioning add lubricant carry out mixing homogenizing.
Wherein, lubricant is the Tissuemat E of Honeywell Inc. of U.S. production, using the quality sum of said components 1 and component 2 as 100
Parts by weight meter, the addition of lubricant is 1 parts by weight.The mixture that homogenized feed bin is homogenized is added to W＆P company systems afterwards
In the feeder for the double screw extruder made, material enters in twin-screw via feeder, and the temperature of screw rod is protected in process
Hold between 170-230 DEG C, through screw rod melting mixing uniformly, extrude, be granulated and dry, obtain polyethylene composition pellet, pass through
Detect its melt index MI=8.2g/10min.
(2) preparation of polyethylene film：
The preparation of polyethylene film is carried out according to the method for embodiment 3, the results showed that, by repeatedly attempting, biaxial tension
The maximum tension multiplying power of film is only 2 times of (TD) × 2 times (MD), and film TD highest stretching ratios are only 10%/s, i.e. stretching times
Rate and rate of extension are too low, and stretching film forming is poor, does not possess practicality.
Test case
Test case is used for the test for illustrating polyethylene film and reference polyethylene film performance.
(1) Film Haze：It is measured according to method specified in GB/T 2410-2008, wherein, film sample thickness
For 25 ± 5 μm, acquired results are as shown in table 1；
(2) film tensile strength, modulus 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 1；
(3) membrane puncture intensity：It is measured according to method specified in GB/T10004-2008, wherein, film sample
Thickness is 25 ± 5 μm, and acquired results are as shown in table 1.
Table 1
It can draw, be prepared in embodiment 1-3 using polyethylene composition provided by the invention two-way from the result in table 1
PE films are stretched, with film forming multiplying power is big, rate of extension is fast, mechanical strength is high, optical property compared with the film of prior art
The advantages of good, the performance of prepared film can meet longitudinally (MD) tensile strength >=55MPa, transverse direction (TD) tensile strength >=
65MPa, puncture strength >=2.5N, tension fracture elongation rate≤350%.It can be seen that from the contrast of embodiment 1 and embodiment 5
When the density p of component A, component B and component C in the polyethylene compositionA、ρBAnd ρCBetween relation meet -0.04≤ρA-ρB
≤ 0.02, and -0.04≤ρA-ρCWhen≤0.02, the polyethylene composition is on the basis of with preferable film forming, by the poly- second
The film that ene compositions are prepared also has higher tensile strength and punctured resistance and relatively low mist degree.From embodiment
1 and comparative example 1-2 contrast can not stretch film forming as can be seen that using the commercial polyethylene raw material of prior art preparation, thus
Be not suitable for being processed using Flat film strength, and compared with the inflation film of prior art, processed using Flat film strength
The mechanical strength and puncture strength of the film of shaping are higher and Film Haze is relatively low.In addition, from embodiment 1-3 and comparative example 3-5
Contrast as can be seen that using polyethylene composition provided by the invention as the raw material for preparing film, there is more preferable film forming
Performance, more prospects for commercial application.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
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 equally be considered as content disclosed in this invention.
Claims (31)
1. a kind of polyethylene composition, it is characterised in that the polyethylene composition contains component A, component C and component B；Institute
The LLDPE that component A is ethylene/alpha-olefin copolymerization is stated, it is molten in the case where temperature is 190 DEG C, load is 2.16kg
Melt index M IAFor 0.01-2g/10min, density pAFor 0.915-0.926g/cm3；The component B is ethylene/alpha-olefin copolymerization
LLDPE, its melt index MI in the case where temperature is 190 DEG C, load is 2.16kgBFor 2.1-9.9g/10min,
Density pBFor 0.913-0.928g/cm3；The component C is the LLDPE of ethylene/alpha-olefin copolymerization, and it is in temperature
Melt index MI under being 2.16kg for 190 DEG C, loadCFor 10-80g/10min, density pCFor 0.905-0.928g/cm3；
Wherein, the molecular weight distributing index of the component A and component B meet Mw/Mn≤ 4.5, and the molecular weight of the component C point
Cloth index meets Mw/Mn≤8.0。
2. polyethylene composition according to claim 1, wherein, the component A temperature be 190 DEG C, load be
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 3-8g/10min, melt index MIs of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor
10-60g/10min。
3. polyethylene composition according to claim 1, wherein, the component A temperature be 190 DEG C, load be
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 MIs of the component C in the case where temperature is 190 DEG C, load is 2.16kgCFor
15-40g/10min。
4. polyethylene composition according to claim 1, wherein, the density p of the component BBFor 0.913-0.924g/
cm3, the density p of the component CCFor 0.910-0.926g/cm3。
5. polyethylene composition according to claim 4, wherein, component A, component B and group in the polyethylene composition
Part C density pA、ρBAnd ρCBetween relation meet -0.04≤ρA-ρB≤ 0.02, and -0.04≤ρA-ρC≤0.02。
6. according to the polyethylene composition described in any one in claim 1-5, wherein, in the polyethylene composition,
The mass fraction W of the component AAFor 25-90 parts by weight, the mass fraction W of the component BBFor 0.1-10 parts by weight, described group
Divide C mass fraction WCFor 10-75 parts by weight.
