AU5458394A - Process for polymerizing alpha-olefin - Google Patents

Description

WO 94/11409 PCT/US93/10653

DESCRIPTION

PROCESS FOR POLYMERIZING ALPHA-OLEFIN Technical Field This invention relates to a process for producing aolefin polymers. More particularly, the invention relates to a process that utilizes a novel high activity stereoregular polymerization catalyst system to produce a-olefin polymers having improved polymer properties.

Background Art The use of a solid, transition-metal based, olefin polymerization catalyst system including a titanium-containing, magnesium halide-based catalyst component to produce a polymer of an a-olefin such as ethylene, propylene, and butene-l, is well known in the art. Such polymerization catalyst systems are typically obtained by the combination of a magnesium halide-based catalyst component, an organoaluminum compound and one or more electron donors. For convenience of reference, the solid titanium-containing catalyst component is referred to herein as "procatalyst", the organoaluminum compound, as "cocatalyst", and an ele,'tron donor compound, which is typically used separately, or used partially or totally complexed with the organoaluminum compound, as "selectivity control agent" (SCA). It is also known to incorporate electron donor compounds into the pro-catalyst. The electron donor which is incorporated with the titanium-containing compounds serves a different purpose than the electron donor referred to as the selectivity control agent. The compounds which are used as the electron donor are the same as or different from compounds which are used as the selectivity control agent. The above-described stereoregular high activity catalysts are broadly conventional and are described in numerous patents and other references including Nestlerode et al, U. S. Patent 4,728,705, which is incorporated herein by reference.

Although a broad range of compounds are known generally as selectivity control agents, a particular catalyst component may have a specific compound or groups of compounds with which it is specially compatible. For any given WO 94/11409 I'CI'/US93/10653 procatalyst and/or cocatalyst, discovery of an appropriate type of selectivity control agent can lead to significant increases in catalyst efficiency, hydrogen utilization efficiency as well San improvement in polymer product properties.

Many classes of selectivity control agents have been disclosed for possible use in polymerization catalysts. One class of such selectivity control agents is the class of organo-silanes. For example, Hoppin et al, U.S. Patent 4,990,478, describe branched C 3

C

10 alkyl-tbutoxydimethoxysilanes. Other aliphatic silanes are described in Hoppin et al, U.S. Patent 4,829,038. Kioka et al, U.S.

Patent 5,028,671, describe a catalyst system which incorporates various alkylalkoxysilanes, such as di-noctadecyldimethoxysilane and di-n-octadecyldiethoxysilane as selectivity control agents.

Although many methods are known for producing highly stereoregular a-olefin polymers, it is still desired to improve the activity of the catalyst and produce polymers or copolymers that exhibit improved properties such as high melt flow and broad molecular weight distribution. Further, it is desired to produce polymers or copolymers that exhibit a reduction in the amount of volatiles.

Disclosure of the Invention The invention relates to an improved process for the production of homopolymers or copolymers of a-olefins that have improved polymer properties.

More particularly, the present invention is a process for the production of polymers using a high activity olefin polymerization catalyst system which comprises a titanium halide-containing procatalyst component obtained by halogenating a magnesium compound of the formula MgR'R", wherein R' and R" are alkoxide groups containing from 1 to carbon atoms with a halogenated tetravalent titanium compound in the presence of a polycarboxylic acid ester electron donor, with or without a halohydrocarbon, an organoaluminum cocatalyst component, and an organosilane selectivity control agent haviAg the general formula: WO 94/11409 PCI/US93/10653 Si R R wherein R' is linear alkyl group of 13 to 30 carbon atoms, alkaryl group of 16 to 36 carbon atoms or aralkyl group of 16 to 36 carbon atoms; R 2 and R 3 are, independently, methyl or alkyl groups of 13 to 30 carbon atoms, or hydrocarboxyloxy group of 1 to 6 carbon atoms; and R 4 is hydrocarbyloxy group of 1 to 6 carbon atoms.

Description of the Invention Although a variety of chemical compounds are useful fo- the production of the procatalyst, a typical procatalyst of the invention is prepared by halogenating a magnesium compound of the formula MgR'R", wherein R' is an alkoxide, aryloxide group or hydrocarbyl carbonate and R" is an alkoxide, hydrocarbyl carbonate, aryloxide group or halogen, with a halogenated tetravalent titanium compound in the presence of a halohydrocarbon and an electron donor.

