CN1358215A - Polyethylene film composition - Google Patents

Polyethylene film composition Download PDF

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Publication number
CN1358215A
CN1358215A CN98814224A CN98814224A CN1358215A CN 1358215 A CN1358215 A CN 1358215A CN 98814224 A CN98814224 A CN 98814224A CN 98814224 A CN98814224 A CN 98814224A CN 1358215 A CN1358215 A CN 1358215A
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multipolymer
reactor
density
ethene
alpha
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M·W·蒂尔斯顿
S·M·乌普哈姆
小W·J·米赤
G·E·埃勒
J·O·布勒－维达尔
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Union Carbide Chemicals and Plastics Technology LLC
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Union Carbide Chemicals and Plastics Technology LLC
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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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/001—Multistage polymerisation processes characterised by a change in reactor conditions without deactivating the intermediate polymer
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

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  • 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)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

An in situ blend comprising a mixture of first and second ethylene/alpha-olefin copolymers wherein the alpha-olefin has 3 to 8 carbon atoms, the first copolymer having a density in the range of 0.9035 to 0.908 gram per cubic centimeter and a roll-milled flow index in the range of about 1.4 to about 2.6 grams per 10 minutes and the second copolymer having a density in the range of 0.925 to 0.945 gram per cubic centimeter and a melt index in the range of about 200 to about 400 grams per 10 minutes; the weight ratio of the first copolymer to the second copolymer being in the range of about 45.55 to about 60:40 and the in situ blend having a density in the range of 0.919 to 0.924 gram per cubic centimeter, a melt flow ratio in the range of about 85 to about 115 and a flow index of 65 to 90 grams per 10 minutes.

Description

Polyethylene film composition
Technical field
The present invention relates to the blend of so a kind of polyethylene and ethylene copolymers, the film of extruding from this blend does not have gel (or flake) basically.
Background information
Made the polyethylene of various density and be processed into film, this film is characterised in that its excellent tensile strength, high ultimate elongation, good shock strength and excellent puncture resistance.These performances and toughness are just improved when polyethylene has high molecular.Yet, along with the common variation of workability of the increase resin of molecular weight of polyethylene.By the concurrent mixture of high molecular and low-molecular-weight polymkeric substance is provided, can keeps the performance characteristic of high molecular weight resin and improve workability, especially extrudable property (characteristic of lower-molecular-weight component).
According to being similar to United States Patent (USP) 5,047,468 and 5,149, the segmentation reactor process described in 738 can successfully be realized the blend effect of these polymkeric substance.Briefly, this technology is a kind of in-situ blending technology of polymkeric substance, wherein prepares high molecular weight ethylene copolymer in a reactor, and prepares the low-molecular-weight ethylenic multipolymer in another reactor.This technology typically is included in the mixture that makes ethene and one or more alpha-olefins under the polymerizing condition and ties up in 2 placed in-line gas-phase fluidized-bed reactors with catalyst body and contact continuously, and described catalyst system comprises: (i) loading type magnesium/Ti-base catalyst precursor; (ii) one or more contain the aluminium activator compound; (iii) a kind of hydrocarbyl aluminium promoter.
Though have been found that, has aforesaid excellent specific property by the in-situ blending thing of above-mentioned preparation with by the film of this blend production, but the polymkeric substance of these particulate state wide molecular weight distribution is for the high-quality thin film purposes, and its commercial application value usually is restricted owing to the gained gel level.This gel to aesthetic appearance, can anti-plasticity and the physicals of product all have negative impact.The gel property of film product generally uses the objective scale of film appearance grade (FAR) to represent, FAR is from bearing 50 (very poor, this film has a large amount of big gels) to positive 50 (fine, this film has only on a small quantity or do not have basically gel).For commercial acceptability, FAR should be positive 20 or higher.
Disclosure of an invention
Therefore, an object of the present invention is to provide and a kind ofly can be processed into in-situ blending thing with high especially FAR.It is very clear that other purpose and advantage below will become.
