WO2002092640A1 - Copolymeres et homopolymeres de polypropylene a faible densite apparente - Google Patents

Copolymeres et homopolymeres de polypropylene a faible densite apparente Download PDF

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Publication number
WO2002092640A1
WO2002092640A1 PCT/US2002/013485 US0213485W WO02092640A1 WO 2002092640 A1 WO2002092640 A1 WO 2002092640A1 US 0213485 W US0213485 W US 0213485W WO 02092640 A1 WO02092640 A1 WO 02092640A1
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Prior art keywords
homopolymer
ppm
methacrylate
titanium
chloride
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PCT/US2002/013485
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English (en)
Inventor
Nemesio D. Miro
Jennifer H. Ward
Richard P. White
Michael C. Chen
Bernard L. Bossaert
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Exxonmobil Chemical Patents Inc. A Corporation Of State Of Delaware
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Publication of WO2002092640A1 publication Critical patent/WO2002092640A1/fr

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    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene

Definitions

  • TITLE LOW BULK DENSITY POLYPROPYLENE
  • the present invention relates to copolymers and homopolymers of propylene derived from unsupported Ziegler-Natta catalyzed polymerization processes, wherein the bulk density of the resultant polymer is reduced by use of an acrylate compound and a silane-based electron donor.
  • polypropylene in the industry is very dependent on the end-use application.
  • polypropylene with special properties such as broad polymer molecular weight distribution (MWD), high stiffness, and high-crystallinity are required.
  • MWD broad polymer molecular weight distribution
  • properties that are opposite to the previously mentioned properties may be required, while some require properties that are in between the two.
  • common to most applications is the need for a clean, low-ash polypropylene resin.
  • magnesium supported catalysts such as disclosed in US 6,127,303; EP 0 320 150 Bl; EP 0 340 688 A2; EP 0 831 103 Al ; EP 1 061 088 Al ; EP 0 641 807 A2; and WO 99/20663 are undesirable, as they leave an unacceptably large magnesium residue in the polyolefins produced therefrom. This is especially so in the biaxially oriented polypropylene films that are used in packaging and capacitor film production.
  • the process to make polypropylene resins that have low "ash", or low metal residual values depends on the catalyst system that is used.
  • the process requires an extraction step where the catalyst residues left in the polymer granules in the reactor are reacted downstream of the process with solvents such as alcohols.
  • solvents such as alcohols.
  • the compactness or density of the polymer granules (as measured by the settled bulk density) needs to be controlled - where lower bulk density indicates a less compact granule and will extract with higher efficiency.
  • HDT heat deflection temperature
  • the high- crystallinity property is achieved by the addition of an electron-donating compound, such as organic phosphites, or methyl-methacrylate (MMA).
  • an electron-donating compound such as organic phosphites, or methyl-methacrylate (MMA).
  • MMA methyl-methacrylate
  • Our experience has shown that when the polymer crystallinity is increased by the addition of more electron-donating compound during the manufacturing process, this also results in an increase in polymer bulk density (BD, g/cm 3 ) and poor efficiency of deashing. What is needed is a polypropylene that has a lower BD and thus a lower metal residuals value upon typical washing processes.
  • One embodiment of the present invention is a polyolefin such as, for example, a propylene copolymer or homopolymer, the polyolefin having a bulk density of from 0.38 to 0.52 and a titanium residuals value of from less than 15 ppm.
  • the heat deflection temperature of the polyolefin is from 86 to 105°C in another embodiment
  • the melt flow rate of the homopolymer is from 1 to 100 g/10 min in yet another embodiment.
  • the heptane insolubles value of the polyolefin is typically from greater than 93% of the weight of the total polymer in a desirable embodiment. Since an unsupported Ziegler-Natta catalyst is used, magnesium compounds such as magnesium chloride or organomagnesium compounds are substantially or completely absent from the polymerization system and resulting polymer.
  • Another embodiment of the invention also includes a process for producing a polyolefin such as a propylene copolymer and homopolymer.
