CN105802033A - Preparation method and application of polyethylene film - Google Patents
Preparation method and application of polyethylene film Download PDFInfo
- Publication number
- CN105802033A CN105802033A CN201610144252.0A CN201610144252A CN105802033A CN 105802033 A CN105802033 A CN 105802033A CN 201610144252 A CN201610144252 A CN 201610144252A CN 105802033 A CN105802033 A CN 105802033A
- Authority
- CN
- China
- Prior art keywords
- stream
- reactor
- olefin
- alkane
- alpha
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
-
- 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
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
-
- 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
- C08F210/14—Monomers containing five or more carbon atoms
-
- 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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/412—Transparent
-
- 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
- B32B2307/582—Tearability
- B32B2307/5825—Tear resistant
-
- 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
- B32B2519/00—Labels, badges
-
- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
- C08L2203/162—Applications used for films sealable films
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (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 preparation method of a polyethylene film.The preparation method comprises the following steps of 1, conveying a main catalyst in a catalyst system into a reactor with mixed liquor I as carrier material flow, wherein the mixed liquor I comprises alkene, olefin and promoter; feeding olefin to material flow II flowing out of the reactor for replenishment, so that material flow III is obtained, and dividing the material flow III into material flow IIIa and material flow IIIb, wherein the material flow IIIa and the material flow IIIb flow back to the side and the bottom of the reactor respectively; in the reactor, obtaining polyvinyl through polymerization, and discharging the material out of the reactor, wherein olefin comprises alpha-olefin and ethene, and the mole concentration ratio of alpha-olefin to ethene in the mixed liquor I is 1 or higher; 2, making polyvinyl obtained in step 1 be subjected to a blow molding process, so that the polyethylene film is obtained.By means of the method, longitudinal and transverse tensile strength of the film is improved, and uniform longitudinal and transverse tensile strength is achieved.
Description
Technical field
The present invention relates to the preparation method of a kind of polyethylene film, specifically, the present invention relates to a kind of polyethylene
The preparation method of thin film and its application.
Background technology
At present, polypropylene double-way stretched film (BOPP) is the major product of high-grade packaging field, because its
There is light weight, transparent, nontoxic, moistureproof and mechanical strength advantages of higher.And novel polyethylene biaxial tension is thin
Film (BOPE) has shown more excellent performance than BOPP, and its quality is lighter, transparency, glossiness
More preferable with printing effect.BOPE is mainly 3-5 film structure, most commonly 3 layers, is respectively outside basic unit,
Sandwich layer basic unit and functional layer.Sandwich layer be mainly composed of polyethylene (PE), the addition of PE accounts for sandwich layer weight
About 99%.Traditional polyethylene film is much larger than in horizontal hot strength in longitudinal hot strength, this
Thin film transverse breakage percentage elongation in use can be caused inadequate, thus affect the serviceability of polyethylene film.
The main linear Low Density Polyethylene of the PE (LLDPE), the low-density that use in traditional polyethylene film are gathered
Ethylene (LDPE) and metallocene linear-low density polyethylene (mLLDPE).
Chinese patent CN 101608004B disclose one utilize pressure autoclave type reactor with ethylene, propylene and
1-butylene is the method for Material synthesis linear low density polyethylene, and catalyst carrier is SiO2, solvent is normal hexane,
Catalyst is triethyl aluminum, reaction pressure 0.8MPa, and temperature 80 DEG C, the mist degree of the polyethylene obtained is minimum
11%, molecular weight distributing index 6-40, melt flow rate (MFR) 0.2-20g/10min, density 0.910-0.940g/cm3,
Its longitudinal tensile strength is about 15MPa, and transverse tensile strength is about 11MPa.This linear low density polyethylene visible
The longitudinally, laterally hot strength difference of alkene is relatively big, is unfavorable for the core material as BOPE.
For this reason, the present invention seeks to solve the problem that association area prior art is come out, phase
Hope provide a kind of utilize fluidized-bed reactor prepare longitudinally, laterally hot strength very close to high-performance ethylene gather
The method of composition powder.
Summary of the invention
In view of above the deficiencies in the prior art, an object of the present invention is to provide one to utilize fluidized-bed reaction
Polyvinyl method prepared by device, the method achieves and utilizes single reactor to prepare longitudinally, laterally stretching by force
Spend very close to high-performance ethene polymers product.
Another object of the present invention is to provide a kind of polyethylene film prepared according to described method at bag
Application in the film article such as package material or Commercial goods labels.
According to an aspect of the invention, it is provided the preparation method of a kind of polyethylene film, including:
1) with mixing liquid I be that the major catalyst in catalyst system is transported in reactor by carrier logistics, institute
State mixing liquid I and comprise alkane, alkene and promoter；Add in stream I I flowed out from reactor and mend
Fill olefin feedstocks, obtain stream I II, stream I II is divided into stream I IIa and IIIb, stream I IIa and IIIb respectively
It is back to sidepiece and the bottom of reactor；In the reactor, aggregated ethene polymers is obtained and from reactor
Discharging；Wherein, described alkene includes alpha-olefin and ethylene, and in described mixing liquid I, alpha-olefin and ethylene rubs
Your ratio is at least 1；
2) by step 1) ethene polymers for preparing by blow molding process, obtain polyethylene film.
The method provided according to the present invention, it is possible to prepare the thin film with uniform vertical and horizontal hot strength, and
The mist degree of thin film is low, and puncture resistance is good, and tearing toughness, hot strength and tangent modulus are high.Side in the present invention
Legal system thin film, combination property is good, has the application prospect of broadness.
In the method for the present invention, whole reaction system carries out Matter Transfer, thus recycling raw materials.Its
In, relatively big from the mass flow of stream I I of reactor outflow, for big flow Matter Transfer, enters on a small quantity through supplementary
After material, obtain stream I II.In the method for the invention, mixing liquid I and stream I IIa and IIIb join
In reactor, the alkane wherein contained, the latent heat of vaporization of alkane is high, and the shifting heat of alkane is big so that reaction
The conversion zone that temperature is different is presented in device；And mixing liquid I has high alpha-olefin content；Therefore, alkene
Hydrocarbon monomer can respectively obtain high side chain, low close in fluidized-bed reactor under the condition of different temperatures of zones of different
The olefin polymer of the high molecular of degree and low side chain, the olefin polymer of highdensity low-molecular-weight, thus
The olefin polymer that can obtain high low-molecular-weight constantly mixes the product of fluidisation, and improves highly-branched degree
Molecule segment or the content of strand, and owing to alkane can remove heat energy in bigger raising fluidized-bed reactor
Power, therefore the method for the present invention can prepare high and low molecular weight and high and low degree of branching microcosmic mix homogeneously
Olefin polymer product, improve the light transmittance of ethylene copolymer, mist degree and autohension, and the space-time produced
Yield is significantly improved.Then, the ethene polymers obtained by utilization passes through blow molding process, obtains performance good
Good such as uniform vertical and horizontal hot strength, high autohension, low haze and high transmission rate, and puncture resistance,
The polyethylene film of tearing toughness, hot 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, at fluid bed
It is polymerized respectively in the reaction zone that in reactor, multiple temperature are different.Different polymerization temperatures and different alkene
Monomer concentration can obtain the olefin polymer that structure is the most different from performance.According to the present invention, comprise alkane by one
The mixing solution of hydrocarbon and alkene does carrier by catalyst transport to reactor, it is possible to shape in reactor further
Become multiple cryogenic reaction zone, improve the content of the strand of highly-branched degree further.The poly-second according to said method made
Vertical/horizontal hot strength, mist degree and the autohension of alkene are improved；And then, improve the film article that obtains
Combination property, as puncture resistance, tangent modulus, tearing toughness, autohension and light transmittance are improved,
Mist degree reduces.
