CA1079485A - Titanium trichloride catalyst component - Google Patents
Titanium trichloride catalyst componentInfo
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- CA1079485A CA1079485A CA241,208A CA241208A CA1079485A CA 1079485 A CA1079485 A CA 1079485A CA 241208 A CA241208 A CA 241208A CA 1079485 A CA1079485 A CA 1079485A
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- Prior art keywords
- temperature
- titanium tetrachloride
- catalyst component
- reaction mixture
- polymerization
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A catalyst component for polymerization of alpha-olefins which is prepared by treating titanium tetrachloride with a mixture of a dialkyl aluminum monohalide and a monoalkyl aluminum dihalide wherein the dialkyl aluminum monohalide is present in a proportion at least equimolar with the titanium tetrachloride. If desired, the product of the first reaction is subjected to a beat treatment or alternatively it is treated successively with a Lewis base and then a hydrocarbon solution of titanium tetrachloride.
A catalyst component for polymerization of alpha-olefins which is prepared by treating titanium tetrachloride with a mixture of a dialkyl aluminum monohalide and a monoalkyl aluminum dihalide wherein the dialkyl aluminum monohalide is present in a proportion at least equimolar with the titanium tetrachloride. If desired, the product of the first reaction is subjected to a beat treatment or alternatively it is treated successively with a Lewis base and then a hydrocarbon solution of titanium tetrachloride.
Description
10794~
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2 This invention relates to an improvement in a
3 catalyst component (hereinafter referred to as ~atalyst
4 Component) for use in the polymerization of alpha-olefins and more particularly, to a process for the production of 6 a catalyst component of excellent Catalytic properties, 7 whereby in the stereoregular polymerization o~ alpha-olefins 8 such as propylene, in particular, not only the stereoregu-9 larity is improved but also the polymerization speed is lo markedly increased.
12 As a method of producing a crystalline polyolefin 13 on a commercial scale, it has hitherto been proposed to use 14 a polymerization catalyst comprising3 in combination, a catalyst component consisting of a low valence transition 16 metal halide and a promoter component consisting of an 17 organic metal compound. Particularly a titanium trichloride 8 composition has been used as the transition metal halideO
19 A known method of preparing a titanium trichloride composition consists in reducing titanium tetrachloride by 21 metallic aluminum at high temperature and then grinding the 22 product for activation The catalyst component prepared in 23 this way is ordinarily called Grade AA titanium trichloride, 24 which contains9 in addition to titanium trichloride9 aluminum chloride in an eutectic form, but has the disadvantage that 26 when used as a polymerization catalyst, the polymerization 27 speed and stereoregularity are unsatisfactory and9 on a 28 commercial scale, a large amount of the expensive catalyst 29 is necessary, while a great cost is simultaneously required for the treatment of non-crystalline polymers produced as 31 by product. FurthermoreJ the catalyst component obtained by 32 this method has a wide particle size distribution, and the 1 ~ 7~ ~8 5 PO/~17erJZeJ
1 polymer po~Jmcr~icd using this ~atalyst component also has 2 a wide particle size distribution~ resulting in various 3 difficulties in handllng the polymer powder.
4Another known method of preparing a titanium tri-chloride composition consists in reduclng titanium tetra-6 chloride by die~hylaluminum chloride wherein the latter is 7 used in a proportion which is equimolar or less than the 8 moles of titanium atom present, at a low temperature, as 9 disclosed in, for example, Japanese Patent Publication Nos.
1010415/1971~ 21575/1972 and 11807/1972O This method has the 11 advantage that a catalytic component with a relatively even 2 particle size can be obtained, but, on the other handg the 13 titanium trichloride composition obtained by this method 14 is a brown beta-titanium trichloride composition whose poly-merization capacity is very inferiorO Therefore9 it is 16 necessary to sub~ect this composition to a heat activation 17 treatment to convert it into a violet titanium trichloride 18 compositionO In this case, however9 the polymerization 19 speed and stereoregularity when used as a polymerization catalyst are not superior to those in the case of the above 21 described Grade AA titanium trichloride composition.
22As a further method of preparing a titanium tri-23 chloride composition3 it has been proposed to obtain a 24 catalyst component giving a relatively high polymerization speed, high stereoregularity and e~cellent particle size 26 distribution by reducing titanium tetrachloride by diethyl-27 aluminum chloride at a low temperature, obtaining a beta-28 type titailium trichloride composition and then treating with 29 an ether compound and titanium tetrachloride to convert into a violet delta-type reduced solid, as disclosed in Japanese 31Patent Application (OPI) NoO 34478/1972. HoweverJ this . . , 32 method needs a large amount of titanium tetrachloride and a . 3 _ 0 79 4~ 5 1 high concentration of titanium tetrachloride in an inert 2 diluent, for exampleg 15 % by volume, preferably 30 to 40 %
3 by volume. Th~t is to say, it is found that in the case of 4 treating with a titanium tetrachloride solution with a con-centratlon of 40 % by volume, a catalyst component for 6 polymerization, having a relatively high polymerization 7 activity and stereoregularity can be obtained9 whilst in 8 the case of treating with a titanium tetrachloride solution 9 with a concentration of 10 % by volume, a catalyst component having unsatisfactory properties is obtainedO In this 11 method, moreover, it is found very difficult to obtain a l2 catalyst component having substantially a good particle ~ze 13 distribution. That is to say, in the case of treating with l4 a high concentration titanium tetrachloride solution~ a catalyst having a uniform particle size distribution tends 16 to break to fine particles with a wide particle size distri-l7 bution.
19 In accordance with the present invention9 it has been found that a cat~ yst component having excellent cata-21 lytic properties can be obtained by reducing titanium tetra-22 chloride with a mixture of dialkyl aluminum halide and alkyl-23 aluminum dihalide wherein the dialkyl aluminum halide is used 24 in a proportion which is equal to or more than the moles of titanium tetrachloride present.
26 Thus the invention provides a process for the pro-27 duction of a catalyst component for the polymerization of 28 alpha-olefinsg which comprises treating titanium tetrachloride 29 with a dialkyl aluminum monohalide and monoalk~laluminum dihalide, the dialkylaluminum monohalide being in a propor-31 tion at least equimolar to the titanium tetrachloride, and reacting these compounds to obtain a violet reduced solid.
:
.~ .
1 In another embodiment the reduced sol~d obtained 2 by the above described process is sub~ected to a heat treat-3 ment.
4 In a further embodiment the reduced solid obtained by the first step is treated with a Lewi8 base compound and 6 then with a hydrocarbon solution of titanium tetrachloride.
7 Useful examples of the dialkylalum~num monohalide 8 which can be used for the reductbn of titanium tetrachloride 9 in the process of the invention are dimethylaluminum chloride, o dlethylaluminum chlori~e, dibutylaluminum chloride, diethyl-11 aluminum bromide, diethylaluminum iodide and the like. Di-12 ethylaluminum chloride is preferred.
13 Useful examples of the noalkylaluminum dihalide 14 used together with the dialkylaluminum monohalide in the process of the invention are methylaluminum dichloride, l6 ethylaluminum dichloride, butylaluminum dichloride9 ethyl-17 aluminum dibromide and ethylaluminum diiodide~ Ethylalumi-8 num dichloride is preferred.
; 20 For purposes of illustration and net limitation, 21 the present invention will now be described using ethyl~
22 aluminum dichloride and diethylaluminum chloride in combina-23 tion.
24 As stated above, a method of reducing titanium 2s tetrachloride by means of diethylaluminum chloride is well 26 known to those skilled in the art. This reaction i8 repre-27 sented by the following equations.
28 TiC14 + 0.5Et2AlCl ~ TiC13 ~ 0.5 AlC13 + Et' 29 TiC14 + l.OEt2AlCl ~ TiC13 + EtAlC12 ~ Et- -As is apparent from these relations, the ratio of diethyl-31 aluminum chloride and titanium tetrachloride is ordinarily 32 0.5 : 1 to 1.0 : 1. It i8 well known that the compound
12 As a method of producing a crystalline polyolefin 13 on a commercial scale, it has hitherto been proposed to use 14 a polymerization catalyst comprising3 in combination, a catalyst component consisting of a low valence transition 16 metal halide and a promoter component consisting of an 17 organic metal compound. Particularly a titanium trichloride 8 composition has been used as the transition metal halideO
19 A known method of preparing a titanium trichloride composition consists in reducing titanium tetrachloride by 21 metallic aluminum at high temperature and then grinding the 22 product for activation The catalyst component prepared in 23 this way is ordinarily called Grade AA titanium trichloride, 24 which contains9 in addition to titanium trichloride9 aluminum chloride in an eutectic form, but has the disadvantage that 26 when used as a polymerization catalyst, the polymerization 27 speed and stereoregularity are unsatisfactory and9 on a 28 commercial scale, a large amount of the expensive catalyst 29 is necessary, while a great cost is simultaneously required for the treatment of non-crystalline polymers produced as 31 by product. FurthermoreJ the catalyst component obtained by 32 this method has a wide particle size distribution, and the 1 ~ 7~ ~8 5 PO/~17erJZeJ
1 polymer po~Jmcr~icd using this ~atalyst component also has 2 a wide particle size distribution~ resulting in various 3 difficulties in handllng the polymer powder.
4Another known method of preparing a titanium tri-chloride composition consists in reduclng titanium tetra-6 chloride by die~hylaluminum chloride wherein the latter is 7 used in a proportion which is equimolar or less than the 8 moles of titanium atom present, at a low temperature, as 9 disclosed in, for example, Japanese Patent Publication Nos.
1010415/1971~ 21575/1972 and 11807/1972O This method has the 11 advantage that a catalytic component with a relatively even 2 particle size can be obtained, but, on the other handg the 13 titanium trichloride composition obtained by this method 14 is a brown beta-titanium trichloride composition whose poly-merization capacity is very inferiorO Therefore9 it is 16 necessary to sub~ect this composition to a heat activation 17 treatment to convert it into a violet titanium trichloride 18 compositionO In this case, however9 the polymerization 19 speed and stereoregularity when used as a polymerization catalyst are not superior to those in the case of the above 21 described Grade AA titanium trichloride composition.
