WO1996004320A1 - Systeme de catalyseur contenant un composant en titane solide pour la stereoregulation des olefines - Google Patents

Systeme de catalyseur contenant un composant en titane solide pour la stereoregulation des olefines Download PDF

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Publication number
WO1996004320A1
WO1996004320A1 PCT/US1995/009670 US9509670W WO9604320A1 WO 1996004320 A1 WO1996004320 A1 WO 1996004320A1 US 9509670 W US9509670 W US 9509670W WO 9604320 A1 WO9604320 A1 WO 9604320A1
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catalyst
catalyst system
polypropylene
polyolefin
organoaluminum
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PCT/US1995/009670
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English (en)
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Nemesio Delgado Miro
James Carlton Randall
George Byron Georgellis
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Exxon Chemical Patents, Inc.
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Publication of WO1996004320A1 publication Critical patent/WO1996004320A1/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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • 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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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

Definitions

  • the present invention relates to a catalyst system and an olefin
  • Catalyst systems for the polymerization of olefins are well known in the art. Typically, these systems include a Ziegler-Natta type polymerization catalyst component; a co-catalyst, usually an organoaluminum compound; and an electron donor compound. Examples of such catalyst systems are shown in U. S. Patent Numbers: 5,066,738 (Ewen); 4,990,479 (Ishimaru); 4,990,477
  • Ziegler-Natta type polymerization catalyst components are basically a complex derived from a halide of a transition mmeetal, f example, titanium, chromium, or vanadium with a metal hydride and/or a metal alkyl that is typically an organoalumium compound.
  • the catalyst is usually comprised of a titanium halide composition supported on a magnesium compound complexed with an alkylaluminum compound.
  • the co-catalysts that work well with the newer generations of solid titanium-supported catalysts are organoaluminum compounds, most typically the alkylaluminum series such as triethylaluminum (“TEAT), diethyl-aluminum chloride (“DEAC”) and trisobutylaluminum.
  • organoaluminum compounds most typically the alkylaluminum series such as triethylaluminum (“TEAT), diethyl-aluminum chloride (“DEAC”) and trisobutylaluminum.
  • TEAT triethylaluminum
  • DEC diethyl-aluminum chloride
  • trisobutylaluminum trisobutylaluminum
  • examples of other useful organoaluminum compounds include alkylaluminum dihahdes and trialkoxyaluminum compounds.
  • % HI percentage heptane insolubles
  • the success of the various donors is generally established by determining the percent of heptane insolubles, "% HI" (U. S. Patent numbers 4,246,136; 4,335,015; 4,634,687; 4,678,768; 4,716,206; and 4,463,102).
  • the % HI is also often used as an index of the isotacticity of a crystalline polypropylene.
  • the level of polypropylene isotacticity shall be defined by the average undisturbed stercoregular run lengths of meso diads in the crystalline fraction of the subject polyolefin polymers composition.
  • the % HI shall be used to indicate the level of the crystalline fraction of a polypropylene composition.
  • Specified % HI levels are generally important in processing of polypropylene polymer compositions as the atactic polymer contained therein will act as a processing aid. This is particularly true for processes that make polypropylene films. A particular example is oriented polypropylene films made by a process called the tenter frame. An example where low levels of atactic polypropylene are desirable are in molding applications which require good heat resistance as reflected by a higher heat distortion temperature (“HDT").
  • HDT heat distortion temperature
  • the present invention involves the discovery of a certain catalyst system that can be used to control the stereoregularity of polyolefin polymers and thereby achieve polymer compositions of moderate to low crystallinity which contain relatively low levels of amorphous or atactic polymer.
  • a (1) a particular organoaluminum co-catalyst mixture and (2) a specific group of silane compounds serving as electron donors in combination with a TiCl 4 supported catalyst component results in a catalyst system which can generate a polyolefin composition having a low to moderate crystallinity and an unexpectedly lower amount of by-product heptane soluble amorphous polymer than ordinarily generated in the preparation of olefin polymer compositions of comparable crystallinity.