The method provided according to the present invention, does carrier by catalyst with a kind of mixing solution comprising alkane and alkene
It is transported in reactor, and in mixing liquid, the molar content of alpha-olefin is not less than ethylene, at catalyst action
The content of initial stage alpha-olefin is high so that the degree of branching of polyethylene raises, and density reduces (LDPE low density polyethylene
Alkene).The polymer obtained according to the present invention, in the case of close molecular weight so that the longitudinal direction of polymer and
Transverse tensile strength is improved.
According to a preferred embodiment of the present invention, described mixing liquid I can be as carrier logistics, it is possible to
Major catalyst powder is delivered in reaction system.Wherein, first with a rotating machinery, major catalyst is the most defeated
Deliver in the pipeline that is connected with polymer reactor or pipe fitting, the most again with mixing liquid I by defeated for major catalyst powder
Deliver in reaction system.A specific embodiment according to the present invention, described rotating machinery selected from pump, compressor,
Blower fan and reductor.
According to a preferred embodiment of the present invention, described catalyst system include Ziegler-Natta catalyst,
Metallocene catalyst, transition-metal catalyst, inorganic chromium catalyst and organic chromium catalyst.Described caltalyst
System includes promoter and major catalyst.In a concrete example, major catalyst with the amount of promoter is
Conventional amount used in this area, if the mol ratio of major catalyst and promoter is with the active metal in major catalyst
Element is 1:1-6:1 with the mol ratio of the active metal metallic element in promoter.A specific embodiment
In, comprising promoter in described mixing liquid I is triethyl aluminum.In the example that another is concrete, described
Promoter amount in mixing liquid is at least 150ppm (weight content).
According to a preferred embodiment of the present invention, alpha-olefin and the mol ratio of ethylene in described mixing liquid I
For 1-5, such as 1.3-5.In situations where it is preferred, alpha-olefin with the mol ratio of ethylene is in described mixing liquid I
1.5-5.Now, the content of alpha-olefin is higher so that the degree of branching of polyethylene raises, and density reduces, meanwhile,
In the case of same molecular amount so that and polyethylene (or claim ethene polymers, refer both to copolymerization of ethylene herein)
Vertical and horizontal hot strength be further improved.
According to another preferred embodiment of the present invention, in described 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 mixing
Determination of Alkane Content in liquid, is conducive to controlling reaction temperature, forms cryogenic reaction zone.
According to another preferred embodiment of the present invention, the mass flow of described mixing liquid I accounts for stream I I
The 0.05%-5% of mass flow, preferably at 0.1%-3%.
In a specific embodiment, the alkane in the present invention comprises butane, iso-butane, pentane, isoamyl
At least one in alkane, normal hexane, hexamethylene and heptane.Alkane in the range of described restriction, its latent heat of vaporization
Height, moves heat big；Be conducive to being formed the reaction zone of differential responses temperature in reactor.
According to a preferred embodiment of the present invention, the reaction pressure in described reactor is 0.5-10MPa,
Reaction temperature is 40-150 DEG C.In a concrete example, the reaction pressure in reactor is 1.5-5MPa.
In another specific embodiment, the reaction temperature in described reactor is 60-100 DEG C.
According to the present invention, described alkane, as mixed the alkane in liquid I, such as the alkane in stream I IIa or IIIb
Hydrocarbon etc., its latent heat of vaporization is high, moves heat big, it is possible to use as condensing agent.Therefore, in reactor, has alkane
The reaction temperature of the polymerization zone of hydrocarbon input is different from the reaction temperature of other polymerization zones.According to this
A bright specific embodiment, described reactor is fluidized-bed reactor.Logistics include fluidized-bed reactor,
Pipeline, heat-exchange apparatus, separation equipment etc. carry out Matter Transfer in interior whole reaction system.
In a concrete preferred implementation according to the present invention, in described reactor, comprise the reaction that temperature is different
District.Having the polymerization zone that condensing agent (alkane) inputs in described reactor, polymerization temperature is relatively low, for
Cryogenic reaction zone, does not has the polymerization zone that condensing agent inputs, and polymerization temperature is of a relatively high, for high temperature reaction zone.
A specific embodiment according to the present invention, the reaction temperature of described cryogenic reaction zone controls at 60-75 DEG C, excellent
Select 65-75 DEG C；The reaction temperature of high temperature reaction zone controls 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 described fluidized-bed reactor is 0.1
-10m/s.The purpose of the apparent fluidizing gas velocity that the method for the present invention strictly controls fluidized-bed reactor is to ensure instead
Answer device fluidized state to avoid powder to be taken out of in a large number the most simultaneously.When apparent fluidizing gas velocity is 0.3-0.8m/s,
The method of the present invention may further ensure that fluidized-bed reactor quiet run, ensures cryogenic reaction zone and height simultaneously
The stable existence of temperature reaction zone.Reason may is that the apparent fluidizing gas velocity initial fluidisation speed higher than body series powder
Rate speed is simultaneously less than the carrying velocity of overwhelming majority powder particle.
According to a preferred embodiment of the present invention, from stream I I that reactor flows out, comprise alkane, also may be used
Unreacted olefinic monomer (may relate to ethylene and alpha-olefin) can be comprised.Stream I I and stream I II, wherein
Component be more or less the same, mass flow is also more or less the same.In a concrete example, the quality stream of stream I I
Amount accounts for more than the 90% of stream I II mass flow, and preferably 95% with up to 100%.
Along with carrying out and the discharging of polymer of reaction, require supplementation with olefin feedstocks.(relate to through supplementing olefin feedstocks
And make-up ethylene charging and supplement alpha-olefin charging) charging after, in described stream I II obtained, containing of alkene
Amount is 1.0-60.0mol%, such as preferred 5.0-55.0mol%.Wherein, in a concrete example, described thing
In stream III, the molar concentration of alpha-olefin accounts for the molar concentration of ethylene at 20%-60%.
According to a preferred embodiment of the present invention, described stream I II comprises regulator and/or inert component.
Use regulator, the polyvinyl molecular weight of gained can be polymerized according to the different adjustment of regulator content and divide
Son amount distribution.Wherein, described regulator is preferably hydrogen.Use inert component, can remove in polymerization process
Produced partial heat, it is also possible to the composition of regulation logistics III.Wherein, described inert component is preferably nitrogen
Gas.Now, from stream I I that reactor flows out, regulator and/or inert component may be comprised.At a tool
In body example, in described stream I II, the content of described regulator controls as 0.3-14.5mol%.At another
In instantiation, in described stream I II, the amount of described inert component controls as 25.0-75.0%.At a tool
In body example, in stream I II described in described logistics, the content of alkane controls to be 0.5-50.0mol%, as
1.0-35.0mol%.According to technique needs, stream I II also can comprise the charging of supplementary alkane, inert component charging
At least one in feeding with supplementary regulator, to better control over the composition in stream I II.
According to a preferred embodiment of the present invention, described stream I II is compressed and after gas-liquid separation, is divided into
Stream I IIa and IIIb.Wherein, stream I IIa flows into reactor by the sidepiece of reactor.And stream I IIb is led to
The bottom crossing reactor flows into reactor.A specific embodiment according to the present invention, the alkane in stream I IIa
Account for the 60-90wt% of alkane total amount in stream I II.Namely the alkane great majority in stream I II are by stream I IIa
Reactor is flowed into from the sidepiece of reactor.A specific embodiment according to the present invention, the alkene in stream I IIa
Account for the 10-50wt% of alkene total amount in stream I II.
According to another specific embodiment of the present invention, in IIIa and IIIb, there are regulator and inert component.
