WO1998045338A1 - Modification de la repartition du poids moleculaire d'un polymere a l'aide de systemes de silanes melanges dans des catalyseurs de polymerisation a haute activite - Google Patents

Modification de la repartition du poids moleculaire d'un polymere a l'aide de systemes de silanes melanges dans des catalyseurs de polymerisation a haute activite Download PDF

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WO1998045338A1
WO1998045338A1 PCT/US1998/006783 US9806783W WO9845338A1 WO 1998045338 A1 WO1998045338 A1 WO 1998045338A1 US 9806783 W US9806783 W US 9806783W WO 9845338 A1 WO9845338 A1 WO 9845338A1
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organic
polymerization
catalyst
compound
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PCT/US1998/006783
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Chung-Ping Cheng
Paul D. Smith
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Engelhard Corporation
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Priority to AU69526/98A priority Critical patent/AU6952698A/en
Publication of WO1998045338A1 publication Critical patent/WO1998045338A1/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
    • 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 generally to polymerization or copolymerization catalyst compositions and processes wherein mixed silanes are used to modify the molecular weight distribution of the resultant polymer.
  • High activity polypropylene catalysts generally consist of a solid, comprised of magnesium dichloride and titanium tetrachloride, along with some amount of a complexed organic electron donor such as a phthalate ester.
  • the solid catalyst component is normally used in conjunction with a) an aluminum alkyl, and b) an organic silane.
  • Catalyst systems of this type differ from the earlier generation titanium trichloride catalyst in several aspects, one being the breadth of the resultant polymer molecular weight distribution (MWD).
  • polypropylenes used in making BOPP Biaxially Oriented
  • Polypropylene films must have a relatively broad molecular weight distribution.
  • MWD is important in giving the polymer sufficient strength so it will not easily tear when stretched. This is important in the application of the polymer as well as in processing the polymer. The higher strength also allows the processing equipment that stretches the polymer into a film to run faster without film breakage.
  • older first and second-generation Ziegler-Natta titanium trichloride catalysts yielded polypropylene with a MWD in the range of 8 to 10 (as measured by MJM,, using GPC). This range has been found to be suitable for making BOPP films.
  • the silane component in prior catalyst systems, in conjunction with high activity co- catalysts, is used to control polymer isotacticity.
  • Traditionally only one type of silane compound is used and the isotacticity is controlled by varying the amount of silane used in the polymerization.
  • Polymers obtained with this type of catalyst system typically have narrower molecular weight distributions compared to older catalyst systems. Broader molecular weight distributions are desirable for certain applications such as BOPP film and HCPP (high crystallinity polypropylene).
  • a traditional titanium trichloride catalyst system is used.
  • the disadvantage or the traditional catalyst system is the low catalyst activity obtained.
  • High activity catalysts normally give much narrower MWD and, thus, are not suitable for applications such as BOPP film and HCPP.
  • the present invention allows the production of polymers using high activity catalysts and produces polymers with the broad MWD desirable for producing such product grades.
  • a mixture of at least two different silanes is used to obtain polymers with MWD similar to those of the older generation catalysts.
  • the silanes are selected based on their hydrogen response.
  • the two different silanes used in the combination should have sufficiently different hydrogen response so as to achieve the desired MWD broadening effect.
  • the choice of silanes in the present invention allows one to tailor the MWD to the desired level. This method of MWD control is applicable to other ⁇ -olefin polymerization catalysts which utilize silanes for isotacticity control. If the hydrogen response of the two different silanes is similar, no broadening of the MWD is possible, because the polymer made from the two different silanes will merely have the same MWD. If the hydrogen response of the two different silanes is too dissimilar, a polymer with a bi-modal MWD is obtained, and often this is undesirable.
  • the silane mixture comprises a first organic silane compound, characterized in that, when said first silane is used for polymerization in the absence of any other silanes, the slope of the line fitted to a plot of the amount of hydrogen used in the polymerization (X-axis) v. resultant polymer melt flow rate (Y-axis) is between 2.5 and 5.0, preferably 3.25 to 3.75; and a second organic silane compound, characterized in that, when said second silane is used for polymerization in the absence of any other silanes, the slope of the line fitted to a plot of the amount of hydrogen used in the polymerization (X-axis) v. resultant polymer melt flow rate (Y- axis) is between 0 and 1.5, preferably 0.5 to 1.0 (see Fig. 2).