  • the instant catalyst system enables the practice of a polymerization process exhibiting an improved control of the stereoregularity of the polymer product than otherwise provided with catalyst systems of the prior art.
  • the present invention provides a catalyst system for the polymerization of olefins which system includes a combination of a solid titanium component with a specific composition comprised of an organoaluminum co-catalyst mixture and an organosilane electron donor compound, resulting in unexpected and significant control of the properties of the polymer product generated therewith.
  • the catalyst component is a solid titanium component which contains magnesium, titanium, halogen, and an internal electron donor as essential elements.
  • the organoaluminum co-catalyst mixture is comprised of diethyl aluminum chloride ("DEAC") in an amount of 3 to 75 mole percent and at least one other organoaluminum compound such as triethylaluminum, in an amount of 97 to 25 mole percent.
  • the external electron donor is an
  • organosilane compound such as methylcyclohexyl dimethoxysilane ("MCMS"), or dicyclopentyldimethoxysilane (“DCPMS”).
  • MCMS methylcyclohexyl dimethoxysilane
  • DCPMS dicyclopentyldimethoxysilane
  • the present catalyst system is used in polymerization processes to generate a novel polyolefin polymer composition of moderate to low (relatively low) crystallinity having lower than expected atactic (amorphous) polymer formation as reflected in lower heptane solubles in the polymer than comparable prior art polyolefin compositions.
  • the invention also provides for a process for the polymerization of olefins.
  • the process comprises: (a) providing a catalyst system comprised of (i) a solid titanium catalyst component comprising magnesium, titanium, halogen, and an internal electron donor; (ii) a co-catalyst comprised of a mixture of diethylaluminum chloride in an amount of 3 to 75 mole percent and at least one other organoaluminum compound, such as triethylaluminum, in an amount of 97 to 25 mole percent; and (iii) an external organosilane electron donor such as MCMS or DCPMS; (b) introducing the catalyst system into a polymerization reaction zone containing additional amounts of (i) the organoaluminum co-catalyst mixture, (ii) the external organosilane electron donor, and (iii) olefin monomer wherein polymerization of the monomer takes place.
  • the process may include the optional step of prepolymerizing the catalyst system by contacting a small amount of olefin monomer with the catalyst system prior to entry into the reaction zone.
  • the instant polymerization process further includes the steps of (c) maintaining the mole percent of DEAC in the reaction zone between about 3 to 75 mole percent of the total amount of organoaluminum co-catalyst employed, and (d) withdrawing from the reaction zone a polyolefin composition containing heptane soluble polymer in an amount of 2 to 10 weight percent of total polyolefin polymer. It is further preferable that the Al/Si mole ratio in the reaction zone be maintained within the range of from 5 to 1000.
  • polypropylene compositions having crystalline polypropylene portions of low stereoregularity accompanied by lower than expected amorphous polymer formation as measured by differentials in the heptane soluble portions of the respective polypropylene compositions.
  • the stereoregularity of the polymer chains can be controlled and manipulated to the extent of achieving a polyolefin composition having relatively higher portions of low or moderately crystalline polymers and a lower than expected amount of amorphous polypropylene than demonstrated by polypropylenes of comparable similar crystallinity in the prior art
  • Figure 1 is a characteristic diagram illustrating the correlation between heats of fusion and corresponding average meso run lengths of the crystalline portions of the series of polypropylene compositions.
  • Figure 2 is the plot of Figure 1 further illustrating the crystallinity region of interest for the polypropylene compositions of the present invention.
  • Figure 3 is a characteristic diagram illustrating and highlighting the correlation between the heats of fusion, as a measure of crystallinity, and corresponding heptane insoluble contents of polypropylene compositions of the prior art and the present invention.
  • Figure 4 is an expanded view of the highlighted compositions of the present invention shown in Figure 3.
  • Figure 5 is a characteristic diagram illustrating and highlighting the correlation between the average meso run lengths, as an indicator of crystallinity, versus percentage of heptane insolubles in polypropylene compositions of the prior art and of the present invention.
  • Figure 6 is an expanded view of the highlighted compositions of the present invention shown in Figure 5.