The magnesium compound employed in the preparation of the solid catalyst component contains alkoxide, aryloxide, hydrocarbyl carbonate or halogen. The alkoxide, when present, contains from 1 to 10 carbon atoms. Alkoxides containing from 1 to 8 carbon atoms are preferable, with alkoxides of 2 to 4 carbon atoms being more preferable. The aryloxide, when present, contains from 6 to 10 carbon atoms, with 6 to 8 carbon atoms being preferred. The hydrocarbyl carbonate, when present, contains 1 to 10 carbon atoms. When halogen is present, it is present as bromine, fluorine, iodine or chlorine, with chlorine being preferred.

Suitable magnesium compounds are magnesium chloride, magnesium bromide, magnesium fluoride, ethoxy magnesium bromide, isobutoxy magnesium chloride, phenoxy magnesium iodide, cumyloxy magnesium bromide, magnesium diethoxide, magnesium isopropoxide, magnesium ethyl carbonate, ethoxy magnesium, magnesium stearate, magnesium laurate, and naphthoxy magnesium chloride. Especially preferred as the magnesium WO 94/11409 PCIUS93/10653 compounds are magnesium dialkoxides. Preferred magnesium compound is magnesium diethoxide.

Halogenation of the magnesium compound with the halogenated tetravalent titanium compound is effected by using an excess of the titanium compound. At least 2 moles of the titanium compound are used per mole of the magnesium compound.

Preferably from 4 moles to 100 moles of the titanium compound are used per mo'i of the magnesium compound, and most preferably from 4 Koles to 20 moles of the titanium compound are used per mole of the magnesium compound.

Halogenation of 'the magnesium compound with the halogenated tetravalent titanium compound is effected by contacting the compounds at an elevated temperature in the range from about 60 0 C to about 150 0 C, preferably from about 70 0 C to about 1200C. Usually the reaction is allowed to proceed over a period of 0.1 to 6, hours, preferably from about 0.6 to about 3.5 hours. The halogenated product is a solid material which is isolated from the liquid reaction medium by a suitable separation method, such as conventional filtration.

The halogenated tetravalent compound employed to halogenate the magnesium compound contains at least two halogen atoms, and preferably contains four halogen atoms. The halogen atoms are chlorine atoms, bromine atoms, iodine atoms or fluorine atoms. The halogenated tetravalent titanium compound has up to two alkoxy or aryloxy groups. examples of suitable halogenated tetravalent titanium compounds include diethoxytitanium dibromide, isopropoxytitanium triiodide, dihexoxytitanium dichloride, phenoxytitanium trichloride, titanium tetrachloride and titanium tetrabromide. The preferred halogenated tetravalent titanium compound is titanium tetrachloride.

Halogenation of the magnesium compound with the halogenated tetravalent titanium compound, as noted, is conducted in the presence of a ha'.hydrocarbon and an electron donor with or without a halohydrocarbon. If desired, an inert hydrocarbon diluent or solvent may also be present.

WO 94/11409 PCI/US93/10653 Suitable halohydrocarbons include aromatic or aliphatic, including cyclic and alicyclic compounds.

Preferably the halohydrocarbon contains 1 or 2 halogen atoms, although more may be present if desired. It is preferred that the halogen is, independently, chlorine, bromine or fluorine.

Exemplary of suitable aromatic halohydrocarbons are chlorobenzene, bromobenzene, dichlorobenzene, dichlorodibromobenzene, o-chlorotoluene, chlorotoluene, dichlorotoluene, chloronaphthalene. Chlorobenzene, ochlorotoluene and dichlorobenzene are the preferred halohydrocarbons, with chlorobenzene and o-chlorotoluene being more preferred.

The aliphatic halohydrocarbons which can be employed suitably of 1 to 12 carbon atoms. Preferably such halohydrocarbons of 1 to 9 carbon atoms and at least 2 halogen atoms. Most preferably the halogen is present as chlorine.

Suitable aliphatic halohydrocarbons include dibromomethane, trichloromethane, 1,2-dichloroethane, trichloroethane, dichlorofluoroethane, hexachloroethane, trichloropropane, chlorobutane, dichlorobutane, chloropentane, trichlorofluorooctane, tetrachloroisooctane, dibromodi-fluorodecane.

The preferred aliphatic halohydrocarbons are carbon tetrachloride and trichloroethane.

Aromatic halohydrocarbons are preferred, particularly those of 6 to 12 carbon atoms, and especially those of 6 to carbon atoms.

Typical electron donors that are incorporated within the procatalyst include esters, particularly aromatic esters, ethers, particularly aromatic ethers, ketones, phenols, amines, amides, imines, nitriles, phosphines, phosphites, stibines, arsines, phosphoramides and alcoholates. Esters of polycarboxylic acids are the preferred electron donors.