22As a further method of preparing a titanium tri-23 chloride composition3 it has been proposed to obtain a 24 catalyst component giving a relatively high polymerization speed, high stereoregularity and e~cellent particle size 26 distribution by reducing titanium tetrachloride by diethyl-27 aluminum chloride at a low temperature, obtaining a beta-28 type titailium trichloride composition and then treating with 29 an ether compound and titanium tetrachloride to convert into a violet delta-type reduced solid, as disclosed in Japanese 31Patent Application (OPI) NoO 34478/1972. HoweverJ this . . , 32 method needs a large amount of titanium tetrachloride and a . 3 _ 0 79 4~ 5 1 high concentration of titanium tetrachloride in an inert 2 diluent, for exampleg 15 % by volume, preferably 30 to 40 %
3 by volume. Th~t is to say, it is found that in the case of 4 treating with a titanium tetrachloride solution with a con-centratlon of 40 % by volume, a catalyst component for 6 polymerization, having a relatively high polymerization 7 activity and stereoregularity can be obtained9 whilst in 8 the case of treating with a titanium tetrachloride solution 9 with a concentration of 10 % by volume, a catalyst component having unsatisfactory properties is obtainedO In this 11 method, moreover, it is found very difficult to obtain a l2 catalyst component having substantially a good particle ~ze 13 distribution. That is to say, in the case of treating with l4 a high concentration titanium tetrachloride solution~ a catalyst having a uniform particle size distribution tends 16 to break to fine particles with a wide particle size distri-l7 bution.
19 In accordance with the present invention9 it has been found that a cat~ yst component having excellent cata-21 lytic properties can be obtained by reducing titanium tetra-22 chloride with a mixture of dialkyl aluminum halide and alkyl-23 aluminum dihalide wherein the dialkyl aluminum halide is used 24 in a proportion which is equal to or more than the moles of titanium tetrachloride present.
26 Thus the invention provides a process for the pro-27 duction of a catalyst component for the polymerization of 28 alpha-olefinsg which comprises treating titanium tetrachloride 29 with a dialkyl aluminum monohalide and monoalk~laluminum dihalide, the dialkylaluminum monohalide being in a propor-31 tion at least equimolar to the titanium tetrachloride, and reacting these compounds to obtain a violet reduced solid.
:
.~ .
1 In another embodiment the reduced sol~d obtained 2 by the above described process is sub~ected to a heat treat-3 ment.
4 In a further embodiment the reduced solid obtained by the first step is treated with a Lewi8 base compound and 6 then with a hydrocarbon solution of titanium tetrachloride.
7 Useful examples of the dialkylalum~num monohalide 8 which can be used for the reductbn of titanium tetrachloride 9 in the process of the invention are dimethylaluminum chloride, o dlethylaluminum chlori~e, dibutylaluminum chloride, diethyl-11 aluminum bromide, diethylaluminum iodide and the like. Di-12 ethylaluminum chloride is preferred.
13 Useful examples of the noalkylaluminum dihalide 14 used together with the dialkylaluminum monohalide in the process of the invention are methylaluminum dichloride, l6 ethylaluminum dichloride, butylaluminum dichloride9 ethyl-17 aluminum dibromide and ethylaluminum diiodide~ Ethylalumi-8 num dichloride is preferred.
; 20 For purposes of illustration and net limitation, 21 the present invention will now be described using ethyl~
22 aluminum dichloride and diethylaluminum chloride in combina-23 tion.
24 As stated above, a method of reducing titanium 2s tetrachloride by means of diethylaluminum chloride is well 26 known to those skilled in the art. This reaction i8 repre-27 sented by the following equations.
28 TiC14 + 0.5Et2AlCl ~ TiC13 ~ 0.5 AlC13 + Et' 29 TiC14 + l.OEt2AlCl ~ TiC13 + EtAlC12 ~ Et- -As is apparent from these relations, the ratio of diethyl-31 aluminum chloride and titanium tetrachloride is ordinarily 32 0.5 : 1 to 1.0 : 1. It i8 well known that the compound
- 5 -~' 1 formed by this reaction9 i.e., ethylaluminum dichloride i8 2 a harmful material for the polymerization reaction and, 3 therefore, efforts have been made to remove it as far as 4 possible after the reducing reaction~ However, the inventors 5 have found that a violet reduced solid is obtained by re-
6 ducing titanium tetrachloride by diethylaluminum chloride
7 and ethylaluminum dichloride in a suitable amount in a
8 proportion of l mol or more of diethyl aluminum chloride to
9 l mol of the titanium tetrachloride, in particular9 in a 0 proportion of 0.3 to lo 2 mol to l mol of the titanium tetra chloride, and this reduced solid, when used as a catalyst 12 component for the polymerization of alpha~olefins9 shows a 13 higher polymerization activity than a catalyst component 14 obtained by reducing titanium tetrachloride by diethylalumi-num chloride alone. It is further found that a catalyst 16 component (heat-treated solid) having an improved polymeri-17 zation activity and stereoregularity which are at least 18 equal to those of the marketed titanium trichloride as well 19 as a markedly excellent particle size uniformity can be ob~
tained by subjecting the former reduced solid to a heat 21 treatment~ Moreover, the inventors have succeeded in ob-22 taining a catalyst component having a more improved polymeri-23 zation activity, stereoregularity and particle size uniformity 24 by treating the reduced solid with a Lewis base such as ether and then with a hydrocarbon solution of titanium tetrachloride.
26 A feature of the process of the invention is that, 27 when titanium tetrachloride is reduced by diethylaluminum 28 chloride and ethylaluminum dichloride in a suitable amount 29 in a proportion of l mol o~ more of diethylaluminum chloride to l mol of the titanium tetrachloride, in particular9 in a 31 praportion of 0.3 to 1.2 mol to l mol of the titanium tetra-32 chloride, a violet reduced solid is obtained. This phenom-.
?
1 enon is very surprising in view of the prior art process 2 wherein the reduction is carried out using no ethylaluminum 3 dichloride but using 4 diethylaluminum chloride only. X-ray diffraction spectra show that, in the case of a brown reduced solid obtained by the prior art process, the peak at 2~ ~ 42.2 (beta-7 type crystal) is considerably larger than the peak at 2~ =
8 51.3 (gamma-type crystal), while in the case of a ~iolet 9 reduced solid obtained according to the present invention, lo the peak at 2~ c 42.2 is very small and the peak at 2~ =
11 51.3 is large.
12 Another feature of the present invention consists 13 in the composition of the above described reduced solid.
14 When titanium tetrachloride is reduced by diethylaluminum chloride in an equimolar amount, there are formed titanium 16 trichloride and ethylaluminum dichloride in an equimolar 17 amount as a byproduct. This byproduct is readily soluble 18 in solvents, but9 even when the reduced solid is washed 19 adequately with a solvent after the reducing reaction9 a considerable amount of the aluminum dichloride compound 21 remains in the solid. It is assumed that the aluminum di-~2 chloride compo~nd is present as one component to form a 23 reduced solid with some cohesive strength, which rends the 24 compound difficult to remove by washing. When a reducing agent to which ethylaluminum dichloride is added is used 26 for the reduction of titanium tetrachloride according to 27 the process of the present invention, the content of the 28 aluminum compound in the reduced solid is more than in a 29 reduced solid obtained by the prior art process wherein no ethylaluminum dichloride is added. This tendency observed 31 in the process of the invention is of interest in view of 32 the fact that when using diethylaluminum chloride alone as 1079~S5 1 a reducing agent~ the content of the aluminum dichloride com-2 pound in the reduced solid tends to decrease with a diethyl-3 aluminum chloride to titanium tetrachloride ratio of 1 or 4 more. Examples of the analytical composition of the reduced solids are tabulated below:
6 Reducing Agent Al/Ti Ratio atAl/Ti Ratio In 7 ~ 5,_____Reduced S~lld 8 Et2AlC1 1 0035 9 1.5 0 22 2 0~26 11 2.5 0018 12 Et2AlCl + 0.5EtAlC12 1.5 0~56 13 Et2AlCl + l.OEtAlC12 2 0.56 14 Et2AlCl + 1.5EtAlC12 2.5 0.62 The above described reduced solid of the invention 16 is characterized by a higher polymerization activity when 17 used as a catalyst component for polymerization as compared l8 with a reduced solid obtained by the prior art process using l9 diethylaluminum chloride only. That is to say, the stereo-regularity and activity are very inferior as polymerization 21 properties when an organo aluminum compound is added as a 22 co-catalyst to a reduced solid of the prior art process and 23 polymerization of alpha-olefins is effected, for example9 24 approximately half as much as those of the titanium tri-chloride of commercial Grade AA. On the contrary, the 26 reduced solid of the present invention has substantially the 27 same polymerization activity as the titanium trichloride of : 28 Grade~AA
29 When the reduced solid obtained by the .~irst .
process of the present invention is subjected to a heat 31 treatment in an inert solvent such as a hydrocarbon, there 32 is thereby obtained a catslyst component (heat-treated solid) ~C~79~85 excellent in polymerization activity as well as stereoregu-2 larity. This catalyst cornponent is superior to the commer-3 cial titanium trichloride of Grade AA in particle size uni-4 formity ~nd has a polymerization activity and stereoregularity ~ich are at least equal to those of the titanium trichloride 6 of Grade AA.
7 When a reduced solid obtained by reducing titanium 8 tetrachloride by diethylaluminum chloride only is subjected 9 to the similar heat treatment9 however, the polymerization 0 activity and stereoregularity are both inferior to those 11 of the con~nercial titanium trichloride of Grade AA.
12 Where the heat-treated solid obtained by the 13 process of the present invention is used as a catalyst 14 component, there can be obtained a polymerization activity and stereoregular~ty which are at least equal to those in 16 the case of using the ordinary commercial tit~iium tri-17 chloride of Grade AA and a polymer with a narrow particle 8 size distributionO
19 In accordance with another feature of the inve~-tion a catalyst component whose polymerization performance 21 is markedly improved can be obtained by subjecting the 22 first catalyst component of the invention further to another 23 effective after-treatmentD That is to say, the reduced 24 solid obtained by the first process of the invention is treated with a Lewis base such as ether and then with a 26 solution of titanl~un tetrachloride, thereby obtaining a 27 catalyst component having a much higher polymerization 28 activity and stereoregularity than a catalyst component 29 obtained by reducing titanium tetrachloride by diethylalumi-num chloride only and subjecting the resulting reduced solid 31 to the similar after-treatment.
