WO1998052982A1 - Procede de preparation d'un melange de polyethylene in situ - Google Patents

Procede de preparation d'un melange de polyethylene in situ Download PDF

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Publication number
WO1998052982A1
WO1998052982A1 PCT/US1998/010253 US9810253W WO9852982A1 WO 1998052982 A1 WO1998052982 A1 WO 1998052982A1 US 9810253 W US9810253 W US 9810253W WO 9852982 A1 WO9852982 A1 WO 9852982A1
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WIPO (PCT)
Prior art keywords
reactor
range
ratio
density
copolymer
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Application number
PCT/US1998/010253
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English (en)
Inventor
Sandra Ann Kupperblatt
George Edward Ealer
Michael William Tilston
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Union Carbide Chemicals & Plastics Technology Corporation
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Publication date
Application filed by Union Carbide Chemicals & Plastics Technology Corporation filed Critical Union Carbide Chemicals & Plastics Technology Corporation
Priority to EP98923534A priority Critical patent/EP0983307A1/fr
Priority to AU75804/98A priority patent/AU730068B2/en
Priority to BR9809654-0A priority patent/BR9809654A/pt
Priority to CA002291106A priority patent/CA2291106A1/fr
Priority to JP55053898A priority patent/JP2001526725A/ja
Publication of WO1998052982A1 publication Critical patent/WO1998052982A1/fr

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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