According to the present invention, such blend has been found that.In-situ blending thing of the present invention comprises the mixture of first and second ethylene/alpha-olefin copolymers, and wherein alpha-olefin contains 3～8 carbon atoms, and the density of first multipolymer is 0.9035～0.908g/cm 3, it is about 1.4～about 2.6g/10 minute that roller grinds flow index, the density of second multipolymer is 0.925～0.945g/cm 3, melt index is about 200～about 400g/10 minute; The weight ratio of first multipolymer and second multipolymer is about 45: 55～about 60: 40; The density of this in-situ blending thing is 0.919～0.924g/cm 3, flow index is 65～90g/10 minute, the melt flow ratio is about 85～about 115.
Preferred embodiment is described
This film usually by extrusion molding form, forcing machine is traditional forcing machine that an employing can provide the die head of required specification.Here useful film specification is about 0.4～about 10 mils, preferred about 0.5～about 6 mils.An example that can be used to film forming forcing machine be one with inflation film die head and vane and the single-bolt type forcing machine of drawing equipment improvement continuously.Typical single-bolt type forcing machine can be described as a forcing machine that a hopper is arranged at its upstream end and a die head is arranged in its downstream end.Raw material enters into sleeve by hopper, and a screw rod is arranged in the sleeve.In downstream end, the broken flitch of net superimposition is housed between screw rod end and die head.The screw portion of forcing machine is divided into three sections, i.e. feed zone, compression section and metering zone, and a plurality of heating zone from the post-heating district to preceding heating zone, and multistage and multi-region are from upstream to arranged downstream.If sleeve is more than 1, then each sleeve connects with series system.Each telescopic length-to-diameter is about 16: 1～about 30: 1.Extruding operation can carry out in about 160～about 270 ℃ temperature range, preferably carries out in about 180～about 240 ℃ temperature range.
Blend is produced by the in-situ blending of 2 kinds of polymkeric substance.The flow index of first multipolymer can be in about 1.4～about 2.6g/10 minute scope, preferably in about 1.7～about 2.4g/10 minute scope.The melt index of second multipolymer can be in about 200～about 400g/10 minute scope, preferably in about 250～about 350g/10 minute scope.
This multipolymer is ethene and the 'alpha '-olefin monomers that contains 3～8 carbon atoms, for example multipolymer of propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene or 1-octene.Preferred monomer is 1-butylene and 1-hexene.
The linear polyethylene blend component can be with various transition-metal catalyst productions.Polyethylene blend of the present invention preferably adopts low pressure process to produce in gas phase.This blend also can adopt conventional art also under low pressure to produce in the liquid phase of solution or slurry.Low-pressure process is typically carried out being lower than under the pressure of 1000psi, and high-pressure process is typically 15, carries out under the above pressure of 000psi.The typical transition metal catalyst system that can be used for preparing this blend is magnesium/Ti-base catalyst system, and its example is a United States Patent (USP) 4,302, the catalyst system described in 565; Vanadium-based catalyst systems, as United States Patent (USP) 4,508,842,5,332,793,5,342,907 and 5,410, those described in 003; Chromium-based catalyst systems is as United States Patent (USP) 4,101, those described in 445; And metallocene catalyst system, as United States Patent (USP) 4,937,299,5,317,036 and 5,527, those catalyst systems described in 752.Many ziegler-natta catalyst systems that often are called as are arranged in these catalyst systems.Use carrier band on silica-alumina carriers chromium or the catalyst system of the oxide compound of molybdenum also be useful.The preferred catalyst systems that is used to prepare blend component of the present invention is magnesium/titanium catalyst system and metallocene catalyst system.
Magnesium/Ti-base catalyst system will be used for illustrating this technology, for example a kind of catalyst system, and wherein precursor forms by spraying drying, and uses with slurry form.For example, such catalyst precursor contains titanium, magnesium and electron donor(ED), and randomly also can contain aluminum halide.This precursor is introduced in hydrocarbon medium such as the mineral oil subsequently to form slurry form.This catalyst system can be referring to United States Patent (USP) 5,290,745.
