CN107226878A - A kind of preparation method and applications of polyethylene film - Google Patents
A kind of preparation method and applications of polyethylene film Download PDFInfo
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- CN107226878A CN107226878A CN201610168290.XA CN201610168290A CN107226878A CN 107226878 A CN107226878 A CN 107226878A CN 201610168290 A CN201610168290 A CN 201610168290A CN 107226878 A CN107226878 A CN 107226878A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
- B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/03—3 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
- B32B2250/242—All polymers belonging to those covered by group B32B27/32
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/04—Polyethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of preparation method of polyethylene film, comprise the following steps:1) it is that the major catalyst in catalyst system is transported in reactor by carrier logistics with mixing liquid I, the mixing liquid I includes alkane, alkene and co-catalyst;Stream I II is obtained after supplement olefin feedstocks are added into the stream I I flowed out from reactor, stream I II is divided into stream I IIa and IIIb, stream I IIa and IIIb are back to sidepiece and the bottom of reactor respectively;In the reactor, it is aggregated to obtain ethene polymers and discharged from reactor;Wherein, the alkene includes the mole specific concentration ratio at least 1 of alhpa olefin and ethene in alhpa olefin and ethene, the mixing liquid I;2) by step 1) made from ethene polymers by blow molding process, obtain polyethylene film.The method provided according to the present invention improves the tack of gained film, reduces mist degree.
Description
Technical field
The present invention relates to a kind of preparation method of polyethylene film, specifically, the present invention relates to a kind of polyethylene film
Preparation method and its apply.
Background technology
At present, polypropylene double-way stretched film (BOPP) is the major product of high-grade packaging field, because it has quality
Gently, the advantages of transparent, nontoxic, moistureproof and high mechanical strength.And novel polyethylene biaxially oriented film (BOPE) shows than BOPP
More excellent performance is gone out, its quality lighter, transparency, glossiness and printing effect is more preferable.BOPE is mainly 3-5 tunic knots
Structure, most commonly 3 layers, be respectively outside basic unit, sandwich layer basic unit and functional layer.The main component of sandwich layer is polyethylene (PE), PE
Addition account for 99% or so of sandwich layer weight.Tensile strength of traditional polyethylene film in longitudinal direction is much larger than in horizontal drawing
Intensity is stretched, this can cause the transverse breakage elongation of film when in use not enough, so as to influence the performance of polyethylene film.
The main linear low density polyethylene (LDPE) (LLDPE) of the PE that is used in traditional polyethylene film, low density polyethylene (LDPE) (LDPE) and
Metallocene linear-low density polyethylene (mLLDPE).
Although there is document to disclose a kind of method for adjusting addO-on therapy raising polyethylene film tack at present.By adding
Plus the collocation of the adjacent octanoic acid of two phthalic acid two of plasticizer and dioctyl adipate, and inorganic filler calcium carbonate and aluminum oxide match somebody with somebody
Close so that the extensibility and obdurability of preservative film are improved, and then tack is strengthened.But the certain applications field of film, such as
Food fresh keeping etc., its tack relies primarily on the realization of plastics self-characteristic.And additive the problem of be related to spilling unavoidably, Jin Erke
The application of film can be influenceed.
For this reason, the present inventor is studied, it is therefore an objective to solve association area prior art institute sudden and violent
The problem of exposing, expect to provide and a kind of the high-performance ethene that mist degree is low, tack is high is prepared using fluidized-bed reactor gather
The method of composition powder.
The content of the invention
In view of above the deficiencies in the prior art, an object of the present invention is that providing one kind prepares polyethylene film, especially
It is the method for BOPE films, such as prepares polyethylene film using fluidized-bed reactor.
Another object of the present invention is to provide a kind of polyethylene film prepared according to methods described in packing timber
Application in the film article such as material or Commercial goods labelses.
According to an aspect of the invention, there is provided a kind of preparation method of polyethylene film, including:
1) it is that the major catalyst in catalyst system is transported in reactor by carrier logistics with mixing liquid I, it is described mixed
Close liquid I and include alkane, alkene and co-catalyst;Supplement olefin feedstocks are added into the stream I I flowed out from reactor, are obtained
To stream I II, stream I II is divided into stream I IIa and IIIb, stream I IIa and IIIb be back to respectively reactor sidepiece and
Bottom;In the reactor, it is aggregated to obtain ethene polymers and discharged from reactor;Wherein, the alkene includes alpha-olefin
With ethene, the mol ratio of alpha-olefin and ethene is at least 1 in the mixing liquid I;
2) by step 1) made from ethene polymers by blow molding process, obtain polyethylene film.
According to the method that provides of the present invention, the film of high tack, low haze and high transmission rate can be made, and film
Puncture resistance is good, and tearing toughness, tensile strength and tangent modulus are high.The film of method in the present invention, combination property is good
It is good, with broad application prospect.
In the method for the present invention, Matter Transfer is carried out in whole reaction system, so that recycling raw materials.Wherein, from
The stream I I of reactor outflow mass flow is larger, is big flow Matter Transfer, after a small amount of charging of supplement, obtains logistics
III.In the method for the invention, mixing liquid I and stream I IIa and IIIb are added in reactor, wherein the alkane contained
Hydrocarbon, the latent heat of vaporization of alkane is high, and the shifting heat of alkane is big so that the different conversion zone of temperature is presented in reactor;And it is mixed
Closing has high alpha-olefin content in liquid I;Therefore, the different temperatures bar of olefinic monomer different zones in fluidized-bed reactor
High side chain, the olefin polymer of the HMW of low-density and low side chain, highdensity low molecule can be respectively obtained under part
The olefin polymer of amount, it is hereby achieved that the olefin polymer of height molecular weight constantly mixes the product of fluidisation, and is improved
The molecule segment or the content of strand of highly -branched degree, and because alkane can be with removing in larger raising fluidized-bed reactor
Heat energy power, therefore the method for the present invention can prepare high and low molecular weight and the microcosmic well mixed alkene of the high and low degree of branching
Polymeric articles, improve the light transmittance, mist degree and tack of ethylene copolymer, and the space-time yield of production is significantly carried
It is high.Then, using resulting ethene polymers by blow molding process, obtain functional such as high tack, low haze and height
Light transmittance, and puncture resistance, tearing toughness, the polyethylene film of tensile strength and tangent modulus.
In the method for the invention, the olefinic monomer in stream I II and mixing liquid I is as raw material, in fluidized-bed reaction
It is polymerize respectively in the different reaction zone of multiple temperature in device.Different polymerization temperature and different olefin monomer concentrations can be with
Obtain structure and performance different olefin polymer.According to the present invention, made of a kind of mixing solution comprising alkane and alkene
Carrier can further form multiple cryogenic reaction zones by catalyst transport to reactor in reactor, further improve
The content of the strand of highly -branched degree.Tensile strength, mist degree and the tack of the polyethylene according to said method made are improved;Enter
And, improve the combination property of obtained film article, such as puncture resistance, tangent modulus, tearing toughness, tack and printing opacity
Rate is improved, and reduces mist degree.