  • the process includes first contacting ⁇ -olefin monomers and an unsupported, titanium based Ziegler-Natta catalyst system, the catalyst system comprising an organic ester present during the polymerization from 1 to 30 ppm, and an organoaluminum compound present during the polymerization from 50 to 600 ppm. Next the polyolefin is washed (deashed). Finally the polyolefin thus produced is isolated having a titanium residuals value of from less than 15 ppm in one embodiment.
  • Figure 1 is a graphical representation of data for bulk density of polypropylene homopolymer of the invention as a function of donor concentration when no silane is present during polymerization;
  • Figure 2 is a graphical representation of data for bulk density of polypropylene homopolymer of the invention as a function of donor concentration when silane is present during polymerization
  • Figure 3 is a graphical representation of data for ash (metal residuals) of polypropylene homopolymer of the invention as a function of donor concentration
  • Figure 4 is a graphical representation of data for HDT as a function of
  • Figure 5 is a graphical representation of data for decalin solubles as a function of MMA concentration for the polypropylene homopolymer of the invention.
  • metal and ionic recoverables refers to the metal, either ionized or in a neutral state, and non-metal ions that can be recovered from finished polyolefin (homopolymer or copolymer).
  • metals include, but are not limited to ions, radicals or neutral species of titanium (Ti), aluminum (Al), magnesium (Mg), zirconium (Zr), and silicon (Si).
  • ionic recoverable such species as halogen ions, and halogen containing oxide species. Reference may be made to specific metal and/or ion recoverables, such as titanium or chlorine recoverables.
  • polymerization system refers to the ethylene and/or ⁇ -olefin present with a catalyst and its components in order to effectuate the polymerization of the ethylene and/or ⁇ -olefins.
  • the term "catalyst system” includes a so called second generation, unsupported titanium (Ti) chloride based Ziegler-Natta catalyst, which can also include an organo-metal co-catalyst, an internal electron donor, an external electron donor, hydrogen or other chain termination agents, and other agents.
  • Typical second generation titanium catalysts useful in the invention are disclosed in, for example, US 4,295,991, 5,604,171 and GB 1 391 068.
  • the unsupported Ziegler-Natta catalyst system useful in the present invention typically does not include any support, in particular, magnesium-based compounds used as supports in supported (e.g., "third generation") Ziegler-Natta systems.
  • the unsupported Ziegler-Natta catalyst consists essentially of at least one titanium based compound, at least one organoaluminum based compound, and chloride, such as described in, for example, POLYPROPYLENE HANDBOOK 20-21 (Edward P Moore, ed., Hanser Publishing
  • magnesium-based compounds and other compounds known in the art used to support Ziegler-Natta catalyst systems are substantially absent.
  • substantially absent is meant that these compounds are present to an extent no greater than 5 ppm relative to the total amount of ethylene or ⁇ -olefin in the polymerization system (or less than 0.5 ppm relative to the catalyst composition alone).
  • magnesium-based compounds are not present to any extent. Examples of magnesium-based compounds include those traditionally used to support titanium based Ziegler-Natta catalysts such as, for example, halogen salts of magnesium, organo-magnesium compounds such as disclosed in EP 0 641 807 A2, and blends thereof.
  • Embodiments of the present invention include homopolymers and copolymers of polypropylene made using a second-generation Ziegler-Natta catalyst system described herein.
  • the polymerization of propylene using an unsupported Ziegler-Natta catalyst system may be facilitated by the use of a modifier compound, such as, for example, an acrylate compound, to promote the decrease of decalin soluble (DS) content as a measure of the polymer crystallinity.
  • a modifier compound such as, for example, an acrylate compound
  • the decrease in DS for this type of catalyst system is accompanied by an increase in polymer granule bulk density (BD) which results in difficulty of removing the catalyst metal residues during the manufacturing deashing steps.
  • a silane compound such as, for example, tetraethoxysilane (TEOS)
  • TEOS tetraethoxysilane
  • the lower polymer granule BD showed lower catalyst residues in the final washed (deashed) polymer of the present invention.
  • Such a product is useful in applications that require low ash content, high stiffness and high temperature usage, including capacitor films, appliances, etc.
  • An embodiment of the catalyst system useful in the present invention is an unsupported titanium (Ti) based catalyst containing an amount of an organoaluminum (R n Al) compound.