  • the present invention is directed to an olefin polymerization catalyst system which is the combination of (i) a solid titanium-supported Ziegler-Natta catalyst component; (ii) a particular mixture of organoaluminum compounds as co-catalysts; and (iii) an external organosilane electron donor for use in the polymerization of propylene.
  • This catalyst system is based on the discovery that the use of certain co-catalyst mixtures in combination with silane donors are factors controlling the isotacticity of polypropylene compositions as measured by the heptane insoluble portions of same.
  • isotacticity and isotactic level refers to the average run length of unperturbed stereoregular so-called "meso diad sequences". This is the length of the meso diad sequences that are terminated by some type of "stereo-defect" in the recurring stereoregular sequence.
  • Theoretically predicted stereo-defects that disrupt continuous meso diad sequences are shown as follows: ("1" is used to designate one type of stereochemical configuration, and "0" is used to designate the other, and only second, type of stereochemical configuration.
  • a meso diad sequence can be either "00" or "11".
  • a racemic diad can either be "01 " or "10”.).
  • each type of stereo-defect begins with the sequence, mmmr, and ends with the sequence, rmmm.
  • the frequency of these stereo-defects will determine the run lengths of the meso diad sequences.
  • An average meso run length per 10,000 repeat units can be determined from carbon 13 NMR methyl pentad data from a heptane insoluble polypropylene fraction and the following relationship:
  • Atactic polypropylenes are produced concurrently by the catalysts and polymerization processes that produce these polypropylene compositions. Atactic polypropylene has no stereoregularity and, consequendy, it is amorphous and has no melting point Atactic polypropylene, in contrast to crystalline polypropylene, is soluble in most aromatic solvents (including heptane) at room temperature and can be extracted from crystalline polypropylenes with aliphatic hydrocarbon solvents near their boihng point. Historically, there has been a systematic relationship between % HI and polypropylene crystallinity.
  • % HI has often been used in literature and patents as a method to establish the level of polypropylene crystallinity. Values for % HI generally range from percentages in the mid 80s to the upper 90s with the higher % HI levels usually indicating higher levels of crystallinity in the heptane insoluble portion of the polymer composition.
  • the heart of the present invention resides in the use of critical amounts of diethylaluminum chloride in the catalyst system to achieve a polyolefin polymer having desirable meso diad (or recurring stereoregular sequences) resulting in relatively lower crystallinity in the polyolefin without an increase in the concurrent formation of undesirable atactic (amorphous) polyolefin.
  • This catalyst system enables the preparation of a more processable polyolefin composition because of the relatively lower % heptane insolubles which produces a polymer composition with an unexpected lower content of undesirable amorphous polymer.
  • the instant catalyst system generates a novel polypropylene composition having adequately and consistently distributed perturbations in the polymers thereof resulting in a composition of relatively low crystallinity, and low amounts of amorphous (atactic) polypropylene, as measured by a relatively higher heptane insolubility (% HI) than would ordinarily be expected from prior art polyolefins of comparably lower crystallinity.
  • the instant polypropylene compositions and those of the prior art having crystalline portions thereof at the same isotactic level have different heptane solubilities. Accordingly, the catalyst system provides a polymerization process exhibiting better control of undesirable amorphous (atactic) polymer, an unexpected result over prior art processes employing other combinations of co-catalysts and electron donors.
  • Electron donors are typically used in two ways in the formation of a Ziegler-Natta catalyst component and a catalyst system.
  • an internal electron donor may be used as a stereoregulator in the formation reaction of the catalyst as the transition metal halide is reacted with the metal hydride or metal alkyl.
  • the second use for an electron donor in a catalyst system is as an external electron donor. It may exchange with the internal donor and change the direction of stereoregulation of the catalyst system. The same compound may be used in both instances, although typically they are different.
  • Organic silicon compounds for example, dicyclopentyldimethoxysilane (“DCPMS"), are common external electron donors. Examples of electron donors that are organic silicon compounds are disclosed in U. S.
  • Patent numbers 4,218,339; 4,395,360; 4,328,122; and 4,473,660 the entire disclosures of these patents being hereby incorporated by reference for purposes of US patent practice.