The method provided according to the present invention, carrier is done by catalyst transport with a kind of mixing solution comprising alkane and alkene
Into reactor, and in mixing liquid the molar content of alpha-olefin is not less than ethene, in the alpha-olefin at initial stage of catalyst action
Content is high so that the degree of branching rise of polyethylene, density reduction (LDPE low density polyethylene (LDPE)s).The polymerization obtained according to the present invention
Thing, in the case of close molecular weight so that the mist degree and tack of polymer are improved.
According to a preferred embodiment of the present invention, the mixing liquid I be able to will can be sponsored as carrier logistics
Agent powder is delivered in reaction system.Wherein, preferably first major catalyst is transported to and polymerisation with a rotating machinery
In the pipeline or pipe fitting of device connection, then major catalyst powder is delivered in reaction system with mixing liquid I again.According to this hair
A bright specific embodiment, the rotating machinery is selected from pump, compressor, blower fan and reductor.
According to a preferred embodiment of the present invention, the catalyst system includes Ziegler-Natta catalyst, cyclopentadienyl gold
Metal catalyst, transition-metal catalyst, inorganic chrome catalysts and organic chrome catalysts.The catalyst system includes co-catalyst
And major catalyst.In a specific example, the amount of major catalyst and co-catalyst is conventional amount used in the art, such as main
The mol ratio of catalyst and co-catalyst is with the active metal metal in the active metallic element and co-catalyst in major catalyst
The mol ratio of element is 1:1-6:1.It is three second that co-catalyst is included in a specific embodiment, in the mixing liquid I
Base aluminium.In another specific example, amount of the co-catalyst in mixing liquid is at least 150ppm (weight content).
According to a preferred embodiment of the present invention, the mol ratio of alpha-olefin and ethene is 1- in the mixing liquid I
5, such as 1.3-5.In situations where it is preferred, the mol ratio of alpha-olefin and ethene is 1.5-5 in the mixing liquid I.Now, α-alkene
The content of hydrocarbon is higher so that the degree of branching rise of polyethylene, density reduction, meanwhile, in the case of identical molecular weight so that poly-
The mist degree and tack of ethene (or ethene polymers, copolymerization of ethylene is referred both to herein) are further improved.
According to another preferred embodiment of the present invention, in the mixing liquid I, the content of alkane is 5-
80wt%.In situations where it is preferred, the content of the alkane in mixing liquid I is 10-65wt%.Control the alkane in mixing liquid
Content, is conducive to controlling reaction temperature, forms cryogenic reaction zone.
According to another preferred embodiment of the present invention, the mass flow of the mixing liquid I accounts for stream I I quality
The 0.05%-5% of flow, preferably in 0.1%-3%.
In a specific embodiment, the present invention in alkane comprising butane, iso-butane, pentane, isopentane, just oneself
At least one of alkane, hexamethylene and heptane.Alkane in the range of the restriction, its latent heat of vaporization is high, moves heat big;Be conducive to
The reaction zone of differential responses temperature is formed in reactor.
According to a preferred embodiment of the present invention, the reaction pressure in the reactor is 0.5-10MPa, reaction temperature
Spend for 40-150 DEG C.In a specific example, the reaction pressure in reactor is 1.5-5MPa.It is specific real at another
Apply in example, the reaction temperature in the reactor is 60-100 DEG C.
According to the present invention, the alkane in the alkane in the alkane, such as mixing liquid I, such as stream I IIa or IIIb, its
The latent heat of vaporization is high, moves heat greatly, can be used as condensing agent.Therefore, there is the polymerization zone that alkane is inputted in reactor
Reaction temperature it is different from the reaction temperature of other polymerization zones.It is described anti-according to the specific embodiment of the present invention
It is fluidized-bed reactor to answer device.Logistics is whole including fluidized-bed reactor, pipeline, heat-exchange apparatus, separation equipment etc.
Matter Transfer is carried out in individual reaction system.
According in the specific preferred embodiment of the present invention, the reaction zone that temperature is different is included in the reactor.
There is the polymerization zone that condensing agent (alkane) is inputted in the reactor, polymerization temperature is relatively low, is cryogenic reaction zone, does not have
The polymerization zone of condensing agent input, polymerization temperature is of a relatively high, is high temperature reaction zone.According to one of present invention specific implementation
Example, the reaction temperature of the cryogenic reaction zone is controlled at 60-75 DEG C, preferably 65-75 DEG C;The reaction temperature control of high temperature reaction zone
At 75-100 DEG C, preferably 80-90 DEG C.
According to a preferred embodiment of the present invention, the apparent fluidizing gas velocity of the fluidized-bed reactor is 0.1-10m/
s.The method of the present invention strictly controls the purpose of the apparent fluidizing gas velocity of fluidized-bed reactor to be to ensure reactor fluidized state
It is good to avoid powder from largely being taken out of simultaneously.When apparent fluidizing gas velocity is 0.3-0.8m/s, method of the invention can enter one
Step ensures fluidized-bed reactor quiet run, while ensureing being stabilized for cryogenic reaction zone and high temperature reaction zone.Reason may
It is apparent fluidizing gas velocity higher than the starting fluidization rate speed of body series powder while less than the band of most powder particles
Go out speed.
According to a preferred embodiment of the present invention, in the stream I I flowed out from reactor, alkane is included, it is also possible to include
Unreacted olefinic monomer (may relate to ethene and alpha-olefin).Stream I I and stream I II, component therein is more or less the same, matter
Amount flow is also more or less the same.In a specific example, stream I I mass flow account for the 90% of stream I II mass flows with
On, preferably 95% with up to 100%.
As the progress of reaction and the discharging of polymer are, it is necessary to supplement olefin feedstocks.(it is related to supplement through supplementing olefin feedstocks
Ethylene feed and the charging of supplement alpha-olefin) after charging, in the obtained stream I II, the content of alkene is 1.0-
60.0mol%, such as preferred 5.0-55.0mol%.Wherein, in a specific example, in the stream I II, alpha-olefin
Molar concentration accounts for the molar concentration of ethene in 20%-60%.
According to a preferred embodiment of the present invention, conditioning agent and/or inert component are included in the stream I II.Adopt
With conditioning agent, the polyvinyl molecular weight of gained and molecular weight distribution can be polymerize according to the different adjustment of regulation agent content.
Wherein, the conditioning agent is preferably hydrogen.Using inert component, the partial heat produced by can removing in polymerization process, also
Logistics III composition can be adjusted.Wherein, the inert component is preferably nitrogen.Now, the stream I I flowed out from reactor
In, conditioning agent and/or inert component may be included.In an instantiation, in the stream I II, the conditioning agent contains
Amount control is 0.3-14.5mol%.In another instantiation, in the stream I II, the amount control of the inert component
For 25.0-75.0mol%.In an instantiation, in stream I II described in the logistics, the content control of alkane is 0.5-
50.0mol%, such as 1.0-35.0mol%.According to technique needs, the charging of supplement alkane, inert component can be also included in stream I II
At least one of charging and supplement conditioning agent charging, to better control over the composition in stream I II.