  • the organoaluminum employed can be represented by the formula R n AlX 3-n , wherein R represents an alkyl group having from 1 to 18 carbon atoms in one embodiment, from 2 to 6 in another embodiment, and wherein X represents a halogen atom, a chloride (CI) in one embodiment, and n is an integer in the range of from 0 to 3 in one embodiment, from 1 to 3 in another embodiment, or complex mixtures thereof.
  • suitable alkylaluminum compounds are any one or blend of the following: trialkylaluminums, dialkylaluminum compounds, monoalkylaluminum compounds, and the corresponding halides.
  • suitable alkylaluminum compounds include any one or a blend of dimethylaluminum chloride, diethylaluminum chloride, trimethylaluminum, triethylaluminum, methylaluminum chloride, ethylaluminum chloride, ethylaluminum sesquichloride, triethylaluminum chloride, diethylaluminum chloride, and the like.
  • the organoaluminum compound is present in the polymerization reaction (relative to the total amount of ethylene or ⁇ -olefin) in the concentration range from 90 to 800 ppm in one embodiment, from 50 to 600 ppm in another embodiment, from 100 to 300 ppm in another embodiment, and from
  • the titanium catalyst used in the present invention may be obtained by reduction of titanium tetrachloride with the organoaluminum compound described above. The reduction is carried out at a temperature of from -50°C to 30°C by contacting the titanium compound with the organoaluminum compound in a diluent such as a hydrocarbon.
  • a diluent such as a hydrocarbon.
  • suitable hydrocarbon diluents include hydrocarbons having from 5 to 12 carbon atoms such as n-pentane, isopentane, n-hexane, isooctane, and the like.
  • the specific temperatures and amounts of organoaluminum compound employed may vary.
  • a desirable organoaluminum compound is diethylaluminum chloride (DEAC).
  • the catalyst thus obtained may be prepolymerized, that is, contacted with a polymerizable ⁇ -olefin under polymerization conditions, directly without the addition of reducing co-catalyst or it can be separated, washed in an inert diluent, if desirable, and them prepolymerized upon addition of a co-catalyst
  • the ⁇ -olefins which can be employed in the prepolymerization step include ethylene and ⁇ - olefins having from 3 to 22 carbon atoms in one embodiment, and from 3 to 8 carbon atoms in another embodiment.
  • homopolymers of propylene are made by the method of the invention, and using the catalyst system of the invention.
  • a copolymer of propylene and from 0.5 wt% to 10 wt% of ethylene and/or a 4 to 8 carbon ⁇ -olefin is produced in another embodiment of the process and catalyst system of the invention.
  • the temperature of the reaction mixture during the ⁇ -olefin prepolymerization can be from about 0°C to 100°C in one embodiment, and from 25°C to 60°C in another embodiment.
  • the resulting prepolymerized titanium trichloride reduced solid product can be activated by either employing a chlorinated hydrocarbon with a Lewis base complexing agent or a Lewis acid in combination with a Lewis base complexing agent.
  • a chlorinated hydrocarbons which can be employed include hexachloroethane, pentachloroethane, tetrachloroethane, and other halogenated C 2 to C 6 hydrocarbons, or mixtures thereof.
  • the Lewis base complexing agent can be a dialkyl ether such as, for example, diethyl ether, diisopropyl ether, and the like, or thioether, organophosphorus, or organonitrogen compounds. In one embodiment,
  • Lewis acid may be used such as halogenated Group 2 to 13 metals such as MgCl 2 , MnCl 4 , FeCl 3 , TiCl 4 , BC1 3 , and the like.
  • MgCl is desirably absent.
  • Polymerization techniques for olefin polymerization can be solution polymerization, slurry polymerization, or gas phase polymerization techniques. Methods and apparatus for effecting such polymerization reactions are well known and described in, for example, 12 ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 504-541 (John Wiley and Sons, 1988) and in 2 METALLOCENE- BASED POLYOLEFINS 366-378 (John Wiley and Sons, 2000).
  • the catalyst of the present invention can be used in similar amounts and under similar conditions to known olefin polymerization catalysts.
  • the polymers of this invention can be prepared with the catalyst system just described in either batch, semi-continuous, or continuous polyolefin polymerization systems.