32 A further feature of the present invention consists _ g _ ~o79~85 1 in the effect of concentration in the step of treating with 2 titanium tetrachloride. That is to S2y, a catalyst component 3 having an e~cellent polymerization activity and stereoregular-4 ity is obtained by treatment of the reduced solid obtained s by the firs~ process of the present invention with a titan-6 ium tetrachloride solution having a lower concentration 7 than in the case of a reduced solid obtained by the prior 8 art process. In the treatment with a titanium tetrachloride 9 solution according ~o the prior art process3 a titanium 0 tetrachloride concentration of 15 % by volume or more, in particular, 30 to 40 % by volume is required~ Thus, a 12 catalyst component having a considerably improved activity 13 can be obtained if a titanium tetrachloride concentra~ion of 14 40 % by volume is employed, even in the after-treatment of a reduced solid obtained by reducing titanium tetrachloride 16 by diethylaluminum chloride alone according to the prior 17 art process9 but the use of a titanium tetrachloride solu-18 tion having a lower concentration9 for example lO % by volume 19 results in a catalyst component having unsatisfactory properties. On the other hand9 the reduced solid obtained 21 by the first process of the present invention ~s capable of 22 giving a catalyst component having an equal polymerization 23 activity to that in the case of treating with a titanium 24 tetrachloride solution having a concentration of 40 % by volume according to the prior art process9 even by treatment 26 with a titanium tetrachloride solution having a lower con-27 centration, for example 5 % by volumè~following treatment 28 with a Lewis base compound such as ether compownds. More-29 over, when the treatment is carried out using a titanium tetrachloride solution having a concentration of lO % by 31 volume, a catalyst component having a higher polymerization 32 ac~ivity can be obtained than when the treatment is carried
tained by subjecting the former reduced solid to a heat 21 treatment~ Moreover, the inventors have succeeded in ob-22 taining a catalyst component having a more improved polymeri-23 zation activity, stereoregularity and particle size uniformity 24 by treating the reduced solid with a Lewis base such as ether and then with a hydrocarbon solution of titanium tetrachloride.
26 A feature of the process of the invention is that, 27 when titanium tetrachloride is reduced by diethylaluminum 28 chloride and ethylaluminum dichloride in a suitable amount 29 in a proportion of l mol o~ more of diethylaluminum chloride to l mol of the titanium tetrachloride, in particular9 in a 31 praportion of 0.3 to 1.2 mol to l mol of the titanium tetra-32 chloride, a violet reduced solid is obtained. This phenom-.
?
1 enon is very surprising in view of the prior art process 2 wherein the reduction is carried out using no ethylaluminum 3 dichloride but using 4 diethylaluminum chloride only. X-ray diffraction spectra show that, in the case of a brown reduced solid obtained by the prior art process, the peak at 2~ ~ 42.2 (beta-7 type crystal) is considerably larger than the peak at 2~ =
8 51.3 (gamma-type crystal), while in the case of a ~iolet 9 reduced solid obtained according to the present invention, lo the peak at 2~ c 42.2 is very small and the peak at 2~ =
11 51.3 is large.
12 Another feature of the present invention consists 13 in the composition of the above described reduced solid.
14 When titanium tetrachloride is reduced by diethylaluminum chloride in an equimolar amount, there are formed titanium 16 trichloride and ethylaluminum dichloride in an equimolar 17 amount as a byproduct. This byproduct is readily soluble 18 in solvents, but9 even when the reduced solid is washed 19 adequately with a solvent after the reducing reaction9 a considerable amount of the aluminum dichloride compound 21 remains in the solid. It is assumed that the aluminum di-~2 chloride compo~nd is present as one component to form a 23 reduced solid with some cohesive strength, which rends the 24 compound difficult to remove by washing. When a reducing agent to which ethylaluminum dichloride is added is used 26 for the reduction of titanium tetrachloride according to 27 the process of the present invention, the content of the 28 aluminum compound in the reduced solid is more than in a 29 reduced solid obtained by the prior art process wherein no ethylaluminum dichloride is added. This tendency observed 31 in the process of the invention is of interest in view of 32 the fact that when using diethylaluminum chloride alone as 1079~S5 1 a reducing agent~ the content of the aluminum dichloride com-2 pound in the reduced solid tends to decrease with a diethyl-3 aluminum chloride to titanium tetrachloride ratio of 1 or 4 more. Examples of the analytical composition of the reduced solids are tabulated below:
6 Reducing Agent Al/Ti Ratio atAl/Ti Ratio In 7 ~ 5,_____Reduced S~lld 8 Et2AlC1 1 0035 9 1.5 0 22 2 0~26 11 2.5 0018 12 Et2AlCl + 0.5EtAlC12 1.5 0~56 13 Et2AlCl + l.OEtAlC12 2 0.56 14 Et2AlCl + 1.5EtAlC12 2.5 0.62 The above described reduced solid of the invention 16 is characterized by a higher polymerization activity when 17 used as a catalyst component for polymerization as compared l8 with a reduced solid obtained by the prior art process using l9 diethylaluminum chloride only. That is to say, the stereo-regularity and activity are very inferior as polymerization 21 properties when an organo aluminum compound is added as a 22 co-catalyst to a reduced solid of the prior art process and 23 polymerization of alpha-olefins is effected, for example9 24 approximately half as much as those of the titanium tri-chloride of commercial Grade AA. On the contrary, the 26 reduced solid of the present invention has substantially the 27 same polymerization activity as the titanium trichloride of : 28 Grade~AA
29 When the reduced solid obtained by the .~irst .
process of the present invention is subjected to a heat 31 treatment in an inert solvent such as a hydrocarbon, there 32 is thereby obtained a catslyst component (heat-treated solid) ~C~79~85 excellent in polymerization activity as well as stereoregu-2 larity. This catalyst cornponent is superior to the commer-3 cial titanium trichloride of Grade AA in particle size uni-4 formity ~nd has a polymerization activity and stereoregularity ~ich are at least equal to those of the titanium trichloride 6 of Grade AA.
7 When a reduced solid obtained by reducing titanium 8 tetrachloride by diethylaluminum chloride only is subjected 9 to the similar heat treatment9 however, the polymerization 0 activity and stereoregularity are both inferior to those 11 of the con~nercial titanium trichloride of Grade AA.
12 Where the heat-treated solid obtained by the 13 process of the present invention is used as a catalyst 14 component, there can be obtained a polymerization activity and stereoregular~ty which are at least equal to those in 16 the case of using the ordinary commercial tit~iium tri-17 chloride of Grade AA and a polymer with a narrow particle 8 size distributionO
19 In accordance with another feature of the inve~-tion a catalyst component whose polymerization performance 21 is markedly improved can be obtained by subjecting the 22 first catalyst component of the invention further to another 23 effective after-treatmentD That is to say, the reduced 24 solid obtained by the first process of the invention is treated with a Lewis base such as ether and then with a 26 solution of titanl~un tetrachloride, thereby obtaining a 27 catalyst component having a much higher polymerization 28 activity and stereoregularity than a catalyst component 29 obtained by reducing titanium tetrachloride by diethylalumi-num chloride only and subjecting the resulting reduced solid 31 to the similar after-treatment.
32 A further feature of the present invention consists _ g _ ~o79~85 1 in the effect of concentration in the step of treating with 2 titanium tetrachloride. That is to S2y, a catalyst component 3 having an e~cellent polymerization activity and stereoregular-4 ity is obtained by treatment of the reduced solid obtained s by the firs~ process of the present invention with a titan-6 ium tetrachloride solution having a lower concentration 7 than in the case of a reduced solid obtained by the prior 8 art process. In the treatment with a titanium tetrachloride 9 solution according ~o the prior art process3 a titanium 0 tetrachloride concentration of 15 % by volume or more, in particular, 30 to 40 % by volume is required~ Thus, a 12 catalyst component having a considerably improved activity 13 can be obtained if a titanium tetrachloride concentra~ion of 14 40 % by volume is employed, even in the after-treatment of a reduced solid obtained by reducing titanium tetrachloride 16 by diethylaluminum chloride alone according to the prior 17 art process9 but the use of a titanium tetrachloride solu-18 tion having a lower concentration9 for example lO % by volume 19 results in a catalyst component having unsatisfactory properties. On the other hand9 the reduced solid obtained 21 by the first process of the present invention ~s capable of 22 giving a catalyst component having an equal polymerization 23 activity to that in the case of treating with a titanium 24 tetrachloride solution having a concentration of 40 % by volume according to the prior art process9 even by treatment 26 with a titanium tetrachloride solution having a lower con-27 centration, for example 5 % by volumè~following treatment 28 with a Lewis base compound such as ether compownds. More-29 over, when the treatment is carried out using a titanium tetrachloride solution having a concentration of lO % by 31 volume, a catalyst component having a higher polymerization 32 ac~ivity can be obtained than when the treatment is carried
- 10 -~07 9 48 S
1 out using a titanium tetrachloride solution with a concen-2 tration of 40 % by volume in the prior art process.
3 Since it is possible to use a dilute solution of 4 titanium tetrachloride in the process of the invention, there are given various advantages that not only a high 6 ac~ivity can be ob~ained without using a large amount of 7 the expensive reagent9 but also a catalyst component ob-8 tained has a very excellent particle property. As will be 9 apparent from Examples and Comparative Examples given here-0 inafter, a catalyst component finally contains a considerable
1 out using a titanium tetrachloride solution with a concen-2 tration of 40 % by volume in the prior art process.
3 Since it is possible to use a dilute solution of 4 titanium tetrachloride in the process of the invention, there are given various advantages that not only a high 6 ac~ivity can be ob~ained without using a large amount of 7 the expensive reagent9 but also a catalyst component ob-8 tained has a very excellent particle property. As will be 9 apparent from Examples and Comparative Examples given here-0 inafter, a catalyst component finally contains a considerable
11 quantity of fine particles when the reduced solid is treated
12 with an ether compound and then with titanium eetrachloride.
13 The use of such a catalyst component is disadvantageous for
14 the polymerization since a polymer powder containing a large amount of fine particles is produced thereby. The process of 16 the present invention, howeverJ has an advantage that the 17 content of fine powder in a catalyst component can be re-8 duced by lowering the concentration of titanium tetrachloride.