According to a preferred embodiment of the present invention, the stream I II is compressed with after gas-liquid separation, is divided into logistics
IIIa and IIIb.Wherein, stream I IIa flows into reactor by the sidepiece of reactor.And the bottom that stream I IIb passes through reactor
Flow into reactor.According to the specific embodiment of the present invention, the alkane total amount that the alkane in stream I IIa is accounted in stream I II
60-90wt%.Namely most of the alkane in stream I II flows into reactor by stream I IIa from the sidepiece of reactor.According to
The 10-50wt% for the alkene total amount that alkene in the specific embodiment of the present invention, stream I IIa is accounted in stream I II.
According to another specific embodiment of the present invention, in IIIa and IIIb, there are conditioning agent and inert component.Wherein
The amount of conditioning agent is the amount 50-100%wt of conditioning agent in III in IIIb.The amount of inert component is inert component in III in IIIa
Amount 10-100%wt.Wherein, the 10-100wt% for the alpha-olefin total amount that the alpha-olefin in stream I IIa is accounted in stream I II.
In the method for the invention, the temperature of the polymerization zone refers to the maximum temperature in the polymerization zone.
According to the specific embodiment of the present invention, alkane and olefinic monomer in stream I IIa are passed through fluidized-bed reactor from side,
And the remaining alkane and olefinic monomer in stream I II in the form of stream I IIb from bottom input fluidized-bed reactor.By
This, can further improve the removal efficiency of heat and the space-time yield of reaction in reactor.
In the method for the invention, olefin polymer is after fluidized-bed reactor outflow, into storage tank and scavenging tank
The olefinic monomer in removing olefin polymer is purged with inert component, further removing olefinic polymerization in degassing cabin is then entered back into
Olefinic monomer inside thing, from degassing cabin bottom, discharge is granulated last ethene polymers.
According to the present invention, the alpha-olefin is in propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes and 1- decene
It is at least one.
According to a preferred embodiment of the present invention, prepared ethene polymers, the 'alpha '-olefin monomers unit
Molar content is 1-30%.Molar content such as 'alpha '-olefin monomers unit is 1-10%.The 'alpha '-olefin monomers list of the polymer
The content of member (can pass through C13- NMR is determined) it is higher than prepared by other method, the degree of branching is high;And wherein, 'alpha '-olefin monomers unit
Head be connected (refer to be connected with two carbon atoms of side base be joined directly together) monomer unit content it is higher than prepared by other method;Enter
And, be conducive to improving mist degree and tack.
According to a preferred embodiment of the present invention, prepared polyvinyl density is in 0.890g/cm3Extremely
0.922g/cm3, preferably 0.895 to 0.917g/cm3.It is molten under conditions of 230 DEG C and 2.16kg in the ethene polymers
Body flow rate is 0.1-10g/10min, preferably 0.5-5.0g/10min.The polyvinyl weight average molecular weight is
20000-250000, molecular weight distributing index is 2-15.
According to a preferred embodiment of the present invention, according to ISO11357-3 by differential scanning calorimetry with 20 DEG C/minute
The rate of heat addition of clock is determined, and polyvinyl fusing point is 110-130 DEG C, preferably 115-125 DEG C.It is described polyvinyl
Mist degree is less than 12.0%, preferably shorter than 10.3%, more preferably less than 9.6%, is such as less than 9.0%.It is described it is polyvinyl from
Viscosity value is in 0.2N/cm2-1N/cm2, preferably 0.3N/cm2-1N/cm2。
In the method for the invention, the space-time yield refers to the production of the olefin polymer of unit bed volume unit interval
Amount.
According to a preferred embodiment of the present invention, the tack of the film is 0.2N/cm2-2N/cm2, it is preferably
0.3N/cm2-1N/cm2.In a specific embodiment, the tack of the film is not less than 0.6N/cm2.The film
Mist degree is less than 6.0%, preferably shorter than 5.0%, more preferably less than 4.0%.In a specific embodiment, the mist of the film
Degree not higher than 1.5%.
According to the present invention, in step 2) in, by step 1) made from ethene polymers by blow molding process, obtain polyethylene
Film.The thickness of the film is general thickness in the art.In an instantiation, the film is that BOPE films are (double
To stretching polyethylene film).Blow molding process used is blow molding process commonly used in the art, and its parameter is commonly used in the prior art
Parameter, here is omitted.
According to a preferred embodiment of the present invention, in the step 2) in, with step 1) in obtained vinyl polymerization
Thing is sandwich layer, and BOPE films are made.The BOPE films mediopellis can use cortex commonly used in the prior art, such as COPP
And/or LLDPE is cortex.
According to a further aspect of the invention, additionally provide the above method preparation polyethylene film packaging material and/
Or the application in Commercial goods labelses.Wherein, it is described application prepare film using the above method, be subsequently used for packaging material and/
Or in Commercial goods labelses.The combination property of film is good, and tack is high, mist degree is low and light transmittance is high, and puncture resistance is good, tear-proof
Intensity, tensile strength and tangent modulus height etc., can be widely applied for such as boiling film, high transparency film, barrier protection film, heat-sealing film
Or in label film.
Compared with prior art, the present invention prepares ethene polymers, and profit using fluidized-bed reactor band liquid condensing technique
Major catalyst is sent into reactor, the side that stream I IIa passes through reactor with the mixing liquid containing high alpha-olefin/ethylene molar ratio
Portion flows into reactor, and stream I IIb flows into reactor by the bottom of reactor;Further it can be formed more in reactor
The different reaction zone of many temperature, obtains high and low molecular weight and the high and low degree of branching is microcosmic well mixed and with specific structure
Polymer, further increases the content of the strand of the degree containing highly -branched, and then high performance film has been made.The basic present invention
Method, technical process is simple;It is easy to operate;Facility investment it is with low cost;Continuous-stable is good;It can produce diversified
Polyethylene film;The combination property of obtained film is good, and mist degree reduction, light transmittance are improved, or tack is improved.Meanwhile, it is thin
The puncture resistance of film is good and tearing toughness, tensile strength and tangent modulus height etc..
Brief description of the drawings
Technical scheme in order to illustrate the embodiments of the present invention more clearly, makes required in being described below to embodiment
Accompanying drawing, which is done, simply to be introduced, it is therefore apparent that the accompanying drawing in brief description is only some embodiments of the present invention, for this
For the those of ordinary skill of field, on the premise of not paying creative work, it can also obtain other according to these accompanying drawings
Accompanying drawing.
Fig. 1 represents a kind of schematic diagram for the reaction unit for realizing the inventive method.
Fig. 2 represents to form the schematic diagram in the different olefinic polyreaction area of multiple temperature in fluidized-bed reactor.