  • the term "electron donor” as used herein generally refers to the external donor unless otherwise stipulated. It has been discovered that the particular co-catalyst and electron donor recipe of the present invention does significandy enhance the catalytic properties of a solid titanium Ziegler-Natta catalyst component.
  • the preferred catalyst component demonstrating the most promising results in the present invention is a new generation Ziegler-type titanium catalyst component for the polymerization of olefins.
  • This prefe ⁇ ed catalyst comprises a solid catalyst component obtained by (1) suspending a dialkoxy magnesium in an aromatic hydrocarbon that is liquid at normal temperatures, (ii) contacting the dialkoxy magnesium with a titanium halide and further, (iii) contacting the resulting composition a second time with the titanium halide, and contacting the dialkoxy magnesium with a diester of an aromatic dicarboxylic acid at some point during the treatment with the titanium halide in (ii).
  • a solid catalyst component obtained by (1) suspending a dialkoxy magnesium in an aromatic hydrocarbon that is liquid at normal temperatures, (ii) contacting the dialkoxy magnesium with a titanium halide and further, (iii) contacting the resulting composition a second time with the titanium halide, and contacting the dialkoxy magnesium with a diester of an aromatic dicarboxylic acid at some point during the treatment with the titanium halide in (ii).
  • the present invention employs any magnesium-supported titanium- based catalyst components, such as the new generation Toho THC, or the more conventional Ziegler-Natta components such as Mitsui TK-220, Himont FT4S, and HMC-101.
  • Each can be combined with a mixture of organoaluminum co- catalysts, containing DEAC and a selected amount of an organosilane donor, such as MCMS or DCPMS to yield the catalyst system of this invention.
  • organosilane donor such as MCMS or DCPMS
  • the only constituent concentrations within the instant catalyst system that are allowed to vary are (1) the ratio of DEAC to the other organoaluminum components in the co-catalyst mixture and (a) the amount of the organosilane external donor.
  • polypropylenes can be made with the use of conventional ⁇ CI 4 supported catalyst system employing TEAl as the sole co-catalyst, but with considerably higher levels of atactic polymer.
  • the basic catalyst system recipe within the parameters of the present invention (such as the new generation Toho component catalyst with a specified amount of DEAC/TEAl co-catalyst and organosilane donor), it is possible to generate novel stereoregular polypropylenes of low crystallinity characterized by average meso run lengths of less than 200 and lower than expected amounts of heptane solubles.
  • polypropylene polymers of low crystallinity can be prepared only with unacceptable amounts of atactic polypropylene as reflected in relatively low heptane insolubles (% HI). While the ratios of (a) the catalyst component (b) the organoaluminum co-catalyst and (c) the silane electron donor components of the instant catalyst system are generally not critical one to the other, (1) the relative amounts of DEAC to other organoaluminum co-catalysts and (2) the presence of organosilane external donor are important to the practice of this invention.
  • the ratio of DEAC to the other organoaluminum compounds in the co-catalyst mixture must be in an amount of from 3 to 75 mole percent, and the organosilane electron donor is used in an amount of at least 0.1 part per million (ppm) of total propylene in the reaction mixture.
  • organoaluminum co-catalysts with the purview of the present invention are alkylaluminum compounds such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butyl-aluminum,
  • Methods for determining the crystallinity of polypropylene include measurements of the average meso run lengths ("MRL) and heats of fusion ( ⁇ H) of polypropylene.
  • the heat of fusion is essentially a measurement of the energy to melt the crystalline portion of a polypropylene composition and is a direct measurement of crystallinity.
  • the MRL is a structural measurement of the average unperturbed lengths of the meso sequences in polypropylene chains, which have the capability to crystallize in the polymer composition.
  • a characterization curve of average meso run length versus heat of fusion for traditionally prepared polypropylene and those polymers generated with the catalyst system of the present invention is demonstrated in Figure 1.
  • the heat of fusion is determined by Differential Scanning Calorimetry ("DSC") reflecting the crystallinity of the crystalline portion of the polymerized propylene.