Amount 50-100%wt of regulator during wherein the amount of regulator is III in IIIb.In IIIa, the amount of inert component is III
Amount 10-100%wt of middle inert component.Wherein, the alpha-olefin in stream I IIa accounts for the alpha-olefin in stream I II
The 10-100wt% of total amount.
In the method for the invention, the temperature of described polymerization zone refers to the highest temperature in this polymerization zone
Degree.A specific embodiment according to the present invention, alkane and olefinic monomer in stream I IIa are passed through stream from side
Fluidized bed reactor, and remaining alkane in stream I II and olefinic monomer with the form of stream I IIb from bottom
Inlet flow fluidized bed reactor.Thus, it is possible to improve further the removal efficiency of heat in reactor and reaction
Space-time yield.
In the method for the invention, olefin polymer, after fluidized-bed reactor flows out, enters storage tank and blows
Sweep the olefinic monomer in tank inert component purging removing olefin polymer, further in then entering back into degassing cabin
Removing olefinic monomer within olefin polymer, last ethene polymers is discharged from degassing cabin bottom and is carried out pelletize.
According to the present invention, described alpha-olefin is selected from propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene and 1-
At least one in decene.
According to a preferred embodiment of the present invention, prepared ethene polymers, described 'alpha '-olefin monomers list
The molar content of unit is 1-30%.If the molar content of 'alpha '-olefin monomers unit is 1-10%.Described polymer
The content of 'alpha '-olefin monomers unit is higher than prepared by additive method, and the degree of branching is high；And wherein, 'alpha '-olefin monomers
The monomer unit content of unit head connected (referring to that two carbon atoms being connected with side base are joined directly together) compares additive method
Wanting of preparation is high；And then, be conducive to improving vertical and horizontal hot strength.
According to a preferred embodiment of the present invention, prepared polyvinyl density is at 0.890g/cm3
To 0.922g/cm3, preferably 0.895 to 0.917g/cm3.In described ethene polymers, at 230 DEG C and 2.16kg
Under conditions of melt flow rate (MFR) be 0.1-10g/10min, preferably 0.5-5.0g/10min.Described vinyl polymerization
The weight average molecular weight of thing is 20000-250000, and 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
The rate of heat addition of 20 DEG C/min measures, and polyvinyl fusing point is 110-130 DEG C, preferably 115-125 DEG C.
The polyvinyl longitudinal tensile strength of described ethene polymers (MD) and transverse tensile strength (TD) are more than
15MPa, and its ratio MD/TD is less than 1.15, preferably smaller than 1.1.
In the method for the invention, described space-time yield refers to the olefin polymer of unit bed volume unit interval
Yield.
Compared with prior art, the one of the present invention utilize fluidized-bed reactor band liquid condensing technique prepare alkene gather
The method of compound has following Advantageous Effects: process is simple；Easy and simple to handle；Facility investment with low cost；
Continuous-stable is good；Diversified ethene polymers product can be produced；The ethene polymers product of preparation has
Uniform vertical and horizontal hot strength, its longitudinal direction/transverse tensile strength ratio is close to 1.
According to the present invention, in step 2) in, by step 1) ethene polymers for preparing by blow molding process,
Obtain polyethylene film.The thickness of described thin film is the general thickness in this area.In an instantiation,
Described thin film is BOPE film (Biaxial tension polyethylene film).
According to a preferred embodiment of the present invention, in described step 2) in, with step 1) in prepare
Ethene polymers is sandwich layer, prepares BOPE thin film.Described BOPE film mediopellis can use in prior art normal
Cortex, if COPP and/or linear low density polyethylene are cortex.
According to a further aspect of the invention, polyethylene film prepared by said method is additionally provided at packaging material
And/or the application in Commercial goods labels.Wherein, described application includes utilizing said method to prepare thin film, is subsequently used for
In packaging material and/or Commercial goods labels.The combination property of thin film is good, has the stretching of uniform vertical and horizontal strong
Degree, and puncture resistance is good, and tearing toughness, hot strength and tangent modulus are high etc., it is possible to be widely used in as
In steaming and decocting film, high transparency film, obstruct protecting film, heat-sealing film or label film.
Compared with prior art, the present invention utilizes fluidized-bed reactor band liquid condensing technique to prepare ethene polymers,
And utilizing the mixing liquid containing high alpha-olefin/ethylene molar ratio that major catalyst is sent into reactor, stream I IIa is led to
The sidepiece crossing reactor flows into reactor, and stream I IIb flows into reactor by the bottom of reactor；Can enter
One step forms the reaction zone that more temperature is different in reactor, obtains high and low molecular weight and high and low branched
Degree microcosmic mix homogeneously and have the polymer of ad hoc structure, further increases strand containing highly-branched degree
Content, and then prepared high performance thin film.The method of the basic present invention, technical process is simple；Easy and simple to handle；
Facility investment with low cost；Continuous-stable is good；Diversified polyethylene film can be produced；Obtain is thin
The combination property of film is good, uniform vertical and horizontal hot strength, meanwhile, and the light transmission of thin film and puncture resistant
Property good and tearing toughness, hot strength and tangent modulus high etc..
Accompanying drawing explanation
For the technical scheme being illustrated more clearly that in the embodiment of the present invention, required in embodiment being described below
Accompanying drawing to be used does to be introduced simply, it is therefore apparent that the accompanying drawing in brief description is only some of the present invention
Embodiment, for those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to
Other accompanying drawing is obtained according to these accompanying drawings.
Fig. 1 represents the schematic diagram of a kind of reaction unit realizing the inventive method.
Fig. 2 forms the schematic diagram in the different olefinic polyreaction district of multiple temperature in representing fluidized-bed reactor.
In the drawings, identical component is indicated by identical reference.Accompanying drawing is not drawn according to actual ratio.
Being described as follows of reference:
1 distribution grid
2 fluidized-bed reactors；
3 compression devices；
4 heat-exchange apparatus；
5 separation equipments；
6 feed pumps；
7 gas circulation line；
8 discharge tanks；
9 scavenging tanks；
10 degassing cabins；
11 for introducing the fluid line of reactor using mixed solution I as carrier logistics by major catalyst；
12 for introducing the fluid line of reactor by stream I IIa；
13 for taking out the fluid line of solid ethylene polymer from reactor；
14 for by H2、N2With the fluid line that ethylene introduces circulation line；
15 for introducing the fluid line of circulation line by alpha-olefin comonomer；
16 for introducing the fluid line of circulation line by condensing agent；
17 for introducing the fluid line of reactor by isolated for separation equipment stream I IIb；
18 for being delivered to the pump of pipeline 11 by mixing liquid I；
19. for joining the device of pipeline 11 by major catalyst powder.
Detailed description of the invention
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but those skilled in the art
It will be appreciated that the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Implement
Unreceipted actual conditions person in example, the condition advised according to normal condition or manufacturer is carried out.Agents useful for same or instrument
Device unreceipted production firm person, be can by city available from conventional products.
Ethene polymers structure and the characterizing method of performance
(1) melt temperature and the sign of crystallization temperature: differential scanning calorimetry (DSC).
Weigh testing sample about 6mg, be heated to about 220 DEG C with the speed of 20 DEG C/min, and at nitrogen stream
Middle holding 2min, is then cooled to about 40 DEG C by it with the speed of 20 DEG C/min, keeps 2min at this temperature
With crystallized sample.Then with the heating rate of 20 DEG C/min, this sample is warming up to 220 DEG C again melt.Record
Melted scanning, it is thus achieved that thermal analysis curue, and thus read melt temperature and crystallization temperature.
(2) sign of weight average molecular weight (Mw): gel permeation chromatography (GPC).