In figure, identical component is indicated by identical reference.Accompanying drawing is not drawn according to actual ratio.Accompanying drawing
What is marked is described as follows:
1 distribution grid
2 fluidized-bed reactors;
3 compression devices;
4 heat-exchange apparatus;
5 separation equipments;
6 feed pumps;
7 gas circulation lines;
8 discharge tanks;
9 scavenging tanks;
10 degassing cabins;
11 fluid line for mixed solution I to be introduced major catalyst as carrier logistics to reactor;
12 and 19 are used for the fluid line of stream I IIa introducing reactors;
13 are used for the fluid line of the taking-up solid ethylene polymer from reactor;
14 are used for H2、N2The fluid line of circulation line is introduced with ethene;
15 are used for the fluid line of alpha-olefin comonomer introducing circulation line;
16 are used for the fluid line of condensing agent introducing circulation line;
17 for the fluid line for the stream I IIb introducing reactors for isolating separation equipment;
18 pump for mixing liquid I to be delivered to pipeline 11;
19. the device for major catalyst powder to be added to pipeline 11.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is unreceipted specific in embodiment
Condition person, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or the unreceipted production firm person of instrument, be
Can be by the conventional products of acquisition purchased in market.
The characterizing method of ethene polymers structure and performance
(1) sign of melting temperature and crystallization temperature:Differential scanning calorimetry (DSC).
Testing sample 6mg or so is weighed, 220 DEG C or so are heated to 20 DEG C/min speed, and kept in nitrogen stream
2min, is then cooled to 40 DEG C or so by it with 20 DEG C/min speed, and 2min is kept at this temperature with crystallized sample.Then
The sample is warming up into 220 DEG C with 20 DEG C/min heating rate to melt again.Record melting scanning, obtains thermal analysis curue, and
Thus melting temperature and crystallization temperature are read.
(2) sign of weight average molecular weight (Mw):Gel permeation chromatography (GPC).
By testing sample with 70mg/50ml stabilisation 1,2,4- trichloro-benzenes (250 μ g/ml BHT (CAS REGISTRY
NUMBER 128-37-0) concentration prepare;Then sample is heated to 170 DEG C and is kept for 2.5 hours to be dissolved;Measurement is
Stabilize solvent to enter on Waters GPCV2000, under the conditions of 145 DEG C, with 1.0ml/min. flow rate, with identical
Capable;Three Polymer Lab posts are used in series (Plgel, 20 μm of mixing ALS, 300X 7.5mm).
(3) measure of molecular weight distributing index (PDI):The RMS-800 type plate rheometers of Rheometrics companies.
Operated under the conditions of vibration frequency increases to 100rad/s from 0.1rad/s.Intersect modulus (crossover
Modulus) PI can be derived by below equation:PI=105/Gc, wherein, Gc is intersects modulus, and it is true as G '=G "
Fixed value (being represented with Pa), wherein G ' is storage modulus, and G " is loss modulus.
(4) sign of melt flow index (MFR):Determined under the conditions of 230 DEG C/2.16kg according to ISO method 1133.
(5) measure of ethylene contents:IR spectroscopic methodologies.
(6) measure of alpha-olefin content:IR spectroscopic methodologies.
(7) measure of density:Determined according to ISO 1183.
(8) thickness:Determined according to GB/T 6672-2001.
(9) tearing strength:Determined according to ASTM D1922.
(10) puncture resistance:Determined according to BB/T 0024-2004.
(11) transparency:Determined according to BB/T 0024-2004;
(12) mist degree:Determined according to GB/T 2410-2008,.
(13) tack:Determined according to GB/T 10457-2009.
In a specific example, as shown in figure 1, internally having in the fluidized-bed reactor 2 that nitrogen is fluidized, lead to first
Cross device 19 as the major catalyst powder in Ziegler-Natta catalyst is added to by feeding device be connected with reactor 2
In pipeline 11, the mixing liquid I containing alkane and alkene is transported in pipeline 11 using pumping unit 18, done using mixing liquid 11
Major catalyst powder is transported in reactor 2 by carrier, and cocatalyst is also contained in mixing liquid I, wherein, pipeline 11 and reaction
The connector of device 2 can have one or more.Pipeline 7 is connected with the top expanded section of fluidized-bed reactor 2, is come from for receiving
Stream I I in fluidized-bed reactor 2.Material in stream I I may include unreacted olefinic monomer and alkane etc..Through mending
Stream I II is obtained after filling olefin feedstocks (can be by 14 and pipeline 15).According to experiment needs, also alkane can be supplemented into stream I I
Hydrocarbon charging (by pipeline 16) and supplement conditioning agent (can pass through pipeline 14, such as H2) and inert component charging (pipe can be passed through
Line 14, such as N2) etc., to obtain stream I II.Stream I II is given into the bottom that stream I IIa and IIIb distribution are passed through reactor
And top.In an instantiation, from heat exchanger 4 come out stream I II pass through gas-liquid separator 5, be divided into stream I IIa and
IIIb.Condensing agent total content is predominantly located in stream I IIa in stream I II, and stream I IIa passes through fluid line 12 and 19
(can increase feed rate by pump 6) sprays into fluidized-bed reactor 2, and remaining condensing agent is located in stream I IIb, and with fluid hose
Road 17 enters fluidized-bed reactor 2 in the lower section of distribution grid 1, wherein, the connector of pipeline 19 and reactor 2 can have one or
It is multiple.Method in the present invention, forms high temperature reaction zone A and cryogenic reaction zone B, such as Fig. 2 institutes in fluidized-bed reactor
Show.
The solid polymer generated in polymerisation is intermittently from the discharging of fluid line 13, successively by discharge tank 8, purging
After tank 9 and the devolatilization of degassing cabin 10 processing, it is transported to downstream section and is processed further.Obtain ethene polymers.
Embodiment 1
The present embodiment uses the TiCl of magnesium chloride load3For major catalyst (major catalyst inlet amount 2.18kg/h), with three
Aluminium ethide as co-catalyst Ziegler-Natta catalyst.Wherein, the molar ratio of major catalyst and co-catalyst is with Ti/
Al is calculated as 3.11.Reaction process is shown in Fig. 1.
Mixing liquid I mass flow is 1.8t/h, accounts for the 0.42% of stream I I mass flow.In mixing liquid I,
Alkane isopentane content accounts for the 50 weight % (molar content is 49%) of mixing liquid, and olefin(e) centent accounts for 50 weights of mixing liquid
% (molar content is 51%) is measured, wherein, ethylene contents account for the 4.9 weight % (molar content is 12.5%) of mixing liquid, 1-
Ahexene content accounts for the 45.1 weight % of mixing liquid (molar content is 38.5%).In mixing liquid I also containing 200ppm three
Ethyl aluminum cocatalyst.
Apparent fluidizing gas velocity in reactor is 0.75m/s.The pressure of reactor is 2.1MPa, and temperature is 89 DEG C.