Definitions

  • This invention relates to a process for preparing an in situ polyethylene blend, which can be converted into film having a small number or essentially no gels (or fish-eyes).
  • Polyethylenes of various densities have been prepared and converted into film characterized by excellent tensile strength, high ultimate elongation, good impact strength, and excellent puncture resistance. These properties together with toughness are enhanced when the polyethylene is of high molecular weight.
  • the processability of the resin usually decreases.
  • the blending of these polymers is successfully achieved in a staged reactor process similar to those described in United States patents 5,047,468 and 5,149,738. Briefly, the process is one for the in situ blending of polymers wherein a high molecular weight ethylene copolymer is prepared in one reactor and a low molecular weight ethylene copolymer is prepared in another reactor.
  • the process typically comprises continuously contacting, under polymerization conditions, a mixture of ethylene and one or more alpha-olefins with a catalyst system in two gas phase, fluidized bed reactors connected in series, said catalyst system comprising: (i) a supported magnesium/titanium based catalyst precursor; (ii) one or more aluminum containing activator compounds; and (iii) a hydrocarbyl aluminum cocatalyst,
  • the in situ blends prepared as above and the films produced therefrom are found to have the advantageous characteristics heretofore mentioned, the commercial application of these granular broad molecular weight distribution polymers for high quality film applications is frequently limited by the level of gels obtained.
  • Particle size distribution and flow characteristics studies indicate that the gas phase resins having an average particle size (APS) of about 400 to about 600 microns exhibit significant compositional, molecular, and rheological heterogeneities.
  • APS average particle size
  • the film exhibits a high level of gels ranging in size from about 100 microns to about 500 microns.
  • the gel characteristics of a film product are usually designated by a subjective scale of Film Appearance Rating (FAR) varying from minus 50 (very poor; these films have a large number of large gels) to plus 50 (very good; these films have a small amount of, or essentially no, gels).
  • FAR Film Appearance Rating
  • the FAR of the single pass film product mentioned above is generally much worse than minus 50. For commercial acceptability, the FAR should be plus 20 or better.
  • An object of this invention is to provide a process for preparing an in situ blend, which can be extruded into a film having a commercially acceptable FAR.
  • the process comprises contacting ethylene and one or two alpha-olefin comonomers, each having 3 to 8 carbon atoms, with a transition metal catalyst system including a hydrocarbylaluminum cocatalyst in each of two fluidized bed reactors connected in series, in the gas phase, under polymerization conditions, with the provisos that:
  • hydrogen is present in a ratio of about 0.01 to about 0.7 mole of hydrogen per mole of ethylene; and (d) in the second reactor, in which a high density copolymer is made:
  • alpha-olefin is present in a ratio of about 0.005 to about 0.8 mole of alpha-olefin per mole of ethylene;
  • hydrogen is present in a ratio of about 0.01 to about 2.51 moles of hydrogen per mole of ethylene
  • the length to diameter ratio of each barrel is in the range of about 16:1 to about 30:1.
  • the extrusion can take place at temperatures in the range of about 160 to about 270 degrees C, and is preferably carried out at temperatures in the range of about 180 to about 240 degrees C.
  • the blend is produced in two staged reactors connected in series wherein a mixture of resin and active catalyst is transferred from the first reactor to the second reactor in which another copolymer is prepared and blends in situ with the copolymer from the first reactor.
  • the term "two ... reactors" can mean two independent reactors or two stages in one reactor.
  • the first reactor is the low density reactor and the second reactor is the high density reactor.
  • the reactor is named according to the relative density of the polymer produced in the reactor.
  • the copolymers produced in each of the reactors are copolymers of ethylene and one or two alpha-olefin comonomers, each having 3 to 8 carbon atoms, and can be, for example, propylene, 1- butene, 1-hexene, 4-methyl-l-pentene, and 1-octene. It will be understood that the term copolymers includes terpolymers. It is preferred that the comonomers be the same in each reactor; however, different comonomers can be used in each reactor, if desired. The preferred comonomers are 1-butene and 1-hexene.
  • Catalyst systems which use chromium or molybdenum oxides on silica- lumina supports, are also useful.
  • Typical processes for preparing in situ polyethylene blends are described in United States Patents 5,371,145 and 5,405,901
  • Preferred catalyst systems for preparing the in situ blends of this invention are magnesium/titanium catalyst systems and metallocene catalyst systems.
  • Suitable electron donors are methyl formate, ethyl acetate, butyl acetate, ethyl ether, dioxane, di-n-propyl ether, dibutyl ether, ethyl formate, methyl acetate, ethyl anisate, ethylene carbonate, tetrahydropyran, and ethyl propionate.
  • reaction product While an excess of electron donor is used initially to provide the reaction product of titanium compound and electron donor, the reaction product finally contains about 1 to about 20 moles of electron donor per mole of titanium compound and preferably about 1 to about 10 moles of electron donor per mole of titanium compound.
  • Preferred activators include alkylaluminum mono- and dichlorides wherein each alkyl radical has 1 to 6 carbon atoms and the trialkylaluminums. Examples are diethylaluminum chloride and tri-n-hexylaluminum.
  • activator About 0.10 to about 10 moles, and preferably about 0.15 to about 2.5 moles, of activator are used per mole of electron donor.
  • the molar ratio of activator to titanium is in the range of about 1:1 to about 10:1, and is preferably in the range of about 2:1 to about 5:1.
  • silica is the preferred support.
  • suitable supports are inorganic oxides such as aluminum phosphate, alumina, silica/alumina mixtures, silica modified with an organoaluminum compound such as triethylaluminum, and silica modified with diethyl zinc.
  • a typical support is a solid, particulate, porous material essentially inert to the polymerization.
  • a catalyst precursor having the formula MgdTi(OR) e Xf(ED)g wherein R is an aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms or COR' wherein R is a aliphatic or aromatic hydrocarbon radical having 1 to 14 carbon atoms; each OR group is the same or different; X is independently chlorine, bromine or iodine; ED is an electron donor; d is 0.5 to 56; e is 0, 1, or 2; f is 2 to 116; and g is 1.5d+2;
  • the molar ratio of modifier to titanium can be in the range of about 1:1 to about 10:1 and is preferably in the range of about 2:1 to about 5:1.
  • the entire catalyst system which includes the precursor or activated precursor and the cocatalyst, is added to the first reactor.
  • the catalyst is admixed with the copolymer produced in the first reactor, and the mixture is transferred to the second reactor. Insofar as the catalyst is concerned, only cocatalyst is added to the second reactor from an outside source.
  • each reactor is, preferably, conducted in the gas phase using a continuous fluidized process.
  • a typical fluidized bed reactor is described in United States patent 4,482,687.
  • the first reactor is generally smaller in size than the second reactor because only a portion of the final product is made in the first reactor.