  • Desirable polymerization systems are the continuous processes, including diluent slurry, bulk slurry (loop and stirred tank), and gas phase (stirred and fluid bed).
  • Continuous polymerization can be carried out in a single reactor of any of the above types, in two or more reactors operating in series, or in two or more reactors operating in parallel. When two or more reactors are operating in a continuous process, the multiple reactors can be all of the same type or they may be any combination of the types.
  • the polymerization step includes contacting either the unsupported Ziegler-Natta catalyst with one or more polymerizable monomers, or contacting a prepolymerized catalyst with polymerizable monomers.
  • the polymerizable monomers include ethylene and ⁇ -olefins having from 3 to 22 carbon atoms in one embodiment, and from 3 to 8 carbon atoms in another embodiment, thus producing an ⁇ -olefin.
  • homopolymers of propylene are made by the method of the invention, and using the catalyst system of the invention.
  • a copolymer of propylene and from 0.5 wt% to 10 wt% of ethylene and/or a 4 to 8 carbon ⁇ -olefin is produced in another embodiment of the process and catalyst system of the invention
  • Hydrogen gas is often used in olefin polymerization to control the final properties of the polyolefin, such as described in POLYPROPYLENE HANDBOOK 76- 78 (1996).
  • catalyst system of the present invention is known that higher concentrations (partial pressures) of hydrogen increase the melt flow rate
  • Electron donors are employed in the present invention during the polymerization process. Electron donors are typically used in two ways in the formation of a catalyst system. First, an "internal" electron donor may be used in the formation reaction of the catalyst as the transition metal halide is reacted with the metal hydride or metal alkyl. Second, an “external” electron donor may be used.
  • Examples of internal electron donors include one or a blend of: amines, amides, ethers, esters, aromatic esters, ketones, nitriles, phosphines, stibines, arsines, phosphoramides, thioethers, thioesters, aldehydes, alcoholates, and salts of organic acids.
  • an alkylacrylate, (acrylate), or an organic ester is present in the polymerization system.
  • the organic ester is present in the polymerization system.
  • R COOR is a hydrogen, or an alkyl of from 1 to 6 carbons, and R is hydrogen, or an alkyl or alkenyl of from 2 to 8 carbons, or a hydroxyalkyl from 2 to 8 carbons.
  • Examples of desirable organic ester internal electron donors are methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isodecyl methacrylate, lauryl methacrylate, 2-hydroxyethyl methacrylate, 2- hydroxypropyl methacrylate, 1,3-butylene dimethacrylate, trimethylpropane trimethacrylate, ethylene methacrylate, butylacrylate, and mixtures of these.
  • the internal electron donor is methylmethacrylate (MMA), CH 2 CHCOOCH 3 .
  • the internal electron donor, or organic ester in one embodiment is present in the polymerization reaction (relative to the total amount of ethylene or ⁇ -olefin) from 1 to 30 ppm in one embodiment, from 2 to 20 ppm in another embodiment, and from 3 to 15 ppm in yet another embodiment.
  • the second use for an electron donor in a catalyst system is as an external electron donor and stereoregulator in the polymerization reaction.
  • the same compound may be used in both instances, although typically they are different.
  • a common external electron donor is an organic silane compound, for example, tetraethoxysilane. A description of the two types of electron donors is provided in
  • the external electron donor acts as a stereoregulator to control the amount of atactic form of polymer produced. It may also increase the production of isotactic polymers. In these functions, the molecular weight distribution (MWD), high crystallinity, and MFR of produced polymer will be affected by the particular donor used.
  • Organic silicon compounds are known in the art for use as electron donors. Examples of electron donors that are organic silicon (or "silane") compounds are disclosed in US 4,218,339; 4,395,360;
  • a suitable silane compound useful in the invention may be described by the following general formula R 3 q Si(OR 4 ) 4-q ; wherein R 3 represents a hydrocarbon group having from 1 to 20 carbon atoms or a hydrogen atom, R 4 represents a hydrocarbon group having from 1 to 20 carbon atoms, and q represents an number wherein 0 ⁇ q ⁇ 4.
  • suitable "external" electron donors, or silane donors include any one or a blend of the following:
  • 2-norbornanemethyldimethoxysilane trimethylphenoxysilane, methyltriallyloxysilane, and the like.