  • U.S. Patent 5,100,981 describes the use of a mixture of cyclohexylmethyldimethoxy- silane (CMDMS) and phenyltriethoxysilane to narrow a polymer's molecular weight distribution (MWD). They do not attempt to use any other combinations of mixed silanes nor do they attempt to use mixed silanes to create a polymer with a broad MWD.
  • CMS cyclohexylmethyldimethoxy- silane
  • MWD molecular weight distribution
  • Published PCT application WO 95/21203 describes the use of a two-stage reaction, first using a weak silane, then at the second stage, adding a dominating silane.
  • This two-stage reaction is used to create a polymer that has the characteristics of a polymer created using the dominant silane, but with a slightly broader MWD.
  • the present invention does not use a weak/dominant silane system like the one disclosed in this patent. Additionally, the catalytic composition of the present invention has a higher catalytic efficiency and gives polymer with a broader molecular weight distribution.
  • European Patent 0385765 A2 describes the use of two electron donors, (a) and (b), with very different independent MFR values, such that log
  • the current invention uses a novel mixture of silanes having a loglMFRJMFRJ value well below 1.5. Additionally, the catalytic composition of the present invention exhibits a higher catalytic efficiency and provides a polymer with a broader molecular weight distribution.
  • Japanese Patent 2-170803 describes a catalyst comprising an organic silicon compound, of the formula R_Si(OR') 4. tenu, and an ethylsilicate.
  • the present invention has a unique catalytic composition and does not use ethylsilicates as required by this patent.
  • the efficiency of the present catalyst is also greater than 270% higher.
  • Japanese Patents 4-117411 and 4-117412 describe a catalyst comprising a mixture of a dimethoxysilane and an alkoxysilane to produce a polymer with a broad MWD.
  • the unique catalytic composition of the present invention does not use alkoxysilanes, as they are defined and required in these patents. Additionally, the present invention exhibits substantially higher catalyst efficiency.
  • Japanese Patent 4-136006 describes a catalyst comprising a di-branched-alkyldialkoxy- silane and a cycloalkylalkyldialkoxysilane.
  • the present invention does not use the required di- branched-alkyldialkoxy silanes and has a different catalytic composition providing a more desirable molecular weight distribution.
  • Japanese Patent 4-239008 describes a catalyst comprising at least a di- or trialkoxysilane and a branched alkoxysilane.
  • the most relevant example uses cyclohexylmethyldimethoxysilane and triisopropoxymethylsilane.
  • the present invention does not use the same silane combinations as those disclosed in this patent. Additionally, the catalytic composition of the present invention provides polymer with a more desirable molecular weight distribution.
  • Japanese Patent 6-248019 describes a catalyst comprising at least two silane compounds.
  • the most relevant example uses cyclopentylethyldimethoxysilane and 0-phenethylmethyl- dimethoxysilane.
  • the current invention does not use the silane mixtures disclosed in this patent.
  • the present invention has a catalytic composition that provides significantly higher catalyst efficiency and gives a polymer with a more desirable melt flow index.
  • Japanese Patent 6-298835 describes a catalyst comprising component obtained by reacting a Ti/Mg Hal compound with two silicon compounds.
  • the most relevant example discloses the use of dicyclopentyldimethoxysilane and tert-butyldiethoxysilane.
  • the present invention uses a different catalytic composition and silane system with a substantially higher (>600%) catalyst efficiency to give polymer with a more desirable melt flow index and a higher molecular weight distribution.
  • Japanese Patent 6-145204 describes a catalyst comprising two silicon compounds.
  • the most relevant example uses t-butyl-n-propyldimethoxysilane and t-butyldimethoxysilane.
  • the present invention uses a different catalytic composition and silane system with a substantially higher (>500%) catalyst efficiency to give polymer with a more desirable melt flow index and a higher molecular weight distribution.