  • the mixture of polymer and an active catalyst is usually transferred from the first reactor to the second reactor via an interconnecting device using nitrogen or second reactor recycle gas as a transfer medium.
  • a relatively high density copolymer is prepared in this reactor.
  • the melt index can be in the range of about 0.2 to about 100 grams per 10 minutes, and is preferably in the range of about 0.4 to about 90 grams per 10 minutes.
  • the molecular weight of the high density copolymer is, generally, in the range of about 31,000 to about 164,000.
  • the density of the copolymer prepared in this reactor can be in the range of 0.900 to 0.965 gram per cubic centimeter, and is preferably in the range of 0.910 to 0.960 gram per cubic centimeter.
  • the melt flow ratio of this copolymer can be in the range of about 10 to about 40, and is preferably about 12 to about 35.
  • the blend or final product, as removed from the second reactor can have a flow index in the range of about 5 to about 100 grams per 10 minutes, and preferably has a flow index in the range of about 7 to about 80 grams per 10 minutes.
  • the molecular weight of the final product is, generally, in the range of about 150,000 to about 350,000.
  • the density of the blend can be in the range of 0.880 to 0.960 gram per cubic centimeter, and is preferably in the range of 0.900 to 0.955 gram per cubic centimeter.
  • the melt flow ratio of the blend can be in the range of about 10 to about 100, and is preferably in the range of about 12 to about 70.
  • melt index-corrected density is defined below.
  • the blend can have an Mw/Mn ratio of about 2 to about 20, and preferably has an Mw/Mn ratio of about 3 to about 15.
  • Mw is the weight average molecular weight
  • Mn is the number average molecular weight
  • the Mw/Mn ratio can be referred to as the polydispersity index, which is a measure of the breadth of the molecular weight distribution.
  • the term "molecular weight” is used by itself , it means weight average molecular weight.
  • the catalyst system, ethylene, alpha-olefin, and, optionally, hydrogen are continuously fed into the first reactor; the polymer/catalyst mixture is continuously transferred from the first reactor to the second reactor; ethylene, alpha-olefin, and hydrogen, as well as cocatalyst are continuously fed to the second reactor.
  • the final product is continuously removed from the second reactor.
  • the mole ratio of alpha-olefin to ethylene can be in the range of about 0.04:1 to about 1.48:1, and is preferably in the range of about 0.09:1 to about 1.04:1.
  • the mole ratio of hydrogen (if used) to ethylene can be in the range of about 0.01:1 to about 0.7:1, and is preferably in the range of about 0.01:1 to about 0.5:1.
  • the operating temperature is generally in the range of about 60 degrees C to about 100 degrees C. Preferred operating temperatures vary depending on the density desired, i.e., lower temperatures for lower densities and higher temperatures for higher densities.
  • the mole ratio of alpha-olefin to ethylene can be in the range of about 0.005:1 to about 0.8:1, and is preferably in the range of about 0.005:1 to about 0.6:1.
  • the mole ratio of hydrogen to ethylene can be in the range of about 0.01:1 to about 2.51:1, and is preferably in the range of about 0.01:1 to about 2.41:1.
  • the operating temperature is generally in the range of about 70 degrees C to about 100 degrees C. As mentioned above, the temperature is preferably varied with the desired density.
  • the pressure is generally the same in both the first and second reactors.
  • the pressure can be in the range of about 200 to about 450 psig and is preferably in the range of about 280 to about 350 psig.
  • a typical fluidized bed reactor can be described as follows:
  • the bed is usually made up of the same granular resin that is to be produced in the reactor.
  • the bed comprises formed polymer particles, growing polymer particles, and catalyst particles fluidized by polymerization and modifying gaseous components introduced at a flow rate or velocity sufficient to cause the particles to separate and act as a fluid.
  • the fluidizing gas is made up of the initial feed, make-up feed, and cycle (recycle) gas, i.e., comonomers and, if desired, modifiers and/or an inert carrier gas.
  • the essential parts of the reaction system are the vessel, the bed, the gas distribution plate, inlet and outlet piping, a compressor, cycle gas cooler, and a product discharge system.
  • the vessel above the bed, there is a velocity reduction zone, and, in the bed, a reaction zone. Both are above the gas distribution plate.
  • additives which can be introduced into the blend, are exemplified by antioxidants, ultraviolet absorbers, antistatic agents, pigments, dyes, nucleating agents, fillers, slip agents, fire retardants, plasticizers, processing aids, lubricants, stabilizers, smoke inhibitors, viscosity control agents, crosslinking agents, catalysts, and boosters, tackifiers, and anti-blocking agents.
  • the additives can be present in the blend in amounts of about 0.1 to about 10 parts by weight of additive for each 100 parts by weight of polymer blend.
  • Fillers can be added in amounts of up to 200 parts by weight and more for each 100 parts by weight of the blend.
  • An advantage of the film prepared from the in situ blend of this invention is an FAR of at least plus 30 under high and low shear compounding conditions..
  • Example 1 is an embodiment of the invention showing the narrow density difference and higher FAR, and example 2 is a comparative example showing a greater density difference and lower FAR.
  • the preferred catalyst system is one where the precursor is formed by spray drying and is used in slurry form.
  • a catalyst precursor for example, contains titanium, magnesium, aluminum halides, and an electron donor.
  • the precursor is then introduced into a hydrocarbon medium such as mineral oil to provide the slurry form. See United States patent 5,290,745 (' 745).
  • the catalyst composition and method of preparing same used in this example is of the same composition and preparation method as example 1 of ' 745 except that 0.45 mol of diethylaluminum chloride per mol of tetrahydrofuran is used instead of 0.5 mol.
  • Ethylene is copolymerized with 1-hexene in each reactor.
  • Trimethylaluminum (TMA) cocatalyst is added to each reactor during polymerization as a 2 weight percent solution in isopentane in the first reactor and a 1 weight percent solution in isopentane in the second reactor.
  • the temperature in the first reactor is 70 degrees C and the temperature in the second reactor is 80 degrees C.
  • the pressure in each reactor is 300 pounds per square inch absolute (psia). Each polymerization is continuously conducted after equilibrium is reached under the conditions set forth here and in Tables I and II.
  • Polymerization is initiated in the first reactor by continuously feeding the above catalyst precursor and cocatalyst into a fluidized bed of polyethylene granules together with ethylene, 1- hexene, and hydrogen.
  • the resulting copolymer mixed with active catalyst is withdrawn from the first reactor and transferred to the second reactor using nitrogen as a transfer medium.
  • the second reactor also contains a fluidized bed of polyethylene granules. Again, ethylene, 1-hexene, and hydrogen are introduced into the second reactor where they come into contact with the copolymer and catalyst from the first reactor. Additional cocatalyst is also introduced.
  • the product blend is continuously removed. It is compounded in a BanburyTM mixer at 100 revolutions per minute (rpm) for 90 seconds using a 20 mesh screen.
  • Fines less than 0.5 0.31 120 mesh (wt %)
  • Frostline height is that distance off of the base of the die during which the polymer undergoes a phase transformation from a viscous liquid to a solid.
  • Blow up ratio is the ratio of the bubble diameter to the die diameter.