7. polyethylene composition according to claim 6, wherein, in the polyethylene composition, the matter of the component A
Measure number WAFor 30-80 parts by weight, the mass fraction W of the component BBFor 0.5-8 parts by weight, the mass fraction W of the component CC
For 20-70 parts by weight.
8. polyethylene composition according to claim 7, wherein, the mass fraction W of the component AAWith component C quality
Number WCWith component A melt index MIARelation meet 5.2 × lgMIA+11.6≥WA/WC≥0.9×lgMIA+2.1。
9. polyethylene composition according to claim 8, wherein, the mass fraction W of the component AAWith component C quality
Number WCWith component A melt index MIARelation meet 2.9 × lgMIA+6.8≥WA/WC≥1.1×lgMIA+2.7。
10. polyethylene composition according to claim 9, wherein, on the basis of the gross weight of the polyethylene composition,
The mass percentage content M of the component BB≤ 35 weight %.
11. polyethylene composition according to claim 10, wherein, using the gross weight of the polyethylene composition as base
Standard, the mass percentage content M of the component BB≤ 25 weight %.
12. according to the polyethylene composition described in any one in claim 1-5,9 and 11, wherein, the polyethylene composition
Melt index of the thing in the case where temperature is 190 DEG C, load is 2.16kg is 0.1-20g/10min.
13. polyethylene composition according to claim 12, wherein, the polyethylene composition is 190 DEG C, carried in temperature
Melt index under lotus is 2.16kg is 0.5-10g/10min.
14. according to the polyethylene composition described in any one in claim 1-5, wherein, point of the component A and component B
Son amount profile exponent meets 2.0≤Mw/Mn≤ 4.2, and the molecular weight distributing index of the component C meets 3.5≤Mw/Mn≤
6.0。
15. polyethylene composition according to claim 14, wherein, the component A and component B use metallocene catalyst
Polymerization obtains, and the component C polymerize to obtain using Ziegler-Natta catalyst.
16. according to the polyethylene composition described in any one in claim 1-5, wherein, the component A, component B and component
The molar content of alhpa olefin comonomer is each independently 0.2-15mol% in C.
17. polyethylene composition according to claim 16, wherein, alhpa olefin is total in the component A, component B and component C
The molar content of polycondensation monomer is each independently 1.5-10mol%.
18. polyethylene composition according to claim 17, wherein, the alhpa olefin in the component A, component B and component C
It is each independently C3-C20At least one of alkene.
19. polyethylene composition according to claim 18, 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, 1- amylenes, 3- Methyl-1-pentenes, 4- methyl-1-pentenes
Alkene, 3,3- dimethyl -1- amylenes, 3,4- dimethyl -1- amylenes, 4,4- dimethyl -1- amylenes, 1- hexenes, 4- methyl isophthalic acids-oneself
Alkene, 5- methyl isophthalic acids-hexene, 1- heptene, 2- heptene, 1- octenes, 1- decene, 1- dodecylenes, tetradecene, the carbon of 1- 16
At least one of alkene, 1- vaccenic acids and 1- eicosylenes.
20. polyethylene composition according to claim 19, wherein, the alhpa olefin in the component A, component B and component C
It is each independently at least one of 1- butylene, 1- hexenes and 1- octenes.
21. according to the polyethylene composition described in any one in claim 1-5, wherein, the polyethylene composition also contains
There is lubricant.
22. polyethylene composition according to claim 21, wherein, with the component A, component B and component C gross weight
For 100 parts by weight benchmark, the content of the lubricant is 0.05-5 parts by weight.