19 The reducing reaction of the invention is carried out by bringing titanium tetrachloride into contact with a 21 reducing agen~ compr~sing a monoalkylaluminum dihalide and 22 dialkylaluminum monohalide, for example, ethylaluminum di-23 chloride and diethylaluminum chloride in an inert diluent.
24 In particularJ the reducing agent which is used for the re-duction of titanium tetrachloride consists of diethylaluminum 26 chloride in a proportion of equimolar or more to the titanium 27 tetrachloride and ethylaluminum dichloride in a suitable 28 proport~on~ If diethylaluminum chloride is used in a pro-29 portion less than equimolar to the titanium tetrachlorideJ
the resultant reduced solid9 heat-treated solid and ether 31 and titanium tetrachloride-treated solid all show unfavorable 32 properties. The quantity of ethylaluminum dichloride used 107~85 1 is preferably within a range of 0O3 to l.2 mol per l mol 2 of the titanium tetrachloride.
3 As the inert diluent there can be used aliphatic 4 hydrocarbons having 4 to 12 carbon atoms or alicyclic hydrocarbons, which are substantially free from aromatic 6 hydrocarbons~ The temperature of the reducing reaction is 7 relatively important for the properties of the final product 8 and thus should be adjusted to ~50 to +30Co The reaction 9 is initiated by contacting titanium tetrachloride with a 0 reducing agent with agitation and a reduced solid insoluble 11 in the inert diluent is then deposited. The reaction is 12 ordinarily carried out9 for example9 by adding dropwise 13 either the solution of titanium tetrachloride and the 14 solution of the reducing agent gradually to the other or vice versa. The time necessary for mixing all the solutions 16 is l hour or more9 preferably 3 hours or more and during 17 the same time3 the reaction system should be held at the 8 above described temperature. After both the solutions are 19 mixed completely and held at the same temperature for at le~st 30 minutes9 preferably9 l hour or~more9 the temperature 21 is gradually raised and the system is held for 15 minutes 22 or more at a constant temperature in the range of from 20 23 to 120C, preferably 60 to 100C. The reduced solid obtained 24 in this way should be adequately washed with a fresh solvent.
2s Heat treatment of the reduced solid is optionally 26 carried out in an inert medium at a temperature of 120 to 27 180C for 30 minutes or more, preferably l to 3 hours. In 28 this case, aliphatic hydrocarbons or alicyclic hydrocarbons, 29 which are substan~ially free from aromatic hydrocarbons, are used. For example9 pentane, hexane, heptane9 octane9 cyclo-31 hexane, cyclopentane and the like can be used~
32 In the case of effecting treatment of the reduced 10794~5 1 solid with a Lewis b~se compound9 the reduced solid is sub-2 jected to a solvent extraction treatment in the presence of 3 the Lewis base compound. As the Lewis base compound there 4 can be used ethe~g thioethersD thiols~ organic phosphorus-conta~ning compoundsg organic nitrogen~containing compounds, 6 ketones and estersO Useful examples of the ether are dl-7 ethyl ether, diisopropyl etherg di~nbutyl ether~ diisobutyl 8 ether, diisoamyl ether9 di~2 ethylhe~y1 ether9 di~2ethyl-9 heptyl ether, allyl ethyl ether~ allyl butyl etherg diphenyl ether, annisole9 phenetole3 chloroanisoleg bromoanisole and ll dimethoxybenzeneO Useful examples of the thioether are di-l2 ethyl thioether~ di~n~propyl thioetherS dicyclohexyl thio-l3 ether, diphenyl thioether5 ditolyl thioetherg ethyl phenyl 14 thioether, propyl phenyl thioether and diallyl thioether.
Useful examples of the organic phosphorus-containlng com~
16 pound are tri-n~butylphosphine~ ~riphenylphosphineO tri~
7 ethyl phosphite and tributyl phosphiteO Useful examples 18 of the organic nitrogen~containing compound are diethylamine, 19 triethylamine, n~propylamineg di~n-propylamine9 tri n propylamine, aniline and dimethylanilineO In particularg 21 ethers, preferably having 4 to 16 carbon atoms are suitable.
22 The extraction method can be carried out by any of the 23 commonly used methodsg for example9 by stirring adequately 24 the reduced solid with an ether compo~nd in an inert medium to separate into a liquid phase and solid phase. As the 26 medium can also be used those solvents used in the reducing 27 reaction. The extraction is ordinarily carried out for 5 28 minutes or more9 preferably 30 minutes to 2 hours at a constant temperature selected from O to 80Co The quantity Of the Lewis base compound used is Ool to 205 mols, preferably 31 0.8 to 1.0 mol per l mol of titanium atomO
32 The solid treated ~i~h the above described Lewis ~ 13 ~
~0794~5 1 base is subsequently s~bjected to a treahment with a titanium 2 tetrachloride solution which should have a concentration of 3 5 % by volume or more. If the concentration is less than 4 5 % by volume, only an insufficient polymerization activity and insufficient stereoregularity of the polymerizatlon 6 product are obtainedg while if the concentration of titanium 7 tetrachloride is increased9 good results are obtained as to 8 the polymerization ac~ivity and stereoregularity of the 9 product but there is a tendency9 as described above9 that the particle size distribution is widened with ~he increase 11 of fine particlesD Therefore~ a titanium tetrachloride con-12 centration of 5 to 20 % by volume is preferredO As the 13 hydrocarbon solvent used in this case there can be given 14 pentane, hexane9 heptaneD octane9 cyclohexane~ cyclopentane and the:likeO The temperature d~ring treatment wi~ a titan-6 ium tetrachloride solution is within a range of ~30 to 7 +100C, preferably 40 to 80C~ This titanium tetrac~loride 18 treatment may be completed in abouf 30 minutes9 but should 9 ordinarily be continued over a period of l to 3 hours in order to obtain good results with a high reproducibility~
21 After the titanium tetrachloride treatment9 the resultant 22 catalyst component should be adequately washed with a fresh 23 solvent3 because the polymerization is unfavorably affected 24 if there remains a large amount of titanium tetrachlorideO
The thus obtained catalyst component is used for 26 the polymerization together with a co-catalyst componentO
27 As the co-catalystg organometallic compounds of Group I, II
28 and III elements of Periodic Table are usedO In particular, 29 organo aluminum compounds are preferably used and~ above all, triethylaluminum and diethylaluminum chloride are most 31 suitable for the polymerization of propyleneO Any polymeri-32 zation methods known in the art can be usedO For example3 ~ 14 -1079D~85 1 as an economi~a} method, a liquid m~nomer may be used as the 2 polymerization medium without using a polymerization diluent;
3 or a gaseous monomer may be used similarly.
4 Example 1 150 ml of purified heptane and 34.8 ml of titanium 6 tetrachloride were charged in a 500 ml flask equipped with a 7 stirrer and kept at 09C in a bath. 40 ml of diethylaluminum 8 chloride (equimolar to the titanium tetrachloride~ and 16.5 9 ml of ethylaluminum dichloride (0.5 mol/mol to the titanium tetrachloride) were dissolved in 160 ml of heptane and 11 added dropwise from a dropping funnel. The dropping was 12 continued for a period of time of about 3 hours and, during 13 the same time, the reaction system was kept at O~C. After 14 the dropwise addition, the reaction mixture was gradually heated for 1 hour to 65C with agitation. The reaction was 16 further continued at the same temperature for another 1 hour.
17 After the reaction, the reaction mixture was allowed to stand 18 to separate5 A solid formed and the supernatant liquid and 19 the solid were washed with 150 ml of purified heptane repeat-edly three timeC~ followed by drying at 65~C for 30 minutes 21 under reduced pressure. The reduced solid was red violet and 22 the X-ray diffraction spectrum thereof showed that the peak 23 at 2~ = 42,4~ ~beta-type crystal~ was considerably smaller 24 than the peak at 2e = 51.3 (delta-type crystal). The propor-tion of fine particles of 5 microns or less in the reduced 26 solid was 1 ~ or lessr 27 100 mg of the reduced solid obtained in this way 28 was charged in a 1000 ml autoclave to which 180 mg of diethyl-29 aluminum chloride as a co-catalyst, 600 ml of hydrogen (standard state) was a molecular weight regulator and 800 ml 31 of li~uid propylene were then addedO The polymerization was 32 carried out at 68~C for 1 hou~ and the unreacted propylene i - 15 -1079~5 was subjected to flashing to thus obtain 96 g of polypropy-~
2 lene powder. The polymer yield per l g of the reduced solid 3 (which will hereinafter be referred to as "catalyst efficien-4 cy E") was 960. The melt flow rate according to ASTM D
1238 (MFR) of this polymer was 6~0O The heptane-insoluble 6 content (HI) of the polymer was 70.7 % measured by extracting 7 with boiling heptane for 5 hours using a Soxhlet extractor.
8 20 g of the above described reduced solid was sus-9 pended in 200 ml of purified heptane and heat-treated at 150C for 2 hoursO Then the solid was separated and dried 11 at 65C for 30 minutes under reduced pressure, thus obtaining 12 a heat-treated solid, The proportion of fine particles of 5 13 microns or less in this heat-treated solid was 5 %. Using 14 this heat-treated solid, a polymerization test was carried o~t under the same conditions as described above, thus ob-16 taining a polymer yield (E~ per l g of the heat-treated solid 17 of 960 and MFR and HI of the formed polymer of 5Q and 93,7 %
18 respectivelyO
19 Comparative Example l The procedure of Eacample 1 was repeated except that 21 no ethylaluminum dichloride was used but diethylaluminum 22 chloride alone was used during the reduction, The color of 23 the reduced solid formed by the reduction was brown and X-ray 24 diffraction spectrum thereof showed that the peak at 2~ =
42.4 was larger than l~he peak at 2a = 51,3~ The proportion 26 of fine particles of 5 microns or less was l % or less.
27 Using this reduced solid, a polymerization test 28 was carried out under the same conditions as in Example l 29 and the following results were obtained:
E = 520, HI = 68~3 %, MFR = 6.5 31 When this reduced solid was heat-treated in an analogous 32 manner to Example l, the color was changed from brown to .