Electron donor(ED) is a kind of organic Lewis base, is liquid in about 0～about 200 ℃ temperature range, and magnesium and titanium compound are dissolved in wherein.This electron donor(ED) can be aliphatic series or aromatic carboxylic acid's alkyl ester, aliphatic ketone, aliphatic amine, fatty alcohol, an alkyl or cycloalkyl ether, or their mixture, various electron donor(ED)s can contain 2～20 carbon atoms, in these electron donor(ED)s, the alkyl and the cycloalkyl ethers that preferably contain 2～20 carbon atoms, contain dialkyl group, diaryl and the alkylaryl ketone of 3～20 carbon atoms, and contain the alkyl of 2～20 carbon atoms and alkyl, alkoxyl group and the alkyl alkoxy ester of aryl carboxylic acid.Most preferred electron donor(ED) is a tetrahydrofuran (THF).Other example of suitable electron donor(ED) is methyl-formiate, ethyl acetate, butylacetate, ether, diox, di ether, dibutyl ether, ethyl formate, methyl acetate, ethyl anisate, ethylene carbonate, tetrahydrofuran (THF) and ethyl propionate.
Use excessive electron donor(ED) so that the reaction product of titanium compound and electron donor(ED) to be provided when when beginning, reaction product finally contains the 1～about 20 moles of electron donor(ED)s/every mole of titanium compound of having an appointment, preferred about 1～about 10 moles of electron donor(ED)s/every mole of titanium compound.
Usually the activator compound that uses with any Ti-base catalyst precursor can have general formula AlR aX bH c, wherein each X is chlorine, bromine, iodine or OR ' independently; Each R and R ' are the radical of saturated aliphatic alkyl that contains 1～14 carbon atom independently; B is 0～1.5; C is 0 or 1; A+b+c=3.Preferred activator comprises chlorine or dichloro aluminum alkyls, and wherein each alkyl contains 1～6 carbon atom, and trialkylaluminium.Its example is diethylaluminum chloride and tri-n-hexyl aluminum.Every mole of electron donor(ED) uses about 0.10～about 10 moles, preferred about 0.15～about 2.5 moles of activators.The mol ratio of activator and titanium is about 1: 1～about 10: 1, is preferably about 2: 1～about 5: 1.
Hydrocarbyl aluminium promoter can be used general formula R 3Al or R 2AlX represents that wherein each R is alkyl, cycloalkyl, aryl or hydrogen independently; At least 1 R is an alkyl; 2 or 3 R groups can connect together and form 1 heterocycle structure.Each alkyl R can contain 1～20 carbon atom, preferably contains 1～10 carbon atom.X is a halogen, preferred chlorine, bromine or iodine.The example of hydrocarbyl aluminium compound is as follows: triisobutyl aluminium, tri-n-hexyl aluminum, diisobutyl aluminium hydride, dihexyl aluminum hydride, diisobutyl hexyl aluminium, isobutyl-dihexyl aluminium, trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisopropylaluminiuand, three n-butylaluminum, trioctylaluminum, three decyl aluminium, three (dodecyl) aluminium, tribenzyl aluminium, triphenyl aluminum, three naphthyl aluminium, three (tolyl) aluminium, dibutyl aluminum chloride, diethyl aluminum chloride and ethyl sesquialter aluminum chloride.Preferred promotor is a trimethyl aluminium.Cocatalyst compound also can be used as activator and properties-correcting agent.
Preferably do not use carrier.But under the situation of wishing the carrier band precursor, preferred carrier is a silicon-dioxide.Other suitable carriers is an inorganic oxide, as aluminum phosphate, aluminum oxide, silica/alumina mixture, and with the silicon-dioxide of organo-aluminium compound such as triethyl modification, and with the silicon-dioxide of magnesium ethide modification.Typical carrier be a kind of be inert solid granular porous material basically to polyreaction.This material uses with dry powder form, about 10～about 250 microns of its median size, preferred about 30～about 100 microns; Surface-area is 200m at least 2/ g is preferably at least about 250m 2/ g; The aperture is at least about 100 dusts, preferably at least about 200 dusts.Generally speaking, the consumption of carrier should make can provide about 0.1～about 1.0 mmole titaniums/every gram carrier, preferred about 0.4～about 0.9 mmole titanium/every gram carrier.Above-mentioned catalyst precursor and silica dioxide gel are blended in electron donor(ED) solvent or other solvent, under reduced pressure remove to desolvate then and just can finish the dip operation of this precursor in silica supports.When not needing carrier, this catalyst precursor generally uses with liquid form.