Particularly preferred are alkyl esters of aromatic polycarboxylic acid. Illustrative of suitable esters of polycarboxylic acid electron donors are diethyl phthalate, diisoamyl phthalate, ethyl p-ethoxybenzoate, methyl pethoxybenzoate, diisobutyl phthalate, dimethyl WO 94/11409 PCI/US93/10653 napthalenedicarboxylate, diisobutyl maleate, diisoprcpyl terephthalate, and diisoamyl phthalate. Diisobutyl phthalate and ethyl-p-ethoxybenzoate are the preferred alkyl ester of an aromatic carboxylic acid.

After the solid halogenated product has been separated from the liquid reaction medium, it is treated one or more times with additional halogenated tetravalent titanium compound. Preferably, the halogenated product is treated multiple times with separate portions of the halogenated tetravalent titanium compound. Better results are obtained if the .alogenated product is treated twice with separate portions of the halogenated tetravalent titanium compound. If desired, the solid halogenated product is treated one or more times with a mixture of halogenated tetravalent titanium compound and a halohydrocarbon. As in the initial halogenation, at least 2 moles of the titanium compound are employed per mole of the magnesium compound, and preferably from 4 moles to 100 moles of the titanium compound are employed per mole of the magnesium compound. Most preferably from 4 moles to 20 moles of the titanium compound per mole of the magnesium compound.

Optionally, the solid halogenated product is treated at least once with one or more acid chlorides during the additional treatments with the halogenated tetravalent titanium compound. Suitable acid chlorides include benzoyl chloride and phthaloyl chloride. The preferred acid chloride is phthaloyl chloride.

After the solid halogenated product has been treated one or more times with additional halogenated tetravalent titanium compound, it is separated from the liquid reaction medium, washed at least once with an inert hydrocarbon of up to carbon atoms to remove unreacted titanium compounds, and dried. Exemplary of the inert hydrocarbons that are suitable for the invention are isopentane, isooctane, hexane, heptane and cyclohexane.

Preferred final washed products have a titanium content of from 0.5 percent by weight to 6.0 percent by weight.

A more preferred final wash product has from 1.5 percent by WO) 94/11409) 44IPC7US93/14)653 weight to 4.0 percent by weight. The atomic ratio of titanium to magnesium in the final product is between 0.01:1 and 0.2:1.

A preferred final product has an atomic ratio of titanium to magnesium from about 0.02:1 to 0.15:1.

The cocatalyst is an organoaluminum compound which is typically an alkylaluminum compound. Suitable alkylaluminum compounds include trialkylaluminum compounds, such as triethylaluminum or triisobutylaluminum; dialkylaluminum halides such as diethylaluminum chloride and dipropylaluminum chloride; and dialkylaluminum alkoxides such as diethylaluminum ethoxide.

Trialkylaluminum compounds are preferred, with triethylaluminum being the preferred trialkylaluminum compound.

The organosilane selectivity control agents in the catalyst system contain at least one silicon-oxygen-carbon linkage. Suitable organosilane compounds include compounds having the following general formula: Si R2 R wherein R is a linear alkyl group of 13 to 30 carbon atoms, alkaryl group of 16 to 36 carbon atoms or aralkyl group of 16 to 36 carbon atoms. It is preferred that R' is alkyl group of 16 to 30 carbon atoms, alkaryl group of 19 to 30 carbon atoms or aralkyl group of 19 to 30 carbon atoms. It is further preferred that R' is alkyl group of 18 to 28 carbon atoms. R and R 3 are, independently, methyl or alkyl group of 13 to carbon atoms, or hydrocarbyloxy groups of 1 to 6 carbon atoms.

It is preferred that R 2 and R 3 are, independently, methyl or alkyl group of 16 to 30 carbon atoms or alkoxy group of 1 to 4 carbon atoms. It is further preferred that R 2 is methyl or alkyl group of 18 to 28 carbon atoms or alkoxy group of 1 to 4 carbon atoms and R 3 is alkoxy group of 1 to 4 carbon atoms. It is preferred that R 4 is alkoxy group of 1 to 4 carbon atoms.