By testing sample with stabilisation 1,2,4-trichloro-benzenes (the 250 μ g/ml BHT (CAS of 70mg/50ml
REGISTRY NUMBER 128-37-0) concentration prepare；Then sample is heated to 170 DEG C of holdings 2.5
Hour to dissolve；Measurement is on Waters GPCV2000, under the conditions of 145 DEG C, with 1.0ml/min.
Flow rate, carry out with identical stabilisation solvent；Three Polymer Lab posts be used in series (Plgel,
20 μm mixing ALS, 300X 7.5mm).
(3) mensuration of molecular weight distributing index (PDI): the RMS-800 type of Rheometrics company is put down
Plate rheometer.
Operate under the conditions of 0.1rad/s increases to 100rad/s at frequency of vibration.Intersection modulus (crossover
Modulus) can derive PI:PI=105/Gc by below equation, wherein, Gc is for intersecting modulus, and it is for working as
G '=G " time the value (representing with Pa) that determines, wherein G ' is storage modulus, G " be loss modulus.
(4) sign of melt flow index (MFR): according to ISO side under the conditions of 230 DEG C/2.16kg
Method 1133 measures.
(5) mensuration of ethylene contents: IR spectrographic method.
(6) mensuration of alpha-olefin content: IR spectrographic method.
(7) mensuration of density: measure according to ISO 1183.
(8) thickness: measure according to GB/T 6672-2001.
(9) hot strength and tension fracture elongation rate: measure according to ISO 527.
(10) tearing strength: according to ASTM D1922, simultaneously in longitudinal direction (MD) with laterally (TD)
Upper mensuration.
(11) puncture resistance: measure according to BB/T 0024-2004.
(12) tangent modulus: according to ASTM D882, simultaneously in longitudinal direction (MD) with laterally (TD)
Upper mensuration.
(13) transparency: measure according to BB/T 0024-2004；
(14) mist degree: measure according to GB/T 2410-2008.
In a concrete example, as it is shown in figure 1, in the fluidized-bed reactor 2 that inside has nitrogen to fluidize,
First pass through device 19 such as feeding device the major catalyst powder in Ziegler-Natta catalyst is joined with instead
Answer in the pipeline 11 that device 2 is connected, utilize pumping unit 18 to be transported to by the mixing liquid I containing alkane and alkene
In pipeline 11, utilize mixing liquid 11 to do carrier and major catalyst powder is transported in reactor 2, mixed liquor
Possibly together with promoter in body I, wherein, pipeline 11 can have one or more with the connector of reactor 2.
Pipeline 7 is connected with the top expanded section of fluidized-bed reactor 2, for receiving in fluidized-bed reactor 2
Stream I I.Material in stream I I may comprise unreacted olefinic monomer and alkane etc..Enter through supplementing alkene
Stream I II is obtained after material (can by 14 and pipeline 15).According to experiment needs, also can mend in stream I I
Fill alkane charging (by pipeline 16) and supplementary regulator and (pipeline 14, such as H can be passed through2) and inertia
Component charging (can pass through pipeline 14, such as N2) etc., to obtain stream I II.Stream I II is given stream I IIa
With bottom and the top that IIIb distribution is passed through reactor.In an instantiation, from heat exchanger 4 thing out
Stream III, through gas-liquid separator 5, is divided into stream I IIa and IIIb.The major part of condensing agent total content in stream I II
Being positioned in stream I IIa, stream I IIa is by fluid line 12 and 19 (can pass through pump 6, increase feed rate)
Spraying into fluidized-bed reactor 2, remaining condensing agent is positioned in stream I IIb, and with fluid line 17 at distribution grid 1
Lower section enter fluidized-bed reactor 2, wherein, pipeline 19 can have one or many with the connector of reactor 2
Individual.According to the method in the present invention, in fluidized-bed reactor, form high temperature reaction zone A and cryogenic reaction zone B,
As shown in Figure 2.
In polyreaction generate solid polymer off and on from fluid line 13 discharging, successively through discharge tank 8,
After scavenging tank 9 and degassing cabin 10 devolatilization process, it is transported to downstream section and is processed further.Obtain vinyl polymerization
Thing.
Embodiment 1
The present embodiment uses the TiCl of magnesium chloride load3For major catalyst (major catalyst inlet amount 2.18kg/h),
Using triethyl aluminum as the Ziegler-Natta catalyst of promoter.Wherein, the rubbing of major catalyst and promoter
You are calculated as 3.11 with Ti/Al at ratio.Reaction process is shown in Fig. 1.
Mixing liquid I mass flow be 1.8t/h, account for stream I I mass flow 0.42%.At mixing liquid
In I, alkane isopentane content accounts for 50 weight % (molar content is 49%) of mixing liquid, and olefin(e) centent accounts for
50 weight % (molar content is 51%) of mixing liquid, wherein, ethylene contents accounts for 4.9 weights of mixing liquid
Amount % (molar content is 12.5%), 1-ahexene content account for mixing liquid 45.1 weight % (molar content is
38.5%).Possibly together with the triethyl aluminum catalyst of 200ppm in mixing liquid I.
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 supplementing charging, obtain stream I II.The mass flow of stream I I accounts for the quality of stream I II
Flow-rate ratio is 97.8%.Isopentane in stream I II, 80wt% is positioned in stream I IIa, and remaining is positioned at logistics
In IIIb.
Polymerization time is 2h, finally obtains the bipolymer of ethylene/1-hexene, i.e. second own binary polymer A.
In the present embodiment, each constituent content of stream I II asks for an interview table 1 below.
Table 1
The performance of second own binary polymer A and the characterization result of structure prepared by the present embodiment ask for an interview table 4 below.
Embodiment 2
The present embodiment uses the TiCl of magnesium chloride load3For major catalyst (load capacity is 1.75kg/h), with three second
Base aluminum is as the Ziegler-Natta catalyst of promoter.Wherein, major catalyst and the molar ratio of promoter
It is calculated as 3.11 with Ti/Al.Reaction process is shown in Fig. 1.
Mixing liquid I mass flow be 1.3t/h, account for stream I I mass flow 0.30%.Mixing liquid I
In, alkane isopentane content accounts for 45 weight % (molar content is 35%) of mixing liquid, and olefin(e) centent accounts for mixed
Closing 55 weight % (molar content is 65%) of liquid, wherein, ethylene contents accounts for 8.8 weight of mixing liquid
% (molar content is 17.8%), 1-butylene content accounts for 46.2 weight % of mixing liquid) (molar content is
47.2%), possibly together with the triethyl aluminum catalyst of 180ppm in mixing liquid.
Apparent fluidizing gas velocity in reactor is 0.70m/s.The pressure of fluidized-bed reactor is 2.0MPa, temperature
It it is 88 DEG C.
In stream I I after supplementing charging, obtain stream I II.The mass flow of stream I I accounts for the quality of stream I II
The 96.8% of flow.Isopentane in stream I II, 80wt% is positioned in stream I IIa, and remaining is positioned at stream I IIb
In.
Polymerization time is 2h, finally obtains the bipolymer of Ethylene/1-butene, i.e. second fourth binary polymer B.
In the present embodiment, each constituent content of stream I II asks for an interview table 2 below.
Table 2
The performance of second fourth binary polymer B and the characterization result of structure prepared by the present embodiment ask for an interview 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), using triethyl aluminum as promoter.Wherein, major catalyst and the molar ratio of promoter
It is calculated as 3.11 with Ti/Al.Reaction process is shown in Fig. 1.