  • external electron donor materials include but are not limited to one or a blend of organic silane compounds, such as tetraethoxysilane ("TEOS”), methylcyclohexyldimethoxysilane (“MCMS”), propyltrimethoxysilane (“PTMS”), propyltriethoxysilane (“PTES”), methytrimethoxysilane (“MTMS”), dimethyldimethoxysilane (“DMDMS”) and dicyclopentydimethoxysilane (“DCPMS”).
  • TEOS tetraethoxysilane
  • MCMS methylcyclohexyldimethoxysilane
  • PTMS propyltrimethoxysilane
  • PTES propyltriethoxysilane
  • MTMS methytrimethoxysilane
  • DDMDMS dimethyldimethoxysilane
  • DCPMS dicyclopentydimethoxysilane
  • the external electron donor, or silane donor is present in the polymerization reaction (relative to the total amount of ethylene or ⁇ -olefin) from 0.1 to 50 ppm in one embodiment, and from 1 to 20 ppm in another embodiment, and from 4 to
  • advantageous properties of the polyolefin of the invention are achieved by contacting under suitable polymerization conditions at least one polymerizable ethylene and/or olefin unit with the unsupported catalyst described above in conjunction with an "external" electron donor such as a silane, and
  • the present invention is a polyolefin such as a propylene copolymer or homopolymer having a bulk density of from 0.38 to 0.52 and a titanium residuals value of from less than 15 ppm.
  • the polyolefin can be described as having a bulk density of from 0.38 to 0.52 and a heat deflection temperature of from 86 to 105°C.
  • the bulk density of the polyolefin is from 0.39 to 0.50.
  • the titanium residuals value of the polyolefin is from less than 10 ppm in another embodiment.
  • the heat deflection temperature of the polyolefin is from 86 to 105°C in one embodiment, and from 90 to 101°C in another embodiment.
  • the melt flow rate of the polyolefin is from 0.1 to 100 g/10 min in one embodiment, and from 0.1 to 30 g/10 min in another embodiment, and from 1 to
  • the polyolefin of the invention has a heptane insolubles value of from less than 98% of the weight of the total polymer in another embodiment.
  • magnesium-based compounds are present to less than 5 ppm, and magnesium-based compounds are absent in yet another embodiment, the polyolefin copolymer or homopolymer being made from a second generation (unsupported) Ziegler-Natta catalyst system.
  • the aluminum residuals value of the homopolymer is from less than 55 ppm.
  • the polyolefin copolymer or homopolymer produced using the catalyst system and method of polymerization of the present invention is useful for many applications such as, for example, biaxially oriented films and capacitor films. These films are made using conventional techniques known to those in the art.
  • the present invention also includes a process for producing a polyolefin such as, for example, a propylene homopolymer or copolymer, the process comprising in one embodiment: (a) contacting ⁇ -olefin monomers selected from ethylene, propylene, 1-butene, 1-hexene, 1-heptene, and 1-octene; propylene in a preferred embodiment; and a titanium based unsupported Ziegler-Natta catalyst system, the catalyst system comprising at least one organic ester present during the polymerization from 1 to 30 ppm, and at least one organoaluminum compound present during the polymerization from 50 to 400 ppm; and optionally at least one silane present during polymerization from 0.1 to 50 ppm; (b) washing the polymer thus produced; and (c) isolating a polymer having a titanium residuals value of from less than 15 ppm.
  • ⁇ -olefin monomers selected from ethylene, propylene, 1-butene,
  • Another embodiment of the process for making a polyolefin of the invention includes: (a) contacting ⁇ -olefin monomers and a titanium based unsupported Ziegler-Natta catalyst system, the catalyst system consisting essentially of at least one organic ester present during the polymerization from 1 to 30 ppm, and at least one organoaluminum compound present during the polymerization from 50 to 400 ppm and from 50 to 500 ppm of an organoaluminum compound present during the polymerization; and optionally at least one silane present during polymerization from 0.1 to 50 ppm; (b) washing the polymer thus produced; and (c) isolating a polymer having a titanium residuals value of from less than 15 ppm.