R

4 is hydrocarbyloxy group of 1 to 6 carbon atoms. It is further preferred that R 2

R

3 and R 4 are ethoxy or methoxy groups. Examples of suitable organosilane selectivity control agents include n-octadecyltriethoxysilane, n-triacontyl- WO 94/11409 IPCIUS93/10653 triethoxysilane, methyl-n-octadecyldimetho sysilane, methyl-noctadecyldiethoxysilane, n-octadecyltrimethoxysilane, ntriacontyltrimethoxysilane and mixtures thereof. The preferred organosilane selectivity control agents are n-octadecyltriethoxysilane, n-methyloctadecyldimethoxysilane and noctadecyltrimethoxysilane. The invention also contemplates the use of mixtures of two or more selectivity control agents. The selectivity control agent is pre r;ed in a quantity such that the molar ratio of the selectivity control agent to the titanium present in the procatalyst is from about 0.5 to about Molar ratios from about 2 to about 60 are preferred, with molar ratios from about 5 to about 40 being more preferred.

The high activity stereoregular polymerization catalyst is utilized to effect polymerization by contacting at least one a-olefin under polymerization conditions. In accordance with the invention, the procatalyst component, organoaluminum cocatalyst, and selectivity control agent are introduced into the polymerization reactor separately or, if desired, two or all of the components are partially or completely mixed with each other before they are introduced into the reactor.

The particular type of polymerization process utilized is not critical to the operation of the present invention and the polymerization processes now regarded as conventional are suitable in the process of the invention. The polymerization is conducted under polymerization conditions as a liquid phase or a gas-phass process employing a fluidized catalyst bed.

The polymerization conducted in the liquid phase employs as reaction diluent an added inert liquid diluent or alternatively a liquid diluent which comprises the olefin, such as propylene or 1-butene, undergoing polymerization. If a copolymer is prepared wherein ethylene is one of the monomers, ethylene is introduced by conventional means to a diluent.

Typical polymerization conditions include a reaction temperature from about 25 0 c to about 1250C, with temperatures from about 35 0 C to about 900c being preferred, and a pressure WO 9)4/11409) PCIUS93/1 0653 sufficient to maintain the reaction mixture in a liquid phase.

Such pressures are from about 150 psi to about 1200 psi, with pressures from about 250 psi to about 900 psi are preferred.

The liquid phase reaction is operated in a batchwise manner or as a continuous or semi-continuous process. Subsequent to reaction, the polymer product is recovered by conventional procedures. The precise controls of the polymerization conditions and reaction parameters of the liquid phase process are within the skill of the art.

As an alternate embodiment of the invention, the polymerization is conducted in a gas phase process in the presence of a fluidized catalyst bed. One such gas phase process polymerization process is described in Goeke et al, U.S. Patent 4,379,759, incorporated herein by reference. The gas phase process typically involves charging to reactor an amount of preformed polymer particles, gaseous monomer and separately charge a lesser amount of each catalyst component.

Gaseous monomer, such as propylene, is passed through the bed of solid particles at a high rate under conditions of temperature and pressure sufficient to initiate and maintain polymerization. Unreacted olefin is separated and recovered and polymerized olefin particles are separated at a rate substantially equivalent to its production. The process is conducted in a batchwise manner or a continuous or semicontinuous process with constant or intermittent addition of the catalyst components and/or a-olofin to the polymorization reactor. Typical polymerization temperatures for a gas phase process are from about 300C to about 120 0 C and typical pressures are up to about 1000 psi, with pressures from about 100 to about 500 psi being preferred.

In both the liquid phase and the gas-phase polymerization processes, molecular hydrogen is added to the reaction mixture as a chain transfer agent to regulate the molecular weight of the polymeric product. Hydrogen is typically employed for this purpose in a manner well known to persons skilled in the art. The precise control of reaction WO 94/11409) 'PCI/US93/10653 conditions, the rate of addition of feed component and molecular hydrogen is broadly within the skill of the art.

The present invention is useful in the polymerization of a-olefins of up to 20 carbon atoms, such as propylene, dodecane, including mixtures thereof. It is preferred that aolefins of 3 carbon atoms to 8 carbon atoms, such as propylene, butene-l and pentene-l and hexane-l, are polymerized.

The polymers produced according to this invention are predominantly isotactic. Polymer yields are high relative to the amount of catalyst employed. The process of the invention produce homopolymers and copolymers including both random and impact copolymers having a relatively high stiffness while having a broad molecular weight distribution and maintaining an oligomers content (determined by the weight fraction of C 21 oligomer) of less than 300 ppm if a homopolymer and less than 600 ppm if a copolymer. The preferred homopolymers of the invention have an oligomers content of less than 150 ppm is preferred. More preferred homopolymors have oligomers content of less than 80 ppm. A reduction in oligomers content is indicative of a reduction in volatiles, e.g. smoke and/or oil, liberated during subsequent processing, e.g. extrusion.

Other features, advantages and embodiments of the invention disclosed herein will be readily apparent to those exercising ordinary skill after reading the foregoing disclosure. In this regard, while specific embodiments of the invention have been described in detail, variations and modifications of these embodiments can be effected without departing from the spirit and scope of the invention as described and claimed.