Activator can be before polyreaction and/or during join in the precursor.In 1 operation steps, this precursor is activation fully before polymerization.In other 1 operation steps, this precursor is the part activation before polymerization, and activation is finished in reactor.When replacing activator, usually properties-correcting agent is dissolved in organic solvent such as the iso-pentane, and when using carrier, behind dipping titanium compound or title complex, it is immersed in the carrier, then with this loaded catalyst precursor drying with properties-correcting agent.Perhaps this modifier solution itself is directly joined in the reactor.Properties-correcting agent is similar to activator on chemical structure, and plays a part activator, is promotor.For various properties-correcting agent, can be referring to for example United States Patent (USP) 5,106,926.This promotor preferably joins in the polymerization reactor separately with net phase or with the solution form in inert solvent such as iso-pentane when beginning to add ethylene streams.
Polyreaction preferably adopts continuous fluid technology to carry out in gas phase.
In first reactor, prepare more low-density multipolymer (first multipolymer), and in second reactor, prepare the multipolymer (second multipolymer) of higher density.First multipolymer has higher molecular weight, and second multipolymer then has lower molecular weight.The weight ratio of first multipolymer and second multipolymer can be in about 45: 55～about 60: 40 scope.
Low density copolymer:
Flow index can be in about 1.4～about 2.6g/10 minute scope, preferably in about 1.7～about 2.4g/10 minute scope.Note that this is that roller grinds flow index, it can provide more accurate flow index.This is by taking a sample from the reactor that has made low density copolymer, and carries out roll-in and mill and finish before measuring flow index.The molecular weight of this polymkeric substance is generally about 275,000～about 230,000 dalton.The density of this multipolymer can be 0.9035～0.908g/cm 3, be preferably 0.9035～0.908g/cm 3Mw/Mn can be in about 3.5～about 8 scopes, preferably in about 3.5～about 5.5 scopes.
Melt index is by ASTM D-1238, and condition E (being also referred to as 190/2.16) measures.It was to measure under 190 ℃ and 2.16 kilogram load, with report in g/10 minute.Flow index is by ASTM D-1238, and condition F (being also referred to as 190/21.6) measures.It was at 190 ℃ and measures under 10 times the condition of used weight when measuring melt index, with report in g/10 minute.The roll-in grinding technology as mentioned above.The melt flow ratio is meant the ratio of flow index and melt index.
High-density component:
Melt index can be in about 200～about 400g/10 minute scope, preferably in about 250～about 350g/10 minute scope.The molecular weight of this high density copolymer is generally about 25,000～about 20,000 dalton.The density of this multipolymer can be 0.925～0.945g/cm 3, be preferably 0.930～0.940g/cm 3Mw/Mn can be in about 3.5～about 8 scopes, preferably in about 3.5～about 5.5 scopes.
The flow index of in-situ blending thing or final product can be in about 65～about 90g/10 minute scope.The molecular weight of final product is generally about 160,000～about 200,000.The density of this blend can be 0.919～0.924g/cm 3, be preferably 0.919～0.923g/cm 3The melt flow ratio of blend can be in about 85～about 115 scopes, preferably in about 90～about 110 scopes.The Mw/Mn of this blend can be about 12～about 18, preferred about 12～about 17.Mw is a weight-average molecular weight, and Mn is a number-average molecular weight, and Mw/Mn can be called polydispersity index, and it is that a kind of of molecular weight distribution width measures.
Low-density fraction (processing condition):
The mol ratio of alpha-olefin and ethene can be about 0.12: 1～and about 0.18: 1, be preferably about 0.14: 1～about 0.17: 1.Hydrogen (as the words of using) can be about 0.02: 1 with the mol ratio of ethene～and about 0.06: 1, be preferably about 0.03: 1～about 0.05: 1.Service temperature is generally in about 65～about 75 ℃ of scopes.The dividing potential drop of ethene can be about 25～about 50psi in low density (high molecular) reactor, but has been found that when ethylene partial pressure is easier when being about 40～about 50psi and obtain high FAR.Stagnation pressure is generally 250～320psig.