  • Japanese Patent 6-179513 describes a catalyst comprising two organic silicon compounds.
  • the most relevant example uses cyclohexylmethyldimethoxysilane and ethyltriethoxysilane.
  • the present invention uses a different catalytic composition and silane system with a higher catalyst efficiency.
  • U.S. Patent 5,550,094 suggests the addition of "one or several organosilicon compounds" to form a catalyst. (Col. 3, 11. 64-65; Claim 2(ii)).
  • the specification discloses the possible use of hydrocarbyl- substituted silanes, including aryl and alkyl substituted silanes, but excluding cycloalkylsilanes.
  • U.S. Patent 5,258,345 suggests the use of "at least one silane” (Col. 2, 11. 37-47) in an invention that is attempting to achieve a bimodal MWD. However, there is no mention of cycloalkyl substituted silanes.
  • U.S. Patent 5,550,094 suggests the addition of "one or several organosilicon compounds" to form a catalyst. (Col. 3, 11. 64-65; Claim 2(ii)).
  • the specification discloses the possible use of hydrocarbyl- substituted silanes, including aryl and alkyl substituted silanes, but excluding cycloal
  • Patent 5,489,634 suggests that "compounds of silicon may be used alone or more of them may be mixed or reacted for use.”
  • U.S. Patent 5,498,770 mentions the use of mixed asymmetric silanes (Col. 11, 11, 61-63), but does not refer directly to the use of mixed silanes when symmetric silanes are used. It does disclose the use of DCPDMS and CMDMS as individual symmetric silanes (Col. 5, 11. 41-43).
  • U.S. Patent 5,547,912 discloses that "silicon compounds may be used independently or as admixture thereof (Col. 8, 11. 7-8). DCPDMS and CMDMS are disclosed as possible silanes. (Col. 8, 11. 1-3).
  • Patent 4,990,478 mentions that "mixtures of silanes may be used," (Col. 2, 11. 24-25) but gives no reason why one would want to, such as to broaden the polymer MWD. There is no disclosure of any cycloalkyl substituted silanes. Summary of the Invention
  • Component (A) may be prepared in the same manner as set forth in Example 1 of U.S. Letters Patent Nos. 4,784,983 and/or 4,861,847.
  • Component (A) may be prepared using a supported catalyst, such as a traditional ball-milled Ziegler-Natta catalyst.
  • Component (B) is an organic aluminum compound, having a general formula AIR_X 3 . n , wherein R is hydrogen, or a hydrocarbon group having 1-20 carbon atoms, preferably an alkyl, aralkyl or aromatic group; X is halogen, preferably chlorine or bromine and n is an integer of from 1 to 3.
  • Examples of such compounds are triethyl aluminum, triisobutyl aluminum, trioctyl aluminum; hydrogenated alkyl aluminums, such as diethyl aluminum hydride, diisobutyl aluminum hydride; halogenated alkyl aluminums, such as diethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride; with triethyl aluminum and triisobutyl aluminum being preferred.
  • hydrogenated alkyl aluminums such as diethyl aluminum hydride, diisobutyl aluminum hydride
  • halogenated alkyl aluminums such as diethyl aluminum chloride, diisobutyl aluminum chloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride
  • triethyl aluminum and triisobutyl aluminum being preferred.
  • the organic aluminum compound is used in the catalyst composition in such an amount that the mole ratio of aluminum to titanium in solid component (A) is about 5-5000 and preferably about 20-500.
  • Component (C) is a mixture of organic silane compounds such that the difference in the hydrogen response between the two is optimal for broadening the molecular weight distribution (MWD) of the resultant polymer.
  • the most preferred silane mixture is a 60:40 molar ratio of CMDMS (cyclohexylmethyldimethoxysilane) and DCPDMS (dicyclopentyldimethoxysilane).
  • CMDMS cyclohexylmethyldimethoxysilane
  • DCPDMS dicyclopentyldimethoxysilane
  • other mixtures of silanes are possible.
  • the organic silane compound is used in the catalyst composition in such an amount that the mole ratio of the organic aluminum compound to the organic silicon compounds is about 1 to 100, preferably 5 to 80.