Mixing liquid I mass flow be 1.7t/h, account for stream I I mass flow 0.37%.Mixing liquid I
In, alkane normal hexane content accounts for 25 weight % (molar content is 25%) of mixing liquid, and olefin(e) centent accounts for mixed
Closing 75 weight % (molar content is 75%) of liquid, wherein, ethylene contents accounts for 7.8 weight of mixing liquid
% (molar content 23.8%), 1-octene content accounts for 67.2 weight % (molar content is 51.2%) of mixing liquid,
Possibly together with the triethyl aluminum catalyst of 180ppm in mixing liquid.
Apparent fluidizing gas velocity in reactor is 0.68m/s.The pressure of fluidized-bed reactor is 2.1MPa, temperature
It it is 87 DEG C.
In stream I I after supplementing charging, obtain stream I II.The mass flow of stream I I accounts for the quality of stream I II
The 97.2% of flow.Isopentane in stream I II, 80wt% is positioned in stream I IIa, itself and be positioned at stream I IIb
In.
In the present embodiment, each constituent content of stream I II asks for an interview table 3 below.
Table 3
The performance of second pungent binary polymer C and the characterization result of structure prepared by the present embodiment ask for an interview table 4 below.
Comparative example 1
This comparative example uses the method in WO00/02929A1 disclosed in embodiment 35, with ethylene and 1-hexene
Second own binary polymer D is prepared as raw material.
The performance of second own binary polymer D and the characterization result of structure prepared by this comparative example please participate in following table
4。
Comparative example 2
With embodiment 1, difference is, without mixing liquid I, promoter and major catalyst are added directly into
In reactor, prepare second own binary polymer E using ethylene and 1-hexene as raw material.Namely this comparative example
In method be similar to CN104628904CN.The performance of the second own binary polymer E prepared by this comparative example
And the characterization result of structure please participate in table 4 below.
Comparative example 3
With embodiment 2, difference is, does not mix liquid I, promoter and major catalyst and is directly added into
In reactor, prepare second fourth binary polymer F using ethylene and 1-butylene as raw material.Namely this is right
Method in ratio is similar to CN104628904CN.Second own binary polymer F's prepared by this comparative example
The characterization result of performance and structure please participate in table 4 below.
Table 4
From above example 1-3 and the preparation-obtained polyvinyl characterization result of comparative example, implement
The own polymer A of second, second fourth polymer B and the second pungent polymer C that prepare in example 1-3 are compared to right
For the polymer D-F of ratio 1-3, 'alpha '-olefin monomers unit content, and wherein, the alpha-olefin that head connects
Monomer unit content is high, and the ethene polymers that this explanation utilizes the inventive method to obtain has more side chain and more
The high degree of branching.
Additionally, in same monomer, and the weight average molecular weight of polymer relatively in the case of, utilize the present invention
The copolymer that method prepares, its melt index MFR is relatively low, and molecular weight distribution index PI, density,
Mist degree is significantly lower than the polymer of comparative example, and vertical and horizontal hot strength is superior to the copolymer in comparative example
(see embodiment 1 and comparative example 1 and 2, embodiment 2 and comparative example 3), particularly, copolymer A, B,
The longitudinally, laterally hot strength of C is sufficiently close to, and its ratio is respectively 1.014,1.006 and 1.005, hence it is evident that excellent
In copolymer D-F.This is relevant to production method.According to the production method in the present invention, highly-branched degree
Strand content is many, and chain entanglement degree rises, and vertical and horizontal tensile property improves, and then density reduces, mist
Degree reduces.
From above example 1-3 and the preparation-obtained polyvinyl characterization result of comparative example 1-3, enter
One step uses a kind of mixing solution containing alkane and alkene to do carrier and is transported in reactor by major catalyst, and controls
Make wherein alpha-olefin and the mol ratio of ethylene, be more beneficial for improving the degree of branching, be conducive to making polymer tensile property
Improve, density reduces, mist degree reduces and molecular weight distribution sharp.
It it is below the embodiment of BOPE film preparation
Embodiment 4
(1) preparation of BOPE film
The BOPE film of the present embodiment includes exterior layer 1, sandwich layer and exterior layer 2 totally three layers, exterior layer 1 successively
Being connected with the two sides of sandwich layer respectively with exterior layer 2, exterior layer 1 is that thin film directly contacts with external environment with 2
Outermost layer.
Exterior layer 1 and exterior layer 2 is raw materials used and proportioning is: the Mitsui chemical company trade mark of 70wt% is
The linear low density polyethylene (LLDPE) of SP1520, LG chemical company of the Korea S trade mark of 10wt% is H5200
COPP (MFR=2g/10min), the Exxon Mobil chemical company trade mark of 16wt% is Exceed
The metallocene PE (MPE) of 1327KD, the bonding-prevention master batch (ABPP 905DCPP) of 4wt%.
Sandwich layer is raw materials used and proportioning is: the ethylene obtained in the embodiment 1 of 94wt%/1-hexene copolymer (second
Own binary polymer A), the smooth functional master batch (603PP) of 3wt%, the carbon eight material (metallocene catalysis of 3wt%
The ethylene-octene copolymer of agent synthesis, Tao Shi 488-4A).
By exterior layer 1, exterior layer 2 and sandwich layer material in above ratio mix homogeneously, it is then sent to storage tank,
Delivering to three single screw extrusion machine extrusions respectively through pipeline, then be extruded into pipe through triple extrusion die head, pipe divides
Layer part by weight is exterior layer 1: sandwich layer: exterior layer 2=20:60:20, the spiral shell of the single screw extrusion machine of exterior layer
Shank diameter is 50mm, and draw ratio is 30:1, and extrusion temperature is 220 DEG C, the spiral shell of the single screw extrusion machine of sandwich layer
Shank diameter is 100mm, and draw ratio is 30:1, and extrusion temperature is 220 DEG C, and extruded material is at three-layer co-extruded mould
Head converges formation pipe, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is pulled into stretching after cooling
Baking oven.Pipe is filled with compressed air in drawing oven and stretches, and draft temperature is 116 DEG C, cross directional stretch
Multiple is 2.2-2.7, and longitudinal stretching multiple is 2.2-2.7, i.e. can get the thin film that thickness is 25 μm, two-way draws
Thin film after stretching forces cooling through vane, cuts rear rolling open to point, cuts and obtain final products, i.e. BOPE film
G。
(2) performance characterization of BOPE film
The performance characterization of the BOPE film G prepared by the present embodiment is the results detailed in table 5 below.
Embodiment 5
(1) preparation of BOPE film
The BOPE film of the present embodiment includes exterior layer 1, sandwich layer and exterior layer 2 totally three layers, exterior layer 1 successively
Being connected with the two sides of sandwich layer respectively with exterior layer 2, exterior layer 1 is that thin film directly contacts with external environment with 2
Outermost layer.
Exterior layer 1 and exterior layer 2 is raw materials used and proportioning is: the Mitsui chemical company trade mark of 70wt% is
The linear low density polyethylene (LLDPE) of SP1520, LG chemical company of the Korea S trade mark of 10wt% is H5200
COPP (MFR=2g/10min), the Exxon Mobil chemical company trade mark of 16wt% is Exceed
The metallocene PE (MPE) of 1327KD, the bonding-prevention master batch of 4wt%.
Sandwich layer is raw materials used and proportioning is: the Ethylene/1-butene copolymer (second obtained in the embodiment 2 of 94wt%
Fourth binary polymer B), the smooth functional master batch (with embodiment 4) of 3wt%, carbon eight material of 3wt% is (with implementing
Example 4).