23. polyethylene composition according to claim 22, wherein, the lubricant be selected from polyethylene glycol series lubricant agent,
Fluoropolymer series lubricant agent, organic silicon lubricant, fatty alcohol type emollients, fatty acid lubricant, fatty acid ester profit
Lubrication prescription, stearic amide series lubricant agent, fatty acid metal soaps lubricant, alkane and oxidation of alkanes series lubricant agent and the micro-nano grain of rice
At least one of subclass lubricant.
24. a kind of film, the film comprises at least one layer as the polyethylene composition described in any one in claim 1-23
The polyethylene layer that thing is formed.
25. film according to claim 24, wherein, the film has the composite junction of upper epidermis, sandwich layer and layer
Structure, and at least described sandwich layer is the polyethylene layer formed by the polyethylene composition.
26. film according to claim 25, wherein, when the film has the compound of upper epidermis, sandwich layer and layer
During structure, the thickness of the upper epidermis and layer is each independently the 1-25% of the film thickness.
27. film according to claim 24, wherein, the film is that two-way drawing is prepared by flat film biaxial tension method
Stretch film.
28. film according to claim 27, wherein, the biaxially oriented film is being prepared using flat film biaxial tension method
During, longitudinal stretching multiplying power >=4 times, cross directional stretch multiplying power >=5 times；It is described two-way being prepared using flat film biaxial tension method
During oriented film, cross directional stretch speed >=50%/s.
29. according to the film described in any one in claim 24-28, wherein, the thickness of the film is 10-200 μm.
30. film according to claim 29, wherein, the thickness of the film is 10-100 μm.
31. film according to claim 28, wherein, longitudinal tensile strength >=55MPa of the biaxially oriented film is horizontal
To tensile strength >=65MPa；Puncture strength >=2.5N of the biaxially oriented film；The tension failure of the biaxially oriented film
Elongation≤350%.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
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| CN201410584803.6A CN105623060B (en) | 2014-10-27 | 2014-10-27 | A kind of polyethylene composition and its film |
| BR102015027108-5A BR102015027108B1 (en) | 2014-10-27 | 2015-10-26 | polyethylene composition and film |
| EP15191626.9A EP3015502B1 (en) | 2014-10-27 | 2015-10-27 | A polyethylene composition and a film formed therefrom |
| ES15191626.9T ES2619196T3 (en) | 2014-10-27 | 2015-10-27 | Composition of polyethylene and film formed from it |
| JP2015211332A JP6615572B2 (en) | 2014-10-27 | 2015-10-27 | Polyethylene compositions and films formed therefrom |
| KR1020150149448A KR102400379B1 (en) | 2014-10-27 | 2015-10-27 | A polyethylen composition and a film formed therefrom |
| US14/924,302 US9988505B2 (en) | 2014-10-27 | 2015-10-27 | Polyethylene compositions and films formed therefrom |
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| CN201410584803.6A CN105623060B (en) | 2014-10-27 | 2014-10-27 | A kind of polyethylene composition and its film |
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| CN111100366B (en) * | 2018-10-26 | 2022-08-19 | 中国石油化工股份有限公司 | Polyethylene composition, preparation method thereof and film packaging product |
| CN111662498B (en) * | 2019-03-08 | 2023-01-24 | 中国石油化工股份有限公司 | Polyolefin composition and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1543483A (en) * | 2001-08-17 | 2004-11-03 | Bimodal polyethylene pipe composition and article made therefrom | |
| CN101291959A (en) * | 2005-10-18 | 2008-10-22 | 博里利斯技术公司 | Polyethylene blend component and blends containing the same |
| CN103254342A (en) * | 2012-02-17 | 2013-08-21 | 中国石油化工股份有限公司 | Preparation method of doublet linear low density polyethylene composition used for producing films |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1543483A (en) * | 2001-08-17 | 2004-11-03 | Bimodal polyethylene pipe composition and article made therefrom | |
| CN101291959A (en) * | 2005-10-18 | 2008-10-22 | 博里利斯技术公司 | Polyethylene blend component and blends containing the same |
| CN103254342A (en) * | 2012-02-17 | 2013-08-21 | 中国石油化工股份有限公司 | Preparation method of doublet linear low density polyethylene composition used for producing films |
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Application publication date: 20160601 Assignee: TIANJIN BRANCH OF CHINA PETROLEUM & CHEMCIAL Corp. Assignor: BEIJING RESEARCH INSTITUTE OF CHEMICAL INDUSTRY, CHINA PETROLEUM & CHEMICAL Corp. Contract record no.: X2022980018274 Denomination of invention: Polyethylene composition and film thereof Granted publication date: 20180213 License type: Common License Record date: 20221013 |