1 violet. The proportion of fine particles of 5 microns or 2 less in the heat-treated solid particles was 5 %. Using ~ this solid, a polymerization test was carried out in an 4 analogous manner to Example l and the following results were obtained:
6 E = 750, HI = 92.5 %, MFR = 5.0 7 Comparative Example 2 8 Using titanium trichloride of Grade AA manufactured 9 by Toyo Stauffer Co., a polymerization test was carried out under the same conditions as those of Example l and the 11 following results were obtained:
12 E = 850, HI = 93.3%, MFR = 4.0 13 The proportion of fine particles of 5 microns or less in 14 this titanium trichloride particles of Grade AA was 12 %.
Ex~mples 2 and 3 16 The procedure of Example l was repeated except 17 varying the ratio of ethylaluminum dichloride used as a 18 reducing agent to titanium tetrachloride. The quantity of 19 diethylaluminum chloride was the same as that of Example l.
The results of a polymerization test of the reduced solid 21 and heat-treated solid are show~ in Table l~
22 Table l 23 Example Nos 2 3 24 Et2AlCl/TiCl4 Molar Ratio le 0 1~ 0 25 EtAlCl2/TiCl4 Molar Ratio 0.3 l.2 26 Porportion Of Fine Particles Of 5 Microns 27 Or Less In Reduced Solid (%) l;
28 Polymerization Test Results Of Reduced 29 Solid E 722 840 30 HI 73.9 78.0 31 Proportion Of Fine Particles Of 5 Microns 32 Or Less In Heat-Treated Solid (%) 5 5 33 Polvmerization Test Results Of Heat- ..... .E 664 800 ~g Treated Solid HI 92.9 93.5 ~0794~5 1 Comparative Examples 3, 4 and 5 2 The procedure of Comparative Example 1 was repeated 3 except varying the ratio of diethylaluminum chloride used as 4 a reducing agent ~ titanium tetrachloride. The results are shown in Table 2. This table shows that the use of the re-~ 6 ducing agent in an excess amount to titanium tetrachloride is 7 not beneficial.
8 Table 2 9 Comparative Example No. 3 4 5 10 Et2AlCl/TiC14 Molar Ratio 0.51.5 2.0 11 EtAlC12/TiC14 Molar Ratio 0 0 0 12 Proportion Of Particles Of 5 Microns Or 13 Less In Reduced Solid (~) 1 1 2 14 Polymerization Test Results Of Reduced
19 The reducing reaction of the invention is carried out by bringing titanium tetrachloride into contact with a 21 reducing agen~ compr~sing a monoalkylaluminum dihalide and 22 dialkylaluminum monohalide, for example, ethylaluminum di-23 chloride and diethylaluminum chloride in an inert diluent.
24 In particularJ the reducing agent which is used for the re-duction of titanium tetrachloride consists of diethylaluminum 26 chloride in a proportion of equimolar or more to the titanium 27 tetrachloride and ethylaluminum dichloride in a suitable 28 proport~on~ If diethylaluminum chloride is used in a pro-29 portion less than equimolar to the titanium tetrachlorideJ
the resultant reduced solid9 heat-treated solid and ether 31 and titanium tetrachloride-treated solid all show unfavorable 32 properties. The quantity of ethylaluminum dichloride used 107~85 1 is preferably within a range of 0O3 to l.2 mol per l mol 2 of the titanium tetrachloride.
3 As the inert diluent there can be used aliphatic 4 hydrocarbons having 4 to 12 carbon atoms or alicyclic hydrocarbons, which are substantially free from aromatic 6 hydrocarbons~ The temperature of the reducing reaction is 7 relatively important for the properties of the final product 8 and thus should be adjusted to ~50 to +30Co The reaction 9 is initiated by contacting titanium tetrachloride with a 0 reducing agent with agitation and a reduced solid insoluble 11 in the inert diluent is then deposited. The reaction is 12 ordinarily carried out9 for example9 by adding dropwise 13 either the solution of titanium tetrachloride and the 14 solution of the reducing agent gradually to the other or vice versa. The time necessary for mixing all the solutions 16 is l hour or more9 preferably 3 hours or more and during 17 the same time3 the reaction system should be held at the 8 above described temperature. After both the solutions are 19 mixed completely and held at the same temperature for at le~st 30 minutes9 preferably9 l hour or~more9 the temperature 21 is gradually raised and the system is held for 15 minutes 22 or more at a constant temperature in the range of from 20 23 to 120C, preferably 60 to 100C. The reduced solid obtained 24 in this way should be adequately washed with a fresh solvent.
2s Heat treatment of the reduced solid is optionally 26 carried out in an inert medium at a temperature of 120 to 27 180C for 30 minutes or more, preferably l to 3 hours. In 28 this case, aliphatic hydrocarbons or alicyclic hydrocarbons, 29 which are substan~ially free from aromatic hydrocarbons, are used. For example9 pentane, hexane, heptane9 octane9 cyclo-31 hexane, cyclopentane and the like can be used~
32 In the case of effecting treatment of the reduced 10794~5 1 solid with a Lewis b~se compound9 the reduced solid is sub-2 jected to a solvent extraction treatment in the presence of 3 the Lewis base compound. As the Lewis base compound there 4 can be used ethe~g thioethersD thiols~ organic phosphorus-conta~ning compoundsg organic nitrogen~containing compounds, 6 ketones and estersO Useful examples of the ether are dl-7 ethyl ether, diisopropyl etherg di~nbutyl ether~ diisobutyl 8 ether, diisoamyl ether9 di~2 ethylhe~y1 ether9 di~2ethyl-9 heptyl ether, allyl ethyl ether~ allyl butyl etherg diphenyl ether, annisole9 phenetole3 chloroanisoleg bromoanisole and ll dimethoxybenzeneO Useful examples of the thioether are di-l2 ethyl thioether~ di~n~propyl thioetherS dicyclohexyl thio-l3 ether, diphenyl thioether5 ditolyl thioetherg ethyl phenyl 14 thioether, propyl phenyl thioether and diallyl thioether.
Useful examples of the organic phosphorus-containlng com~
16 pound are tri-n~butylphosphine~ ~riphenylphosphineO tri~
7 ethyl phosphite and tributyl phosphiteO Useful examples 18 of the organic nitrogen~containing compound are diethylamine, 19 triethylamine, n~propylamineg di~n-propylamine9 tri n propylamine, aniline and dimethylanilineO In particularg 21 ethers, preferably having 4 to 16 carbon atoms are suitable.
22 The extraction method can be carried out by any of the 23 commonly used methodsg for example9 by stirring adequately 24 the reduced solid with an ether compo~nd in an inert medium to separate into a liquid phase and solid phase. As the 26 medium can also be used those solvents used in the reducing 27 reaction. The extraction is ordinarily carried out for 5 28 minutes or more9 preferably 30 minutes to 2 hours at a constant temperature selected from O to 80Co The quantity Of the Lewis base compound used is Ool to 205 mols, preferably 31 0.8 to 1.0 mol per l mol of titanium atomO
32 The solid treated ~i~h the above described Lewis ~ 13 ~
~0794~5 1 base is subsequently s~bjected to a treahment with a titanium 2 tetrachloride solution which should have a concentration of 3 5 % by volume or more. If the concentration is less than 4 5 % by volume, only an insufficient polymerization activity and insufficient stereoregularity of the polymerizatlon 6 product are obtainedg while if the concentration of titanium 7 tetrachloride is increased9 good results are obtained as to 8 the polymerization ac~ivity and stereoregularity of the 9 product but there is a tendency9 as described above9 that the particle size distribution is widened with ~he increase 11 of fine particlesD Therefore~ a titanium tetrachloride con-12 centration of 5 to 20 % by volume is preferredO As the 13 hydrocarbon solvent used in this case there can be given 14 pentane, hexane9 heptaneD octane9 cyclohexane~ cyclopentane and the:likeO The temperature d~ring treatment wi~ a titan-6 ium tetrachloride solution is within a range of ~30 to 7 +100C, preferably 40 to 80C~ This titanium tetrac~loride 18 treatment may be completed in abouf 30 minutes9 but should 9 ordinarily be continued over a period of l to 3 hours in order to obtain good results with a high reproducibility~
21 After the titanium tetrachloride treatment9 the resultant 22 catalyst component should be adequately washed with a fresh 23 solvent3 because the polymerization is unfavorably affected 24 if there remains a large amount of titanium tetrachlorideO
The thus obtained catalyst component is used for 26 the polymerization together with a co-catalyst componentO
27 As the co-catalystg organometallic compounds of Group I, II
28 and III elements of Periodic Table are usedO In particular, 29 organo aluminum compounds are preferably used and~ above all, triethylaluminum and diethylaluminum chloride are most 31 suitable for the polymerization of propyleneO Any polymeri-32 zation methods known in the art can be usedO For example3 ~ 14 -1079D~85 1 as an economi~a} method, a liquid m~nomer may be used as the 2 polymerization medium without using a polymerization diluent;
3 or a gaseous monomer may be used similarly.
4 Example 1 150 ml of purified heptane and 34.8 ml of titanium 6 tetrachloride were charged in a 500 ml flask equipped with a 7 stirrer and kept at 09C in a bath. 40 ml of diethylaluminum 8 chloride (equimolar to the titanium tetrachloride~ and 16.5 9 ml of ethylaluminum dichloride (0.5 mol/mol to the titanium tetrachloride) were dissolved in 160 ml of heptane and 11 added dropwise from a dropping funnel. The dropping was 12 continued for a period of time of about 3 hours and, during 13 the same time, the reaction system was kept at O~C. After 14 the dropwise addition, the reaction mixture was gradually heated for 1 hour to 65C with agitation. The reaction was 16 further continued at the same temperature for another 1 hour.