The invention described herein is illustrated, but not limited by the following Illustrative Embodiments and Comparative Example. The following terms are used throughout the Illustrative Embodiments and Comparative Example: ODTMS (n-octadocyltrimothoxysilane) ODTES (n-octadocyltriethoxysilano) DNDDMS (di-n-docyldimothoxysilane) DDTMS (n-dodocyltrimethoxysilano) TCTMS (n-triacontyltrimethoxysilane) WO 94/11409 WO 94/11409PC'/US 93/10653 M1NDDMS (methyl-n-decyldimethoxysilane) MODDEs (mothyl-n-octadecyldithoxysilalc) PEEB (ethyl-p-ethoxybflzoat3) NPTMS (n-propyltrimethoxysilale) DIBDES (diisobutyldiethoxysilane) DIBDMS (diisobutyldimethoxysilane) ILLUSTRA~rIVE EMBODIMENT-T Preparation of Procatalyst Component The procatalyst was prepared by adding magnesium diethoxide (2.17 g, 19 Mmol) to 55 ml of a 50/50 (Vol/Vol) mixture of TiC1 4 /chlorobanzene. After adding diisobuty.

phthalato (0.74 mle 2.75 mxnol), the mixture was heated in an oil bath and stirred at 1100C for 60 Minutes. The mixture was filtered hot and the solid portion was slurried in 55 mal of a 50/50 (vol/vol) mixture of iiC1 4 /chlorobanzene. In the preparation of some of the procatalyst, pkitha3.eyl, chloride (0.13 ml, 0.90 mmol) was added to the slurry at room temperature. The resulting sluriy was stirred at 1100C for G0 minutes, filtered, and the solvent obtained was slurried again ir. a fresh 50/So mixture of TiCl 4 /chlorobenzene. After stirring at 310CQC for 30 minutes, the mixture was filtered and allowed to cool to reom, temperature,~ The procatalyst slurry was washed 6 times with 125 ml portions of isooctane and than dried for 120 minutes, at 250C, under nitrogen.

Polymerization of Propylene Various catalysts were produced using several organosilanes as the selectivity control agent, some of which are within the scope of thQ invention (TCT?4S, ODTES, ODTMS, and MODDES) and others that are not within the scope of the invention (NPThS, DNDDMS# DIDDES, DDTMS, MIIDDMS and DI13DMS), Propylene (2700cc) and molecular hydrogen were introduced into a 1 gallon autoclave. The temperature of the propylene and molecular hydrogen was raised to 676C. An organosilane selectivity control agent, triethylaluminum, and the procatalyst, slurry produced above were premixed for about minutes and then the mixture was introduced into the autoclave.

The amount of silane utilized in the polymerization also varied4 The amount of triethylaluminum (0.70 iumoldo) and the amount of the procathlyst. qlurry (sufficient quantity of WO 94/11409 PCr/US93/10653 procatalyst to provide 0.01 mmoles of titanium) remained constant. The autoclave was then heated to about 67°C and the polymerization was continued at 67 0 C for one hour. The polypropylene product was recovered from the resulting mixture by conventional methods and the weight of the product was used to calculate the reaction yield in millions of grams of polymer product per gram (MMg/g) of titanium in the procatalyst. The term was calculated as the quotient of the weight average molecular weight and the number average molecular weight determined by gel permeation chromatography. The term "Mt" as defined in "Encyclopedia of Polymer Science and Engineering, 2nd Edition", Vol. 10, pp. 1-19 (1987), incorporated herein by reference, is the z-average molecular weight. The term was calculated as the quotient of M and "Melt Flow" is determined according to ASTM D-1238-73, condition L. "Viscosity Ratio! was determined by cone and plate rhoomotry (dynamic viscosity measurements) as a ratio of the viscosity of the product at a frequency of 0.1 Iz dividad by the viscosity of the product at a frequency of 1.0 Hz. As the viscosity ratio of polymer product increasas, the molecular weight distribution increases.

The results of a series of polymerizations are shown in TABLE

I.