In stream I I after supplement charging, stream I II is obtained.Stream I I mass flow accounts for stream I II mass flow
Than for 97.8%.Isopentane in stream I II, 80wt% is located in stream I IIa, and remaining is located in stream I IIb.
Polymerization time is 2h, finally obtains the own binary polymer A of the bipolymer of ethene/1- hexenes, i.e. second.
Stream I II each component content is see table 1 below in the present embodiment.
Table 1
The performance of the own binary polymer A of second prepared by the present embodiment and the characterization result of structure are see table 4 below.
Embodiment 2
The present embodiment uses the TiCl of magnesium chloride load3For major catalyst (load capacity is 1.75kg/h), with triethyl aluminum
It is used as the Ziegler-Natta catalyst of co-catalyst.Wherein, the molar ratio of major catalyst and co-catalyst is calculated as with Ti/Al
3.11.Reaction process is shown in Fig. 1.
Mixing liquid I mass flow is 1.3t/h, accounts for the 0.30% of stream I I mass flow.In mixing liquid I, alkane
Hydrocarbon isopentane content accounts for the 45 weight % (molar content is 35%) of mixing liquid, and olefin(e) centent accounts for 55 weight % of mixing liquid
(molar content is 65%), wherein, ethylene contents account for the 8.8 weight % (molar content is 17.8%) of mixing liquid, 1- butylene
Content accounts for 46.2 weight % of mixing liquid) (molar content is 47.2%), the also triethyl group containing 180ppm in mixing liquid
Aluminum cocatalyst.
Apparent fluidizing gas velocity in reactor is 0.70m/s.The pressure of fluidized-bed reactor is 2.0MPa, and temperature is 88
℃。
In stream I I after supplement charging, stream I II is obtained.Stream I I mass flow accounts for stream I II mass flow
96.8%.Isopentane in stream I II, 80wt% is located in stream I IIa, and remaining is located in stream I IIb.
Polymerization time is 2h, finally obtains the bipolymer of Ethylene/1-butene, i.e. second fourth binary polymer B.
Stream I II each component content is see table 2 below in the present embodiment.
Table 2
The performance of second fourth binary polymer B prepared by the present embodiment and the characterization result of structure are see table 4 below.
Embodiment 3
The present embodiment uses the TiCl of magnesium chloride load3For Ziegler-Natta catalyst (major catalyst inlet amount
2.03kg/h), co-catalyst is used as using triethyl aluminum.Wherein, the molar ratio of major catalyst and co-catalyst is calculated as with Ti/Al
3.11.Reaction process is shown in Fig. 1.
Mixing liquid I mass flow is 1.7t/h, accounts for the 0.37% of stream I I mass flow.In mixing liquid I, alkane
Hydrocarbon n-hexane content accounts for the 25 weight % (molar content is 25%) of mixing liquid, and olefin(e) centent accounts for 75 weight % of mixing liquid
(molar content is 75%), wherein, ethylene contents account for 7.8 weight % (molar content 23.8%) of mixing liquid, and 1- octenes contain
Amount accounts for the also triethyl aluminum containing 180ppm in the 67.2 weight % (molar content is 51.2%) of mixing liquid, mixing liquid and helped
Catalyst.
Apparent fluidizing gas velocity in reactor is 0.68m/s.The pressure of fluidized-bed reactor is 2.1MPa, and temperature is 87
℃。
In stream I I after supplement charging, stream I II is obtained.Stream I I mass flow accounts for stream I II mass flow
97.2%.Isopentane in stream I II, 80wt% be located at stream I IIa in, its be located at stream I IIb in.
Stream I II each component content is see table 3 below in the present embodiment.
Table 3
The performance of the pungent binary polymer C of second prepared by the present embodiment and the characterization result of structure are see table 4 below.
Comparative example 1
This comparative example uses the method disclosed in embodiment 35 in WO00/02929A1, and raw material is used as using ethene and 1- hexenes
To prepare the own binary polymer D of second.
The own binary polymer D of second performance and the characterization result of structure prepared by this comparative example please participate in table 4 below.
Comparative example 2
Be the same as Example 1, difference is, no mixing liquid I, and co-catalyst and major catalyst are added directly into reactor
In, prepare the own binary polymer E of second using ethene and 1- hexenes as raw material.Namely the method in this comparative example is similar to
CN104628904CN, but inlet amount is different.The performance of the own binary polymer E of second prepared by this comparative example and structure
Characterization result please participate in table 4 below.
Comparative example 3
Be the same as Example 2, difference is, does not have mixing liquid I, and co-catalyst and major catalyst are added directly into reaction
In device, second fourth binary polymer F is prepared using ethene and 1- butylene as raw material.Namely the method in this comparative example is similar
In CN104628904CN, but inlet amount is different.The performance and structure of the own binary polymer F of second prepared by this comparative example
Characterization result please participate in table 4 below.
Table 4
From above example 1-3 and the preparation-obtained polyvinyl characterization result of comparative example, embodiment 1-3
In the own polymer A of second, the polymer D-F of second fourth polymer B and the pungent polymer C of second compared to comparative example 1-3 that prepare
For, 'alpha '-olefin monomers unit content, and wherein, the 'alpha '-olefin monomers unit content of head's connection is high, this explanation utilizes this hair
The ethene polymers that bright method is obtained has more side chains and the Geng Gao degree of branching.
In addition, in same monomer, and polymer weight average molecular weight relatively in the case of, utilize the inventive method system
Standby obtained copolymer, its melt index MFR is relatively low, and molecular weight distribution index PI, density, mist degree are significantly lower than comparative example
Polymer, tack is higher than the copolymer in comparative example (see embodiment 1 and comparative example 1 and 2, embodiment 2 and comparative example 3).
This is related to production method.Production method in the present invention, the strand content of highly -branched degree is more, chain entanglement degree
Rise, bond properties is improved, and then density reduction, mist degree are reduced and tack raising.
In embodiment 1-3, octene is most long as the branch lengths of the copolymer of comonomer;Butylene is used as comonomer
The branch lengths of copolymer are most short, therefore mist degree is C < A < B, and tack C > A > B.
From above example 1-3 and the preparation-obtained polyvinyl characterization results of comparative example 1-3, further
Carrier is done using a kind of mixing solution containing alkane and alkene major catalyst is transported in reactor, and control wherein alpha-olefin
With the mol ratio of ethene, it is more beneficial for improving the degree of branching, is conducive to improving density polymer reduction, mist degree reduction and tack
And molecular weight distribution sharp.
It is the embodiment of BOPE film preparations below
Embodiment 4
(1) preparation of BOPE films
The BOPE films of the present embodiment include totally three layers of exterior layer 1, sandwich layer and exterior layer 2, exterior layer 1 and exterior layer 2 successively
It is connected respectively with the two sides of sandwich layer, exterior layer 1 and 2 is the outermost layer that film is directly contacted with external environment.