By exterior layer 1, exterior layer 2 and sandwich layer material in above ratio mix homogeneously, it is then sent to storage tank,
Delivering to three single screw extrusion machine extrusions respectively through pipeline, then be extruded into pipe through triple extrusion die head, pipe divides
Layer part by weight is exterior layer 1: sandwich layer: exterior layer 2=20:60:20, the spiral shell of the single screw extrusion machine of exterior layer
Shank diameter is 50mm, and draw ratio is 30:1, and extrusion temperature is 220 DEG C, the spiral shell of the single screw extrusion machine of sandwich layer
Shank diameter is 100mm, and draw ratio is 30:1, and extrusion temperature is 220 DEG C, and extruded material is at three-layer co-extruded mould
Head converges formation pipe, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is pulled into stretching after cooling
Baking oven.Pipe is filled with compressed air in drawing oven and stretches, and draft temperature is 116 DEG C, cross directional stretch
Multiple is 2.2-2.7, and longitudinal stretching multiple is 2.2-2.7, i.e. can get the thin film that thickness is 25 μm, two-way draws
Thin film after stretching forces cooling through vane, cuts rear rolling open to point, cuts and obtain final products, i.e. BOPE film
H。
(2) performance characterization of BOPE film
The performance characterization of the BOPE film H prepared by the present embodiment is the results detailed in table 5 below.
Embodiment 6
(1) preparation of BOPE film
The BOPE film of the present embodiment includes exterior layer 1, sandwich layer and exterior layer 2 totally three layers, exterior layer 1 successively
Being connected with the two sides of sandwich layer respectively with exterior layer 2, exterior layer 1 is that thin film directly contacts with external environment with 2
Outermost layer.
Exterior layer 1 and exterior layer 2 is raw materials used and proportioning is: the Mitsui chemical company trade mark of 70wt% is
The linear low density polyethylene (LLDPE) of SP1520, LG chemical company of the Korea S trade mark of 10wt% is H5200
COPP (MFR=2g/10min), the Exxon Mobil chemical company trade mark of 16wt% is Exceed
The metallocene PE (MPE) of 1327KD, the bonding-prevention master batch (with embodiment 4) of 4wt%.
Sandwich layer is raw materials used and proportioning is: the ethylene obtained in the embodiment 3 of 94wt%/1-octene copolymer (second
Pungent binary polymer C), the smooth functional master batch (with embodiment 4) of 3wt%, carbon eight material of 3wt% is (with implementing
Example 4).
By exterior layer 1, exterior layer 2 and sandwich layer material in above ratio mix homogeneously, it is then sent to storage tank,
Delivering to three single screw extrusion machine extrusions respectively through pipeline, then be extruded into pipe through triple extrusion die head, pipe divides
Layer part by weight is exterior layer 1: sandwich layer: exterior layer 2=20:60:20, the spiral shell of the single screw extrusion machine of exterior layer
Shank diameter is 50mm, and draw ratio is 30:1, and extrusion temperature is 220 DEG C, the spiral shell of the single screw extrusion machine of sandwich layer
Shank diameter is 100mm, and draw ratio is 30:1, and extrusion temperature is 220 DEG C, and extruded material is at three-layer co-extruded mould
Head converges formation pipe, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is pulled into stretching after cooling
Baking oven.Pipe is filled with compressed air in drawing oven and stretches, and draft temperature is 116 DEG C, cross directional stretch
Multiple is 2.2-2.7, and longitudinal stretching multiple is 2.2-2.7, i.e. can get the thin film that thickness is 25 μm, two-way draws
Thin film after stretching forces cooling through vane, cuts rear rolling open to point, cuts and obtain final products, i.e. BOPE film
I。
(2) performance characterization of BOPE film
The performance characterization of the BOPE film I prepared by the present embodiment is the results detailed in table 5 below.
Comparative example 4
(1) preparation of BOPE film
The BOPE film of the present embodiment includes exterior layer 1, sandwich layer and exterior layer 2 totally three layers, exterior layer 1 successively
Being connected with the two sides of sandwich layer respectively with exterior layer 2, exterior layer 1 is that thin film directly contacts with external environment with 2
Outermost layer.
Exterior layer 1 and exterior layer 2 is raw materials used and proportioning is: the Mitsui chemical company trade mark of 70wt% is
The linear low density polyethylene (LLDPE) of SP1520, LG chemical company of the Korea S trade mark of 10wt% is H5200
COPP (MFR=2g/10min), the Exxon Mobil chemical company trade mark of 16wt% is Exceed
The metallocene PE (MPE) of 1327KD, the bonding-prevention master batch (with embodiment 4) of 4wt%.
Sandwich layer is raw materials used and proportioning is: the ethylene obtained in the comparative example 1 of 94wt%/1-hexene copolymer (second
Own binary polymer D), the smooth functional master batch of 3wt%, carbon eight material of 3wt%.
By exterior layer 1, exterior layer 2 and sandwich layer material in above ratio mix homogeneously, it is then sent to storage tank,
Delivering to three single screw extrusion machine extrusions respectively through pipeline, then be extruded into pipe through triple extrusion die head, pipe divides
Layer part by weight is exterior layer 1: sandwich layer: exterior layer 2=20:60:20, the spiral shell of the single screw extrusion machine of exterior layer
Shank diameter is 50mm, and draw ratio is 30:1, and extrusion temperature is 220 DEG C, the spiral shell of the single screw extrusion machine of sandwich layer
Shank diameter is 100mm, and draw ratio is 30:1, and extrusion temperature is 220 DEG C, and extruded material is at three-layer co-extruded mould
Head converges formation pipe, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is pulled into stretching after cooling
Baking oven.Pipe is filled with compressed air in drawing oven and stretches, and draft temperature is 116 DEG C, cross directional stretch
Multiple is 2.2-2.7, and longitudinal stretching multiple is 2.2-2.7, i.e. can get the thin film that thickness is 25 μm, two-way draws
Thin film after stretching forces cooling through vane, cuts rear rolling open to point, cuts and obtain final products, i.e. BOPE film
J。
(2) performance characterization of BOPE film
The performance characterization of the BOPE film J prepared by the present embodiment is the results detailed in table 5 below.
Comparative example 5
(1) preparation of BOPE film
The BOPE film of the present embodiment includes exterior layer 1, sandwich layer and exterior layer 2 totally three layers, exterior layer 1 successively
Being connected with the two sides of sandwich layer respectively with exterior layer 2, exterior layer 1 is that thin film directly contacts with external environment with 2
Outermost layer.
Exterior layer 1 and exterior layer 2 is raw materials used and proportioning is: the Mitsui chemical company trade mark of 70wt% is
The linear low density polyethylene (LLDPE) of SP1520, LG chemical company of the Korea S trade mark of 10wt% is H5200
COPP (MFR=2g/10min), the Exxon Mobil chemical company trade mark of 16wt% is Exceed
The metallocene PE (MPE) of 1327KD, the bonding-prevention master batch (with embodiment 4) of 4wt%.
Sandwich layer is raw materials used and proportioning is: the ethylene obtained in the comparative example 2 of 94wt%/1-hexene copolymer (second
Own binary polymer E), the smooth functional master batch (with embodiment 4) of 3wt%, carbon eight material of 3wt% is (with implementing
Example 4).
By exterior layer 1, exterior layer 2 and sandwich layer material in above ratio mix homogeneously, it is then sent to storage tank,
Delivering to three single screw extrusion machine extrusions respectively through pipeline, then be extruded into pipe through triple extrusion die head, pipe divides
Layer part by weight is exterior layer 1: sandwich layer: exterior layer 2=20:60:20, the spiral shell of the single screw extrusion machine of exterior layer
Shank diameter is 50mm, and draw ratio is 30:1, and extrusion temperature is 220 DEG C, the spiral shell of the single screw extrusion machine of sandwich layer
Shank diameter is 100mm, and draw ratio is 30:1, and extrusion temperature is 220 DEG C, and extruded material is at three-layer co-extruded mould
Head converges formation pipe, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is pulled into stretching after cooling
Baking oven.Pipe is filled with compressed air in drawing oven and stretches, and draft temperature is 116 DEG C, cross directional stretch
Multiple is 2.2-2.7, and longitudinal stretching multiple is 2.2-2.7, i.e. can get the thin film that thickness is 25 μm, two-way draws
Thin film after stretching forces cooling through vane, cuts rear rolling open to point, cuts and obtain final products, i.e. BOPE film
K。
(2) performance characterization of BOPE film
The performance characterization of the BOPE film K prepared by the present embodiment is the results detailed in table 5 below.