  • the heat of fusion is a measure of the energy required to melt the crystalline polypropylene sample and consequently is direcdy related to the level of polypropylene crystallinity.
  • the meso run length is the polypropylene structural feature that is responsible for any observed crystallinity. Accordingly, the curve illustrates higher crystallinity (heats of fusion) for those
  • the average meso run lengths which are structural measurements, show a systematic relationship to the heats of fusion, which are direct measures of polypropylene crystallinity.
  • the average meso run lengths vary between 5 and 500 while the heats of fusion vary between 80 and 120 J/g. This range allows the relationship between the two different ways of evaluating polypropylene crystallinity to be fully observed.
  • the plot clearly shows that the heat of fusion does not change significantly once the average meso run length reaches values of 200 and higher. Below meso run lengths of 100, the heats of fusion respond dramatically to changes in the average meso run length.
  • Atactic polypropylene typically has an average meso run length of around 5, whereas highly crystalline polypropylenes (heats of fusion above 105) have average meso run lengths in excess of 175 and beyond.
  • the polypropylenes of the present invention have low to moderate crystallinity, and have % HI's that do not follow the traditional relationship between HI and polypropylene crystallinity. In fact, they contain far less heptane soluble polypropylenes than would be ordinarily expected from their average level of crystallinity.
  • polypropylenes were prepared by the indicated catalysts to enable the instant low to moderately crystalline polypropylene polymers to be compared to comparable, traditional polypropylenes (prepared with prior art catalyst systems). The % heptane insolubles for the series of polypropylenes were compared to both their respective heats of fusion and meso run lengths.
  • Tables I and II represent propylene polymerization test runs using the catalyst system of the present invention which employs a new generation catalyst component manufactured by the Toho Titanium Company of Japan and commercially designated as the SP111 series.
  • the characteristic curves of Figures 3 - 6 represent the plotting of % HI, heats of fusion, and meso run length values of Tables 1 and 2.
  • the magnesium-supported Ziegler-Natta type catalysts employed in the preparation of polymers for the test runs of Tables 1 and 2 are also listed along with the commercial polymer examined.
  • a TA-200/DSC-10 instrument purchased from TA Instruments, Inc., was used to measure me thermal properties of the polymers. The polymers were first extruded and pelletized prior to taking a 8-13 mgs samples. A prepared DSC sample was placed in the cell and the cell purged with nitrogen at room temperature for five minutes. The temperature was then raised to 230°C at a heating rate of 50°C per minute. The temperature was held for ten minutes, followed by cooling to 50°C at a cooling rate of 10°C per minute. After reaching 50°C, the sample was again heated to 200°C at the rate of 10°C per minute. The heat of melting during the second heating cycle was measured, by integrating the melting curve between baseline limits of 85 and 175°C, and used to determine relative crystallinities of the indicated polypropylenes.
  • silane donor in a 0.01 M solution in hexane as parts per million donor by weight relative to the total amount of propylene employed
  • a specified total amount of aluminum alkyl (as parts per million by weight at the desired molar mixture of DEAC and TEA1) was then added to the reactor.
  • a desired amount of hydrogen was introduced into the reactor, as measured by the psi drop from a 300 cc vessel.
  • 1000 ml of propylene was added to the reactor.
  • FIGS. 3 and 4 two views of a plot of % HI versus heat of fusion can be found for both the compositions of the invention and traditional polypropylenes over a broad range of crystallinity.
  • the "window" area described as "10" in Figure 3, represents that area of low to moderate crystallinity, which characterize the instant polypropylene compositions. This area is equivalent to the defined area of crystallinity demonstrated in Figure 2.
  • Figure 3 which gives a complete view of the relationship between % heptane insolubles and heats of fusion as an index of crystallinity, contains data points generated from
  • compositions ranging from atactic polypropylene with no low crystallinity to highly crystalline polypropylenes. It is clear in Figure 3 that the % heptane insolubles and heats of fusion demonstrate a proportionally linear relationship with curvature developing only at the higher values for the heats of fusion ( ⁇ H) and % HI. Also shown in Figure 3 is a calculated line, described as "11", which defines the boundary between polypropylenes generated by the traditional catalyst systems and those polypropylenes generated by the instant catalyst system.