High-density component (processing condition):
The mol ratio of alpha-olefin and ethene can be about 0.2: 1～and about 0.4: 1, be preferably about 0.25: 1～about 0.35: 1.The mol ratio of hydrogen and ethene can be about 1.4: 1～and about 2.5: 1, be preferably about 1.6: 1～about 2.0: 1.Service temperature is generally in about 80～about 90 ℃ of scopes.The dividing potential drop of ethene can be about 75～about 150psi, preferred about 90～about 120psi.Stagnation pressure is generally 400～450psig.
The example of typical fluidized-bed reactor can be referring to United States Patent (USP) 4,482,687, and can be described below:
This is made of the same granular resin that will produce in reactor usually.Therefore, this comprises established polymer beads, the polymer beads of growing and granules of catalyst in polymerization process, and these particles are by flow or the polymerization of flow velocity introducing and the gas group branch fluidisation of modification to be enough to make particle separation and play the fluid effect.Fluidizing agent by initial charge, replenish charging and circulation (recirculation) gas, i.e. monomer, words as desired, properties-correcting agent and/or inert carrier gas are formed.
The major portion of reaction system is i.e. bed, gas distribution plate, entrance and exit pipeline, compressor, recycle gas cooler and a product blowdown system of container.At container, in the promptly above-mentioned bed, deceleration area is arranged, the district responds in bed.Both are all on gas distribution plate.
The example that can join the typical additives in this blend is antioxidant, UV light absorber, static inhibitor, pigment, dyestuff, nucleator, filler, surface slip agent, fire retardant chemical, softening agent, processing aid, lubricant, stablizer, smog inhibitor, viscosity control agent, linking agent, catalyzer, and secondary accelerator, tackifier and release agent.Except that filler, the content of these additives in blend can be about 0.1～about 10 weight parts by per 100 parts by weight polymer blends.The add-on of filler can be 200 weight parts at the most by per 100 weight part blends.
The advantage of the film that is made by in-situ blending thing of the present invention is that FAR is high all the time.
All molecular weight of mentioning in this specification sheets all refer to weight-average molecular weight, but except indicating in addition.
The patent of mentioning in this specification sheets is listed this paper in as a reference.
Following examples explanation the present invention.
Embodiment 1 and 2
Embodiment 1 is a specific embodiments of the present invention, and embodiment 2 is comparative examples.These 2 embodiment adopt same step and condition, but the table in list except.
Preferred catalyst system is precursor a kind of catalyst system of forming by spraying drying and using with slurry form wherein.For example, such catalyst precursor contains titanium, magnesium, aluminum halide and electron donor(ED).This precursor is introduced in hydrocarbon medium such as the mineral oil subsequently to form slurry form.See also United States Patent (USP) 5,290,745.The embodiment 1 of the composition of catalyzer and the preparation method that adopted and United States Patent (USP) 5,290,745 is described identical in the present embodiment, and different is every mole of tetrahydrofuran (THF) is with 0.25 mole of tri-n-hexyl aluminum, rather than with 0.2 mole.
Adopt following standard step to prepare polyethylene.
Ethene and 1-hexene carry out copolymerization in first reactor, add 1-butylene in second reactor.Trimethyl aluminium (TMA) promotor joins in polymerization process in each reactor with the hexane solution form of 50% weight.Temperature in first reactor is 70 ℃, and the temperature in second reactor is 85 ℃.Each polyreaction here with in the table is carried out under the listed condition continuously after reaching balance.
By continuously above-mentioned catalyst precursor and promotor being fed in the fluidized-bed that contains polyethylene particle and ethene, 1-hexene and hydrogen initiated polymerization in first reactor.The mixing that is generated the multipolymer of active catalyst extract out from first reactor, and as transfer medium described multipolymer is transferred in second reactor with the gas of second reactor.Second reactor also comprises the fluidized-bed of polyethylene particle.Ethene, 1-butylene and hydrogen are incorporated in second reactor, it is contacted with catalyzer with multipolymer from first reactor.Also add additional promotor.Discharge the product blend continuously.