TABL I Mmol of zSc NPTHS' 0-25 21 Carbon H2 Oligoner Mmle Count (P)1 lie ,2M dcg/tai Viscosity' 2 R Ratio

DIBOHS'

DIBDESU

DOTIMI

MNDDMS'

HNIDDHSt

MOMDDS'

DNODDMSe

TCITHS

TCTHS

OTHS

ODTMS

oDTES' ODTES4 ODTE-S4

ODTES"

ODTES

5

HODDES

0.13 0.*18 I'-25 0.25 0.08 0.05 0.25 0.05 0-25 0.044 0.1 0-175 0.05 0.05 0-175 0.05 0.05 2.2 3.8 10.0 2.2 4.8 4.3 5.3 3.3 8.1 5.1 5.4 4.7 7.3 11.0 10.3 6.5 9.2 12.1 3.2 4.3 5.2 2.3 3.7 2.4 1.7 4.0 3-.2 3.2 3.0 1.4 5.1 4.1 1.8 3-8 3-2 4.3 1720 1560 2070 1670 1500 1720 1870 1340 1900 1950 1850 1820 1800 1960 2440 1840 2060 8.9 8.2 8.0 7.3 7.4 7.5 8.4 7.6 9.6 10.1 8.7 8.1 8.8 9.0 10.5 8.5 8.9 4.5 4.3 5.4 4.0 4.2 4.1 3.9 5.1 5.0 4.7 3.8 5.0 5.1 4.7 4.8 5.2 1-57 1.54 1.68 1.64 1.56 1.62 1.72 1.72 1.70 1.60 1.79 1.62 1.68 1.94 1.64 1.73 1.77 2210 10.4 5.6 comparison Final melt flow of polymer product Viscosity Ratio ijOU~_ at 2000C Procatalyst prepared with phthaloyl chloride.

Procatalyst prepared without phthaloyl, chloride.

'WO 94/11409 PC/US93/10653 Preparation of Procatalyst Component The procatalyst was prepared by adding magnesium diethoxide (50 mmol) to 150 ml of a 50/50 (vol/vol) mixture of chlorobenzene/TiCl 4 After adding ethyl benzoate (16.7 mmol), the mixture was heated in an oil bath and stirred at 110 0 C for approximately 60 minutes. The resulting slurry was filtered and slurried twice with 150 ml of a fresh 50/50 (vol/vol).

Benzoyl chloride (0.4 ml) was added to the final slurry. After 1C stirring at 110 0 C for approximately 30 minutes, the mixture was filtered. The slurry was washed six times with 150 ml portions of isopentane and then dried for 90 minutes, at 30 0 C, under nitrogen.

Polymerization Using the above-described procatalyst (section a), propylene was polymerized as, described in Illustrative Embodiment I, section except the selectivity control agent was PEEB.

Ill2ustrative EmLodiment II To illustrate a further adva.iage of the catalyst system of the invention, polymer products having a melt flow of about 3.0 dg/min were produced according to the procedures described in Illustrative Embodiment I and the Comparative Example. In particular, the polymer products were produced using 0.2 mmol of the specified selectivity control agent and sufficient hydrogen necessary to produce a polymer having a melt flow of about 3.0 dg/min. The values are shown in TABLE II.

WO 94/11409 WO 94/1409 CIYUS93/ 10653

SCA

1

NPTMS

2 DIE DMS 2 PEEB 3

MODDES

ODTES

MNDDMS

TCTMS

ODTMS

DDTMS

DNDDMS

TABLE II mmol of Reguired 4 1:3 12 13 17 18 22 29 2 3 4 melt 0.2 mmol of each select~vity control agent was used.

For comparison Comparative Example mniol of H 2 required to make a polymer product having a floWT of about 3 dg/min As noted, the catalyst systems of the invention exhibit increased hydrogen utilization efficiency.

Illustrative Embodiment III Viscosity ratio values were taken for the polymers having a melt flow of about 3 dg/min. The values are shown in TABLE III.

viscosity-R~atio

MODDES

TCTMS

ODTES

ODTMS

DNDDMS

M14DDMS NP TM S 1. f-'1 4 1.80 1.78 1.60 1.62 1.60 1.68 IFor comparison It is seen from TABLE III that the catalyst systems of the invention exhibit a higher viscosity ratio and therefore WO 94/11409 I'r/US93/ 10653 a broader molecular weight distribution than convent ,onal catalyst systems using NPTMS as the selectivity control agent.

Claims (18)

1. A process for polymerizing one or more a-olefins of up to 20 carbon atoms which comprises contacting the one or more a-olefins under polymerization conditions with a catalyst system comprising: a magnesium halide-containing procatalyst component containing magnesium, titanium, halide and a polycarboxylic acid ester, said procatalyst component being obtained by halogenating a magnesium compound of the formula MgR'R", wherein R' and R" are alkoxide groups of 1 to 10 carbon atoms, with a halogenated tetravalent titanium compound, in the presence of a halohydrocarbon and a polycarboxylic acid ester electron donor with or without a halohydrocarbon; an organoaluminum cocatalyst component; and an organosilane selectivity control agent having the formula: R 1 Si R 2 R wherein R' is a linear alkyl group of 13 to 30 carbon atoms, alkaryl group of 16 to 36 carbon atoms or aralkyl group of 16 to 3o carbon atoms; R 2 and R 3 are, independently, methyl or alkyl group of 13 to 30 carbon atoms or hydrocarbyloxy group of 1 to 6 carbon atoms; and R 4 is a hydrocarbyloxy group of 1 to 6 carbon atoms.