Exterior layer 1 and exterior layer 2 it is raw materials used and proportioning be:The 70wt% Mitsui chemical company trade mark is SP1520
LLDPE (LLDPE), 10wt% LG chemical companies of the South Korea trade mark is H5200 COPP (MFR=
2g/10min), the 16wt% Exxon Mobil chemical company trade mark is Exceed 1327KD metallocene PE (MPE),
4wt% bonding-prevention master batch (ABPP 905DCPP).
Sandwich layer is raw materials used and proportioning is:The ethene obtained in 94wt% embodiment 1/1- hexene copolymers (second oneself two
First polymer A), 3wt% smooth functional master batch (603PP), the 3wt% material of the carbon eight (ethene of metallocene catalyst synthesis-pungent
Alkene copolymer, Tao Shi 488-4A).
Exterior layer 1, exterior layer 2 and sandwich layer material are well mixed in above ratio, storage tank is then sent to, through pipeline
Three single screw extrusion machine extrusions are delivered to respectively, then are extruded into pipe through triple extrusion die head, and pipe layering part by weight is outer
Portion's layer 1:Sandwich layer:Exterior layer 2=20:60:20, the screw diameter of the single screw extrusion machine of exterior layer is 50mm, and draw ratio is 30:
1, extrusion temperature is 220 DEG C, and the screw diameter of the single screw extrusion machine of sandwich layer is 100mm, and draw ratio is 30:1, extrusion temperature is
220 DEG C, extruded material converges to form pipe in triple extrusion die head, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is through cold
But rear haulage enters drawing oven.Pipe is filled with compressed air in drawing oven and stretched, and draft temperature is 116 DEG C, horizontal
It is 2.2-2.7 to draw ratio, longitudinal stretching multiple is 2.2-2.7, you can the film that thickness is 25 μm is obtained, after biaxial tension
Film force to cool down through vane, to point splitting after wind, cutting obtains final products, i.e. BOPE films G.
(2) performance characterization of BOPE films
The performance characterization of BOPE films G prepared by the present embodiment is the results detailed in table 5 below.
Embodiment 5
(1) preparation of BOPE films
The BOPE films of the present embodiment include totally three layers of exterior layer 1, sandwich layer and exterior layer 2, exterior layer 1 and exterior layer 2 successively
It is connected respectively with the two sides of sandwich layer, exterior layer 1 and 2 is the outermost layer that film is directly contacted with external environment.
Exterior layer 1 and exterior layer 2 it is raw materials used and proportioning be:The 70wt% Mitsui chemical company trade mark is SP1520
LLDPE (LLDPE), 10wt% LG chemical companies of the South Korea trade mark is H5200 COPP (MFR=
2g/10min), the 16wt% Exxon Mobil chemical company trade mark is Exceed 1327KD metallocene PE (MPE),
4wt% bonding-prevention master batch.
Sandwich layer is raw materials used and proportioning is:Ethylene/1-butene copolymer (the second fourth two obtained in 94wt% embodiment 2
First polymer B), 3wt% smooth functional master batch (be the same as Example 4), the 3wt% material of carbon eight (be the same as Example 4).
Exterior layer 1, exterior layer 2 and sandwich layer material are well mixed in above ratio, storage tank is then sent to, through pipeline
Three single screw extrusion machine extrusions are delivered to respectively, then are extruded into pipe through triple extrusion die head, and pipe layering part by weight is outer
Portion's layer 1:Sandwich layer:Exterior layer 2=20:60:20, the screw diameter of the single screw extrusion machine of exterior layer is 50mm, and draw ratio is 30:
1, extrusion temperature is 220 DEG C, and the screw diameter of the single screw extrusion machine of sandwich layer is 100mm, and draw ratio is 30:1, extrusion temperature is
220 DEG C, extruded material converges to form pipe in triple extrusion die head, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is through cold
But rear haulage enters drawing oven.Pipe is filled with compressed air in drawing oven and stretched, and draft temperature is 116 DEG C, horizontal
It is 2.2-2.7 to draw ratio, longitudinal stretching multiple is 2.2-2.7, you can the film that thickness is 25 μm is obtained, after biaxial tension
Film force to cool down through vane, to point splitting after wind, cutting obtains final products, i.e. BOPE films H.
(2) performance characterization of BOPE films
The performance characterization of BOPE films H prepared by the present embodiment is the results detailed in table 5 below.
Embodiment 6
(1) preparation of BOPE films
The BOPE films of the present embodiment include totally three layers of exterior layer 1, sandwich layer and exterior layer 2, exterior layer 1 and exterior layer 2 successively
It is connected respectively with the two sides of sandwich layer, exterior layer 1 and 2 is the outermost layer that film is directly contacted with external environment.
Exterior layer 1 and exterior layer 2 it is raw materials used and proportioning be:The 70wt% Mitsui chemical company trade mark is SP1520
LLDPE (LLDPE), 10wt% LG chemical companies of the South Korea trade mark is H5200 COPP (MFR=
2g/10min), the 16wt% Exxon Mobil chemical company trade mark is Exceed 1327KD metallocene PE (MPE),
4wt% bonding-prevention master batch (be the same as Example 4).
Sandwich layer is raw materials used and proportioning is:The ethene obtained in 94wt% embodiment 3/1- octene copolymers (second pungent two
First polymer C), 3wt% smooth functional master batch (be the same as Example 4), the 3wt% material of carbon eight (be the same as Example 4).
Exterior layer 1, exterior layer 2 and sandwich layer material are well mixed in above ratio, storage tank is then sent to, through pipeline
Three single screw extrusion machine extrusions are delivered to respectively, then are extruded into pipe through triple extrusion die head, and pipe layering part by weight is outer
Portion's layer 1:Sandwich layer:Exterior layer 2=20:60:20, the screw diameter of the single screw extrusion machine of exterior layer is 50mm, and draw ratio is 30:
1, extrusion temperature is 220 DEG C, and the screw diameter of the single screw extrusion machine of sandwich layer is 100mm, and draw ratio is 30:1, extrusion temperature is
220 DEG C, extruded material converges to form pipe in triple extrusion die head, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is through cold
But rear haulage enters drawing oven.Pipe is filled with compressed air in drawing oven and stretched, and draft temperature is 116 DEG C, horizontal
It is 2.2-2.7 to draw ratio, longitudinal stretching multiple is 2.2-2.7, you can the film that thickness is 25 μm is obtained, after biaxial tension
Film force to cool down through vane, to point splitting after wind, cutting obtains final products, i.e. BOPE films I.
(2) performance characterization of BOPE films
The performance characterization of BOPE films I prepared by the present embodiment is the results detailed in table 5 below.
Comparative example 4
(1) preparation of BOPE films
The BOPE films of the present embodiment include totally three layers of exterior layer 1, sandwich layer and exterior layer 2, exterior layer 1 and exterior layer 2 successively
It is connected respectively with the two sides of sandwich layer, exterior layer 1 and 2 is the outermost layer that film is directly contacted with external environment.