  • component (C) is added in the polymerization of propylene either as a mixture or successively.
  • ⁇ -olefins e.g. ethylene, propylene, 1-butylene, 4-methyl-l-pentene, 1-hexylene, 1-octylene, and the like.
  • Homopolymerization as well as static copolymerization and block copolymerization of these olefins can be carried out using the catalyst system of the present invention.
  • Conjugated diene or nonconjugated diene can be selected as a monomer for copolymerization.
  • FIG. 1 therein is disclosed the polymerization apparatus 10 used in the performance of the test runs described in Examples 1 to 5, including the following: 20 3 L jacketed stainless steel reactor, 30 two pitched-blade impeller, 40 glass vessel for stripping solvent, 50 circulating water bath, 60 radiant heater, 70 mercury manostat for nitrogen-actuated siphoning of solvent into reactor, 80 propylene storage vessel located on balance plate, 90 pressure controller, 100 pressure indicator, 110 pressure indicator and controller, 120 pressure indicator, recorder and controller, and a 130 weight indicator.
  • 20 3 L jacketed stainless steel reactor 30 two pitched-blade impeller, 40 glass vessel for stripping solvent, 50 circulating water bath, 60 radiant heater, 70 mercury manostat for nitrogen-actuated siphoning of solvent into reactor, 80 propylene storage vessel located on balance plate, 90 pressure controller, 100 pressure indicator, 110 pressure indicator and controller, 120 pressure indicator, recorder and controller, and a 130 weight indicator.
  • the catalyst system of the present invention was used in preparing the following Examples 1 through 5 below.
  • Titanium tetrachloride (151 ml, 1.37 mol) was added drop-wise over the course of 1 hour. The solution was heated to 80 °C over the course of 2 hours, while a solid product precipitated. Dibutyl phthalate (5.0 ml, 0.018 mol) was added and the mixture was maintained at the temperature of 80 °C for 1 hour.
  • the solid was then treated three times with a mixture of toluene (239 ml) and titanium tetrachloride (26.5 ml) at 110 °C for 30 minutes each.
  • the solid was washed with hexane (4 x 10.5 ml).
  • Component (A) contained 1.91% titanium by weight, 18.86% magnesium by weight, 12.58% dibutyl phthalate by weight.
  • a 50-ml, jacketed, cone-bottom-shaped, glass vessel was used for the prepolymerization step.
  • the reactor was first purged with nitrogen.
  • Heptane 29 ml
  • triethyl aluminum (0.66 g
  • Example 1 The data from Example 1 is also in Run No. 87 of Table 1.
  • Titanium tetrachloride (151 ml, 1.37 mol) was added drop-wise over the course of 1 hour. The solution was heated to 80 °C over the course of 2 hours, while a solid product precipitated. Dibutyl phthalate (2.5 ml, 0.009 mol) was added and the mixture was maintained at a temperature of 80 °C for 1 hour. The solid portion was collected by filtration and washed twice with toluene (239 ml) and titanium tetrachloride (26.5 ml). A brown-yellow solid precipitate was obtained.
  • the solid was then treated three times with a mixture of toluene (239 ml) and titanium tetrachloride (26.5 ml) at 110 °C for 30 minutes each.
  • the solid was washed with hexane (4 x 10.5 ml).
  • Component (B) contained 2.20% titanium by weight, 18.92% magnesium by weight, 9.28% dibutyl phthalate by weight. 2. Preliminary Polymerization (Prepolymerization)
  • a 50-ml, jacketed, cone-bottom-shaped, glass vessel was used for the prepolymerization step.
  • the reactor was first purged with nitrogen.
  • Heptane 29 ml
  • triethyl aluminum (0.66 g, 6 mmol
  • cyclohexylmethyldimethoxysilane (0.113 g, 0.6 mmol) were charged into the reactor.
  • Component (A) (1.5 g) was added. Nitrogen was pumped out and replaced with propylene at 80 torr. Prepolymerization was carried out at ambient temperature (ca. 25 °C) for
  • Example 3 The data from Example 1 is also in Run No. 93 of Table 1.