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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)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

Cette invention concerne un procédé qui consiste à mettre de l'éthylène ainsi qu'un ou deux comonomères d'alpha-oléfine, qui possèdent chacun de 3 à 8 atomes de carbone, en contact avec un système catalyseur à base d'un métal de transition qui comprend un cocatalyseur à base d'hydrocarbylaluminium. Cette mise en contact se fait dans deux réacteurs à lit fluidisé qui sont connectés en série, dans une phase gazeuse et dans des conditions de polymérisation. Le copolymère formé dans le premier réacteur possède un indice de fluidité qui varie environ de 0,1 à 75 grammes par 10 minutes, et une densité qui varie de 0,865 à 0,930 grammes par centimètre cube. Le copolymère formé dans le second réacteur possède un indice de fusion qui varie environ de 0,2 à 100 grammes par 10 minutes, et une densité qui varie environ de 0,900 à 0,965 grammes par centimètre cube. Le rapport en poids entre le copolymère du premier réacteur et le copolymère du second réacteur varie environ de 70:30 à 30:70. Le mélange in situ possède un indice de fluidité qui varie environ de 5 à 100 grammes par 10 minutes, un rapport fusion-fluidité qui varie environ de 10 à 100, une densité qui varie de 0,880 à 0,960 grammes par centimètre cube, et rapport Mw/Mn qui varie environ de 2 à 20.
PCT/US1998/010253 1997-05-20 1998-05-19 Procede de preparation d'un melange de polyethylene in situ WO1998052982A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP98923534A EP0983307A1 (fr) 1997-05-20 1998-05-19 Procede de preparation d'un melange de polyethylene in situ
AU75804/98A AU730068B2 (en) 1997-05-20 1998-05-19 A process for preparing an in situ polyethylene blend
BR9809654-0A BR9809654A (pt) 1997-05-20 1998-05-19 Processo para preparar uma mistura de polietileno in situ
CA002291106A CA2291106A1 (fr) 1997-05-20 1998-05-19 Procede de preparation d'un melange de polyethylene in situ
JP55053898A JP2001526725A (ja) 1997-05-20 1998-05-19 現場ポリエチレンブレンドの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US85895197A 1997-05-20 1997-05-20
US08/858,951 1997-05-20