17 After the reaction, the reaction mixture was allowed to stand 18 to separate5 A solid formed and the supernatant liquid and 19 the solid were washed with 150 ml of purified heptane repeat-edly three timeC~ followed by drying at 65~C for 30 minutes 21 under reduced pressure. The reduced solid was red violet and 22 the X-ray diffraction spectrum thereof showed that the peak 23 at 2~ = 42,4~ ~beta-type crystal~ was considerably smaller 24 than the peak at 2e = 51.3 (delta-type crystal). The propor-tion of fine particles of 5 microns or less in the reduced 26 solid was 1 ~ or lessr 27 100 mg of the reduced solid obtained in this way 28 was charged in a 1000 ml autoclave to which 180 mg of diethyl-29 aluminum chloride as a co-catalyst, 600 ml of hydrogen (standard state) was a molecular weight regulator and 800 ml 31 of li~uid propylene were then addedO The polymerization was 32 carried out at 68~C for 1 hou~ and the unreacted propylene i - 15 -1079~5 was subjected to flashing to thus obtain 96 g of polypropy-~
2 lene powder. The polymer yield per l g of the reduced solid 3 (which will hereinafter be referred to as "catalyst efficien-4 cy E") was 960. The melt flow rate according to ASTM D
1238 (MFR) of this polymer was 6~0O The heptane-insoluble 6 content (HI) of the polymer was 70.7 % measured by extracting 7 with boiling heptane for 5 hours using a Soxhlet extractor.
8 20 g of the above described reduced solid was sus-9 pended in 200 ml of purified heptane and heat-treated at 150C for 2 hoursO Then the solid was separated and dried 11 at 65C for 30 minutes under reduced pressure, thus obtaining 12 a heat-treated solid, The proportion of fine particles of 5 13 microns or less in this heat-treated solid was 5 %. Using 14 this heat-treated solid, a polymerization test was carried o~t under the same conditions as described above, thus ob-16 taining a polymer yield (E~ per l g of the heat-treated solid 17 of 960 and MFR and HI of the formed polymer of 5Q and 93,7 %
18 respectivelyO
19 Comparative Example l The procedure of Eacample 1 was repeated except that 21 no ethylaluminum dichloride was used but diethylaluminum 22 chloride alone was used during the reduction, The color of 23 the reduced solid formed by the reduction was brown and X-ray 24 diffraction spectrum thereof showed that the peak at 2~ =
42.4 was larger than l~he peak at 2a = 51,3~ The proportion 26 of fine particles of 5 microns or less was l % or less.
27 Using this reduced solid, a polymerization test 28 was carried out under the same conditions as in Example l 29 and the following results were obtained:
E = 520, HI = 68~3 %, MFR = 6.5 31 When this reduced solid was heat-treated in an analogous 32 manner to Example l, the color was changed from brown to .
1 violet. The proportion of fine particles of 5 microns or 2 less in the heat-treated solid particles was 5 %. Using ~ this solid, a polymerization test was carried out in an 4 analogous manner to Example l and the following results were obtained:
6 E = 750, HI = 92.5 %, MFR = 5.0 7 Comparative Example 2 8 Using titanium trichloride of Grade AA manufactured 9 by Toyo Stauffer Co., a polymerization test was carried out under the same conditions as those of Example l and the 11 following results were obtained:
12 E = 850, HI = 93.3%, MFR = 4.0 13 The proportion of fine particles of 5 microns or less in 14 this titanium trichloride particles of Grade AA was 12 %.
Ex~mples 2 and 3 16 The procedure of Example l was repeated except 17 varying the ratio of ethylaluminum dichloride used as a 18 reducing agent to titanium tetrachloride. The quantity of 19 diethylaluminum chloride was the same as that of Example l.
The results of a polymerization test of the reduced solid 21 and heat-treated solid are show~ in Table l~
22 Table l 23 Example Nos 2 3 24 Et2AlCl/TiCl4 Molar Ratio le 0 1~ 0 25 EtAlCl2/TiCl4 Molar Ratio 0.3 l.2 26 Porportion Of Fine Particles Of 5 Microns 27 Or Less In Reduced Solid (%) l;
28 Polymerization Test Results Of Reduced 29 Solid E 722 840 30 HI 73.9 78.0 31 Proportion Of Fine Particles Of 5 Microns 32 Or Less In Heat-Treated Solid (%) 5 5 33 Polvmerization Test Results Of Heat- ..... .E 664 800 ~g Treated Solid HI 92.9 93.5 ~0794~5 1 Comparative Examples 3, 4 and 5 2 The procedure of Comparative Example 1 was repeated 3 except varying the ratio of diethylaluminum chloride used as 4 a reducing agent ~ titanium tetrachloride. The results are shown in Table 2. This table shows that the use of the re-~ 6 ducing agent in an excess amount to titanium tetrachloride is 7 not beneficial.
8 Table 2 9 Comparative Example No. 3 4 5 10 Et2AlCl/TiC14 Molar Ratio 0.51.5 2.0 11 EtAlC12/TiC14 Molar Ratio 0 0 0 12 Proportion Of Particles Of 5 Microns Or 13 Less In Reduced Solid (~) 1 1 2 14 Polymerization Test Results Of Reduced
15 Solid E 94 580 720
16 HI 77.465e4 62.1
17 Proportion Of Particle~ Of 5 Microns Or
18 Less In Heat-Treated Solid (%~ - 6 6
19 Polymerization Test Results Of Heat-
20 Treated Solid E - 460 580
21 HI - 90.5 90.1
22 Comparative Examples 6 and 7
23 The procedure of Example 1 was repeated except that
24 the proportion of diethylaluminum chloride~to titanium tetrachloride was adjusted to 1. The results are shown in 26 Table 3. It is apparent from this table that only poor 27 results are obtained where the quantity of diethylaluminum 28 chloride is small even if ethylaluminum dichloride is added 29 thereto~
Table 3 31 Comparative Example No. 6 7 32 Et2AlCl/TiC14 Molar Ratio 0 0.5 33 EtAlC12/TiCl4 Molar Ratio 1.0 0.5 34 Proportion of Particles Of 5 Microns Or 35 Less In Reduced Solid (~) 1 1 - ' 1 Polymerization Test Results Of Reduced 2 Solid E 150 550 3 HI 79.0 77.0 4 Proportion Of Particles Of 5 Microns Or 5 Less In Reduced Solid (~) 4 4 6 Polymerization Test Results Of Heat-7 Treated Solid E 160 -500 8 HI 90.2 86.3 9 Examples 4 and 5 The procedure of Example 1 was repeated except 11 that the quantity of diethylaluminum chloride used was in-12 creased to more than 1 mol to 1 mol of titanium tetrachloride.
13 The quantity of ethylaluminum dichloride was kept constant 14 (0~5 mol to titanium tetrachloride). The results are shown in Table 4.
17 Table 4 18 Example No. 4 5 19 Et2AlCl/TiC14 Molar Ratio 1.25 1.5 20 EtAlC12/TiC14 Molar Ratio 0.5 0~5 21 Proportion Of Particles Of 5 Microns Or 22 Less In Reduced Solid (%) 23 Polymerization Test Results Of Reduced 24 Solid E 848 841
Table 3 31 Comparative Example No. 6 7 32 Et2AlCl/TiC14 Molar Ratio 0 0.5 33 EtAlC12/TiCl4 Molar Ratio 1.0 0.5 34 Proportion of Particles Of 5 Microns Or 35 Less In Reduced Solid (~) 1 1 - ' 1 Polymerization Test Results Of Reduced 2 Solid E 150 550 3 HI 79.0 77.0 4 Proportion Of Particles Of 5 Microns Or 5 Less In Reduced Solid (~) 4 4 6 Polymerization Test Results Of Heat-7 Treated Solid E 160 -500 8 HI 90.2 86.3 9 Examples 4 and 5 The procedure of Example 1 was repeated except 11 that the quantity of diethylaluminum chloride used was in-12 creased to more than 1 mol to 1 mol of titanium tetrachloride.
13 The quantity of ethylaluminum dichloride was kept constant 14 (0~5 mol to titanium tetrachloride). The results are shown in Table 4.
17 Table 4 18 Example No. 4 5 19 Et2AlCl/TiC14 Molar Ratio 1.25 1.5 20 EtAlC12/TiC14 Molar Ratio 0.5 0~5 21 Proportion Of Particles Of 5 Microns Or 22 Less In Reduced Solid (%) 23 Polymerization Test Results Of Reduced 24 Solid E 848 841
25 HI 61,3 69.2
26 Proportion Of Particles Of 5 Microns or
27 Less In Heat-Treated Solid (%) 5 6
28 Polymerization Test Results Of Heat-
29 Treated Solid E 706 762 HI 92.4 90.7 31 Example 6 32 20 g of the reduced solid obtained in Example 1 33 were suspended in 200 ml of purified heptane, mixed with 20 34 ml of diisoamyl ether (equimolar to the titanium in the reduced solid) and reacted at 35C for 1 hour. After the 36 xeaction, the reaction product was washed with 150 ml ~- -- 19 --~079485 of purified heptane two times repeatedly. Then the product was suspended again in a heptane solution containing 40 % by volume of titanium tetra-chloride and reacted at 65C for 2 hours. After the reaction, the reaction product was washed with 150 ml of purified heptane three times repeatedly and drived at 65C for 30 minutes under reduced pressure.
- 100 mg of the catalyst solid obtained above was charged in a 1000 ml autoclave, into which 180 mg of diethylaluminum chloride as a co-catalyst, 600 ml of hydrogen (standard state) as a molecular weight regulator and 800 ml of liquid propylene were introduced. The polymerization was carried out at 68 C for 30 minutes and the unreacted propylene was removed by flashing, thus obtaining 196 g of polypropylene powder. The polymer yield (E) per 1 g of the catalyst solid was 1960, MFR was 4.5 and HI was 97.0%. When the particle size distribution of the catalyst solid particles used was measured, the proportion of fine particles of 5 microns or less was 12 %.
Comparative Example 8 The reduced solid obtained in Comparative Example 1 was subjected to a treatment with diisoamyl ether and then with a titanium tetrachloride solution under the same conditions as those in Example 6 to obtain a catalyst solid and a polymerization test was carried out to obtain the following re-sults:
E = 1410, HI = 97.4 %, MFR = 4.0When the particle size distribution of the catalyst solid particles used was measured, the proportion of fine particles of 5 microns or less reached 36 Z.
Comparative Example 9 Using titanium trichloride of Grade AA manufactured by Toyo Stauffer Co., a similar polymerization test to that :
1~79485 1 of Example 6 was carried out, obtaining the following 2 reSults:
3 E = 430, HI = 93.1 %, MFR = 4.7 4 Examples 7 ! 8,_9 and 10 The procedure of Example 6 was repeated except that ~ 6 the concentration of titanium tetrachloride was varied to 7 40, 15 and 5 % by volume during the treatment with titanium 8 tetrachloride. The results are shown in Table 5 with those 9 of Example 6.