The performance of having listed variable polymerizing condition, resin properties, film extrusion condition and film is explained in the table neutralization below.
1 2 I II I II 296 431 298 433 ( psig ) C2 PP ( psi ) 44.5 112.5 42.4 118.8H2/C2 0.043 1.79 0.033 1.78 ( ) C4/C2 0 0.248 0 0.320 ( ) C6/C2 0.152 0.018 0.143 0.011 ( ) N2 ( ％ ) 74.1 19.4 76.5 14.5H2 ( ％ ) 0.62 45.09 0.45 47.11C2H4 ( ％ ) 14.33 25.23 13.59 26.53C4H8 ( ％ ) 0 6.26 0 8.48IC5 ( ％ ) 6.81 2.58 7.00 2.02C6H12 ( ％ ) 2.18 0.46 1.94 0.28TMA 9.72 4.83 10.05 3.35 ( / ) ( 1000 36.1 41.3 35.9 47.6/ ) 17.5 0 16.9 0 ( / ) C2 30.0 38.5 30.5 43.6 ( 1000/ ) 1 ( ) 2 ( ) I II I IIC4 0 4.00 0 5.88 ( 1000/ ) C6 6141 0 5382 0 ( / ) H2 0.47 177 0.33 233 ( / ) N2 504 0 626 0 ( / ) IC5 1730 0 1599 0 ( / ) 95 173 94 172 ( 1000 ) 2.6 2.2 2.6 2.1 ( ) 0.47 0.53 0.43 0.57 ( ) Ti ( ppm ) 3.49 1.90 3.37 1.69Al/Ti ( 22.4 33.1 28.9 34.6 ) -----0.80-----0.63 ( g/10min ) 1 2 ( ) 1.85 83.7 1.23 81.4 ( g/10 ) ( ) ( ) MFR----104----130 0.9057 0.9216 0.9067 0.9216 ( g/cm3) FAR of film----positive 50----negative 30
The note of his-and-hers watches:
Psig=pound/square inch, gauge pressure.
C2PP=is with the ethylene partial pressure of psi (pound/square inch) expression.
H2/C2, C4/C2 and C6/C2 are respectively the mol ratios of hydrogen, 1-butylene and 1-hexene and ethene.
N2, H2, C2H4, C4H8, IC5 and C6H12 are respectively nitrogen, hydrogen, ethene, 1-butylene, isopentene and 1-hexene.% is meant molecular fraction.
The TMA=trimethyl aluminium.
The weight fraction of each single component=single component.
The percentage ratio of titanium weight in the Tippm=resin.
The mol ratio of aluminium and titanium in the Al/Ti=resin.
Density is by according to ASTM D=1928, and program C produces 1 block of plate, tests through ASTM D-1505 then and measures, with g/cm 3Expression.
FAR=is by film appearance grade explained before.This film is 3.5 inches Gloucester by being 24: 1 a length-to-diameter ratio TMCarrying out extrusion molding in the inflation tubular film forcing machine prepares; This forcing machine has 1 LLDPE screw rod, 16 inches die head, and die gap is 60 and 120 mils.FAR measures each film.
The roll-in mill procedure: the granular resin of autoreactor is placed on the industrial common getable edge-runner mill in the future.The roller temperature is set in 148 ℃, and 2 roller spacings are set in compact state during beginning.Resin is placed on the roller about 5 minutes, carries out roll-in at low RPM (＜5) then and milled about 5 minutes, the gap is 0.008 inch.Crepe rubber after milling should be removed, and about 3 times of charging again during milling.Take out sample then and measure its flowing property.