  • Example 3 The data from Example 1 is also in Run No. 93 of Table 1.
  • Titanium tetrachloride (151 ml, 1.37 mol) was added drop-wise over the course of 1 hour. The solution was heated to 80 °C over the course of 2 hours, while a solid product precipitated. Dibutyl phthalate (5 ml, 0.018 mol) was added and the mixture was maintained at the temperature of 80 °C for 1 hour.
  • a 50-ml, jacketed, cone-bottom-shaped, glass vessel was used for the prepolymerization step.
  • the reactor was first purged with nitrogen.
  • Heptane (29 ml), triethyl aluminum (0.66 g, 6 mmol), and cyclohexylmethyldimethoxysilane (0.113 g, 0.6 mmol) were charged into the reactor.
  • Component (A) (1.5 g) was added.
  • Nitrogen was pumped out and replaced with propylene at 80 torr.
  • Prepolymerization was carried out at ambient temperature (ca. 25 °C) for 0.5 hr to reach a PP/catalyst level of 2-3.
  • the dissolved propylene was pumped out and replaced with nitrogen.
  • Aliquots (2 ml) from the prepolymerized slurry was syringed into small vials, diluted 10 times with heptane, and used for subsequent polymerization experiments.
  • the standard 3 liter reactor was employed. Heptane (1200 ml), triethyl aluminum (0.095 g, 0.83 mmol), silane donor (0.002 g of a 60/40 molar mixture of CHMDMS and DCPDMS) at an Al:Si:Ti molar ratio of 200:2.5:1 were first charged into the reactor. The prepolymerized catalyst mix (2.2 ml slurry, 11 mg catalyst) was charged at 55 °C against a gaseous propylene into the polymerization reactor. The reactor was then closed, hydrogen (400 ml) was added, and temperature and pressure set to final values of 70 °C and 1 Mpa within about 5 minutes. Polymerization was conducted for 2 hours. The following results were obtained:
  • Example 1 The data from Example 1 is also in Run No. 90 of Table 1.
  • Titanium tetrachloride (151 ml, 1.37 mol) was added drop-wise over the course of 1 hour. The solution was heated to 80 °C over the course of 2 hours, while a solid product precipitated. Dibutyl phthalate (2.5 ml, 0.009 mol) was added and the mixture was maintained at the temperature of 80 °C for 1 hour.
  • the solid portion was collected by filtration and washed twice with a mixture of toluene (239 ml) and titanium tetrachloride (26.5 ml). A brown-yellow solid precipitate was obtained. The solid was then treated thee times with a mixture of toluene (239 ml) and titanium tetrachloride (26.5 ml) at 110 °C for 30 minutes each. The solid was washed with hexane (4 x 10.5 ml).
  • Component (B) contained 2.20% titanium by weight, 18.92%) magnesium by weight and 9.28% dibutyl phthalate by weight.
  • a 50-ml, jacketed, cone-bottom-shaped, glass vessel was used for the prepolymerization step.
  • the reactor was first purged with nitrogen.
  • Heptane 29 ml
  • triethyl aluminum (0.66 g, 6 mmol
  • cyclohexylmethyldimethoxysilane (0.113 g, 0.6 mmol) were charged into the reactor.
  • Component (A) (1.5 g) was added. Nitrogen was pumped out and replaced with propylene at 80 torr. Prepolymerization was carried out at ambient temperature (ca. 25 °C) for
  • silane donor 0.002 g of a 60/40 molar mixture of CHMDMS and DCPDMS
  • Al:Si:Ti molar ratio of 200:2.5:1 were first charged into the reactor.
  • the prepolymerized catalyst mix (2.2 ml slurry, 11 mg catalyst) was charged at 55 °C against gaseous propylene into the polymerization reactor.
  • the reactor was then closed, hydrogen (400 ml) was added, and temperature and pressure set to final values of 70 °C and 1 Mpa within about 5 minutes.
