OLEFIN POLYMERIZATION CATALYST COMPONENTS AND POLYMERIZATION PROCESS

Abstract: An olefin polymerization catalyst component is obtain­ ed by halogenating a magnesium compound of the formula MgR′R″ wherein R′ is an alkoxideoraryloxidegroup and R″ is an alkoxide or aryl-oxide group or halogen, with a halide of tetravalent titanium in the presence of a halohydrocarbon, and contacting the halogenated product with thionylchloride or an acid halide and a tetravalent titanium compound.

Description: OLEFIN POLYMERIZATION CATALYST COMPONENTS AND POLYMERIZATION PROCESS This invention relates to olefin polymerizatlon catalyst components catprising a magnesium halide ana a titanium halide and to a process for the polymarization of olefins using such catalyst components. It is known to provlde olefin polymerérization catalysts by catining a solid component comprising magnesium, titanium and chlorine witn an activating organoaluminium compound. me activity and stereospecific performance or such compositions is ensured by incorporating an electron donor in tne solid com- ponent and by employing as a third catalyst component an aromatic ester which may be catplexed with the activating organoalummium compound. For convenience of reference, the solla titaniumrcon- tanning component of such catalysts is referred to wherein as "procatalyst", tne organoaluminium, compound, whether usea separately or partially or totally complexed with an electron donor, as cocatalyst", and tne electron donor ocopuna, whether used separately or partially or totally complexed witn the organcaIuminium compouna, as "selectivity control agent" (SCk) . Among tne methods of preparing procatalysts, a distinction may be made between tnose in which the starting material is a magnesium chloride and tnose m which magnesium chloride is produced by halogenation of an organic compounds in the course or tne procatalyst syntnesis. Procatalysts or tne latter type have been disclosed in European Patent 19,330. These procatalysts are i.a. prepared by halogenating a magnesium compound MgR'R" (wherein R' and R" are, alkoxide or aryloxide groups and R" may also be a halogen) by reaction with a halide of tetravalent titanium in the presence of an electron donor and a halohydrocarbon followed by contact of the halogenated product with a tetravalent titanium compound. This invention provides still further improvements of the catalysts and processes of the prior art. Catalysts which comprise the solid titanium-containing catalyst constituents of this invention in cambination with an organoaluminium cocatalyst and a selectivity control agent or with an at least partial reaction product of an organoaluminium compound and a selectivity control agent the latter procatalysts are capable of producing polypropylene of commercially desired isotacticity at a high productivity, expressed in terms of g polymer produced per g catalyst (g pol/g cat). However, the productivity, expressed in terms of g polymer produced per g titanium (g pol/gTi) still leaves to be desired. This invention provides a process for producing an olefin polymerization catalyst component ccanprising a) halogenating a magnesium compound of the formula MgR'R" where R' is an alkoxide or aryloxide group and R" is an alkoxide or aryloxide group or halogen, with a tetravalent titanium halide in the presence of a halohydrocarbon and an electron donor, therein forming a halogenated product; b) contacting said halogenated product with thionylchloride or with an acid halide of the formula EMI2.1 where A is an alkyl, aryl, substituted alkyl, or substituted aryl group and X is a halide at a temperature of about 40 to about 140 OC; c) contacting said halogenated product with a tetravalent titanium halide at a temperature of about 40 to about 140 "C, either simultaneously with or subsequent to contacting step b). The first step in preparing the procatalysts of the present invention comprises halogenating a magnesium compound of the formula MgR'R" where R' is an alkoxide or aryloxide group and R" is an alkoxide or aryloxide group or halogen, with a tetravalent titanium halide in the presence of a halohydrocarbon and an electron donor, therein forming a halogenated product. Examples of halogen containing magnesium compounds that can be used as starting materials for the halogenating reaction are alkoxy and aryloxy magnesium halides, such as isobutoxy magnesium chloride, ethoxy magnesium bromide, phenoxy magnesium iodide, cusyloxy magnesium bromide and naphtenoxy magnesium chloride. Preferred magnesium compounds to be halogenated are selected from magnesium dialkoxides and magnesium diaryloxides. In such ccmpcwnds the alkoxide groups suitable have from 1 to 8 carbon atoms, and preferably from 2 to 8 carbon atoms. Examples of these groups of compounds are magnesium di-isopropoxide, magnesium diethoxide, magnesium dibutoxide, magnesium diphenoxide, magnesium dinaphthenoxide, and ethoxy magnesium isobutoxide. Magnesium diethoxide and magnesium ethoxychloride are preferred. In the halogenation with a halide of tetravalent titanium, the magnesium compounds are preferably reacted to form a magnesium halide in which the atomic ratio of halogen to magnesium is at least 1.5. The most preferred reactions are those leading to fully halogenated reaction products. Such halogenation reactions are suitably effected by employing a molar ratio of magnesium compound to titanium compound of 0.005:1 to 2:1, preferably 0.01:1 to 1:1. These reactions are conducted in the additional presence of a halohydrocarbon and an electron donor. An inert hydrocarbon diluent or solvent may also be present. When using an inert diluent or solvent, this should of course not be used as a complete substitute for the halohydrocarbon. Suitable halides of tetravalent titanium include aryloxyor alkoxy-di- and -trihaldes, such as dehexanoxy-titanium dichloride, diethoxy-titanium dibromide, isopropoxy-titanium tri-iodide and phenoxytitanium trichloride; titanium tetrahalides are preferred; most preferred is titanium tetrachloride. Suitable halohydrocarbons are compounds comprising carbon, halogen and optionally hydrogen, but no other atoms, such as butyl chloride, anyl chloride and the following more preferred compounds. Preferred aliphatic halohydrocaons are halogen-substituted hydrocarbons with 1 to 12, particularly less than 9, carbon atoms per molecule, comprising at least two halogen atoms, such as trichloromethane, 1,2-dichloroethane, dichlorobutane, 1,1, 3-trichloroethane, trichiorocyclohexane, dichlorofluoroethane, trichloropropane, trichlorofluorooane, hexachloroethane and te trachloro i sooctane. Carbon tetrachloride and 1,1,3-trichloroethane are preferred aliphatic halohydrocarbons. Aromatic halohydrocarbons may also be employed, e.g., chlorobenzene, brarcbenzene, dichlorobenzene, dichlorodibromobenzene, naphthyl chloride, chlorortoluene, dichlorotolueees, and the like; chlorobenzene and dichlorobenzene are preferred aromatic halohydrocarbons. Chlorobenzene is the most preferred halohydrocarbon. The halogenation normally proceeds under formation of a solid reaction product which may be isolated from the liquid reaction medium by filtration, decantation or another suitable method and may be subsequently washed with an inert hydrocarbon diluent, such as n-hexane, iso-octane or toluene, to remove any unreacted material, including physically absorbed halohydrocarbon. The above halogenated product is then treated with thionylchloride or with a particular acid halide prior to or concurrent with treatment with a tetravalent titanium halide. Acid halides employed herein have the formula EMI5.1 where A is an alkyl, aryl, substituted alkyl or substituted aryl group and X is a halide. Preferably, A is a phenyl group and X is chloride. Accordingly, the preferred acid halide is benzoyl chloride. The acid halide treatment results in an increase of the productivity of the procatalysts, measured as g pol/g Ti. The amount of thionylchloride or acid halide employed is 50 to 200 rrrrol per mole of Mg and preferably less than the total equivalent amount of residual alkoxide contained in the halogenated magnesium compound. Suitably, the treatment is carried out at a temperature of 40 to 140 OC during 0.1 to 4 hours. Particularly preferred contacting temperatures are from 60 to 110 OC and the most preferred contacting periods are 0.3 to 1 hour. The use of acid halides is more preferred than that of thionylchloride. The product is also contacted with a tetravalent titanium compound such as a dialkoxy-titanium dihalide, alkoxy-titanium trihalide, phenoxy-titanium trihalide or titanium tetrahalide. The most preferred titanium compounds are titanium tetrahalides and especially titanium tetrachloride. This treatment increases the content of titanium tetrachloride in the solid catalyst component. This increase should preferably be sufficient to achieve a final atomic ratio of tetravalent titanium to magnesium in the solid catalyst component of from 0.005 to 3.0, particularly of from 0.02 to 1.0. To this purpose the con tacting with the tetravalent titanium compound is most suitably carried out at a tenmperature of from 60 to 136 OC during 0.1-6 hours, optionally in the presence of an inert hydrocarbon diluent. Particularly preferred contacting temperatures are from 70 to 120 OC and the most preferred contacting periods are in between 0.5 to 3.5 hours. The treatment preferably follows the treatment with thionylchloride or acid halide and it may be carried out in successive contacts of the solid with separate portions of TiC 14 After the treatment with tetravalent titanium compound the catalyst component is suitably isolated from the liquid reaction medium and preferably washed to remove unreacted titanium compound. The titanium content of the final, washed catalyst constituent is suitably between about 1.5 to 3.6 percent by weight or up to about 4.5 percent. The preferred halogen atom, possibly contained in the magnesium compound to be halogenated, and contained in the titanium compound which serves as halogenating agent and in the tetravalent titanium compound with which the halogenated product is contacted, is chlorine. Suitable electron donors, which in this invention are used in combination with or reacted with an organoaluminium compound as selectivity control agents and which are also used in the preparation of the solid catalyst component are ethers, esters, ketones, phenols, amines, amides, imines, nitriles, phosphines, phosphites, stibines, arsines, phosphoramides and alcoholates. Examples of suitable donors are those referred to in U.S. Patent 4,136,243 or its equivalent British Specification 1,486,194 and in British Specification 1,554,340 or its equivalent German Offenlegungsschrift 2,729,126. Preferred donors are esters and diamines, particularly esters of aromatic carboxylic acids, such as ethyl and methyl benzoate, p-rrethoxy ethyl benzoate, petboxy ethyl benzoate, ethyl acrylate, methyl methacrylate, ethyl acetate, dimethyl carbonate, dimethyl adipate, dihexyl fumarate, dibutyl maleate, ethylisopropyl oxalate, p-chloro ethyl benzoate, p-amino hexyl benzoate, isopropyl naphthenate, n-amyl toluate, ethyl cyclohexanoate, propyl pivalate, N,N ,N' ,N' -tetrairthylethylene diamine, 1,2,4-trimethyl piperazine, 2,3,4,5-tetramethyl piperidine and similar compounds. The donor used as selectivity control agent in the catalyst may be the sarre as or different from the donor used for preparing the titanium containing catalyst component. Preferred electron donors for use in preparing the titanium constituent are ethyl benzoate and prnethyl toluate. Preferred as selectivity control agent in the catalyst are p-rrethoxy ethyl benzoate and p-ethoxy ethyl benzoate. The organoaluminium compound to be employed as cocatalyst may be chosen from any of the knawn activators in olefin polymerization catalyst systems comprising a titanium halide but is most suitably free of halogens. While aluminium trialkyl compounds, dialkylaluminlum halides and dialkylaluminium alkoxides may be used, alunnniumtrialkyl compounds are preferred, particularly those wherein each of the alkyl groups has 2 to 6 carbon atoms, e.g, aluminiumtriethyl, aluminium tri-n-propyl, aluminiumtri-isobuty 1, aluminiumtri-isopropyl and aluminiumdibutyl-n-amyl. Preferred proportions of selectivity control agent, employed separately, in ccmbination with, or reacted with an organoaluminium compound, calculated as mol per mol aluminium compound, are in the range from 0.1 to 1.5, particularly from 0.2 to 0.5. Proportions of electron donor contained in the solid catalyst component, calculated as mol per mol of magnesium, are suitably in the range of from 0.01 to 10, e.g., from 0.05 to 10 and from 0.1 to 5.0 and especially from 0.8 to 2.2. To prepare the final polymerization catalyst composition, procatalyst, cocatalyst and selectivity control agent, if used separately, may be simply combined, most suitably employing a molar ratio to produce in the final catalyst an atomic ratio of aluminium to titanium of from 1 to 150, and preferably from 30 to 80. Improved procatalysts prepared according to this invention are useful in the same types of polymerization of alpha-monoolefins in which the unimproved procatalysts are useful. The catalysts may be employed in the polymerization or copolymerization of alpha-monoolefins of 2 to 8 carbon atoms per molecule, conducted at conditions known for the polymerization of the respective olefins when using MgC12-supported coordination catalysts. Polymerization of propylene as sole olefin feed or in cam- bination with small amounts, e.g., from 1 to 20 mole percent, of ethylene, l-butene or other alpha olefin cononomer, may be conducted with the catalysts of the invention, in a liquid system with an inert diluent such as a paraffinic liquid of 3 to 15 carbon atoms per molecule, or in a liquid system containing propylene as sole diluent or together with a small amount of propane, or in vapour phase. Propylene polymerization in liquid phase is conducted at temperatures of 50 to 80 OC and at a pressure sufficient to maintain liquid conditions. Olefin polymerization may also be conducted as a solution process in which the polymer is produced as a solution in monomer or diluent. Such a process is preferred in the poly merization of l-butene as described, for example, in U.S. Patent 3,362,940. In the following Examples the selectivity to isotactic polypropylene is determined by treasuring the amount of xylene soluble polymer (XS), in accordance with regulations of the U.S. Food and Drug Administration. The XS test is carried out as follows: the sample is completely dissolved in xylene in a stirred flask by heating under reflux at 120 OC. The flask is then immersed in a water bath at 25 OC without stirring for one hour, during which the insoluble portion precipitates. The precipitate is filtered off and the solubles present in the filtrate are determined by evaporating a 20 ml aliquot of the filtrate, drying the residue under vacuum, and weighing the residue. The xylene-solubles consist of amorphous material with some low molecular weight crystalline material. (FDA regulations 121.2501 and 121.2510, 1971). The numerical value of XS in the case of propylene howo- polymer is typically about 2 percent greater than the amount of polymers extractable in refluxing n-heptane. Thus the isotacticity index of polypropylene (amount insoluble in refluxing n-heptane) is approximately 100-(XS-2). Catalyst productivity at standard conditions exhibits an inverse relationship with stereoselectivity. This relationship is characteristic for any given procatalyst. It is generally possible to control these variables, within limits, by changing the proportion of selectivity control agent (SCA). Increasing the amount of SCA increases selectivity to isotactic or stereoregular polymer but reduces activity, and hence productivity in a standard one hour test. The relationship in propylene polymerization is such that a decrease of 1% of XS, e.g., from 5 to 4, corresponds approximately to a decrease in productivity of 160 kg pol/gTi. For purposes of comparison, the following examples of the invention in propylene polymerization show not only the measured data but productivity normalized to 4% wt XS. Examples 1. Magnesium ethoxide (5.72 g, 50 mrol) was stirred at room tflmperature with ethyl benzoate (2.4 ml, 16.7 mmol) and 75 ml of chlorobenzene as titanium tetrachloride (75 ml, 680 mmol) was added over the course of 10 min. The mixture was brought to 110 OC and stirred for 60 min then filtered hot. The resulting solid ("S") was slurried in chlorobenzene (60 ml) containing benzoyl chloride (0.31 ml, 2.7 mmol) and held at 110 OC for 20 min then filtered hot. The resulting solid was washed for 10 minutes each with two 60 ml portions of TiC14 at 110 OC and filtered hot. The resulting solid was washed at room temperature with six 150 ml portions of isopentane then dried under moving nitrogen at 40 OC. Yield 5.77 g of procatalyst "A". 2. Procatalyst "B" was prepared by essentially the sane procedure except that the benzoyl chloride treatment was carried out for 60 min at 110 OC and that the two succeeding 110 OC TiCl4 washes were with only 40 ml of titanium tetrachloride. Yield 6.5 g. 3. Magnesium ethoxide (5.72 g, 50 nmol) was stirred at room temperature with benzoyl chloride (1.8 ml, 15.6 mmol) and 75 ml of chlorobenzene as titanium tetrachloride (75 ml, 680 meal) was added over the course of 10 min. The mixture was brought to 100 OC and stirred for 180 min then filtered hot. The resulting solid was slurried in 40 ml of chlorobenzene and held at 100 OC for 120 min then filtered hot. The resulting solid was slurried in titanium tetrachloride (40 ml) containing benzoyl chloride (0.6 ml, 5.2 mmol) and held at 100 OC for 120 min then filtered hot. The resulting solid was washed at room temperature with seven 150 ml portions of isopentane then dried under moving nitrogen at 40 OC for 100 min. Yield 5.82 g of procatalyst "C". 4. Solid "S", as prepared in example 1, was slurried in 40 ml of titanium tetrachloride and held at 110 C for 60 min then filtered hot. The resulting solid was slurried in 40 ml of titanium tetrachloride containing benzoyl chloride (0.4 ml, 3.5 imGl) and held at 110 OC for 60 min then filtered hot. The resulting solid was washed, at room temperature, with six 150 ml portions of isopentane then dried under moving nitrogen at 40 OC. Yield 6.2 g of procatalyst "D". 5. Solid "S", as prepared in Example 1, was treated with SOCl2 (0.49 g) in chlorobenzene at 80 OC during 1 hr then filtered hot. The resulting solid was slurried in titanium tetrachloride (40 ml) and held at 110 OC for 5 min, then filtered hot and then washed with seven 150 ml portions of isopentane at room temperature, then dried under nitrogen at 40 OC for 100 min. Yield 6.2 g of procatalyst "E". 6. (Control) Solid "S", as prepared in example 1, was treated three times with 40 ml of TiCl4 held at 110 OC for 10 min each and filtered hot. The resulting solid was washed, at room temperature, with six 150 ml portions of isopentane then dried under moving nitrogen at 40 "C for 100 min. Yield 6.32 g of procatalyst "F". About 1400 g of liquid propylene and 132 itrrol of hydrogen in a one gallon (about 4 liter) autoclave equipped with an agitator, was heated to 60 OC under sufficient pressure to maintain it in liquid phase. A predetermined amount (0.18-0.22 mmDl) of p-ethyl anisate and 2.5 ml (0.7 rrrrol) of triethyl aluminium as a 5% wt solution in C7 8 paraffin diluent were then successively added to the propylene. To the agitated mixture there was added a sufficient amount of the slurry of procatalyst in mineral oil to provide about 0.01 milliatoms of titanium. The mixture was agitated and maintained at 67 "C for one hour. The pressure was then released and powdered polypropylene was recovered. For the six examples the xylene solubles were analyzed to be from 3.8 to 4.8%. For convenience of comparison the measured productivities were corrected to equivalent productivities at 4% xylene solubles by using the aforeentioned, experimentally determined ratio of 160 kg pol/g Ti/%XS. Productivity Procatalyst Kg pol/g Ti A 976 B 950 C 1040 D 994 E 928 F x 790 x for comparison.

Claims: CLAIMS 1. A process for producing an olefin polymerization catalyst component comprising a) halogenating a magnesium compound of the fonnula MgR'R" where R' is an alkoxide or aryloxide group and R" is an alkoxide or aryloxide group or halogen, with a tetravalent titanium halide in the presence of a halohydrocarbon and an electron donor, therein forming a halogenated product; b) contacting said halogenated product with thionylchloride or with an acid halide of the foritiula EMI13.1 where A is an alkyl, aryl, substituted alkyl, or substi tuted aryl group and X is a halide at a temperature of about 40 to about 140 C; c) contacting said halogenated product with a tetravalent titanium halide at a temperature of about 40 to about 140 "C, either simultaneously with or subsequent to contacting step b). 2. A process as claimed in claim 1 wherein said magnesium compound is a magnesium dialkoxide. 3. A process as claimed in claim 1 wherein said halohydrocarbon is a chlorohydrocarbon. 4. A process as claimed in claim 1 wherein said acid halide is an acid chloride. 5. A process as claimed in claim 1 wherein said electron donor is an aromatic ester. 6. A process as claimed in claim 1 wherein said magnesium compound is magnesium diethoxide, said halohydrocarbon is chlorobenzene, said titanium halide is titanium tetrachloride, said electron donor is ethylbenzoate, and said acid chloride is benzoyl chloride. 7. An olefin polymerization catalyst composition comprising an organoaluminium compound, an electron donor, and the catalyst component produced with a process as claimed in any of claims 1 to 6, in which the atomic ratio of aluminium to titanium is from 30:1 to 80:1. 8. A process for the catalytic polymeflzation of an olefin in the presence of the olefin polymerization catalyst of claim 7. 9. A catalyst component produced with a process as claimed in any of claims 1 to 6.

Inventors: JOB, ROBERT CHARLES, NOZAKI, KENZIE
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1984
Main classification: C08F10
IPC codes: C08F4, C08F10