Comparative example 6
(1) preparation of BOPE film
The BOPE film of the present embodiment includes exterior layer 1, sandwich layer and exterior layer 2 totally three layers, exterior layer 1 successively
Being connected with the two sides of sandwich layer respectively with exterior layer 2, exterior layer 1 is that thin film directly contacts with external environment with 2
Outermost layer.
Exterior layer 1 and exterior layer 2 is raw materials used and proportioning is: the Mitsui chemical company trade mark of 70wt% is
The linear low density polyethylene (LLDPE) of SP1520, LG chemical company of the Korea S trade mark of 10wt% is H5200
COPP (MFR=2g/10min), the Exxon Mobil chemical company trade mark of 16wt% is Exceed
The metallocene PE (MPE) of 1327KD, the bonding-prevention master batch (with embodiment 4) of 4wt%.
Sandwich layer is raw materials used and proportioning is: the Ethylene/1-butene copolymer (second obtained in the comparative example 3 of 94wt%
Fourth binary polymer F), the smooth functional master batch (with embodiment 4) of 3wt%, carbon eight material of 3wt% is (with implementing
Example 4).
By exterior layer 1, exterior layer 2 and sandwich layer material in above ratio mix homogeneously, it is then sent to storage tank,
Delivering to three single screw extrusion machine extrusions respectively through pipeline, then be extruded into pipe through triple extrusion die head, pipe divides
Layer part by weight is exterior layer 1: sandwich layer: exterior layer 2=20:60:20, the spiral shell of the single screw extrusion machine of exterior layer
Shank diameter is 50mm, and draw ratio is 30:1, and extrusion temperature is 220 DEG C, the spiral shell of the single screw extrusion machine of sandwich layer
Shank diameter is 100mm, and draw ratio is 30:1, and extrusion temperature is 220 DEG C, and extruded material is at three-layer co-extruded mould
Head converges formation pipe, and the temperature of extrusion die is 223 DEG C, and the pipe of extrusion is pulled into stretching after cooling
Baking oven.Pipe is filled with compressed air in drawing oven and stretches, and draft temperature is 116 DEG C, cross directional stretch
Multiple is 2.2-2.7, and longitudinal stretching multiple is 2.2-2.7, i.e. can get the thin film that thickness is 25 μm, two-way draws
Thin film after stretching forces cooling through vane, cuts rear rolling open to point, cuts and obtain final products, i.e. BOPE film
L。
(2) performance characterization of BOPE film
The performance characterization of the BOPE film 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 being compared and understand, the stretching of BOPE film G, H and I is strong
Degree, tearing toughness and puncture resistance are all substantially better than BOPE film J, K, L.Especially, this is utilized
BOPE film G, H, I that copolymer A that bright method prepares, B, C are formed, its vertical and horizontal
Hot strength all very close to, its vertically and horizontally hot strength ratio respectively 1.071,1.036,1.032, and contrast
Example BOPE film J, K, L, the hot strength difference of its vertical and horizontal is relatively big, inclined in horizontal hot strength
Little, easily it is pulled off.This is because the polyethylene that the inventive method produces, 'alpha '-olefin monomers unit content, and its
In, the 'alpha '-olefin monomers unit content that head connects is high, and then the degree of branching is high.And wherein, octene is as altogether
The branch lengths of the second pungent copolymer C of poly-monomer is the longest, and chain entanglement degree rises, vertically and horizontally hot strength ratio
Minimum.
The thin film provided according to the present invention, its tensile property is good, light transmittance is high, autohension is high, mist degree is low, and
Density is low, light weight, performance such as tearing toughness and puncture resistance etc. improve, and then have broadness application before
Scape.
Any numerical value mentioned in the present invention, if simply had between any minimum and any of the highest value
The interval of two units, then include all values every time increasing a unit from minimum to peak.Such as,
If the amount of a kind of component of life, or the value of the state-variable such as such as temperature, pressure, time is 50-90,
It means that specifically list 51-89,52-88 in this specification ... and the number such as 69-71 and 70-71
Value.For non-integral value, can be with due regard to a unit with 0.1,0.01,0.001 or 0.0001.This
It is only some special examples indicated.In this application, in a similar manner, cited minimum and peak
Between likely combining of numerical value be considered to disclose.
When it is noted that embodiment described above is only used for explaining the present invention, it is not intended that and the present invention is appointed
What limits.By referring to exemplary embodiments, invention has been described, it should be appreciated that word wherein used
Language is descriptive and explanatory vocabulary rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and in without departing substantially from scope and spirit of the present invention, the present invention is repaiied
Order.Although the present invention described in it relates to specific method, material and embodiment, it is not intended that this
Invention is limited to wherein disclosed particular case, and on the contrary, the present invention can be extended to other all sides with identical function
Method and application.
Claims (10)
1. a preparation method for polyethylene film, comprises the following steps:
1) with mixing liquid I be that the major catalyst in catalyst system is transported in reactor by carrier logistics, institute
State mixing liquid I and comprise alkane, alkene and promoter；Supplement to from stream I I that reactor head flows out
Obtain stream I II after raw material, stream I II is divided into stream I IIa and IIIb, stream I IIa and IIIb and is back to respectively
The sidepiece of reactor and bottom；In the reactor, aggregated ethene polymers is obtained and from sidewall of reactor discharging；
Wherein, described alkene includes alpha-olefin and ethylene, and in described mixing liquid I, the mol ratio of alpha-olefin and ethylene is extremely
It is 1 less；
2) by step 1) ethene polymers for preparing by blow molding process, obtain polyethylene film.
2. according to the method described in claim 1, it is characterised in that described polyethylene film is biaxial tension
Polyethylene film.
Method the most according to claim 1, it is characterised in that alpha-olefin and second in described mixing liquid I
The mol ratio of alkene is 1-5；In described mixing liquid, the mass percentage content of alkane is 5w%-80%；Institute
The mass flow stating mixing liquid I accounts for the 0.05%-5% of mass flow of stream I I.
4. according to the method described in any one in Claims 2 or 3, it is characterised in that in described reactor
Reaction pressure be 0.5-10MPa；Reaction temperature is 40-150 DEG C, the apparent fluidizing gas velocity in described reactor
For 0.1-10m/s, in described reactor, comprise the reaction zone that temperature is different；Described reactor is fluidized-bed reactor.
The most according to the method in claim 2 or 3, it is characterised in that in described stream I II, alkene
Mole percent level is 1.0%-60.0%；The mole percent level of alkane is 0.5%-50.0%, described thing
In stream III, alpha-olefin molar concentration accounts for the 20%-60% of ethylene molar concentration, comprises regulation in described stream I II
Agent and/or inert component；Wherein, described regulator is preferably hydrogen；Described inert component is preferably nitrogen；Institute
The mole percent level stating regulator is 0.3%-14.5%；In described stream I I, rubbing of described inert component
Your degree is 25.0%-75.0%, comprises the charging of supplementary alkane, supplements regulator and enter in described stream I II
At least one in material and the charging of supplementary inert component.