Table 5 11 Example No. 6 7 8 9 10 12 Titanium Tetrachloride 13 vol. % 40 15 15 15 15 HI 97.0 97.8 97.6 97.2 95.4 16 MFR 4.5 5.1 6.0 5.8 4.6 17 Percent Of 5 Microns 18 Or Less 12 11 6 5 5 19 This table shows that even when using titanium tetrachloride in a low concentration, the polymerization ac-21 tivity and HI are not lowered and rather the proportion of 22 fine particles is decreased. Good results can thus be ob-23 tained according to the present invention.
24 Comparative Examples 10, 11, 12 and 13 The procedure of Comparative Example 8 was repeated 26 except that the concentration of titanium tetrachloride was 27 varied to 40, 15 and 5 % by volume during the treatment with 28 titanium tetrachloride. The results are shown in Table 6 29 with those of Comparative Examples 8 and 9.
--~ 1079485 Table 6 Comparative Example No. _ 1011 12 Grade AA
Titanium Tetrachloride Vol. % 40 40 15 5 HI 98.1 96.9 95.597.4 93.1 -MFR 4.0 4.8 6.1 5.0 4.7 Percent of 5 Microns Or Less 36 34 29 30 12 It is apparent from this table that, in the prior art process, i.e., wherein no ethylaluminum dichloride is added during the reduction, the activity is poor when the concentration of titanium tetrachloride is 15 % by volume or less.
Examples 11, 12, 13, 14 and 15 The procedure of Example 6 was repeated except that the proportion of ethylaluminum dichloride used for the reduction to titanium tetrachloride was varied. The molar ratio of diethylaluminum chloride to titanium tetra-chloride was kept at 1. The results are shown in Table 7.
Table 7 Example No. 11 12 13 14 15 Condition For Preparing Reduced Solid - Et2AlCl/TiC14 Molar Ration 1.0 1.0 1.0 1.0 1.0 EtAlC12/TiC14 Molar Ratio 0.3 0.5 0.75 1.0 1.2 Polymerization Test Results HI 97.2 97.9 98.0 97.4 97.5 e ~ MFR 4.9 6.3 2.5 5.2 4.9 Percent of 5 Microns Or Less 16 12 12 14 14 Comparative Examples 14, 15, 16, 17 and 18 The procedure of Comparative Example 8 was repeated except using .
.
~., .~.
~079485 diethylaluminum chloride only for the reduction and varying the proportion thereof to titanium tetrachloride. The results are shown in Table 8. This table shows that the use of diethyl aluminum chloride as the reducing agent is not effective even when used in excess Table 8 Comparative Example No. 14 15 16 17 18 Condition For Preparing Reduced Solid Et2AlCl/TiCl4 Molar Ratio 0.5 0.75 l.O 1.5 2.0 EtAlC12/TiC14 Molar Ratio O O O O O
Polymerization Test Results : E 90350 1390 1280 1400 HI 88.0 94.0 97.9 96.8 96.5 MFR 2.8 4.0 3.9 7.1 6.4 Percent of 5 Microns Or Less 4 8 35 29 39 Examples 16 and 17 The procedure of Example 6 was repeated except that the reduced solids prepared in Examples 4 and 5 were used as a reduced solid and subjected to the ether treatment and titanium tetrachloride treatment. The results are shown in Table 9.
Table 9 Example No. 16 17 Condition For Preparing Reduced Solid Et2AlCl/TiC14 Molar Ratio 1.25 1.5 EtAlC12/TiC14 Molar Ratio O.5 0.5 Polymerization Test Results HI 97.6 99.2 MFR 4.0 3.5 Percent of 5 Microns Or Less 10 ll :`
1 Comparative Examples 19, 20 and 21 2 The procedure of Example 6 was repeated except that 3 a reduced solid prepared by effecting the reduction while 4 adjusting the molar ratio of diethylaluminum chloride to titanium tetrachloride to 1.0 or less was used followed by - 6 the ether treatment and titanium tetrachloride treatment.
7 The results are shown in Table 10.
8 It is apparent from this table that only poor 9 results are obtained when the quantity of diethylaluminum chloride is small, even if there is ethylaluminum dichloride 11 present and the reduced solid is subjected to an ether 12 treatment and titanium tetrachloride treatment.
13 Table 10 14 ComParative Example No. 19 2021 Condition For Preparing Reduced Solid 16 Et2AlCl/TiC14 Molar Ratio 0 0.5 0.75 17 EtAlC12/TiC14 Molar Ratio 1.0 0.5 0.75 18 Polymerization Test Results 20 HI 93.9 82.3 92.4 21 MFR 4.8 3.9 4.7 22 Percent of 5 Microns or Less 6 8 9
- 100 mg of the catalyst solid obtained above was charged in a 1000 ml autoclave, into which 180 mg of diethylaluminum chloride as a co-catalyst, 600 ml of hydrogen (standard state) as a molecular weight regulator and 800 ml of liquid propylene were introduced. The polymerization was carried out at 68 C for 30 minutes and the unreacted propylene was removed by flashing, thus obtaining 196 g of polypropylene powder. The polymer yield (E) per 1 g of the catalyst solid was 1960, MFR was 4.5 and HI was 97.0%. When the particle size distribution of the catalyst solid particles used was measured, the proportion of fine particles of 5 microns or less was 12 %.
Comparative Example 8 The reduced solid obtained in Comparative Example 1 was subjected to a treatment with diisoamyl ether and then with a titanium tetrachloride solution under the same conditions as those in Example 6 to obtain a catalyst solid and a polymerization test was carried out to obtain the following re-sults:
E = 1410, HI = 97.4 %, MFR = 4.0When the particle size distribution of the catalyst solid particles used was measured, the proportion of fine particles of 5 microns or less reached 36 Z.
Comparative Example 9 Using titanium trichloride of Grade AA manufactured by Toyo Stauffer Co., a similar polymerization test to that :
1~79485 1 of Example 6 was carried out, obtaining the following 2 reSults:
3 E = 430, HI = 93.1 %, MFR = 4.7 4 Examples 7 ! 8,_9 and 10 The procedure of Example 6 was repeated except that ~ 6 the concentration of titanium tetrachloride was varied to 7 40, 15 and 5 % by volume during the treatment with titanium 8 tetrachloride. The results are shown in Table 5 with those 9 of Example 6.
Table 5 11 Example No. 6 7 8 9 10 12 Titanium Tetrachloride 13 vol. % 40 15 15 15 15 HI 97.0 97.8 97.6 97.2 95.4 16 MFR 4.5 5.1 6.0 5.8 4.6 17 Percent Of 5 Microns 18 Or Less 12 11 6 5 5 19 This table shows that even when using titanium tetrachloride in a low concentration, the polymerization ac-21 tivity and HI are not lowered and rather the proportion of 22 fine particles is decreased. Good results can thus be ob-23 tained according to the present invention.
24 Comparative Examples 10, 11, 12 and 13 The procedure of Comparative Example 8 was repeated 26 except that the concentration of titanium tetrachloride was 27 varied to 40, 15 and 5 % by volume during the treatment with 28 titanium tetrachloride. The results are shown in Table 6 29 with those of Comparative Examples 8 and 9.
--~ 1079485 Table 6 Comparative Example No. _ 1011 12 Grade AA
Titanium Tetrachloride Vol. % 40 40 15 5 HI 98.1 96.9 95.597.4 93.1 -MFR 4.0 4.8 6.1 5.0 4.7 Percent of 5 Microns Or Less 36 34 29 30 12 It is apparent from this table that, in the prior art process, i.e., wherein no ethylaluminum dichloride is added during the reduction, the activity is poor when the concentration of titanium tetrachloride is 15 % by volume or less.
Examples 11, 12, 13, 14 and 15 The procedure of Example 6 was repeated except that the proportion of ethylaluminum dichloride used for the reduction to titanium tetrachloride was varied. The molar ratio of diethylaluminum chloride to titanium tetra-chloride was kept at 1. The results are shown in Table 7.
Table 7 Example No. 11 12 13 14 15 Condition For Preparing Reduced Solid - Et2AlCl/TiC14 Molar Ration 1.0 1.0 1.0 1.0 1.0 EtAlC12/TiC14 Molar Ratio 0.3 0.5 0.75 1.0 1.2 Polymerization Test Results HI 97.2 97.9 98.0 97.4 97.5 e ~ MFR 4.9 6.3 2.5 5.2 4.9 Percent of 5 Microns Or Less 16 12 12 14 14 Comparative Examples 14, 15, 16, 17 and 18 The procedure of Comparative Example 8 was repeated except using .
.
~., .~.
~079485 diethylaluminum chloride only for the reduction and varying the proportion thereof to titanium tetrachloride. The results are shown in Table 8. This table shows that the use of diethyl aluminum chloride as the reducing agent is not effective even when used in excess Table 8 Comparative Example No. 14 15 16 17 18 Condition For Preparing Reduced Solid Et2AlCl/TiCl4 Molar Ratio 0.5 0.75 l.O 1.5 2.0 EtAlC12/TiC14 Molar Ratio O O O O O
Polymerization Test Results : E 90350 1390 1280 1400 HI 88.0 94.0 97.9 96.8 96.5 MFR 2.8 4.0 3.9 7.1 6.4 Percent of 5 Microns Or Less 4 8 35 29 39 Examples 16 and 17 The procedure of Example 6 was repeated except that the reduced solids prepared in Examples 4 and 5 were used as a reduced solid and subjected to the ether treatment and titanium tetrachloride treatment. The results are shown in Table 9.
Table 9 Example No. 16 17 Condition For Preparing Reduced Solid Et2AlCl/TiC14 Molar Ratio 1.25 1.5 EtAlC12/TiC14 Molar Ratio O.5 0.5 Polymerization Test Results HI 97.6 99.2 MFR 4.0 3.5 Percent of 5 Microns Or Less 10 ll :`
1 Comparative Examples 19, 20 and 21 2 The procedure of Example 6 was repeated except that 3 a reduced solid prepared by effecting the reduction while 4 adjusting the molar ratio of diethylaluminum chloride to titanium tetrachloride to 1.0 or less was used followed by - 6 the ether treatment and titanium tetrachloride treatment.