Exterior layer 1 and exterior layer 2 it is raw materials used and proportioning be:The 70wt% Mitsui chemical company trade mark is SP1520
LLDPE (LLDPE), 10wt% LG chemical companies of the South Korea trade mark is H5200 COPP (MFR=
2g/10min), the 16wt% Exxon Mobil chemical company trade mark is Exceed 1327KD metallocene PE (MPE),
4wt% bonding-prevention master batch (be the same as Example 4).
Sandwich layer is raw materials used and proportioning is:The ethene obtained in 94wt% comparative example 1/1- hexene copolymers (second oneself two
First polymer D), 3wt% smooth functional master batch, the 3wt% material of carbon eight.
Exterior layer 1, exterior layer 2 and sandwich layer material are well mixed in above ratio, storage tank is then sent to, through pipeline
Three single screw extrusion machine extrusions are delivered to respectively, then are extruded into pipe through triple extrusion die head, and pipe layering part by weight is outer
Portion's layer 1:Sandwich layer:Exterior layer 2=20:60:20, the screw diameter of the single screw extrusion machine of exterior layer is 50mm, and draw ratio is 30:
1, extrusion temperature is 220 DEG C, and the screw diameter of the single screw extrusion machine of sandwich layer is 100mm, and draw ratio is 30:1, extrusion temperature is
220 DEG C, extruded material converges to form pipe in triple extrusion die head, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is through cold
But rear haulage enters drawing oven.Pipe is filled with compressed air in drawing oven and stretched, and draft temperature is 116 DEG C, horizontal
It is 2.2-2.7 to draw ratio, longitudinal stretching multiple is 2.2-2.7, you can the film that thickness is 25 μm is obtained, after biaxial tension
Film force to cool down through vane, to point splitting after wind, cutting obtains final products, i.e. BOPE films J.
(2) performance characterization of BOPE films
The performance characterization of BOPE films J prepared by the present embodiment is the results detailed in table 5 below.
Comparative example 5
(1) preparation of BOPE films
The BOPE films of the present embodiment include totally three layers of exterior layer 1, sandwich layer and exterior layer 2, exterior layer 1 and exterior layer 2 successively
It is connected respectively with the two sides of sandwich layer, exterior layer 1 and 2 is the outermost layer that film is directly contacted with external environment.
Exterior layer 1 and exterior layer 2 it is raw materials used and proportioning be:The 70wt% Mitsui chemical company trade mark is SP1520
LLDPE (LLDPE), 10wt% LG chemical companies of the South Korea trade mark is H5200 COPP (MFR=
2g/10min), the 16wt% Exxon Mobil chemical company trade mark is Exceed1327KD metallocene PE (MPE),
4wt% bonding-prevention master batch (be the same as Example 4).
Sandwich layer is raw materials used and proportioning is:The ethene obtained in 94wt% comparative example 2/1- hexene copolymers (second oneself two
First polymer E), 3wt% smooth functional master batch (be the same as Example 4), the 3wt% material of carbon eight (be the same as Example 4).
Exterior layer 1, exterior layer 2 and sandwich layer material are well mixed in above ratio, storage tank is then sent to, through pipeline
Three single screw extrusion machine extrusions are delivered to respectively, then are extruded into pipe through triple extrusion die head, and pipe layering part by weight is outer
Portion's layer 1:Sandwich layer:Exterior layer 2=20:60:20, the screw diameter of the single screw extrusion machine of exterior layer is 50mm, and draw ratio is 30:
1, extrusion temperature is 220 DEG C, and the screw diameter of the single screw extrusion machine of sandwich layer is 100mm, and draw ratio is 30:1, extrusion temperature is
220 DEG C, extruded material converges to form pipe in triple extrusion die head, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is through cold
But rear haulage enters drawing oven.Pipe is filled with compressed air in drawing oven and stretched, and draft temperature is 116 DEG C, horizontal
It is 2.2-2.7 to draw ratio, longitudinal stretching multiple is 2.2-2.7, you can the film that thickness is 25 μm is obtained, after biaxial tension
Film force to cool down through vane, to point splitting after wind, cutting obtains final products, i.e. BOPE films K.
(2) performance characterization of BOPE films
The performance characterization of BOPE films K prepared by the present embodiment is the results detailed in table 5 below.
Comparative example 6
(1) preparation of BOPE films
The BOPE films of the present embodiment include totally three layers of exterior layer 1, sandwich layer and exterior layer 2, exterior layer 1 and exterior layer 2 successively
It is connected respectively with the two sides of sandwich layer, exterior layer 1 and 2 is the outermost layer that film is directly contacted with external environment.
Exterior layer 1 and exterior layer 2 it is raw materials used and proportioning be:The 70wt% Mitsui chemical company trade mark is SP1520
LLDPE (LLDPE), 10wt% LG chemical companies of the South Korea trade mark is H5200 COPP (MFR=
2g/10min), the 16wt% Exxon Mobil chemical company trade mark is Exceed1327KD metallocene PE (MPE),
4wt% bonding-prevention master batch (be the same as Example 4).
Sandwich layer is raw materials used and proportioning is:Ethylene/1-butene copolymer (the second fourth two obtained in 94wt% comparative example 3
First polymer F), 3wt% smooth functional master batch (be the same as Example 4), the 3wt% material of carbon eight (be the same as Example 4).
Exterior layer 1, exterior layer 2 and sandwich layer material are well mixed in above ratio, storage tank is then sent to, through pipeline
Three single screw extrusion machine extrusions are delivered to respectively, then are extruded into pipe through triple extrusion die head, and pipe layering part by weight is outer
Portion's layer 1:Sandwich layer:Exterior layer 2=20:60:20, the screw diameter of the single screw extrusion machine of exterior layer is 50mm, and draw ratio is 30:
1, extrusion temperature is 220 DEG C, and the screw diameter of the single screw extrusion machine of sandwich layer is 100mm, and draw ratio is 30:1, extrusion temperature is
220 DEG C, extruded material converges to form pipe in triple extrusion die head, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is through cold
But rear haulage enters drawing oven.Pipe is filled with compressed air in drawing oven and stretched, and draft temperature is 116 DEG C, horizontal
It is 2.2-2.7 to draw ratio, longitudinal stretching multiple is 2.2-2.7, you can the film that thickness is 25 μm is obtained, after biaxial tension
Film force to cool down through vane, to point splitting after wind, cutting obtains final products, i.e. BOPE films L.
(2) performance characterization of BOPE films
The performance characterization of BOPE films L prepared by the present embodiment is the results detailed in table 5 below.
Table 5
Above example 4-6 and comparative example 4-6 are compared and understood, BOPE films G, H and I tearing toughness and anti-is worn
Thorn performance is all substantially better than BOPE films J, K, L.Especially, the copolymer A that is prepared using the inventive method, B, C are formed
BOPE film G, H, I, its tack, mist degree and translucency be superior to comparative example BOPE film J, K, L, wherein, mist degree is less than contrast
Data in example, light transmittance, tack are higher than the data in comparative example..Because the polyethylene of the inventive method production, α-
Olefin monomer unit content, and wherein, the 'alpha '-olefin monomers unit content of head's connection is high, and then the degree of branching is high, is conducive to increasing
The locomitivity of powerful strand.And wherein, octene is most long as the pungent copolymer C of second of comonomer branch lengths, chain
Entanglement degree rises, bond properties highest.