2. The process of claim 1, wherein said organosilane selectivity control agent is present in a quantity such that the molar ratio of the selectivity control agent to titanium present in the procatalyst component is from about to about

3. The process of claim 2 wherein R I is alkyl group of 16 to 30 carbon atoms, alkyaryl group of 19 to 30 carbon atoms or aralkyl group of 19 to 30 carbon atoms; R 2 and R 3 are, independently, methyl or alkyl group of 16 to 30 carbon atoms or alkoxy group of 1 to 4 carbon atoms, and R 4 is alkoxy group of 1 to 4 carbon atoms. WO 94/11409 PCI/US93/10653

4. The process of claim 3, wherein the organosilane selectivity control agent is n-octadecyltriethoxysilane, n- octadecyltrimethoxysilane, n-triacontyltrimethoxysilane, n- triacontyltriethoxysilane, methyl-n-octadecyldimethoxysilane, methyl-n-octadecyldiethoxysilane or mixtures thereof.

The process of claim 4, wherein the organosilane is n-octadecyltrimethoxysilane, n-octadecyltriethoxysilane, methyl-n-octadecyldiethoxysilane or methyl-n-octadecyldi- methoxysilane.

6. The process of claim 5, wherein the halogenated tetravalent titanium compound is titanium tetrachloride.

7. The process of claim 6, wherein the magnesium compound is magnesium ethoxide.

8. The process of claim 7, wherein the poly- carboxylic acid ester electron donor is diisobutyl phthalate.

9. The process of claim 8, wherein the a-olefins are propylene and ethylene.

The process of claim 9, wherein the a-olefin is propylene.

11. In a process for polymerizing at least one a- olefin of up to 20 carbon atoms which comprises contacting at least one a-olefin under polymerization conditions with a catalyst system comprising: a magnesium halide containing procatalyst obtained by halogenating magnesium compound of the formula MgR'R", wherein R' and R" are, independently, alkoxide group or aryloxide group with a halogenated tetravalent titanium compound, in the presence of a polycarboxylic acid ester with or without a halohydrocarbon, an organoaluminum cocatalyst, and an organosilane selectivity control aqent, the improvement in the process wherein the organosilane selectivity control agent has the formula: RI R' si WO 94/11409 i'cr/US93/1 053 wherein R' is alkyl group of 13 to 30 carbon atoms, alkaryl group of 16 to 36 carbon atoms or aralkyl group of 16 to 36 carbon atoms; R 2 and R 3 are, independently, methyl and alkyl group of 13 to 30 carbon atoms or hydrocarbyloxy group of 1 to 6 carbon atoms; and R 4 is hydrocarbyloxy group of 1 to 6 carbon atoms.

12. The process of claim 11 wherein RI is alkyl group of from 16 to 30 carbon atoms, alkaryl group of 19 to carbon atoms or aralkyl group of 19 to 30 carbon atoms® and R 2 and R 3 are, independently, methyl or alkyl group of 16 to carbon atoms or alkoxy group of 1 to 4 carbon atoms.

13. The process of claim 12 wherein R 3 and R 4 are alkoxy groups of 1 to 2 carbon atoms.

14. The process of claim 13, wherein the organo- silane selectivity control agent is selected from the group consisting of n-octadecyltrimethoxysilane, n-octadecyltri- ethoxysilane, n-triacontyltri-methoxysilane, n-triaccntyltri- ethoxysilane, methyl-n-octadecyldimethoxysilane, methyl-n- octadecyldiethoxysilane and mixtures thereof.

An olefin polymerization catalyst system comprising: a magnesium halide-containing procatalyst component obtained by halogenating a magnesium compound with a halogenated tetravalent titanium compound, in the presence of polycarboxylic acid eater compound with or without a halogenated hydrocarbon, an organoaluMinum cocatalyst component, and an organosilane selectivity control agent having the formula si R R 4 wherein RI is an alkyl group of 13 to 30 carbon atoms, alkaryl group of 16 to 36 carbon atoms or aralkyl group of 16 to 36 carbon atoms; R 2 and R' are, independently, methyl or alkyl group of 13 to 30 carbon atoms or hydrocarbyloxy group of 1 to WO 94/11409~ I'Cr/US93/10653 6 carbon atoms; and R 4 is hydrocarbyloxy group of 1 to 6 carbon atoms.