  • Titanium tetrachloride (151 ml, 1.37 mol) was added drop-wise over the course of 1 hour. The solution was heated to 80 °C over the course of 2 hours, while a solid product precipitated. Dibutyl phthalate (5 ml, 0.018 mol) was added and the mixture was maintained at 80 °C for 1 hour. The solid portion was collected by filtration and washed twice with a mixture of toluene (239 ml) and titanium tetrachloride (26.5 ml). A brown-yellow solid precipitate was obtained.
  • the solid was then treated three times with a mixture of toluene (239 ml) and titanium tetrachloride (26.5 ml) at 110 °C for 30 minutes each.
  • the solid was washed with hexane (4 x 10.5 ml).
  • Component (A) contained 1.91% titanium by weight, 18.86% magnesium by weight, 12.58%) dibutyl phthalate by weight.
  • Preliminary Polymerization A 50-ml, jacketed, cone-bottom-shaped, glass vessel was used for the prepolymerization step. The reactor was first purged with nitrogen. Heptane (29 ml), triethyl aluminum (0.66 g, 6 mmol), and cyclohexylmethyldimethoxysilane (0.113 g, 0.6 mmol) were charged into the
  • Example 1 The data from Example 1 is also Run No. 39 of Table 1.
  • the present invention gives a polymer with a broad molecular weight distribution.
  • the molecular weight distribution (MWD) of a polymer affects many of its physical properties.
  • the propylene polymer that is used for making BOPP film requires a polymer that has a relatively broad MWD.
  • the broad MWD is important in giving the polymer sufficient strength so that it will not tear easily when stretched. This is important in the application of the polymer as well as in processing of the polymer.
  • the higher strength, i.e. broad MWD allows the processing equipment (i.e., the equipment that stretches the polymer to make the film) to run faster without film breakage.
  • polypropylene produced using older first or second generation TiCl 3 catalysts gives polymer with MWD (as measured by MJM n using GPC) in the range of 8 to 10, which has been found to be suitable for making BOPP films.
  • Polypropylene produced using more recent third or forth generation high activity catalyst typically give polymer with MWD of 4 to 5.
  • This type of polymer is not suitable for making BOPP films.
  • the catalyst system of the present invention forms polymers with the MWD in the range of 8-10, suitable for making BOPP films and has a high activity.
  • the silane composition described in the present invention is a convenient starting point in obtaining a broader MWD. While a 60:40 molar ratio of CHMDMS and DCPDMS is preferred, the present invention also works if the silane mixture is changed from the present 60:40 molar ratio. The workable range is actually determined by the type of polymer desired. The important part of this mixture is not in the molar or weight composition of the mixture, but in the choice of components in the mixture.
  • the preferred silanes are chosen based on their hydrogen sensitivity. If the hydrogen sensitivity of the two silanes is similar, the polymer formed does not have a broadened MWD.
  • the primary objective of the present invention is to broaden the MWD by using different external electron donors (donors).
  • the variables studied were the type of donor, materials including: cyclohexylmethyldimethoxysilane (CHMDMS), dicyclopentyldimethoxysilane (DCPDMS), diisobutyldimethoxysilane (DIBDMS), isobutylisopropylmethylmethoxysilane
  • IBIPDMS tetramethylpiperidine
  • TMP tetramethylpiperidine
  • CRM-1 CHMDMS & DCPDMS
  • Characteristic (i) is obtainable using external modifiers exhibiting a high stereospecifying potential, such as DCPDMS. Characteristic (ii) poses problems when prior catalysts are employed and considerable effort has been exerted worldwide to meet demands of both converters and end users. The simplest way to widen the MWD seems to be a tailor-made formulation of external modifier(s) and one of the most important aspects of the present invention is an achievement of this result.
  • the catalyst system of the present invention increases stereospecificity upon increasing the D/Ti ratio for all efficient external modifiers.
  • the stereospecificity can be expressed — under certain simplifications — in terms of the crystallinity of polymer prepared.
  • the crystallinity is most easily obtainable via DSC measurement and the long-term experience shows that the enthalpy of crystallization (- ⁇ HJ is the best correlatable parameter of the DSC data. It will be shown below that the last statement is applicable to most of the data obtained within a study.