Claims (9)

1. in-situ blending thing comprises the mixture of first and second ethylene/alpha-olefin copolymers, and wherein alpha-olefin contains 3～8 carbon atoms, and the density of first multipolymer is 0.9035～0.908g/cm 3, it is about 1.4～about 2.6g/10 minute that roller grinds flow index, the density of second multipolymer is 0.925～0.945g/cm 3, melt index is about 200～about 400g/10 minute; The weight ratio of first multipolymer and second multipolymer is about 45: 55～about 60: 40; The density of this in-situ blending thing is 0.919～0.924g/cm 3, the melt flow ratio is about 85～about 115.
2. the in-situ blending thing of claim 1 definition, wherein the density of first multipolymer is 0.9035～0.908g/cm 3, it is about 1.7～about 2.4g/10 minute that roller grinds flow index, the density of second multipolymer is 0.930～0.940g/cm 3, melt index is about 250～about 350g/10 minute, and the weight ratio of first multipolymer and second multipolymer is about 45: 55～about 50: 50, and the density of this in-situ blending thing is 0.919～0.924g/cm 3, the melt flow ratio is about 90～about 110.
3. the in-situ blending thing of claim 1 definition, wherein this alpha-olefin is 1-hexene and/or 1-butylene.
4. the in-situ blending thing of claim 1 definition, wherein this blend prepares under the catalyzed polymerization condition in 2 placed in-line reactors, described condition comprises: in first reactor, the mol ratio of alpha-olefin and ethene is about 0.12: 1～about 0.18: 1, the optional hydrogen and the mol ratio of ethene are about 0.02: 1～about 0.06: 1, in second reactor, the mol ratio of alpha-olefin and ethene is about 0.2: 1～about 0.4: 1, and the mol ratio of hydrogen and ethene is about 1.4: 1～about 2.5: 1.
5. the in-situ blending thing of claim 4 definition, wherein the dividing potential drop of ethene is about 35～about 50psi in first reactor.
6. the in-situ blending thing of claim 4 definition, wherein this catalyzer comprises magnesium, titanium and aluminum compound, and promotor is a trimethyl aluminium.
7. in-situ blending thing that comprises the mixture of 2 kinds of ethylene/alpha-olefin copolymers, wherein 'alpha '-olefin monomers contains 3～8 carbon atoms, the flow index of described blend is about 65～about 90g/10 minute, melt flow than for about 85～about 115, density is 0.919～0.924g/cm 3, described blend prepares under the catalyzed polymerization condition in 2 placed in-line reactors, and wherein in first reactor, it is about 1.4～about 2.6g/10 minute that the roller of copolymerization grinds flow index, and density is 0.9035～0.908g/cm 3, in second reactor, the melt index of described its polymers is about 200～about 400g/10 minute, density is 0.925～0.945g/cm 3, the weight ratio of the multipolymer for preparing in the multipolymer for preparing in first reactor and second reactor is about 45: 55～about 60: 40, and
Wherein in first reactor, the mol ratio of alpha-olefin and ethene is about 0.12: 1～about 0.18: 1, the optional hydrogen and the mol ratio of ethene are about 0.02: 1～about 0.06: 1, the dividing potential drop of ethene is about 40～about 50psi, in second reactor, the mol ratio of alpha-olefin and ethene is about 0.2: 1～about 0.4: 1, and the mol ratio of hydrogen and ethene is about 1.4: 1～about 2.5: 1.
8. the in-situ blending thing of claim 7 definition, wherein used catalyzer comprises magnesium, titanium and aluminum compound in the polyreaction, and promotor is a trimethyl aluminium.
9. Accessory Right requires the film with high FAR of the in-situ blending thing preparation of 1 definition.
CN98814224A 1998-09-11 1998-09-11 Polyethylene film composition Pending CN1358215A (en)

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CN101048454B (en) * 2004-11-03 2012-01-18 北方技术股份有限公司 Polymer composition for injection moulding

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KR100745319B1 (en) * 2001-12-24 2007-08-01 삼성토탈 주식회사 Linear low density polyethylene resin composition with high impact strength

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US5514455A (en) * 1994-07-08 1996-05-07 Union Carbide Chemicals & Plastics Technology Corporation Film extruded from an in situ blend of ethylene copolymers
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CN101048454B (en) * 2004-11-03 2012-01-18 北方技术股份有限公司 Polymer composition for injection moulding

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