16. The olefin polymerization catalyst system according to claim 15, wherein the molar ratio of the selectivity control agent to the titanium present in the procatalyst is from about 0.5 to about

17. The olefin polymerization catalyst system according to claim 16, wherein the magnesium compound is magnesium alkoxide, the halogenated tetravalent titanium compound contains at least four halogen atoms and the organoaluminum cocatalyst is a trialkylaluminum compound.

18. The olefin polymerization catalyst system according to claim 17, wherein the magnesium compound is magnesium diethoxide, the polycarboxylic acid ester compound is diisobutyl phthalate, and the halohydrocarbon is chlorobenzene or o-chlorotoluene. INTERNATIONAL SEARCH REPORT mWt 3nAI Application No IPCT/US 93/10653 CLASSIFICATION OF SUBJECT MATITERL IPC 5 C08F1O/0O C08F4/646 According to International Patent Classification (IPC) orl~ ollt national classification and IPC U3. FIELDS SEARCHED Minimum documentation searched (classification system followed by classification symbols) IPC 5 C08F Documentation starched other than minimum documentation to the extent that such documents are included in the fields searched Electronic data base consulted duning thc intenational search (name of data base and, where practical, search terms used) C. DOCUMENTS CONSIDERED TO 136 RELEVANT Category Citation of document, with indication, where appropriate, of the relevant pasu~ges Relevant to claim No. A EP,A,0 455 313 (MITSUI PETROCHEMICAL 1 INDUSTRIES) 6 November 1991 see claims 1,8 see page 7, line 43 line 47 see page 7, line 54 line 57 see example 1 A GB,A,2 143 834 (TOHO TITANIUM CO) 20 1 February 1985 see claim 1 A EP,As0 297 163 (TOHO TITANIUM CO) 4 1 January 1989 see comparative example page 8 F urther documents are listed its the continuation of box C. rv Patent family members arc listed in sinndl. *Special categories of cited documents I later document published after the international filing date A doumct dfinng he eneal sateof he rt h~c Isnotor priority date and not in conflict With the application but ''dcnde t h e eal reltae a hcasntcted to Winderstand the principle or theory underlying the consderd t be f pmcuar rlevnceinvention *11' earlier document but published on or aifter the international X' documrrent of particular relevance; the claimed invention filing date cannot be considered novel or cannot be considered to V document whichl may throw doubts onliy claim(s) or involve an inventive step when the docuiment is taken alone which is cited to establish the publicaio date of another document of particulsir relevance; the claimed invention cation or other rpecial reason (as specified) cannot bie considetted to involve an Inventive step when the document referring to an oral disclosure, use, exuhibition or document is combined with one or more other such docu. other meas menti, zsuch comxnation being obvious to a person siolled document published prior to the international filing date but in the art later than the priority date claimed document member of the stine patent family Date or the aictual completion of the international search Date of miailing of the intwcmtional search report 18 Fobruary 1994 18. 01,91j Name and mailing address of the ISA Authorized officer Euroipean Patent Office, PAO 3811 Patenitlaiin I NL 20 RV iv pwil Tel. 31-70) 340-2040, Tx. 31 G5l epoi, Fic er. Fixk 31-10) 340.3016 F shr INTERNATriONAL SEARCH REPORT WeO Aholl N inforniauon on patent (aftly mernbmr PCT/US 93/10653 Patent document I Publication IPatent family I Publication cited In search report date member(s) I date EP-A-0455313 06-11-91 JP-A- 63223008 16-09-88 JP-A- 63223009 16-09-88 OE-A- 3871190 25-06-92 EP-A,B 0282341 14-09-88 US-A- 5028671 02-07-91 GB-A-2143834 20-02-85 JP-A- 60158204 19-08-85 JP-C- 1729132 39-01-93 JP-B- 4017206 25-03-92 JP-A- 60023404 06-02-85 JP-C- 1737191 26-02-93 JP-B- 4025286 30-04-92 JP-A- 60044507 09-03-85 OE-A- 3425407 31-01-85 FR-AwB 2553421 19-04-85 BE-A- 899855 01-10-84 US-A- 4547476 15-10-85 EP-A-0297163 04-01-89 JP-A- 62158704 14-07-87 US-A- 4816433 28-03-89 Farm pCV113NIO IpataMt family WMax) (lul~y 11