  • Figure 4 is an expanded view of the window area 10 in Figure 3 demonstrating two calculated lines, 11 and 12.
  • Upper calculated line 11 corresponds to the same calculated line 11 shown in Figure 3.
  • the position of the lower line 12 in Figure 4 was determined after a linear regression analysis over the ⁇ H, HI relationship for the series of polypropylenes, described as "traditional" i.e., prepared from traditional catalyst systems of the prior art.
  • the algebraic equation for line 12 is as follows:
  • This line provides a boundary between those regions defining the polypropylenes prepared with prior art catalyst systems and those polypropylene compositions prepared with the instant catalyst system.
  • the invention polypropylenes have the highest observed % HI in the ⁇ H range from 85 to 100 J/g. Any catalyst generated polypropylene composition having atactic polymer content and crystallinity values that give a point above line 11 falls within the purview of the instant invention, which is directed toward low to moderately crystalline polypropylenes having relatively high Hi's.
  • the % HI for # 12 is 90.2, which places the composition below the line, and the % HI for composition # 7 is 93.8, which places it above the line.
  • Six of the eight polypropylenes prepared with the instant catalyst system place above the indicated line.
  • Figures 5 and 6 are different views of the % HI versus average meso run length relationship for both prior art and invention polypropylenes.
  • the procedure for producing Figures 5 and 6 is comparable to the procedure for producing Figures 4 and 5.
  • Figure 5 shows the full relationship from atactic polypropylene to highly crystalline polypropylenes while Figure 6 is an expansion of the outlined window area 20 in Figure 5.
  • calculated line "13" line is used in Figure 5 to define the boundary between traditional polypropylenes and those of the polymers prepared with the catalyst system of the present invention.
  • a lower calculated line, "14” is also given in the expanded view of the % HI versus meso run length relationship shown in Figure 6, analogous to the linear relationships shown in Figure 4.
  • Line 14, which defines the "traditional" polypropylene relationship was determined by performing a linear regression analysis over the traditional prior art
  • the second and higher line 13 shown in Figure 6 is the relationship observed for the polypropylenes prepared with the commercial Toho catalyst recipe.
  • the equation for this line which was also shown in Figure 5, defines the boundary between the invention and traditional polypropylenes and is given below:
  • % HI Limit 0.31 (MRL) + 67.4 (4)
  • the invention catalyst recipes give polypropylenes that have higher % HTs than the traditional polypropylenes. Both equations 2 and 4 describe boundaries between similar ranges of crystallinity.
  • the HI limits of 81.3 and 100 were used to establish the MRL range of 45 to 105 and the ⁇ H range of 75 to 109 J/g.
  • the polypropylenes which fall clearly and distinctively within the purview of the present invention will be identified by the combined measurements of average meso run length and % HI. Equations 2 and 4, given above, when used in the range of crystallinity defined by average meso run lengths between 45 and 105 and corresponding heats of fusion, between 75 and 109 J/g define the moderate to low crystalline polypropylene compositions of the present invention.
  • the electron donors included in the present invention are organic silicon compounds such as those described above in the prior art
  • Typical organosilane compounds used as external donors in the catalyst system of the present invention include those disclosed in U. S. Patent 4,990,479 to Ishimaru et al. the entire disclosure of which is hereby incorporated by reference for purposes of US patent practice.
  • Preferred organosilane electron donors include
  • MCMS methylcyclohexyldimethoxysilane
  • DCPMS dicyclopentyldimethoxy-silane
  • DPMS diphenyldimethoxysilane
  • the most preferred electron donor is methylcyclohexyldimethoxysilane (“MCMS”).
  • MCMS methylcyclohexyldimethoxysilane
  • the combination of MCMS and the catalyst/co-catalyst subsystem described herein yields wholly unexpected results that surpass previously known catalyst systems.
  • the electron donors as described for use in the present invention may be limited by the stability of the compound and the ease of handling including storage, transportation, and use in the plant
  • the present invention also provides a process for the polymerization of olefins using the catalyst system described above.