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WO1998052982A1 true WO1998052982A1 (fr) 1998-11-26

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EP (1) EP0983307A1 (fr)
JP (1) JP2001526725A (fr)
AU (1) AU730068B2 (fr)
BR (1) BR9809654A (fr)
CA (1) CA2291106A1 (fr)
WO (1) WO1998052982A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002018461A2 (fr) * 2000-08-25 2002-03-07 Equistar Chemicals, Lp Polyethylene de densite moyenne et de poids moleculaire eleve
WO2016089311A1 (fr) * 2014-12-04 2016-06-09 The Polyolefin Company (Singapore) Pte Ltd Mélange de polyéthylène utilisé seul en tant que support pour procédé de fabrication de microfibres

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111100364B (zh) * 2018-10-26 2022-07-12 中国石油化工股份有限公司 聚乙烯组合物及其制备方法和吹塑包装制品
CN111100365B (zh) * 2018-10-26 2022-07-12 中国石油化工股份有限公司 聚乙烯组合物及其制备方法和挤出成型包装制品

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0691367A1 (fr) * 1994-07-08 1996-01-10 Union Carbide Chemicals & Plastics Technology Corporation Feuille extrudé d'un mélange de copolymères d'éthylène
EP0713888A2 (fr) * 1994-11-23 1996-05-29 Union Carbide Chemicals & Plastics Technology Corporation Procédé de préparation d'un mélange à base de polyéthylène in situ
EP0754708A2 (fr) * 1995-07-21 1997-01-22 Union Carbide Chemicals & Plastics Technology Corporation Procédé de préparation d'un mélange de polyéthylène in situ
EP0770629A2 (fr) * 1995-10-26 1997-05-02 Union Carbide Chemicals & Plastics Technology Corporation Procédé de préparation d'un mélange à base de polyéthylène in situ
EP0794200A2 (fr) * 1996-03-05 1997-09-10 Union Carbide Chemicals & Plastics Technology Corporation Procédé de polymérisation dans une séquence de réacteurs

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0691367A1 (fr) * 1994-07-08 1996-01-10 Union Carbide Chemicals & Plastics Technology Corporation Feuille extrudé d'un mélange de copolymères d'éthylène
EP0713888A2 (fr) * 1994-11-23 1996-05-29 Union Carbide Chemicals & Plastics Technology Corporation Procédé de préparation d'un mélange à base de polyéthylène in situ
EP0754708A2 (fr) * 1995-07-21 1997-01-22 Union Carbide Chemicals & Plastics Technology Corporation Procédé de préparation d'un mélange de polyéthylène in situ
EP0770629A2 (fr) * 1995-10-26 1997-05-02 Union Carbide Chemicals & Plastics Technology Corporation Procédé de préparation d'un mélange à base de polyéthylène in situ
EP0794200A2 (fr) * 1996-03-05 1997-09-10 Union Carbide Chemicals & Plastics Technology Corporation Procédé de polymérisation dans une séquence de réacteurs

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002018461A2 (fr) * 2000-08-25 2002-03-07 Equistar Chemicals, Lp Polyethylene de densite moyenne et de poids moleculaire eleve
WO2002018461A3 (fr) * 2000-08-25 2002-08-29 Equistar Chem Lp Polyethylene de densite moyenne et de poids moleculaire eleve
US6486270B1 (en) 2000-08-25 2002-11-26 Equistar Chemicals, Lp High molecular weight, medium density polyethylene
JP2004507591A (ja) * 2000-08-25 2004-03-11 エクイスター　ケミカルズ、　エルピー 高分子量中密度ポリエチレン
US6770715B2 (en) 2000-08-25 2004-08-03 Equistar Chemicals, Lp High molecular weight, medium density polyethylene
WO2016089311A1 (fr) * 2014-12-04 2016-06-09 The Polyolefin Company (Singapore) Pte Ltd Mélange de polyéthylène utilisé seul en tant que support pour procédé de fabrication de microfibres
CN107001732A (zh) * 2014-12-04 2017-08-01 新加坡聚烯烃私营有限公司 本身作为用于微纤维制造过程的载体使用的聚乙烯共混物

Also Published As

Publication number Publication date
CA2291106A1 (fr) 1998-11-26
EP0983307A1 (fr) 2000-03-08
AU7580498A (en) 1998-12-11
BR9809654A (pt) 2000-07-11
JP2001526725A (ja) 2001-12-18
AU730068B2 (en) 2001-02-22

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