  • the organoaluminum compound can be represented by the formula R n AlX 3-n , wherein R is selected from alkyl groups having from 1 to
  • the organic ester is selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isodecyl methacrylate, lauryl methacrylate, 2-hydroxy ethyl methacrylate, 2-hydroxypropyl methacrylate, 1,3-butylene dimethacrylate, trimethylpropane trimethacrylate, ethylene methacrylate, butylacrylate, and mixtures thereof.
  • the organic ester is present in the polymerization reaction in the range from 2 to 20 ppm in yet -mother embodiment
  • magnesium-based compounds are present to less than 5 ppm, and absent in another embodiment.
  • the properties of the resulting polyolefin such as a propylene homopolymer are as described above.
  • the present invention includes a catalyst composition for polymerizing olefins comprising an unsupported titanium based Ziegler-Natta catalyst system, the catalyst system comprising an organic ester present during the polymerization from 1 to 30 ppm, and a silane present during polymerization from 0.1 to 50 ppm relative to the amount of olefin in the polymerization system.
  • Another embodiment of the catalyst composition consists essentially of a titanium-based compound, desirably an unsupported Ziegler-Natta catalyst in another embodiment; an organoaluminum co-catalyst, an internal electron donor, an external electron donor, and hydrogen or other chain termination agents.
  • the organic ester is selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2- ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n- butyl methacrylate, isobutyl methacrylate, isodecyl methacrylate, lauryl methacrylate, 2-hydroxy ethyl methacrylate, 2-hydroxypropyl methacrylate, 1,3- butylene dimethacrylate, trimethylpropane trimethacrylate, ethylene methacrylate, butylacrylate, and mixtures thereof.
  • the silane useful in the composition is selected from tetraethoxysilane, methylcyclohexyldimethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, methytrimethoxysilane, dimethyldimethoxysilane and dicyclopentydimethoxysilane, and mixtures thereof.
  • the catalyst composition may further includes an organoaluminum compound selected from dimethylaluminum chloride, diethylaluminum chloride, trimethylaluminum, triethylaluminum, methylaluminum chloride, ethylaluminum chloride, ethylaluminum sesquichloride, triethylaluminum chloride, diethylaluminum chloride, and blends thereof.
  • the organoaluminum compound may be present from 100 to 300 ppm in the polymerization system in one embodiment.
  • magnesium-based compounds are present to less than 0.5 ppm of the catalyst composition, and absent in another embodiment.
  • the organoaluminum compound is diethylaluminum chloride, and the silane is tetraethoxysilane in yet another embodiment.
  • MFR Melt Flow Rate
  • ASTM standard D12308 which used a load of 2.16 kg at 230°C, and is expressed in g/10- min.
  • HI Heptane Insoluble
  • HDT Heat Deflection Temperature
  • Decalin Solubles Two grams of polypropylene granules were dissolved in 100 ml decalin containing some BHT by refluxing the decalin solvent for one hour. Then the solution was kept at room temperature for 16 to 24 hours to allow the crystallizable polymer to precipitate out of solution. The precipitate was filtered out and 20 ml of the filtrate was evaporated to dryness. The amount of soluble polymer contained in the 20 ml filtrate was multiplied by 500 to obtained the percent decalin soluble.
  • Constant Stress Rheometer Using a Constant Stress Rheometer, an arbitrary and constant stress is applied to a molten polymer sample and the material response to that stress is monitored until such time that the system has reached a steady state.
  • the stress is relieved and maintained at zero.
  • the energy stored upon deforming the sample is released resulting in a spring back or recovery in the molecules.
  • the magnitude of the recovery is determined and used along with the applied stress to calculate the recoverable compliance.
  • a second-generation catalyst system that was prepared as described in US 4,295,991 and above was used in a series of two pilot-plant scale polymerization reactors.
  • the reactor is suitable for bulk propylene polymerization and is capable of producing 60 to 90 pounds of polymer per hour on a continuous operation.
  • the temperature of the first reactor was 74°C, while the temperature of the second reactor was 68°C.
  • Diethylaluminum chloride (DEAC) was used to activate the second-generation catalyst solid, while the addition of methyl methacrylate (MMA) was used to control the crystallinity of the polypropylene resin.