  • the catalyst itself plays also an important role.
  • the decreasing order of "inherent" stereospecificity of the particular lots are as follows: 9314 > 156 > 241 > 242 > 158. This order is valid for CMDMS and DCPDMS.
  • DCPDMS and CRM-1 provide higher activity in the catalyst system than CMDMS.
  • the activity is less dependent on the Si:Ti ratio (see the table).
  • the flexural modulus is primarily controlled by the polymer crystallinity (expressed in terms of - ⁇ H_) as shown in the above tables.
  • the polymer MWD is of high importance, particularly for BOPP applications.
  • the problem recognized worldwide is that there is no simple tool to measure the MWD with a sufficient accuracy. If GPC data are used for this purpose, it is advisable to obtain the whole set of data within a short period of time to avoid unacceptable shift and scatter of the data. This principle was applied as much as feasible in this study.
  • CRM-1 would be the best performer as the MWD widener.
  • Stereospecificity of the catalyst systems can be controlled within a wide range by : a) the type of catalyst b) the type of silane c) the Si/Ti ratio (or silane concentration), the last variable being the most efficient one.

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Abstract

L'invention porte sur un système catalyseur destiné à être utilisé dans la polymérisation et la copolymérisation oléfiniques, ce système comprenant des composants (A), (B) et (C). Le composant (A) de ce système catalyseur comprend titane, magnésium, halogène et des atomes donneurs d'électrons. Le composant (B) est un composé d'aluminium organique. Le composant (C) est un mélange de plusieurs composés de silicium organique. Le composant préféré (C) est un mélange de cyclohexylméthyldiméthoxysilane/dicyclopentyldiméthoxysilane. Ce système catalyseur est avantageux car il associe la très haute activité des catalyseurs de polymérisation modernes à la répartition très large des poids moléculaires des anciens catalyseurs de trichlorure de titane. Les répartitions très larges des poids moléculaires sont souhaitables pour certaines applications telles que les films BOPP et HCCP (polypropylène à haute cristallinité).
PCT/US1998/006783 1997-04-07 1998-04-06 Modification de la repartition du poids moleculaire d'un polymere a l'aide de systemes de silanes melanges dans des catalyseurs de polymerisation a haute activite WO1998045338A1 (fr)

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Cited By (9)

* Cited by examiner, † Cited by third party
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WO2002051545A1 (fr) * 2000-12-21 2002-07-04 Exxonmobil Chemical Patents Inc. Systeme catalytique a donneurs multiples pour la polymerisation d'olefines
EP1223181A2 (fr) * 2001-01-12 2002-07-17 Fina Technology, Inc. Production de résines polypropylène ayant une vitesse d'écoulement élevée à l état fondu
WO2009050363A1 (fr) 2007-09-25 2009-04-23 Pierre Fabre Medicament Procede de synthese de derives anticancereux de ( poly) aminoalkylaminoacetamide d ' epipodophyllotoxine
WO2013029767A1 (fr) 2011-08-29 2013-03-07 Saudi Basic Industries Corporation Procédé de préparation de succinates disubstitués
US8618220B2 (en) 2004-07-30 2013-12-31 Saudi Basic Industries Corporation Propylene copolymer compositions with high transparency
CN103665204A (zh) * 2012-09-07 2014-03-26 中国石油化工股份有限公司 一种烯烃聚合用固体催化剂组分及催化剂
US10047218B2 (en) 2013-12-20 2018-08-14 Saudi Basic Industries Corporation Polyolefin composition
US10696829B2 (en) 2013-12-20 2020-06-30 Saudi Basic Industries Corporation Heterophasic propylene copolymer