  • the catalyst system may be used in almost any commercially known polymerization process
  • the preferred process of the present invention includes a pre-polymerization of the catalyst with a small amount of monomer as described in numerous prior art patents.
  • a carrier stream for the catalyst is provided, the catalyst is contacted with the co-catalyst organoaluminum compound mixture and subsequently contacted with the electron donor.
  • the catalyst stream is then contacted with a relatively small amount of the total amount of monomer to be polymerized, the catalyst stream passing through a tubular or stirred reactor, and the pre-polymerized catalyst and catalyst stream are introduced into the polymerization reaction zone.
  • the electron donor may be contacted with the catalyst simultaneously with the co-catalyst mixture.
  • a polymer product may men be withdrawn from the reactor.
  • the catalyst system may have an efficiency of at least about 20 kg/gcat. while the Al/Si mole ratio in the reaction is within the range 5-1000.
  • the polymer product will also be characterized by hexane solubles within the range 2-10 weight percent

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Abstract

L'invention concerne un système de catalyseur présentant des capacités de régulation de la stéréorégularité sans précédent et générant un produit polymère oléfinique présentant une cristallinité faible à modérée. Ce système de catalyseur comprend (a) un composant catalyseur en titane solide, (b) un mélange de chlorure de diéthylaluminium et un autre composé d'organoaluminium faisant office de co-catalyseur, et (c) un donneur d'électrons alkylsilane. Lorsqu'il est utilisé dans la polymérisation du propylène, ledit système assure une régulation de la stéréorégularité et de la génération de polymères atactiques indésirables, ce qui permet d'obtenir un nouveau polymère de polypropylène de cristallinité faible à modérée.
PCT/US1995/009670 1994-08-03 1995-08-01 Systeme de catalyseur contenant un composant en titane solide pour la stereoregulation des olefines WO1996004320A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6566294B2 (en) 2000-12-21 2003-05-20 Exxonmobil Chemical Patents Inc. Multi-donor catalyst system for the polymerization of olefins
US6582762B2 (en) 1999-12-22 2003-06-24 Exxonmobil Chemical Patents Inc. Sprayable hot melt adhesives
KR100723365B1 (ko) 2005-09-30 2007-05-30 삼성토탈 주식회사 분자 구조 중에 트리알킬실릴기를 포함하는 알콕시실란화합물을 사용하는 프로필렌 중합체 제조방법
WO2007102652A1 (fr) * 2006-03-06 2007-09-13 Lg Chem, Ltd. Procédé de polymérisation de propylène comprenant une étape de prépolymérisation d'oléfines
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Cited By (9)

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US6582762B2 (en) 1999-12-22 2003-06-24 Exxonmobil Chemical Patents Inc. Sprayable hot melt adhesives
US6566294B2 (en) 2000-12-21 2003-05-20 Exxonmobil Chemical Patents Inc. Multi-donor catalyst system for the polymerization of olefins
KR100723365B1 (ko) 2005-09-30 2007-05-30 삼성토탈 주식회사 분자 구조 중에 트리알킬실릴기를 포함하는 알콕시실란화합물을 사용하는 프로필렌 중합체 제조방법
WO2007102652A1 (fr) * 2006-03-06 2007-09-13 Lg Chem, Ltd. Procédé de polymérisation de propylène comprenant une étape de prépolymérisation d'oléfines
US8008417B2 (en) 2007-01-19 2011-08-30 Toray Tonen Specialty Separator Godo Kaisha Polymeric material and its manufacture and use
US8293857B2 (en) 2007-11-22 2012-10-23 Ineos Europe Limited Process for polymerising ethylene
US7872086B2 (en) 2008-01-17 2011-01-18 Tonen Chemical Corporation Polymeric material and its manufacture and use
WO2014128715A2 (fr) 2013-02-19 2014-08-28 Reliance Industries Limited Composition améliorée de catalyseur de titane supporté sur dichlorure de magnésium pour la polymérisation de polyoléfines
CN104292373A (zh) * 2013-07-18 2015-01-21 中国石油化工股份有限公司 一种用于提高聚丙烯立构规整度的组合物及其应用

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