  • the DEAC and MMA concentrations were expressed as parts per million relative to the total amount of propylene that was fed into the first reactor.
  • the amount of hydrogen used ranged from 4200 to 4800 mole ppm in the reactor vapor phase, as measured by gas chromatography.
  • Controlled amounts of TEOS were added in some of the experiments to determine the effect on the resulting polymer bulk density, residual level of metals or ions such as titanium (Ti), decalin-soluble property, catalyst activity, and heat-deflection-temperature (HDT) property which is another test for crystallinity.
  • the catalyst activity was measured as the amount of polymers made divided by the amount of catalyst solid that was charged.
  • Tables 1 and 2 show the results of the different experimental conditions that were carried out.
  • the invention examples, Samples 8-15, have a lower BD value than the other samples, especially Samples 1 and 7.
  • the metal residuals values for Samples 1 and 7 are relatively high compared to the invention
  • Samples 8-12 where the BD was low.
  • Sample 7 there was a non-optimal amount of the organoaluminum co-catalyst DEAC as compared to Samples 8-15.
  • the organoaluminum co-catalyst concentration is from less than 700 ppm in one embodiment of the invention, and from 50 to 400 ppm in the polymerization reaction in another embodiment.
  • the invention sample (e.g., Sample 12) has a higher modulus than the comparative example of polypropylene PD 4182E3 (ExxonMobil Chemical Company, Houston, TX), a capacitor film grade polypropylene made from another second generation Ziegler-Natta catalyst system.
  • the 1% secant modulus of a biaxially oriented film from Sample 12 is 2,490 MPa (362 kpsi) as compared to 2,360 MPa (342 kpsi) for the comparative example.
  • the biaxially oriented film was prepared on a T.M. Long machine with a draw ratio of 6x6 for MDxTD.
  • the HDT of the invention sample film is 99.3°C as compared to 85°C for the comparative example.
  • the metal residuals value for the invention example are improved relative to the film using the PD 4182 E3.
  • the residual level of titanium left in the polymer was also affected by the amount of MMA that was added.
  • the experiments with TEOS (Figure 3) addition showed a trend of decreasing residual titanium level as the MMA concentration was increased. Without TEOS, the residual titanium level did not show a decreasing trend.
  • Figure 4 and Table 1 show that the experiments with TEOS addition gave a slightly higher HDT compared to without TEOS, as the MMA concentration was increased. This indicates that there may be some crystallinity enhancement effect with TEOS addition. However, for both systems, the HDT increased with increasing amount of MMA as expected.
  • Figure 5 shows that the amount of decalin soluble decreases with increasing MMA concentration, indicating an increase in polymer crystallinity. The experiments with and without TEOS showed similar results.
  • the polyolefin product that is isolated from the polymerization process of the invention after washing, using the catalyst system of the present invention has a titanium residuals value of less than 15 ppm in one embodiment, less than 10 ppm in another embodiment, from 1 to 5 in yet another embodiment, from 1 to 10 in yet another embodiment, and from 1 to 15 in yet another embodiment.
  • the aluminum residuals is less than 75 ppm in one embodiment, and less than 55 ppm in another embodiment, and less than 30 ppm in yet another embodiment, and less than 20 ppm in yet another embodiment of the polyolefin of the invention.
  • the bulk density (BD) value of the polyolefin produced from the catalyst system of the invention ranges from 0.38 to 0.52 in one embodiment, from 0.39 to 0.50 in another embodiment, and from 0.4 to 0.45 in yet another embodiment.
  • the MFR of the polyolefin is from 1 to 100 in one embodiment, from 1 to 25 in another embodiment, and from 1.5 to 10 in yet another embodiment.
  • Decalin solubles values for polyolefins of the present invention range from 2% to 6% in one embodiment, and from 2.5% to 5.5% in another embodiment.
  • the heptane insolubles (HI) value of the polyolefin ranges from greater than 97% in one embodiment, greater than 96% in another embodiment, greater than 95% in yet another embodiment, and greater than 94% in yet another embodiment, and greater than 93% in yet another embodiment, and greater than 92% in yet another embodiment, and from 94% to 99% in yet another embodiment, and from 94% to 98% in yet another embodiment.