CN114437264A (zh) * 2020-10-20 2022-05-06 中国石油化工股份有限公司 一种低voc低气味聚丙烯树脂及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0258485A1 (fr) * 1985-04-01 1988-03-09 Beijing Research Institute of Chemical Industry, Ministry of Chemical Industry Système catalytique à utiliser dans la polymérisation d'oléfines
EP0349772A2 (fr) * 1988-06-09 1990-01-10 Hoechst Aktiengesellschaft Procédé de préparation d'un polypropylène
EP0491584A2 (fr) * 1990-11-27 1992-06-24 Société APPRYL Cocatalyseur de polymérisation du propylène à base de silane et de monoether
EP0676419A1 (fr) * 1994-04-06 1995-10-11 Fina Technology, Inc. Systèmes catalytiques pour la polymérisation des oléfines ayant une stéréoséléctivité améliorée et une large distribution du poids moléculaire
WO1997043321A1 (fr) * 1996-05-15 1997-11-20 Borealis A/S Systeme catalyseur stereospecifique pour la polymerisation des olefines et processus de polymerisation en plusieurs etapes au moyen de ce systeme catalyseur

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0258485A1 (fr) * 1985-04-01 1988-03-09 Beijing Research Institute of Chemical Industry, Ministry of Chemical Industry Système catalytique à utiliser dans la polymérisation d'oléfines
US4861847A (en) * 1985-04-01 1989-08-29 Beijing Research Institute Of Chemical Industry Catalyst system for use in olefinic polymerization
EP0349772A2 (fr) * 1988-06-09 1990-01-10 Hoechst Aktiengesellschaft Procédé de préparation d'un polypropylène
US5100981A (en) * 1988-06-09 1992-03-31 Hoechst Aktiengesellschaft Process for the preparation of a polypropylene
EP0491584A2 (fr) * 1990-11-27 1992-06-24 Société APPRYL Cocatalyseur de polymérisation du propylène à base de silane et de monoether
EP0676419A1 (fr) * 1994-04-06 1995-10-11 Fina Technology, Inc. Systèmes catalytiques pour la polymérisation des oléfines ayant une stéréoséléctivité améliorée et une large distribution du poids moléculaire
WO1997043321A1 (fr) * 1996-05-15 1997-11-20 Borealis A/S Systeme catalyseur stereospecifique pour la polymerisation des olefines et processus de polymerisation en plusieurs etapes au moyen de ce systeme catalyseur

Cited By (14)

* 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
WO2002051545A1 (fr) * 2000-12-21 2002-07-04 Exxonmobil Chemical Patents Inc. Systeme catalytique a donneurs multiples pour la polymerisation d'olefines
EP1223181A2 (fr) * 2001-01-12 2002-07-17 Fina Technology, Inc. Production de résines polypropylène ayant une vitesse d'écoulement élevée à l état fondu
EP1223181A3 (fr) * 2001-01-12 2003-11-26 Fina Technology, Inc. Production de résines polypropylène ayant une vitesse d'écoulement élevée à l état fondu
US7022796B2 (en) 2001-01-12 2006-04-04 Fina Technology, Inc. Production of ultra high melt flow polypropylene resins
US8618220B2 (en) 2004-07-30 2013-12-31 Saudi Basic Industries Corporation Propylene copolymer compositions with high transparency
WO2009050363A1 (fr) 2007-09-25 2009-04-23 Pierre Fabre Medicament Procede de synthese de derives anticancereux de ( poly) aminoalkylaminoacetamide d ' epipodophyllotoxine
WO2013029767A1 (fr) 2011-08-29 2013-03-07 Saudi Basic Industries Corporation Procédé de préparation de succinates disubstitués
US8889898B2 (en) 2011-08-29 2014-11-18 Saudi Basic Industries Corporation Process for preparing di-substituted succinates
CN103665204A (zh) * 2012-09-07 2014-03-26 中国石油化工股份有限公司 一种烯烃聚合用固体催化剂组分及催化剂
US10047218B2 (en) 2013-12-20 2018-08-14 Saudi Basic Industries Corporation Polyolefin composition
US10696829B2 (en) 2013-12-20 2020-06-30 Saudi Basic Industries Corporation Heterophasic propylene copolymer
CN114437264A (zh) * 2020-10-20 2022-05-06 中国石油化工股份有限公司 一种低voc低气味聚丙烯树脂及其制备方法和应用
CN114437264B (zh) * 2020-10-20 2024-03-26 中国石油化工股份有限公司 一种低voc低气味聚丙烯树脂及其制备方法和应用

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