The film provided according to the present invention, its light transmittance is high, tack is high, mist degree is low, and density is low, light weight, but performance
Such as tearing toughness and puncture resistance isosceles are high, and then broad application prospect.
Any numerical value mentioned in the present invention, if simply having two between any minimum and any of the highest value
The interval of unit, then include all values of one unit of each increase from minimum to peak.If for example, life is a kind of
The amount of component, or the value of the state-variable such as temperature, pressure, time is 50-90, in this manual it means that specific
List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to
0.1st, 0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side
Formula, the combination that is possible to of the numerical value between cited minimum and peak is considered to disclose.
When explanation is of the invention it is noted that embodiment described above is only used for, any limit to the present invention is not constituted
System.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein word used to be descriptive and
Explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation and repaiied
Change, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it is related to
Specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, of the invention
It can be extended to other all methods and applications with identical function.
Claims (15)
1. a kind of preparation method of polyethylene film, comprises the following steps:
1) it is that the major catalyst in catalyst system is transported in reactor by carrier logistics with mixing liquid I, the mixed liquor
Body I includes alkane, alkene and co-catalyst;Thing is obtained after supplement olefin feedstocks are added into the stream I I flowed out from reactor
III is flowed, stream I II is divided into stream I IIa and IIIb, stream I IIa and IIIb are back to sidepiece and the bottom of reactor respectively;
In the reactor, it is aggregated to obtain ethene polymers and discharged from reactor;Wherein, the alkene includes alpha-olefin and second
The mole specific concentration ratio at least 1 of alpha-olefin and ethene in alkene, the mixing liquid I;
2) by step 1) made from ethene polymers by blow molding process, obtain polyethylene film.
2. the method according to claim 1, it is characterised in that the polyethylene film is that Biaxially-oriented polyethylene is thin
Film.
3. method according to claim 1 or 2, it is characterised in that mole of alpha-olefin and ethene in the mixing liquid I
Than for 1-5, more preferably preferably 1.3-5,1.5-5;And/or in the mixing liquid, the content of alkane is 5-80wt%, excellent
Elect 10-65wt% as;And/or, the mass flow of the mixing liquid I accounts for the 0.05%-5% of stream I I mass flow, excellent
It is selected in 0.1%-3%.
4. the method according to any one in claim 1-3, it is characterised in that the reaction pressure in the reactor is
0.5-10MPa, preferably 1.5-5MPa;Reaction temperature is 40-150 DEG C, preferably 60-100 DEG C;And/or, the table in the reactor
It is 0.1-10m/s, preferably 0.3-0.8m/s to see vulcanization gas velocity.
5. the method according to any one in claim 1-4, it is characterised in that different comprising temperature in the reactor
Reaction zone;And/or the reactor is fluidized-bed reactor.
6. the method according to any one in claim 1-5, it is characterised in that in the stream I II, the content of alkene
For 1.0-60.0mol%, preferably 5.0-55.0mol%;The content of alkane is 0.5-50.0mol%, preferably 1.0-
35.0mol%;Or in the stream I II, the molar concentration of alpha-olefin accounts for the molar concentration of ethene in 20%-60%.
7. the method according to any one in claim 1-6, it is characterised in that the alkane in stream I IIa accounts for logistics
The 60-90wt% of alkane total amount in III;And/or the 10- of alkene total amount that the alkene in stream I IIa is accounted in stream I II
50wt%;And/or, stream I I mass flow accounts for more than the 90% of stream I II mass flow, preferably more than 95%.
8. the method according to any one in claim 1-7, it is characterised in that conditioning agent is included in the stream I II
And/or inert component;Wherein, the conditioning agent is preferably hydrogen;The inert component is preferably nitrogen;It is highly preferred that described
The content of conditioning agent is 0.3-14.5mol%;And/or in the stream I I, the amount of the inert component is 25.0-
75.0mol%.
9. the method according to any one in claim 5-7, it is characterised in that supplement alkane is included in the stream I II
At least one of hydrocarbon charging, the charging of supplement conditioning agent and supplement inert component charging.
10. the method according to any one in claim 1-9, it is characterised in that the alkane is selected from butane, isobutyl
At least one of alkane, pentane, isopentane, n-hexane, hexamethylene and heptane;And/or the alpha-olefin is selected from propylene, 1- fourths
At least one of alkene, 1- amylenes, 1- hexenes, 1- octenes and 1- decene.
11. the method according to any one in claim 1-10, it is characterised in that the tack of the film is
0.2N/cm2-2N/cm2, preferably 0.3N/cm2-1N/cm2;And/or the mist degree of the film is less than 6.0%, preferably shorter than
5.0%, more preferably less than 4.0%.
12. the method according to any one in claim 1-11, it is characterised in that the catalyst system includes neat lattice
Le-Natta catalyst, metallocene catalyst, transition-metal catalyst, inorganic chrome catalysts and organic chrome catalysts.
13. the method according to any one in claim 1-12, it is characterised in that in prepared ethene polymers,
Molar content shared by 'alpha '-olefin monomers unit is 1-30%, preferably 1-10%;
Or prepared ethene polymers has following characteristic:Density is in 0.890g/cm3To 0.922g/cm3;At 230 DEG C and
Melt flow rate (MFR) under conditions of 2.16kg is 0.1-10g/10min, preferably 0.5-5.0g/10min;Weight average molecular weight is
20000-250000, molecular weight distributing index is 2-15.
14. the method according to any one in claim 1-13, it is characterised in that the polyvinyl mist degree is low
In 12.0%, preferably shorter than 10.3%, more preferably less than 9.6%;And/or the polyvinyl tack is 0.2N/
cm2-1N/cm2, preferably 0.3N/cm2-1N/cm2。
15. the polyethylene film that in claim 1-14 prepared by any one methods described is in packaging material and/or Commercial goods labelses
In application, the preferably application in boiling film, high transparency film, barrier protection film, heat-sealing film or label film.
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Citations (2)
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EP1518867A1 (en) * | 2003-08-11 | 2005-03-30 | Exxonmobil Chemical Patents Inc. | Polymers of ethylene and optionally, copolymerizable esters, films using such polymers and stretch hood packaging processesusing such films |
CN105802033A (en) * | 2016-03-14 | 2016-07-27 | 浙江大学 | Preparation method and application of polyethylene film |
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EP1518867A1 (en) * | 2003-08-11 | 2005-03-30 | Exxonmobil Chemical Patents Inc. | Polymers of ethylene and optionally, copolymerizable esters, films using such polymers and stretch hood packaging processesusing such films |
CN105802033A (en) * | 2016-03-14 | 2016-07-27 | 浙江大学 | Preparation method and application of polyethylene film |
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