  • the HDT of the polyolefin is from 86 to
  • Catalyst activity is grams of polymer/ grams of catalyst. 2. Compliance.

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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)
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  • Manufacturing & Machinery (AREA)
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  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

L'invention concerne un système catalyseur Ziegler-Natta de seconde génération (sans support) permettant de réduire la densité apparente du polypropylène tout en maintenant l'effet de cristallinité élevée d'un premier donneur d'électrons tels qu'un ester organique ou l'acrylate. En ajoutant un ester organique et un donneur d'électrons silane, ce système permet d'obtenir un produit caractérisé par une densité apparente plus faible et une température de déformation à la chaleur plus élevée. L'invention concerne en outre un homopolymère de propylène présentant une densité apparente comprise entre 0,38 et 0,52 g/cm3 et une valeur de résidus de titane inférieure à 15 ppm. Par ailleurs, la température de déformation à la chaleur de l'homopolymère est comprise entre 86 et 105 °C, la vitesse de fusion de l'homopolymère étant comprise entre 1 et 100 g/10 min. La valeur des matières insolubles de l'heptane de l'homopolymère est généralement supérieure à 93 % du poids du polymère total.
PCT/US2002/013485 2001-05-14 2002-04-30 Copolymeres et homopolymeres de polypropylene a faible densite apparente WO2002092640A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2543684A1 (fr) * 2011-07-07 2013-01-09 Borealis AG Procédé de fabrication de polypropylène isotactique
WO2013016478A1 (fr) * 2011-07-28 2013-01-31 Dow Global Technologies Llc Polymère à base de propylène présentant une faible teneur en cendres et procédé correspondant
EP2565221B1 (fr) * 2011-08-30 2015-04-08 Borealis AG Procédé de fabrication d'un film de condensateur
WO2021239594A1 (fr) * 2020-05-27 2021-12-02 Borealis Ag Film bopp destiné à être utilisé dans un condensateur

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EP0340688A2 (fr) * 1988-04-29 1989-11-08 Union Carbide Corporation Procédé d préparation de polymères d'alpha-oléfines à haute pureté
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US4051307A (en) * 1972-06-09 1977-09-27 Imperial Chemical Industries Limited Polymerization process
US4197398A (en) * 1974-12-04 1980-04-08 Exxon Research & Engineering Co. Process for neutralizing and deashing polypropylene
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EP0340688A2 (fr) * 1988-04-29 1989-11-08 Union Carbide Corporation Procédé d préparation de polymères d'alpha-oléfines à haute pureté
US5023223A (en) * 1988-12-16 1991-06-11 Sumitomo Chemical Company, Limited Process for producing highly stereospecific α-olefin polymers
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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2543684A1 (fr) * 2011-07-07 2013-01-09 Borealis AG Procédé de fabrication de polypropylène isotactique
WO2013004781A1 (fr) * 2011-07-07 2013-01-10 Borealis Ag Procédé pour la production de polypropylène isotactique
CN103748119A (zh) * 2011-07-07 2014-04-23 博里利斯股份公司 制备全同立构聚丙烯的方法
US9102770B2 (en) 2011-07-07 2015-08-11 Borealis Ag Process for the manufacture of isotactic polypropylene
WO2013016478A1 (fr) * 2011-07-28 2013-01-31 Dow Global Technologies Llc Polymère à base de propylène présentant une faible teneur en cendres et procédé correspondant
JP2014525969A (ja) * 2011-07-28 2014-10-02 ダウ グローバル テクノロジーズ エルエルシー 低い灰分を有するプロピレン系ポリマーおよび方法
EP2565221B1 (fr) * 2011-08-30 2015-04-08 Borealis AG Procédé de fabrication d'un film de condensateur
WO2021239594A1 (fr) * 2020-05-27 2021-12-02 Borealis Ag Film bopp destiné à être utilisé dans un condensateur
CN115667380A (zh) * 2020-05-27 2023-01-31 博里利斯股份公司 用于电容器的bopp膜
JP7520151B2 (ja) 2020-05-27 2024-07-22 ボレアリス・アクチェンゲゼルシャフト キャパシタに使用するｂｏｐｐフィルム

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