6. according to the method described in claim 5, it is characterised in that the alkane in stream I IIa accounts for stream I II
In the 60-90wt% of alkane total amount；Alkene in stream I IIa accounts for the alkene total amount in stream I II
10-50wt%；The mass flow of stream I I accounts for more than the 90% of the mass flow of stream I II.
7. according to the method described in claim 1 or 3, it is characterised in that described alkane is selected from butane, isobutyl
At least one in alkane, pentane, isopentane, normal hexane, hexamethylene and heptane；Described alpha-olefin is selected from third
At least one in alkene, 1-butylene, 1-amylene, 1-hexene, 1-octene and 1-decene.
Method the most according to claim 1, it is characterised in that described catalyst system include Ziegler-
Natta catalyst, metallocene catalyst, transition-metal catalyst, inorganic chromium catalyst and organic chromium catalyst.
9. according to the method described in any one in claim 1-3, it is characterised in that prepared ethylene gathers
In compound, the molar content shared by 'alpha '-olefin monomers unit is 1%-30%；Prepared ethene polymers has
Following characteristic: density is at 0.890g/cm3To 0.922g/cm3；Melt under conditions of 230 DEG C and 2.16kg
Flow rate is 0.1-10g/10min, and weight average molecular weight is 20000-250000, and molecular weight distributing index is 2-15,
Longitudinal tensile strength MD and transverse tensile strength TD is more than 15MPa, and its ratio MD/TD is less than 1.15,
Step 2) the ratio MD/TD of the longitudinal tensile strength MD and transverse tensile strength TD of polyethylene film for preparing
Less than 1.1.
10. the polyethylene film that in claim 1-9 prepared by method described in any one is packaging material and/or business
Application in product label.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610144252.0A CN105802033B (en) | 2016-03-14 | 2016-03-14 | A kind of preparation method and applications of polyethylene film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610144252.0A CN105802033B (en) | 2016-03-14 | 2016-03-14 | A kind of preparation method and applications of polyethylene film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105802033A true CN105802033A (en) | 2016-07-27 |
| CN105802033B CN105802033B (en) | 2018-02-16 |
Family
ID=56467385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610144252.0A Active CN105802033B (en) | 2016-03-14 | 2016-03-14 | A kind of preparation method and applications of polyethylene film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105802033B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107226876A (en) * | 2016-03-23 | 2017-10-03 | 中国石油化工股份有限公司 | A kind of polyvinyl preparation method |
| CN107226878A (en) * | 2016-03-23 | 2017-10-03 | 中国石油化工股份有限公司 | A kind of preparation method and applications of polyethylene film |
| CN114957530A (en) * | 2022-06-28 | 2022-08-30 | 杭州双安科技有限公司 | Solution polymerization method of ethylene and alpha-olefin |
| CN115044125A (en) * | 2022-08-15 | 2022-09-13 | 汕头市贝斯特科技有限公司 | Special low-friction-coefficient anti-bonding master batch for BOPE (biaxially oriented polyethylene) composite film, preparation method of master batch and BOPE composite film |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1578803A (en) * | 2001-07-19 | 2005-02-09 | 尤尼威蒂恩技术有限责任公司 | Polyethylene films with improved physical properties |
| CN1939943A (en) * | 2005-09-30 | 2007-04-04 | 住友化学株式会社 | Ethylene-alpha-olefin copolymer, resin composition containing the same and molded article thereof |
| WO2008074689A1 (en) * | 2006-12-21 | 2008-06-26 | Ineos Europe Limited | Copolymers and films thereof |
| CN104558349A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Method for performing olefin polymerization by fluidized bed facility, olefin polymer prepared by method and application of olefin polymer |
| CN104558332A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing polymer |
-
2016
- 2016-03-14 CN CN201610144252.0A patent/CN105802033B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1578803A (en) * | 2001-07-19 | 2005-02-09 | 尤尼威蒂恩技术有限责任公司 | Polyethylene films with improved physical properties |
| CN1939943A (en) * | 2005-09-30 | 2007-04-04 | 住友化学株式会社 | Ethylene-alpha-olefin copolymer, resin composition containing the same and molded article thereof |
| WO2008074689A1 (en) * | 2006-12-21 | 2008-06-26 | Ineos Europe Limited | Copolymers and films thereof |
| CN104558349A (en) * | 2013-10-15 | 2015-04-29 | 中国石油化工股份有限公司 | Method for performing olefin polymerization by fluidized bed facility, olefin polymer prepared by method and application of olefin polymer |
| CN104558332A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing polymer |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107226876A (en) * | 2016-03-23 | 2017-10-03 | 中国石油化工股份有限公司 | A kind of polyvinyl preparation method |
| CN107226878A (en) * | 2016-03-23 | 2017-10-03 | 中国石油化工股份有限公司 | A kind of preparation method and applications of polyethylene film |
| CN114957530A (en) * | 2022-06-28 | 2022-08-30 | 杭州双安科技有限公司 | Solution polymerization method of ethylene and alpha-olefin |
| CN114957530B (en) * | 2022-06-28 | 2023-09-29 | 杭州双安科技有限公司 | Solution polymerization method of ethylene and alpha-olefin |
| CN115044125A (en) * | 2022-08-15 | 2022-09-13 | 汕头市贝斯特科技有限公司 | Special low-friction-coefficient anti-bonding master batch for BOPE (biaxially oriented polyethylene) composite film, preparation method of master batch and BOPE composite film |
| CN115044125B (en) * | 2022-08-15 | 2022-11-15 | 汕头市贝斯特科技有限公司 | Special low-friction-coefficient anti-bonding master batch for BOPE (biaxially oriented polyethylene) composite film, preparation method of master batch and BOPE composite film |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105802033B (en) | 2018-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7090643B2 (en) | Multi-reactor solution polymerization | |
| CN102892792B (en) | The technology that is continuously withdrawn of polymer reactor and Stress control | |
| JP2020517767A (en) | Multi reactor solution polymerization, polyethylene and polyethylene film | |
| US10301404B2 (en) | Flashline heater system and method | |
| Demirors | The history of polyethylene | |
| CN102741302B (en) | Compressible liquid thinner in polyolefin polymerization | |
| CN105802033A (en) | Preparation method and application of polyethylene film | |
| JP2017535636A (en) | Solution polymerization process | |
| CN105121002A (en) | Chain transfer agent removal between polyolefin polymerization reactors | |
| US20180258204A1 (en) | Olefin polymerization apparatus and olefin polymerization process | |
| CN101384625A (en) | Monomer recovery by returning column overhead liquid to the reactor | |
| CN105189574A (en) | Polyethylene production with multiple polymerization reactors | |
| CN101831018A (en) | Has polyethylene film of improved barrier properties and preparation method thereof | |
| BR112021010757A2 (en) | PROCESS FOR THE PREPARATION OF AN ETHYLENE POLYMER | |
| Sedov et al. | Single-site catalysts in the industrial production of polyethylene | |
| CN104628904B (en) | A kind of method that utilization multi-temperature reaction zone prepares olefin polymer | |
| CN102060943B (en) | Multi-zone circulating reaction device and method for olefin polymerization | |
| Kanellopoulos et al. | Industrial multimodal processes | |
| CN107226876A (en) | A kind of polyvinyl preparation method | |
| CN106928383B (en) | Olefinic polymerization device and method | |
| CN105377417A (en) | Cooling between multiple polyolefin polymerization reactors | |
| CN104045758A (en) | Novel Medium Density Polyethylene Compositions | |
| CN107226878A (en) | A kind of preparation method and applications of polyethylene film | |
| CN106957382B (en) | A kind of method and apparatus of dynamic operation production polyolefin | |
| CN105984188B (en) | One kind tying up film and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |