CA1081679A - Process and product - Google Patents
Process and productInfo
- Publication number
- CA1081679A CA1081679A CA266,446A CA266446A CA1081679A CA 1081679 A CA1081679 A CA 1081679A CA 266446 A CA266446 A CA 266446A CA 1081679 A CA1081679 A CA 1081679A
- Authority
- CA
- Canada
- Prior art keywords
- ether
- catalyst component
- titanium tetrachloride
- polymerization
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- 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
Abstract
ABSTRACT OF THE DISCLOSURE
The invention relates to a process for the pro-duction of a catalyst component for use in the polymeriza-tion of ?-olefins, which comprises reacting titanium tetrachloride with a dialkylaluminum monohalide and mono-alkylaluminum dihalide, said dialkylaluminum monohalide being in a proportion of at least equimolar to said titanium tetrachloride, to thus obtain a violet reduced solid, then removing aluminum compounds contained in said reduced solid and further activating with a mixture or complex of titanium tetrachloride and a dialkyl ether of the general formula ROR' wherein R and R' are the same or different and are (a) alkyl groups having 1-4 carbon atoms, (b) normal alkyl groups having five carbon atoms or (c) alkyl groups having 6-20 carbon atoms and to a catalyst component prepared by the process of the invention.
The invention relates to a process for the pro-duction of a catalyst component for use in the polymeriza-tion of ?-olefins, which comprises reacting titanium tetrachloride with a dialkylaluminum monohalide and mono-alkylaluminum dihalide, said dialkylaluminum monohalide being in a proportion of at least equimolar to said titanium tetrachloride, to thus obtain a violet reduced solid, then removing aluminum compounds contained in said reduced solid and further activating with a mixture or complex of titanium tetrachloride and a dialkyl ether of the general formula ROR' wherein R and R' are the same or different and are (a) alkyl groups having 1-4 carbon atoms, (b) normal alkyl groups having five carbon atoms or (c) alkyl groups having 6-20 carbon atoms and to a catalyst component prepared by the process of the invention.
Description
8~79 This inventlon relates to an improve~ent in a catalyst component for use ln the polymerizatlon of ~ -olefins (which wlll hereinafter be referred to as "catalyst component") and more particularly, to a process for the pro-duction of a catalyst component capable of producing polymer having a narrow particle size distribution whereby in the stereoregular poly~erization of ~ -olefins such as propylene, in particular, not only the stereoregularity i6 improved but also the polymerization rate is markedly increased.
As a method of producing a crystalline polyolefin on a commercial scale, it has been widely known to use a polymeriæation catalyst comprising, in combination, a catalyst component consisting of a low valence transition metal halide, and an organo metal halide compound. In particular, a titanium trichloride composition has been used as the low ralence metal halide.
~ known method of preparing a titanium trichloride composit;Lon consists in reducing titanium tetrachloride by metallic aluminum at a high temperature and then grinding the product for activation. The catalyst com-ponent prepared in this way is ordinarily called Grade AA titanium trichloride, which contains, in addi~ion to titanium trichloride, aluminum chloride in an eutectic form. When ~:his product is used as a polymerization catalyst, the rate of polymerization and the stereoregularity of the product sre unsatis-factory. For commerc;Lal scale operation, a large amount o~ expenslve catalystis necessary and treatment of non-crystalllne polymer byproducts inrolves substantial costs.
Many efforts have been made to o~ercome these disadvantages.
For example, some of the catalytic components have been removed to improve somewhat the polymerization rate or product stereoregularity by extracting with a solvent (Soga et al. "Shokubai (Catalyst)" Vol, 11, page 75 (1969~)~
reactlng with an ether compound ~ollowed by washing or grinding together with ' ' .- ~ -, ' ~ ' ', :. :
various materials followed by solYent extract~on. ~n these methods, however, the particle size distribution of t'ne catalytic component has not been su~fi-ciently reduced, so that a polymer obtained using this catalyst component may also have a wide particle size distribution, resulting in trouble in handling this polymer powder.
Another known method of preparing a titanium trichloride composi-tion consists in reducing titanium tetrachloride with diethylaluminum chloride in a proportion substantially equimolar or less to the titanium atom present at low temperature. This method has the advantage that a catalytic component with a relatively even particle size can be obtained, but, on the other hand, the titanium trichloride composition obtained by this method is a brown ~ -type titanium trichloride composition which has in~erior polymerization capacity.
Therefore, it is necessary to sub~ect this composition to a heat activation treatment to convert it to a violet tltanium trichloride composition. However, when this product ls used as a polymerizatlon catalyst the polymerization rate and stereoregularity of the product are not superior to those obtained when the above described Grade AA titanium trichloride is used. The alkylaluminu~
dihalide byproduct of the reduction in the above-descrlbed method is regaFded as a harmful material to the catalytic component and, therefore~ it is recom~
mended to treat it with a complexing agent such as an ether compound. Even if this treatment is carried out when the reduced solid is sub~ected to a heat~
ing and activating treatment, the catalytlc activity of the resulting component is deficient.
As a further method o~ preparing a titanium trichloride composi-tion, it has been proposed to obtain a catalyst component capable o~ giving a relatively high poly~erization rate, high stereoregularity and excellent particle size distribution by reducing titanium tetrachloride by diethylaluminum
As a method of producing a crystalline polyolefin on a commercial scale, it has been widely known to use a polymeriæation catalyst comprising, in combination, a catalyst component consisting of a low valence transition metal halide, and an organo metal halide compound. In particular, a titanium trichloride composition has been used as the low ralence metal halide.
~ known method of preparing a titanium trichloride composit;Lon consists in reducing titanium tetrachloride by metallic aluminum at a high temperature and then grinding the product for activation. The catalyst com-ponent prepared in this way is ordinarily called Grade AA titanium trichloride, which contains, in addi~ion to titanium trichloride, aluminum chloride in an eutectic form. When ~:his product is used as a polymerization catalyst, the rate of polymerization and the stereoregularity of the product sre unsatis-factory. For commerc;Lal scale operation, a large amount o~ expenslve catalystis necessary and treatment of non-crystalllne polymer byproducts inrolves substantial costs.
Many efforts have been made to o~ercome these disadvantages.
For example, some of the catalytic components have been removed to improve somewhat the polymerization rate or product stereoregularity by extracting with a solvent (Soga et al. "Shokubai (Catalyst)" Vol, 11, page 75 (1969~)~
reactlng with an ether compound ~ollowed by washing or grinding together with ' ' .- ~ -, ' ~ ' ', :. :
various materials followed by solYent extract~on. ~n these methods, however, the particle size distribution of t'ne catalytic component has not been su~fi-ciently reduced, so that a polymer obtained using this catalyst component may also have a wide particle size distribution, resulting in trouble in handling this polymer powder.
Another known method of preparing a titanium trichloride composi-tion consists in reducing titanium tetrachloride with diethylaluminum chloride in a proportion substantially equimolar or less to the titanium atom present at low temperature. This method has the advantage that a catalytic component with a relatively even particle size can be obtained, but, on the other hand, the titanium trichloride composition obtained by this method is a brown ~ -type titanium trichloride composition which has in~erior polymerization capacity.
Therefore, it is necessary to sub~ect this composition to a heat activation treatment to convert it to a violet tltanium trichloride composition. However, when this product ls used as a polymerizatlon catalyst the polymerization rate and stereoregularity of the product are not superior to those obtained when the above described Grade AA titanium trichloride is used. The alkylaluminu~
dihalide byproduct of the reduction in the above-descrlbed method is regaFded as a harmful material to the catalytic component and, therefore~ it is recom~
mended to treat it with a complexing agent such as an ether compound. Even if this treatment is carried out when the reduced solid is sub~ected to a heat~
ing and activating treatment, the catalytlc activity of the resulting component is deficient.
As a further method o~ preparing a titanium trichloride composi-tion, it has been proposed to obtain a catalyst component capable o~ giving a relatively high poly~erization rate, high stereoregularity and excellent particle size distribution by reducing titanium tetrachloride by diethylaluminum
- 2 -, ~ ' .
1013~675~
chloride at a low temperature to ~orm a ~-type titanium trichloride c~mposition and then to treat it with a complexing agent and titanium tetrachloride to convert it into a violet ~ -type catalyst solid~ as disclosed in British Patents 1,391,067 and 1,391,068 o~ Solvay et Cie. However, this method has the dis-advantage that when using a complexing agent other than diisoamyl ether, the titanium trichloride compositlon ls not substantlally improvéd. Also it is necessary to use a reagent having a concentration of 15% by volume or more, preferably 30 to 40~ by volume when treating titanium tetrachloride. Since diisoamyl ether is an expensive reagent which ls 10 to 20 times more expensive ~0 than other organic ether compounds or about 10 times more expensive than the product marketed as Grade AA titanium trichlorlde, the above-described method has the disadvantage that the production cost of the catalyst component on a commercial scale is high e~en though the product exhibits excellent properties as a catalyst.
The present invention which overcomes the various disadvantages of these known catalyst components provides a catalyst component having excellent catalytic properties obtained by reducing titanium tetrachloride with dialkyl~
aluminum monohalide and, in addltion, alkylaluminum dihalide. Furthermore, it i8 found that the above described catalyst component may be processed to obtain a catalyst component having improved polymerization activity and the capability of producing polymer having hlgh stereoregularity and narrow particle size distribution.
Thus, the present invention provides a process for the production of a catalyst component for use ln the polymerizatlon of ~ -olefins, which comprises reacting titanium tetrachloride with a dialkylaluminum ~onohalide and monoalkylaluminum dihalide (sald dialkylaluminum monohalide being in a propoFtion of e~ui~olar or more to said titanium tetrachloride) to thus obtain
1013~675~
chloride at a low temperature to ~orm a ~-type titanium trichloride c~mposition and then to treat it with a complexing agent and titanium tetrachloride to convert it into a violet ~ -type catalyst solid~ as disclosed in British Patents 1,391,067 and 1,391,068 o~ Solvay et Cie. However, this method has the dis-advantage that when using a complexing agent other than diisoamyl ether, the titanium trichloride compositlon ls not substantlally improvéd. Also it is necessary to use a reagent having a concentration of 15% by volume or more, preferably 30 to 40~ by volume when treating titanium tetrachloride. Since diisoamyl ether is an expensive reagent which ls 10 to 20 times more expensive ~0 than other organic ether compounds or about 10 times more expensive than the product marketed as Grade AA titanium trichlorlde, the above-described method has the disadvantage that the production cost of the catalyst component on a commercial scale is high e~en though the product exhibits excellent properties as a catalyst.
The present invention which overcomes the various disadvantages of these known catalyst components provides a catalyst component having excellent catalytic properties obtained by reducing titanium tetrachloride with dialkyl~
aluminum monohalide and, in addltion, alkylaluminum dihalide. Furthermore, it i8 found that the above described catalyst component may be processed to obtain a catalyst component having improved polymerization activity and the capability of producing polymer having hlgh stereoregularity and narrow particle size distribution.
Thus, the present invention provides a process for the production of a catalyst component for use ln the polymerizatlon of ~ -olefins, which comprises reacting titanium tetrachloride with a dialkylaluminum ~onohalide and monoalkylaluminum dihalide (sald dialkylaluminum monohalide being in a propoFtion of e~ui~olar or more to said titanium tetrachloride) to thus obtain
- 3 -" .
-~
10~1679 a violet reduced solid, then removing alumlnum compounds contalned in said reduced solid and further activating with a complex consisting of a dialkyl ether having the formula RORI wherein R and R' are the same or different and are each selected from (a) alkyl groups having 1 to 4 carbon atoms, (b) normal alkyl groups of flve carbon atoms and (c) alkyl groups having 6 to 20 carbon atoms.
Useful examples of the dialkylaluminum monohallde which can be used for the reduction of titanium tetrachloride in the process of the invention are dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide and the like. Di-ethylaluminum chlorlde is preferable because it is readily obtainable com-mercially and also excellent in processing capacity.
Useful examples of the monoalkylaluminum halLde to be present together with the dialkylaluminum monohallde in the process of the invention are methylaluminum dichloride, ethylaluminum dichloride, butylaluminum di-chloride, ethylaluminum dibromide and ethylaluminum diodide. Ethylaluminum dichloride is preferably used.
The present invention will now be described specifically using the case of ethylalumLnum dichloride and diethylaluminum chloride in combination as illustrated, with no intent to be limited thereby.
As described above, the method of reducing titanium tetrachloride by diethylaluminum chloride is well known to those skilled in the art. This reaction can be represented by the following equations:
TiC14 ~ 0-5Et2AlC~ TiC13 + 0.5~1C13 + Et.
` TiC14 ~ l.OEt2AlCl > TiC13 ~ Et~lC12 + Et.
~ s is apparent ~rom these equations, the ratio o~ diethylaluminum chloride and titanium tetrachloride is ordinarily 0.5:1 to 1.0:1. It ls well known that the presence of the compound, formed by this reaction, i.e., ' 1081ti79 ethylaluminum dichloride is detri~ental to the polymerization reaction and, there~ore, efforts have been made to remove the compound as far as possible after the reducing reaction. However, according to the invention a violet reduced solid is obtained by reducing titanium tetrachloride by diethylalumlnum chloride in a proportion of 1 mol or more to 1 mol of the tltanium tetrachloride together with ethylaluminum dichloride in a suitable amount, in particular, in a proportion of 0.3 to 1.2 mol to 1 mol of the titanium tetrachloride. This phenomenon is very interesting in view of the fact that only a brown reduced solid is obtained according to the prlor art method, that is, in the case of effecting the reduction with diethylaluminum monochloride only without ethyl-aluminum dichloride. X-ray diffraction spectra show that, in the case of a brown reduced solid obtained by the prior art method, the peak of ~ -type crystal is considerably larger than the peak of ~ -type crystal, while in the ca8e of a violet reduced solid obtained according to the present invention, the peak of ~ -type crystal is very small or scarcely appears and the peak of -type crystal appears strongly.
In the process of the present invention, aluminum compou~ds contained in the violet reduced solid are removed and then the red~ced solid is sub~ected to an activation treatment using a complex of a dialkyl ether as described hereinafter and titanium tetrachloride or a mixture of such dialkyl ether and titanium tetrachloride. Even in the combination of the prior art method, that is, for removing aluminum compounds with a heating and activating treatment, the catalyst component obtained is not substantially improved, while according to the present invention, a great advantage is obtained by the use of a small amount of a complex consisting of said dialkyl ether and titanium tetrachloride or a mixture of said dialkyl ether and titanium tetrachloride.
~- 10816'79 It is another feature of the present invention that the method of removing alumlnum compounds contàined in the reduced solid i8 not limlted to treatment with a specific complexing agent, but that any of several methods can effectively be used. The known method has hitherto succeeded in obtained a relatively large improvement by the combination of the method of removing aluminum compounds by treating with a complexing agent followed by an activa-tion treatment with titanium tetrachloride, but, on the otherhand, has the disadvantage that a large improvement cannot be obtained when another complex-ing agent than diisoamyl ether is used. In fact, according to our experiments, the improvement is very unsatisfactory even when the reduced solid is treated with, for example, di-n-butyl ether and then activated by titanium tetrachloride only, as shown in the following Comparative ~xamples.
~ ccording to the present invention, on the contrary, the removal of aluminum compounds can be carried out not only by the use of a specific compound such as diisoamyl ether but also by the applicatlon of other known techniques, so long as the activatlon is carried out using a complex or mixture of titanium tetrachloride and as hereinafter described dialkyl ether.
It is very difficult to explain why a complex or mixture of titanium tetrachloride and said dialkyl ether has a particular action in the final processing step of the catalyst component in the present invention, but it is true that there is a difference as to the object of using such a dialkyl ether between the present invention and the above described known method, since the quantity of dialkyl ether used in the former is small while the quantity of diisoamyl ether used in the latter is very large, that is, 0 8 to 1 mol per 1 mol of titanium. This is possibly due to the fact that the said dialkyl ether is used for the particular acti~ation action in the present invention, while diisoamyl ether is used for the purpose of remo~ing aluminum compounds ., . ._ `:, ,,.' ' , 1~81~i79 present in a large quantity in the known method.
The catalyst component produced by the process of the invention having the above described features is, excellent in activity and produces polymer having a low particle size distribution as is apparent from Examples, and, furthermore, the process of the invention is economical because diisoamyl ether is not used or used in small quantities.
The reducing reaction of the invention is carried out by contact-ing titanium tetrachloride with a reducing agent consisting of a monoalkyl-aluminum dihalide and dialkylaluminum monohalide, for example, ethylaluminum dichloride and diethylaluminum monochloride in an inert diluent. In the present invention, in particular, the reducing agent used for the reduction of titanium tetrachloride is a mixture of diethyl aluminum chloride in a quantity equimolar or more to titanium tetrachloride and ethylaluminum dichloride in a suitable quantity. Where the quantity of diethylaluminum chloride used is less than equimolar to titanium tetrachloride, no favorable results are obtained. On the other hand, the quantity of ethylaluminum dichloride used is preferably within a range of 0.3 to 1.2 mol per l mol of titanium tetrachloride. ~s the inert diluent, C4 to C12 aliphatic hydrocarbons substan~ially free of aromatic hydrocarbons or alicyclic hydrocarbons may be used. The temperature of the reducing reaction is relatively important for the properties of the final product and should be adJusted wlthin a range of -50 to ~30C. The reaction is begun by contacting titanium tetrachloride with the reducing agent while agitating the mixture, resulting in deposition of the reduclng solid, insoluble in the inert diluent. Contacting is carried out by adding dropwise either a solution of titanium tetrachloride or a solution of reducing agent to the other.
~11 the solutions are preferably agitated ~or l hour or more, preferably, 3 hours or more and during the same time, the reaction system should be kept ~ ~ :
. .
- 1081~ 9 at the above-mentloned temperature. After both the solutions are completely mixed, the mixture is kept at the same temperature for at least 30 minutes, preferably 1 hour or more, then gradually heated and kept for 15 minutes or more at a constant temperature between 20 and 120C., preferably between 60 and 100 C. with continuous agitatlon. The reduced solid obtained in this way should be thoroughly washed with a fresh solvent.
The aluminum compounds contained in the thus resulting reduced solid can be removed by known techniques, for example, by sub~ecting the solid to a high vacuum to sublimate the aluminum compounds or by treating the reduced solid with a compound capable of forming a complex compound with the aluminum compounds (i.e. complexing agent) and then extracting with a solvent. As the complexing agent (generally a Lewis base), there are used, for example, ethers, thioethers, thiols, organo phosphorus compounds, organo nitrogen compounds, ketones or esters.
Examples of ether complexing agents are diethyl ether, diiso-propyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, di-2 ethylheptyl ether, allyl ethyl ether, allyl butyl ether, anisole, phenetole, chloroanisole, bromoanisole and dimethoxyben~ene.
Examples of the thioether complexing agents are diethyl thio-ether, di-n-propyl thioether, dicyclohexyl thioether, diphenyl thioether, ditolyl thioether, ethyl phenyl thioether, propyl phenyl thioether and diallyl thioether.
Examples of the organo phosphorus complexing agents are tri-n-butylphosphine, triphenylphosphine, triethyl phosphite and tributyl phosphite.
Examples of the organo nitrogen compounds are diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine and dimethylaniline.
.
: , :
1081~79 Ethers, -ln particular, havlng 4 to 16 carbon atoms are preferable as complexing agents. The extraction can be carried out by any known method, for example, by stirring the reduced solid with an ether compound in an inert medium and separating into a liquid phase and solid phase Such a medium may be the same as that used in the reducing reaction. The extraction ls ordinarily carried out at a constant temperature between 0 and 80C., for 5 minutes or more, for example, 30 minutes to 2 hours. The quantity of complexing agent used is ordinarily 0.1 to 2.5 mols, preferably 0.4 to l.0 mol per 1 mol of titanium atom in the reduced solid.
The solid obtalned by the above-described treatment is then sub~ected to an activation treatment with a complex consisting of a dialkyl ether as hereinafter described and titanium tetrachloride or a mixture of such dialkyl ether and titanium tetrachloride. Preparation of such a complex consisting of the said dialkyl ether and titanium tetrachloride can be carried out by contacting both the compounds in equi=olar amounts as it is or in a hydrocarbon solvent at room temperature or with heating. This complex is a crystal, complex compound of equimolar dlalkyl ether and titanium tetrachloride, which can be confirmecl by analysis after purification, for example, by re-crystalli~ation using a hydrocarbon solvent. In the activation treatment with a complex according to the present invention, the thus prepared complex is used.
The treatment of the solid with a mixture of the dialkyl ether and titanium tetrachloride can be carried out by mixing the solid with dialkyl ether and titanium tetrachloride, but it is preferable to mix both previously before use thereof. The quantity of dialkyl ether used in the activa-tion treatment should be 0.1 mol or more per 1 mol of titanium trichloride in the solid whether the complex or mixture is used. If less than this range of ether is used, the resulting catalyst component is unsatisfactory in regard to polymeri~ation _ 9 _ - ~ . .
~81f~79 activity and stereoregularity o the product polymer.`If more ether is used, the particle size distribution of the catalyst component treated is broadened resulting in an increase of the proportion of fine powder in the product, in addition to poor economics o the process, i.e. use of an excess of an expensive reagent. Therefore, in fact, the quantity o dialkyl ether is preferably 0.1 to 2.0 mol per 1 mol of titanium trichloride. On the other hand, the quantity of titanium tetrachloride is so ad~usted that the concentration thereof may be 1% by volume or more, preferably, 5% by volume or more of the whole liquid phase throughout the treatment. This activation treatment is ordinarily carried out using a hydrocarbon solvent such as pentane, hexane, heptane, octane, cyclo-hexane or cyclopentane in such a manner that the solid concentration in the treating system be 50 to 800 g/l, preferably, 200 to 600 g/l. The temperature of the activation treatment is ordinarily within a range of -30 to 100C., preferably 40 to 80C., and the time required for the activation may be 30 minutes but is preferably 1 to 3 hours for best results. Then the thus treated solid should be thoroughly washed with the hydrocarbon solvent used in the above-described treatment The dialkyl ether used in the invention has the general formula R-O-R', in which R and R~ are the same or different and are each selected from (a) alkyl groups having 1 to 4 carbon atoms, (b) normal alkyl groups o five carbon atoms and (c) alkyl groups having 6 to 20 carbon atoms. Preferably R
and R' have three carbon atoms.
Examples of dialkyl ethers having the above general ormula are di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, isobutyl~n-butyl ether, di-n-amyl ether, di-n-hexyl ether, di-n-heptyl ether, diisoheptyl ether, di-2-ethylhexyl ether, di~n-dodecyl ether, n-butyl-2-ethyl-; hexyl ether, and isobutyl-2-ethylhexyl ether. Mixtures of one or more dialkyl ether can also be used.
o -~'.
1081gj79 The thus obtalned catalyst component is used together with acocatalyst component for the polymerization of ~ -ole~ins. ~s the co-catalyst, organometallic compounds of Group I, II and III elements of the Periodic Table are used. In particular, organic aluminum compounds are preferably used and, above all, triethylaluminum and diethylaluminum chloride are most suitable for the polymerization of propylene. ~ny polymerization methods known in the art can be used. For example, a liquid monomer may be used as the polymerization medium without using a polymerization diluent or a gaseous monomer may be used similarly.
The present invention will be illustrated in detail by the following Examples.
Example 1 700 ml of puri~ied heptane and 250 ml of titanium tetrachloride were charged in a 2,000 ml flask equipped with a stirrer and kept at 0C., in a bath. 315 ml of diethylaluminum chloride (1.1 mol to 1 mol of titanium tetrachloride) and 117 ml of ethylaluminum dichloride (0.5 mol to 1 mol of titanium tetrachloride) were dissolved in 400 ml of heptane and added dFopwise from a dropping funnel. The dropping was continued for a period of about 3 hours and, during the same time, the reaction system was kept st 0 C. After the dropwise addition, the reaction mixture was gradually heated for 1 hour to 65C., with agitation. The reaction was further continued at the same tempera-ture for another hour. ~fter completion of the reaction, the reaction mixture was allowed to stand to separate the solid formed and the solid was washed with 150 ml of purified heptane three times, followed by drying at 65 C. for 30 minutes under reduced pressure. The thus reduced solid was red violet and, according to X-ray diffraction the peaks of 2~ = 15.1, 33 and 51,3 ( ~ -type crystal) were found but the peaks of 20 G 16.3 and 42.4 ~ ~ -type crystal) -.
- , 1~81~;79 were not found or were very small. The particle size dlstribution of the product was very narrow and there was 1% or less of particles of 5 microns or less~ The molar ratio of ~l/Ti ln the reduced solid was 0.57.
150 g, of the reduced solid was suspended in 1,850 ml of purified heptane, to which 127 ml (equimolar to the titanium in the reduced solid) of di-n-butyl ether (referred hereinafter to as "NB~") was dropwise added for 10 minutes with agitation at room temperature, and the mixture was reacted at 35C. for 1 hour. After the reaction, the reduced solid was washed three times with 500 ml of purified heptane to remove aluminum compounds contained therein, followed by drying at 65C. os 30 minutes under reduced pressure.
30 g of the solid, rom which the aluminum compounds were sub-stantially removed by the above-described treatment, were resuspended in 53 ml of purified heptane, to which 47.6 ml of a heptane solution of an equimolar complex of di-n-amyl ether (referred hereinater to as "NAE~') and titanium tetrachloride, adjusted previously to a concentration of 2 mols/l, was added, and the mixture was reacted at 65C. for 2 hours. The molar ratio of N~E to titanium trichloride was 0.6 and the proportion of ti~anium tetrachloride to the whole liquid phase was 10% by volume. After the reaction, the solid was washed three times with 100 ml of purified heptane, followed by drying at 65C.
for 30 minutes under reduced pressure.
The catalyst solid obtained in this way also had a narrow particle size distribution and there was only 2% of fine powder of 5 microns or less. The molar ratio of Al/Ti in the solid was 0,016.
100 mg of the catalyst solid was charged in an autoclave of 1,000 ml, to which lôO mg of diethylaluminum chloride as co-catalyst, 600 ml (Standard State) of hydrogen as a molecular weight regulator and 800 ml of liquid propylene were added. The polymerization was carried out at a , ' , ~081~i79 temperature of 68C. for 30 minutes and the unreacted propylene was removed by flashing, thus obtaining 185 g o~ polypropylene powder. Thus the polymer yield per 1 g of the catalyst solid (catalyst efficiency, referred hereinafter to as "E") was 1850. This polymer had a ~elt flow rate of 5.0 (~elt Flow Rate -ASTM D 1238 - referred to as "MFR") and a heptane insoluble content of 97%
(referred hereinafter to as "HT"), whlch was measured by extracting with heptane for 5 hours by means of a Soxhlet extractor.
The results are shown in Table T.
Comparative Example 1 The procedure of Example 1 was repeated except that the activa-tion treatment with the complex consisting of titanium tetrachloride and NAE
was not carried out and the polymerization test was immediately carried out, whereby results as shown in Table I were obtained.
It is apparent from these results that the activation treatment with the complex is essential.
; Comparative Example 2 The procedure of Example 1 was repeated except that the activa-tion treatment with the complex consisting of titanium tetrachloride and NAE
was not carried out and instead a heating and activating treatment was carried out at 150C. for 1 hour, thereby obtaining results as shown in Table I.
It is apparent from these results that a marked improvement cannot be expected by an activation treatment by heating even after remoVing aluminum compounds.
Comparative Example 3 The procedure of Example 1 was repeated except that, in place of the activation treatment with the complex consisting of titaniun~ tetrachlorlde and NAE, an activation treatment with titanium tetrachloride having the same ` - 13 -:
' .
': ' :
.. . . ~
.
'~., :' , '~ . .
, -~081~79 concentration was csrried out, thereby obtaining results as shown in Table I.
It is apparent from these results that a marked improvement can-not be expected by activating with titanium tetrachloride alone even after aluminum compounds are removed and it is thus essential to add NAE at the time of treatment with titanium tetrachloride.
Comparative Example 4 The procedure of Comparative Example 3 was repeated except that the treatment with NBE was not carried out and instead a treatment with NAE
(equimolar to the titanium trichloride) was carried out, thereby obtaining results as shown in Table I. Not only activity but also particle character was inferior to that obtained by means of this invention. It is apparent from these results that a marked improvement is obtained only when NAE is added at the time of treatment with titanium tetrachloride.
Comparative Example 5 Using titanium trichloride of Grade AA manufactured by Toyo Stauffer Co., a polymerization test as in Example 1 was carried out, obtaining results as shown in Table I.
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1~81~-~9 o . C~ o o ~ o I ~ O O ~ ~D
I , o ., ~ U) C~l o U~
,, , o o ~ U~
~ ~ I
~ o .. o~
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Exam~les 2 to 4 The procedure of Example 1 was repeated except the quantity of the equimolar complex of NAE and titanium tetrachlorlde was varied, obtaining results as shown in Table II.
Example 5 The procedure of Example 1 was repeated except that, in place of the complex consisting of titanium tetrachloride and NAE, titanium tetra-chloride and NAE were separately added to the processed solid to acti~ate it, obtaining results as shown in Table II.
_ 16 -., 10~ 79 U~ I ~ ~~ ~ o , o o oo o ~ .
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~(~81~9 Examples 14 to 22 The procedure o~ Example l was repeated except that, in place of NAE, di-n-heptyl ether (referred hereina~ter to as "NHE"~ was used with titanium tetrachloride, thereby obtaining results as shown in Table IV.
It is apparent from these results that NHE is effective in the same manner as NAE.
Comparative Example 6 The procedure of Comparative Example 4 was repeated except that in place of NAE, NHE was used, thereby obtaining results as shown in Table IV. The procedure is in~erior to this invention not only in respect to activity but also in respect to particle character, it is apparent that a marked improvement is shown only when NHE is added at the time of treatment with titanium tetrachloride.
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~ ' ., ~ . , i~81~79 Examples 23 to 28 The procedure of Example 1 or Example 14 was repeated except varying the quantity of NBE used, thus obtaining results shown in Table V.
It is evident from these results that the effect of the quantity o~ NBE
necessary for removing aluminum compounds is not large within the examined range, .: .
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- O O ~3 p ~ ~5 ,n o o,, . 23 -, 1081~79 Examples 29 and 30 The procedure o~ Example 14 was repeated except that in place of NBE which was used for removing aluminum compound in the reduced solid, diisobutyl ether (IBE) and diisoamyl ether (IAE) was used, thus obtaining results as shown ln Table VI.
TABLE VI
Example Complexing Agent IBE I~E
NHE/TiC13 (Molar Ratio) 0.6 0.6 Quantity of TiC14 in Whole Liquid Phase (% by volume)10 10 Al/Ti (Molar Ratio) 0.020 0.018 Quantity of Particles of 5fU~
or less size in Catalyst Solid (%) 2 2 E 1,790 1,800 MFR 3.9 5.0 Comparative Examples 7 and 8 These experiments involved preparation of a catalyst by known techniques. In Comparative Example 7, titanium tetrachloride was reduced with diethylaluminum chloride alone as a reducing agent in place of the reducing agent consisting of diethylaluminum chloride and ethylaluminum di-chloride in Example 1, and the aluminum compound ~ormed was removed by IAE in amount equimolar to titanium in place of NBE and then an activation treatment was carried out with 40% by volume of titanium tetrachloride. In Comparative Example 8, the procedure of Comparative Example 7 was repeated except the :
I
~081~;79 ~uantity of IAE used was decreased to 0.5 molar to 1 mol of titanium. The results are shown in Table VII.
Table VII
Comparative Example 7 ~ 8 Al/Ti ~Molar Ratio) 0.0180.020 Quantity of Particles of 5 or less size in Catalyst Solid 6 4 E 1,590 690 MER 4,9 3,9 ' i ,~j ., :
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10~1679 a violet reduced solid, then removing alumlnum compounds contalned in said reduced solid and further activating with a complex consisting of a dialkyl ether having the formula RORI wherein R and R' are the same or different and are each selected from (a) alkyl groups having 1 to 4 carbon atoms, (b) normal alkyl groups of flve carbon atoms and (c) alkyl groups having 6 to 20 carbon atoms.
Useful examples of the dialkylaluminum monohallde which can be used for the reduction of titanium tetrachloride in the process of the invention are dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diethylaluminum iodide and the like. Di-ethylaluminum chlorlde is preferable because it is readily obtainable com-mercially and also excellent in processing capacity.
Useful examples of the monoalkylaluminum halLde to be present together with the dialkylaluminum monohallde in the process of the invention are methylaluminum dichloride, ethylaluminum dichloride, butylaluminum di-chloride, ethylaluminum dibromide and ethylaluminum diodide. Ethylaluminum dichloride is preferably used.
The present invention will now be described specifically using the case of ethylalumLnum dichloride and diethylaluminum chloride in combination as illustrated, with no intent to be limited thereby.
As described above, the method of reducing titanium tetrachloride by diethylaluminum chloride is well known to those skilled in the art. This reaction can be represented by the following equations:
TiC14 ~ 0-5Et2AlC~ TiC13 + 0.5~1C13 + Et.
` TiC14 ~ l.OEt2AlCl > TiC13 ~ Et~lC12 + Et.
~ s is apparent ~rom these equations, the ratio o~ diethylaluminum chloride and titanium tetrachloride is ordinarily 0.5:1 to 1.0:1. It ls well known that the presence of the compound, formed by this reaction, i.e., ' 1081ti79 ethylaluminum dichloride is detri~ental to the polymerization reaction and, there~ore, efforts have been made to remove the compound as far as possible after the reducing reaction. However, according to the invention a violet reduced solid is obtained by reducing titanium tetrachloride by diethylalumlnum chloride in a proportion of 1 mol or more to 1 mol of the tltanium tetrachloride together with ethylaluminum dichloride in a suitable amount, in particular, in a proportion of 0.3 to 1.2 mol to 1 mol of the titanium tetrachloride. This phenomenon is very interesting in view of the fact that only a brown reduced solid is obtained according to the prlor art method, that is, in the case of effecting the reduction with diethylaluminum monochloride only without ethyl-aluminum dichloride. X-ray diffraction spectra show that, in the case of a brown reduced solid obtained by the prior art method, the peak of ~ -type crystal is considerably larger than the peak of ~ -type crystal, while in the ca8e of a violet reduced solid obtained according to the present invention, the peak of ~ -type crystal is very small or scarcely appears and the peak of -type crystal appears strongly.
In the process of the present invention, aluminum compou~ds contained in the violet reduced solid are removed and then the red~ced solid is sub~ected to an activation treatment using a complex of a dialkyl ether as described hereinafter and titanium tetrachloride or a mixture of such dialkyl ether and titanium tetrachloride. Even in the combination of the prior art method, that is, for removing aluminum compounds with a heating and activating treatment, the catalyst component obtained is not substantially improved, while according to the present invention, a great advantage is obtained by the use of a small amount of a complex consisting of said dialkyl ether and titanium tetrachloride or a mixture of said dialkyl ether and titanium tetrachloride.
~- 10816'79 It is another feature of the present invention that the method of removing alumlnum compounds contàined in the reduced solid i8 not limlted to treatment with a specific complexing agent, but that any of several methods can effectively be used. The known method has hitherto succeeded in obtained a relatively large improvement by the combination of the method of removing aluminum compounds by treating with a complexing agent followed by an activa-tion treatment with titanium tetrachloride, but, on the otherhand, has the disadvantage that a large improvement cannot be obtained when another complex-ing agent than diisoamyl ether is used. In fact, according to our experiments, the improvement is very unsatisfactory even when the reduced solid is treated with, for example, di-n-butyl ether and then activated by titanium tetrachloride only, as shown in the following Comparative ~xamples.
~ ccording to the present invention, on the contrary, the removal of aluminum compounds can be carried out not only by the use of a specific compound such as diisoamyl ether but also by the applicatlon of other known techniques, so long as the activatlon is carried out using a complex or mixture of titanium tetrachloride and as hereinafter described dialkyl ether.
It is very difficult to explain why a complex or mixture of titanium tetrachloride and said dialkyl ether has a particular action in the final processing step of the catalyst component in the present invention, but it is true that there is a difference as to the object of using such a dialkyl ether between the present invention and the above described known method, since the quantity of dialkyl ether used in the former is small while the quantity of diisoamyl ether used in the latter is very large, that is, 0 8 to 1 mol per 1 mol of titanium. This is possibly due to the fact that the said dialkyl ether is used for the particular acti~ation action in the present invention, while diisoamyl ether is used for the purpose of remo~ing aluminum compounds ., . ._ `:, ,,.' ' , 1~81~i79 present in a large quantity in the known method.
The catalyst component produced by the process of the invention having the above described features is, excellent in activity and produces polymer having a low particle size distribution as is apparent from Examples, and, furthermore, the process of the invention is economical because diisoamyl ether is not used or used in small quantities.
The reducing reaction of the invention is carried out by contact-ing titanium tetrachloride with a reducing agent consisting of a monoalkyl-aluminum dihalide and dialkylaluminum monohalide, for example, ethylaluminum dichloride and diethylaluminum monochloride in an inert diluent. In the present invention, in particular, the reducing agent used for the reduction of titanium tetrachloride is a mixture of diethyl aluminum chloride in a quantity equimolar or more to titanium tetrachloride and ethylaluminum dichloride in a suitable quantity. Where the quantity of diethylaluminum chloride used is less than equimolar to titanium tetrachloride, no favorable results are obtained. On the other hand, the quantity of ethylaluminum dichloride used is preferably within a range of 0.3 to 1.2 mol per l mol of titanium tetrachloride. ~s the inert diluent, C4 to C12 aliphatic hydrocarbons substan~ially free of aromatic hydrocarbons or alicyclic hydrocarbons may be used. The temperature of the reducing reaction is relatively important for the properties of the final product and should be adJusted wlthin a range of -50 to ~30C. The reaction is begun by contacting titanium tetrachloride with the reducing agent while agitating the mixture, resulting in deposition of the reduclng solid, insoluble in the inert diluent. Contacting is carried out by adding dropwise either a solution of titanium tetrachloride or a solution of reducing agent to the other.
~11 the solutions are preferably agitated ~or l hour or more, preferably, 3 hours or more and during the same time, the reaction system should be kept ~ ~ :
. .
- 1081~ 9 at the above-mentloned temperature. After both the solutions are completely mixed, the mixture is kept at the same temperature for at least 30 minutes, preferably 1 hour or more, then gradually heated and kept for 15 minutes or more at a constant temperature between 20 and 120C., preferably between 60 and 100 C. with continuous agitatlon. The reduced solid obtained in this way should be thoroughly washed with a fresh solvent.
The aluminum compounds contained in the thus resulting reduced solid can be removed by known techniques, for example, by sub~ecting the solid to a high vacuum to sublimate the aluminum compounds or by treating the reduced solid with a compound capable of forming a complex compound with the aluminum compounds (i.e. complexing agent) and then extracting with a solvent. As the complexing agent (generally a Lewis base), there are used, for example, ethers, thioethers, thiols, organo phosphorus compounds, organo nitrogen compounds, ketones or esters.
Examples of ether complexing agents are diethyl ether, diiso-propyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylhexyl ether, di-2 ethylheptyl ether, allyl ethyl ether, allyl butyl ether, anisole, phenetole, chloroanisole, bromoanisole and dimethoxyben~ene.
Examples of the thioether complexing agents are diethyl thio-ether, di-n-propyl thioether, dicyclohexyl thioether, diphenyl thioether, ditolyl thioether, ethyl phenyl thioether, propyl phenyl thioether and diallyl thioether.
Examples of the organo phosphorus complexing agents are tri-n-butylphosphine, triphenylphosphine, triethyl phosphite and tributyl phosphite.
Examples of the organo nitrogen compounds are diethylamine, triethylamine, n-propylamine, di-n-propylamine, tri-n-propylamine and dimethylaniline.
.
: , :
1081~79 Ethers, -ln particular, havlng 4 to 16 carbon atoms are preferable as complexing agents. The extraction can be carried out by any known method, for example, by stirring the reduced solid with an ether compound in an inert medium and separating into a liquid phase and solid phase Such a medium may be the same as that used in the reducing reaction. The extraction ls ordinarily carried out at a constant temperature between 0 and 80C., for 5 minutes or more, for example, 30 minutes to 2 hours. The quantity of complexing agent used is ordinarily 0.1 to 2.5 mols, preferably 0.4 to l.0 mol per 1 mol of titanium atom in the reduced solid.
The solid obtalned by the above-described treatment is then sub~ected to an activation treatment with a complex consisting of a dialkyl ether as hereinafter described and titanium tetrachloride or a mixture of such dialkyl ether and titanium tetrachloride. Preparation of such a complex consisting of the said dialkyl ether and titanium tetrachloride can be carried out by contacting both the compounds in equi=olar amounts as it is or in a hydrocarbon solvent at room temperature or with heating. This complex is a crystal, complex compound of equimolar dlalkyl ether and titanium tetrachloride, which can be confirmecl by analysis after purification, for example, by re-crystalli~ation using a hydrocarbon solvent. In the activation treatment with a complex according to the present invention, the thus prepared complex is used.
The treatment of the solid with a mixture of the dialkyl ether and titanium tetrachloride can be carried out by mixing the solid with dialkyl ether and titanium tetrachloride, but it is preferable to mix both previously before use thereof. The quantity of dialkyl ether used in the activa-tion treatment should be 0.1 mol or more per 1 mol of titanium trichloride in the solid whether the complex or mixture is used. If less than this range of ether is used, the resulting catalyst component is unsatisfactory in regard to polymeri~ation _ 9 _ - ~ . .
~81f~79 activity and stereoregularity o the product polymer.`If more ether is used, the particle size distribution of the catalyst component treated is broadened resulting in an increase of the proportion of fine powder in the product, in addition to poor economics o the process, i.e. use of an excess of an expensive reagent. Therefore, in fact, the quantity o dialkyl ether is preferably 0.1 to 2.0 mol per 1 mol of titanium trichloride. On the other hand, the quantity of titanium tetrachloride is so ad~usted that the concentration thereof may be 1% by volume or more, preferably, 5% by volume or more of the whole liquid phase throughout the treatment. This activation treatment is ordinarily carried out using a hydrocarbon solvent such as pentane, hexane, heptane, octane, cyclo-hexane or cyclopentane in such a manner that the solid concentration in the treating system be 50 to 800 g/l, preferably, 200 to 600 g/l. The temperature of the activation treatment is ordinarily within a range of -30 to 100C., preferably 40 to 80C., and the time required for the activation may be 30 minutes but is preferably 1 to 3 hours for best results. Then the thus treated solid should be thoroughly washed with the hydrocarbon solvent used in the above-described treatment The dialkyl ether used in the invention has the general formula R-O-R', in which R and R~ are the same or different and are each selected from (a) alkyl groups having 1 to 4 carbon atoms, (b) normal alkyl groups o five carbon atoms and (c) alkyl groups having 6 to 20 carbon atoms. Preferably R
and R' have three carbon atoms.
Examples of dialkyl ethers having the above general ormula are di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, isobutyl~n-butyl ether, di-n-amyl ether, di-n-hexyl ether, di-n-heptyl ether, diisoheptyl ether, di-2-ethylhexyl ether, di~n-dodecyl ether, n-butyl-2-ethyl-; hexyl ether, and isobutyl-2-ethylhexyl ether. Mixtures of one or more dialkyl ether can also be used.
o -~'.
1081gj79 The thus obtalned catalyst component is used together with acocatalyst component for the polymerization of ~ -ole~ins. ~s the co-catalyst, organometallic compounds of Group I, II and III elements of the Periodic Table are used. In particular, organic aluminum compounds are preferably used and, above all, triethylaluminum and diethylaluminum chloride are most suitable for the polymerization of propylene. ~ny polymerization methods known in the art can be used. For example, a liquid monomer may be used as the polymerization medium without using a polymerization diluent or a gaseous monomer may be used similarly.
The present invention will be illustrated in detail by the following Examples.
Example 1 700 ml of puri~ied heptane and 250 ml of titanium tetrachloride were charged in a 2,000 ml flask equipped with a stirrer and kept at 0C., in a bath. 315 ml of diethylaluminum chloride (1.1 mol to 1 mol of titanium tetrachloride) and 117 ml of ethylaluminum dichloride (0.5 mol to 1 mol of titanium tetrachloride) were dissolved in 400 ml of heptane and added dFopwise from a dropping funnel. The dropping was continued for a period of about 3 hours and, during the same time, the reaction system was kept st 0 C. After the dropwise addition, the reaction mixture was gradually heated for 1 hour to 65C., with agitation. The reaction was further continued at the same tempera-ture for another hour. ~fter completion of the reaction, the reaction mixture was allowed to stand to separate the solid formed and the solid was washed with 150 ml of purified heptane three times, followed by drying at 65 C. for 30 minutes under reduced pressure. The thus reduced solid was red violet and, according to X-ray diffraction the peaks of 2~ = 15.1, 33 and 51,3 ( ~ -type crystal) were found but the peaks of 20 G 16.3 and 42.4 ~ ~ -type crystal) -.
- , 1~81~;79 were not found or were very small. The particle size dlstribution of the product was very narrow and there was 1% or less of particles of 5 microns or less~ The molar ratio of ~l/Ti ln the reduced solid was 0.57.
150 g, of the reduced solid was suspended in 1,850 ml of purified heptane, to which 127 ml (equimolar to the titanium in the reduced solid) of di-n-butyl ether (referred hereinafter to as "NB~") was dropwise added for 10 minutes with agitation at room temperature, and the mixture was reacted at 35C. for 1 hour. After the reaction, the reduced solid was washed three times with 500 ml of purified heptane to remove aluminum compounds contained therein, followed by drying at 65C. os 30 minutes under reduced pressure.
30 g of the solid, rom which the aluminum compounds were sub-stantially removed by the above-described treatment, were resuspended in 53 ml of purified heptane, to which 47.6 ml of a heptane solution of an equimolar complex of di-n-amyl ether (referred hereinater to as "NAE~') and titanium tetrachloride, adjusted previously to a concentration of 2 mols/l, was added, and the mixture was reacted at 65C. for 2 hours. The molar ratio of N~E to titanium trichloride was 0.6 and the proportion of ti~anium tetrachloride to the whole liquid phase was 10% by volume. After the reaction, the solid was washed three times with 100 ml of purified heptane, followed by drying at 65C.
for 30 minutes under reduced pressure.
The catalyst solid obtained in this way also had a narrow particle size distribution and there was only 2% of fine powder of 5 microns or less. The molar ratio of Al/Ti in the solid was 0,016.
100 mg of the catalyst solid was charged in an autoclave of 1,000 ml, to which lôO mg of diethylaluminum chloride as co-catalyst, 600 ml (Standard State) of hydrogen as a molecular weight regulator and 800 ml of liquid propylene were added. The polymerization was carried out at a , ' , ~081~i79 temperature of 68C. for 30 minutes and the unreacted propylene was removed by flashing, thus obtaining 185 g o~ polypropylene powder. Thus the polymer yield per 1 g of the catalyst solid (catalyst efficiency, referred hereinafter to as "E") was 1850. This polymer had a ~elt flow rate of 5.0 (~elt Flow Rate -ASTM D 1238 - referred to as "MFR") and a heptane insoluble content of 97%
(referred hereinafter to as "HT"), whlch was measured by extracting with heptane for 5 hours by means of a Soxhlet extractor.
The results are shown in Table T.
Comparative Example 1 The procedure of Example 1 was repeated except that the activa-tion treatment with the complex consisting of titanium tetrachloride and NAE
was not carried out and the polymerization test was immediately carried out, whereby results as shown in Table I were obtained.
It is apparent from these results that the activation treatment with the complex is essential.
; Comparative Example 2 The procedure of Example 1 was repeated except that the activa-tion treatment with the complex consisting of titanium tetrachloride and NAE
was not carried out and instead a heating and activating treatment was carried out at 150C. for 1 hour, thereby obtaining results as shown in Table I.
It is apparent from these results that a marked improvement cannot be expected by an activation treatment by heating even after remoVing aluminum compounds.
Comparative Example 3 The procedure of Example 1 was repeated except that, in place of the activation treatment with the complex consisting of titaniun~ tetrachlorlde and NAE, an activation treatment with titanium tetrachloride having the same ` - 13 -:
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, -~081~79 concentration was csrried out, thereby obtaining results as shown in Table I.
It is apparent from these results that a marked improvement can-not be expected by activating with titanium tetrachloride alone even after aluminum compounds are removed and it is thus essential to add NAE at the time of treatment with titanium tetrachloride.
Comparative Example 4 The procedure of Comparative Example 3 was repeated except that the treatment with NBE was not carried out and instead a treatment with NAE
(equimolar to the titanium trichloride) was carried out, thereby obtaining results as shown in Table I. Not only activity but also particle character was inferior to that obtained by means of this invention. It is apparent from these results that a marked improvement is obtained only when NAE is added at the time of treatment with titanium tetrachloride.
Comparative Example 5 Using titanium trichloride of Grade AA manufactured by Toyo Stauffer Co., a polymerization test as in Example 1 was carried out, obtaining results as shown in Table I.
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Exam~les 2 to 4 The procedure of Example 1 was repeated except the quantity of the equimolar complex of NAE and titanium tetrachlorlde was varied, obtaining results as shown in Table II.
Example 5 The procedure of Example 1 was repeated except that, in place of the complex consisting of titanium tetrachloride and NAE, titanium tetra-chloride and NAE were separately added to the processed solid to acti~ate it, obtaining results as shown in Table II.
_ 16 -., 10~ 79 U~ I ~ ~~ ~ o , o o oo o ~ .
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~(~81~9 Examples 14 to 22 The procedure o~ Example l was repeated except that, in place of NAE, di-n-heptyl ether (referred hereina~ter to as "NHE"~ was used with titanium tetrachloride, thereby obtaining results as shown in Table IV.
It is apparent from these results that NHE is effective in the same manner as NAE.
Comparative Example 6 The procedure of Comparative Example 4 was repeated except that in place of NAE, NHE was used, thereby obtaining results as shown in Table IV. The procedure is in~erior to this invention not only in respect to activity but also in respect to particle character, it is apparent that a marked improvement is shown only when NHE is added at the time of treatment with titanium tetrachloride.
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.'.~,'' ~ . ' ' .~' .
.
~ ' ., ~ . , i~81~79 Examples 23 to 28 The procedure of Example 1 or Example 14 was repeated except varying the quantity of NBE used, thus obtaining results shown in Table V.
It is evident from these results that the effect of the quantity o~ NBE
necessary for removing aluminum compounds is not large within the examined range, .: .
:
.
' '; ' ' ~ ;
. : ' o ~ ~ o ~ o ~~ , o o oo ,~ o o ~ ~ o ,_ ~. . ~ ~
o , o o ~ U~ , o , ~D u~ ~ O ~ _l O ~ U~
o , o~ o ~ ~ ~o o u~ ~D O O ~ O r-. ~ ~ ~ o a~
. ~ o , o o~
o .
.; ~ ~ o ,~ ~ o ,~ ~
P o o , ~ o ~ ~ ~
, ,, ~ ~ o ~ , o ,~
.; o o , ~ o oo ' U~
:~ o ~ J~
.. ~ o ~
- O O ~3 p ~ ~5 ,n o o,, . 23 -, 1081~79 Examples 29 and 30 The procedure o~ Example 14 was repeated except that in place of NBE which was used for removing aluminum compound in the reduced solid, diisobutyl ether (IBE) and diisoamyl ether (IAE) was used, thus obtaining results as shown ln Table VI.
TABLE VI
Example Complexing Agent IBE I~E
NHE/TiC13 (Molar Ratio) 0.6 0.6 Quantity of TiC14 in Whole Liquid Phase (% by volume)10 10 Al/Ti (Molar Ratio) 0.020 0.018 Quantity of Particles of 5fU~
or less size in Catalyst Solid (%) 2 2 E 1,790 1,800 MFR 3.9 5.0 Comparative Examples 7 and 8 These experiments involved preparation of a catalyst by known techniques. In Comparative Example 7, titanium tetrachloride was reduced with diethylaluminum chloride alone as a reducing agent in place of the reducing agent consisting of diethylaluminum chloride and ethylaluminum di-chloride in Example 1, and the aluminum compound ~ormed was removed by IAE in amount equimolar to titanium in place of NBE and then an activation treatment was carried out with 40% by volume of titanium tetrachloride. In Comparative Example 8, the procedure of Comparative Example 7 was repeated except the :
I
~081~;79 ~uantity of IAE used was decreased to 0.5 molar to 1 mol of titanium. The results are shown in Table VII.
Table VII
Comparative Example 7 ~ 8 Al/Ti ~Molar Ratio) 0.0180.020 Quantity of Particles of 5 or less size in Catalyst Solid 6 4 E 1,590 690 MER 4,9 3,9 ' i ,~j ., :
,, ~
,: ' , . .
:", .
,.'~, ' ' , .~, . ' .
.... .
:, .
:, ~ 25 _ .. . . ..
: ~, .. .
~:
.- ~: .
, :.
- .
Claims (19)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of a catalyst component for use in the polymerization of alpha olefins which comprises reducing titanium tetrachloride at a temperature of from -50° to +30°C with a dialkyl aluminum monohalide and a monoalkyl aluminum dihalide, said dialkyl aluminum monohalide being employed in an amount at least equimolar to said titanium tetrachloride and said monoalkylaluminum dihalide is em-ployed in an amount of 0.3 to 1.2 mols per mol of titanium tetrachloride to obtain a violet titanium trichloride reduced solid containing aluminum compounds, removing aluminum compounds contained in said reduced solids and thereafter contacting said reduced solid in an inert diluent and at a temperature within the range of from -30° to 100°C for at least 30 minutes with an activator which is a complex or mixture of titanium tetrachloride and a dialkyl ether wherein the mol ratio of dialkyl ether to titanium tetrachloride is at least 0.1 and the concentration of titanium tetrachloride is maintained at at least one volume percent of the liquid phase, said dialkyl ether having the formula R'OR" in which R' and R" are the same or different, and each are selected from (a) alkyl groups having 1 to 4 carbon atoms (b) normal alkyl groups having 5 carbon atoms and (c) alkyl groups having 6 to 20 carbon atoms.
2. A process according to claim 1 wherein the dialkylaluminum monohalide is diethyl aluminum chloride.
3. A process according to claim 1 wherein the monoalkyl aluminum dihalide is ethyl aluminum dichloride.
4. A process according to claim 1, wherein after the reduction of titanium tetrachloride effected at a temperature of -50° to +30°C, the temperature of the reaction mixture is raised to 20° to 120°C.
5. A process according to claim 1, wherein the aluminum compounds are removed by complexing with a complexing agent and then extracting with a solvent.
6. A process according to claim 5, wherein the complexing agent is an ether selected from the group consisting of diethyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, diisoamyl ether, di-2-ethylexyl ether, di-2-ethylheptyl ether, allyl ethyl ether, allyl butyl ether, anisole, phenetole, chloroanisole, bromoanisole and dimethoxyben-zene.
7. A process according to claim 1, wherein the activator alkyl ether is selected from the group consisting of di-n-propyl ether, diisopropyl ether, di-n-butyl ether, diisobutyl ether, isobutyl-n-butyl ether, di-n-amyl ether, di-n-hexyl ether, di-n-heptyl ether, diisoheptyl ether, di-2-ethylhexyl ether, di-n-dodecyl ether, n-butyl-2-ethylexyl ether, and isobutyl-2-ethylhexyl ether and mixtures thereof.
8. A process according to claim 7, wherein the albyl ether di-n-amyl ether.
9. The catalyst component produced by the process of claim 1.
10. The catalyst component produced by the process of claim 2.
11. The catalyst component produced by the process of claim 3.
12. The catalyst component produced by the process of claim 4.
13. The catalyst component produced by the process of claim 5.
14. The catalyst component produced by the process of claim 6.
15. The catalyst component produced by the process of claim 7.
16. The catalyst component produced by the process of claim 8.
17. An improved process for the polymerization of .alpha.-olefins wherein the improvement comprises polymerization in the presence of the catalyst component of claim 9, 10 or 11 and an organoaluminum cocatalyst component.
18. An improved process for the polymerization of .alpha.-olefins wherein the improvement comprises polymerization in the presence of the catalyst component of claim 12, 13 or 14 and an organoaluminum cocatalyst component.
19. An improved process for the polymerization of .alpha.-olefins wherein the improvement comprises polymerization in the presence of the catalyst component of claim 15 or 16 and an organoaluminum cocatalyst component.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP140191/75 | 1975-11-25 | ||
| JP50140191A JPS5263981A (en) | 1975-11-25 | 1975-11-25 | Preparation of polymerization catalyst for alpha-olefin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1081679A true CA1081679A (en) | 1980-07-15 |
Family
ID=15263015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA266,446A Expired CA1081679A (en) | 1975-11-25 | 1976-11-24 | Process and product |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4127505A (en) |
| JP (1) | JPS5263981A (en) |
| BE (2) | BE848726A (en) |
| CA (1) | CA1081679A (en) |
| DE (1) | DE2653597A1 (en) |
| FR (1) | FR2333000A1 (en) |
| GB (1) | GB1570295A (en) |
| IT (1) | IT1064489B (en) |
| NL (1) | NL7613150A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52127492A (en) * | 1976-04-20 | 1977-10-26 | Mitsui Petrochem Ind Ltd | Production of titanium catalyst component |
| US4258161A (en) * | 1978-02-14 | 1981-03-24 | Mitsubishi Chemical Industries Ltd. | Process for polymerizing propylene |
| JPS598362B2 (en) * | 1978-06-23 | 1984-02-24 | 有限会社東洋ストウフア−・ケミカル | α-olefin polymerization catalyst |
| US4211670A (en) * | 1979-01-25 | 1980-07-08 | Hercules Incorporated | Titanium trichloride catalyst component for propylene polymerization |
| JPS5922913A (en) * | 1982-07-15 | 1984-02-06 | Chisso Corp | Polypropylene resin for highly-rigid formed item |
| US4626519A (en) * | 1985-09-06 | 1986-12-02 | Phillips Petroleum Company | Supported polyolefin catalyst components and methods of making and using same |
| US4680351A (en) * | 1985-09-06 | 1987-07-14 | Phillips Petroleum Company | Supported polyolefin catalyst components and methods of making and using same |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE35231B1 (en) * | 1970-03-26 | 1975-12-24 | Solvay | Process for the preparation of a ziegler-natta type catalyst |
| JPS5019155B1 (en) * | 1970-10-02 | 1975-07-04 | ||
| US3862257A (en) * | 1972-04-17 | 1975-01-21 | Exxon Research Engineering Co | Modified ziegler catalyst for alpha olefin wax synthesis |
| JPS5236877B2 (en) * | 1973-11-02 | 1977-09-19 | ||
| US3984350A (en) * | 1974-05-09 | 1976-10-05 | Standard Oil Company (Indiana) | Catalyst component comprising brown titanium trichloride |
| JPS5912684B2 (en) * | 1974-08-23 | 1984-03-24 | 住友化学工業株式会社 | Method for producing highly crystalline olefin polymer |
| JPS527892A (en) * | 1975-07-09 | 1977-01-21 | Toa Nenryo Kogyo Kk | Process for producing catalyst components for polymerization of alpha-olefin |
| JPS527891A (en) * | 1975-07-09 | 1977-01-21 | Toa Nenryo Kogyo Kk | Process for producing catalyst components for polymerization of olefi n |
-
1975
- 1975-11-25 JP JP50140191A patent/JPS5263981A/en active Granted
-
1976
- 1976-11-23 US US05/744,236 patent/US4127505A/en not_active Expired - Lifetime
- 1976-11-24 CA CA266,446A patent/CA1081679A/en not_active Expired
- 1976-11-24 IT IT29723/76A patent/IT1064489B/en active
- 1976-11-24 FR FR7635383A patent/FR2333000A1/en active Granted
- 1976-11-25 NL NL7613150A patent/NL7613150A/en not_active Application Discontinuation
- 1976-11-25 BE BE172680A patent/BE848726A/en not_active IP Right Cessation
- 1976-11-25 GB GB49212/76A patent/GB1570295A/en not_active Expired
- 1976-11-25 DE DE19762653597 patent/DE2653597A1/en not_active Withdrawn
- 1976-11-25 BE BE172682A patent/BE848728A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| NL7613150A (en) | 1977-05-27 |
| FR2333000B1 (en) | 1982-08-20 |
| BE848728A (en) | 1977-05-25 |
| DE2653597A1 (en) | 1977-06-02 |
| GB1570295A (en) | 1980-06-25 |
| JPS5610921B2 (en) | 1981-03-11 |
| IT1064489B (en) | 1985-02-18 |
| BE848726A (en) | 1977-05-25 |
| US4127505A (en) | 1978-11-28 |
| FR2333000A1 (en) | 1977-06-24 |
| JPS5263981A (en) | 1977-05-26 |
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