7 The results are shown in Table 10.
8 It is apparent from this table that only poor 9 results are obtained when the quantity of diethylaluminum chloride is small, even if there is ethylaluminum dichloride 11 present and the reduced solid is subjected to an ether 12 treatment and titanium tetrachloride treatment.
13 Table 10 14 ComParative Example No. 19 2021 Condition For Preparing Reduced Solid 16 Et2AlCl/TiC14 Molar Ratio 0 0.5 0.75 17 EtAlC12/TiC14 Molar Ratio 1.0 0.5 0.75 18 Polymerization Test Results 20 HI 93.9 82.3 92.4 21 MFR 4.8 3.9 4.7 22 Percent of 5 Microns or Less 6 8 9
Claims (19)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the production of a titanium trichloride catalyst component for the polymerization of alpha-olefins having a narrow particle size distri-bution, good polymerization activity and good stereo-regularity which comprises:
(a) contacting titanium tetrachloride in an inert diluent with a reducing agent comprising a mixture of a dialkyl aluminum halide and an alkyl aluminum dihalide wherein the dialkyl aluminum halide is used in a pro-portion which is at least equimolar to the titanium tetrachloride present and the alkyl aluminum dihalide is used in a proportion of about 0.3 to about 1.2 mols per mol of titanium tetrachloride present at a temperature of about -50°C to about +30°C;
(b) holding the resulting reaction mixture of (a) at said temperature for at least about 30 minutes thereby obtaining a reaction mixture comprising a violet reduced solid;
(c) gradually raising the temperature of the reaction mixture of (b) to a temperature in the range of about 20°C to about 120°C and holding said reaction mixture at said temperature for at least about 15 minutes;
and (d) recovering said violet reduced solid as said catalyst component.
(a) contacting titanium tetrachloride in an inert diluent with a reducing agent comprising a mixture of a dialkyl aluminum halide and an alkyl aluminum dihalide wherein the dialkyl aluminum halide is used in a pro-portion which is at least equimolar to the titanium tetrachloride present and the alkyl aluminum dihalide is used in a proportion of about 0.3 to about 1.2 mols per mol of titanium tetrachloride present at a temperature of about -50°C to about +30°C;
(b) holding the resulting reaction mixture of (a) at said temperature for at least about 30 minutes thereby obtaining a reaction mixture comprising a violet reduced solid;
(c) gradually raising the temperature of the reaction mixture of (b) to a temperature in the range of about 20°C to about 120°C and holding said reaction mixture at said temperature for at least about 15 minutes;
and (d) recovering said violet reduced solid as said catalyst component.
2. The process of claim 1 wherein the dialkyl aluminum halide is diethylaluminum chloride and the alkyl aluminum dihalide is ethylaluminum dichloride.
3. The process of claim 1 wherein said contacting step (a) is carried out by dropwise addition over about one hour or more and said reaction mixture of (a) is then held at said temperature of about -50 to about +30°C
for at least one hour.
for at least one hour.
4. The process of claim 1 wherein the reaction mixture temperature from (b) is gradually raised to about 60° to about 100°C.
5. The product of the process of claim 1 .
6. A process for the production of a titanium trichloride catalyst component for the polymerization of alpha-olefins having a narrow particle size distribu-tion, high polymerization activity and high stereo-regularity which comprises:
(a) contacting titanium tetrachloride in an inert diluent with a reducing agent comprising a mixture of a dialkyl aluminum halide and an alkyl aluminum dihalide wherein the dialkyl aluminum halide is used in a pro-portion which is at least equimolar to the titanium tetrachloride present and the alkyl aluminum dihalide is used in a proportion of about 0.3 to about 1.2 mols per mol of titanium tetrachloride present at a temperature of about -50°C to about +30°C;
(b) holding the resulting reaction mixture of (a) at said temperature for at least about 30 minutes thereby obtaining a reaction mixture comprising a violet reduced solid;
(c) gradually raising the temperature of the reaction mixture of (b) to a temperature in the range of about 20°C to about 120°C and holding said reaction mixture at said temperature for at least about 15 minutes;
(d) recovering said violet reduced solid; and (e) subjecting the violet reduced solid to a heat treatment by heating the violet reduced solid of (d) in an inert diluent at a temperature of about 120°C to about 180°C for at least 30 minutes, whereby the polymerization activity and stereoregularity are respectively increased without adversely affecting particle size distribution of the resulting catalyst component.
(a) contacting titanium tetrachloride in an inert diluent with a reducing agent comprising a mixture of a dialkyl aluminum halide and an alkyl aluminum dihalide wherein the dialkyl aluminum halide is used in a pro-portion which is at least equimolar to the titanium tetrachloride present and the alkyl aluminum dihalide is used in a proportion of about 0.3 to about 1.2 mols per mol of titanium tetrachloride present at a temperature of about -50°C to about +30°C;
(b) holding the resulting reaction mixture of (a) at said temperature for at least about 30 minutes thereby obtaining a reaction mixture comprising a violet reduced solid;
(c) gradually raising the temperature of the reaction mixture of (b) to a temperature in the range of about 20°C to about 120°C and holding said reaction mixture at said temperature for at least about 15 minutes;
(d) recovering said violet reduced solid; and (e) subjecting the violet reduced solid to a heat treatment by heating the violet reduced solid of (d) in an inert diluent at a temperature of about 120°C to about 180°C for at least 30 minutes, whereby the polymerization activity and stereoregularity are respectively increased without adversely affecting particle size distribution of the resulting catalyst component.
7. The process of claim 6 wherein the dialkyl aluminum halide is diethylaluminum chloride and the alkyl aluminum dihalide is ethylaluminum dichloride.
8. The process of claim 6 wherein said contacting step (a) is carried out by dropwise addition over about one hour or more and said reaction mixture of (a) is then held at said temperature of about -50 to about +30°C for at least one hour.
9. The process of claim 6 wherein the reaction mix-ture temperature from (b) is gradually raised to about 60° to about 100°C.
10. The product of the process of claim 6.
11. A process for the production of a titanium tri-chloride catalyst component for the polymerization of alpha-olefins having a narrow particle size distribution, high poly-merization activity and high stereoregularity which comprises:
(a) contacting titanium tetrachloride in an inert diluent with a reducing agent comprising a mixture of a dialkyl aluminum halide and an alkyl aluminum dihalide wherein the dialkyl aluminum halide is used in a proportion which is at least equimolar to the titanium tetrachloride present and the alkyl aluminum dihalide is used in a proportion of about 0.3 to about 1.2 mols per mol of titanium tetrachloride present at a temperature of about -50°C to about +30°C;
(b) holding the resulting reaction mixture of (a) at said temperature for at least about 30 minutes thereby ob-taining a reaction mixture comprising a violet reduced solid;
(c) gradually raising the temperature of the reaction mixture of (b) to a temperature in the range of about 20°C to about 120°C and holding said reaction mixture at said tempera-ture for at least about 15 minutes;
(d) recovering said violet reduced solid; and thereafter (e) solvent extracting the violet reduced solid in the presence of about 0.1 to about 2.5 mols of a Lewis base per 1 mol of titanium atom, at a temperature of about 0° to about 80°C for at least 5 minutes; and then (f) contacting the solvent extracted solid of (e) with a hydrocarbon solution of titanium tetrachloride having a concentration of at least 5 volume % titanium tetrachloride, at a temperature of about -30°C to about +100°C for about 1 to about 3 hours, whereby the resulting titanium trichloride catalyst component polymerization activity and stereoregularity are respectively increased without adversely affecting catalyst particle size distribution.
(a) contacting titanium tetrachloride in an inert diluent with a reducing agent comprising a mixture of a dialkyl aluminum halide and an alkyl aluminum dihalide wherein the dialkyl aluminum halide is used in a proportion which is at least equimolar to the titanium tetrachloride present and the alkyl aluminum dihalide is used in a proportion of about 0.3 to about 1.2 mols per mol of titanium tetrachloride present at a temperature of about -50°C to about +30°C;
(b) holding the resulting reaction mixture of (a) at said temperature for at least about 30 minutes thereby ob-taining a reaction mixture comprising a violet reduced solid;
(c) gradually raising the temperature of the reaction mixture of (b) to a temperature in the range of about 20°C to about 120°C and holding said reaction mixture at said tempera-ture for at least about 15 minutes;
(d) recovering said violet reduced solid; and thereafter (e) solvent extracting the violet reduced solid in the presence of about 0.1 to about 2.5 mols of a Lewis base per 1 mol of titanium atom, at a temperature of about 0° to about 80°C for at least 5 minutes; and then (f) contacting the solvent extracted solid of (e) with a hydrocarbon solution of titanium tetrachloride having a concentration of at least 5 volume % titanium tetrachloride, at a temperature of about -30°C to about +100°C for about 1 to about 3 hours, whereby the resulting titanium trichloride catalyst component polymerization activity and stereoregularity are respectively increased without adversely affecting catalyst particle size distribution.
12. The process of claim 11 wherein the dialkyl aluminum halide is diethylaluminum chloride and the alkyl aluminum dihalide is ethylaaluminum dichloride.
13. The process of claim 11 wherein said contacting step (a) is carried out by dropwise addition over about one hour or more and said reaction mixture of (a) is then held at said temperature of about -50 to about +30°C for at least one hour.
14. The process of claim 11 wherein the reaction mix-ture temperature from (b) is gradually raised to about 60° to about 100°C.
15. The process of claim 11 wherein the Lewis base is an ether having 4 to 16 carbon atoms.
16. The product of the process of claim 11.
17. A process for the polymerization of an alpha-ofe-fin which comprises adding an organo aluminum compound to the catalyst component prepared by the process of claim 1 and thereafter polymerizing the alpha-olefin in the presence of the catalyst component and organo aluminum compound.
18. A process for the polymerizaton of an alpha-olefin which comprises adding an organo aluminum compound to the catalyst component prepared by the process of claim 6 and thereafter polymerizing the alpha-olefin in the presence of the catalyst component and organo aluminum compound.
19. A process of the polymerization of an alpha-olefin which comprises adding an organo aluminum compound to the catalyst component prepared by the process of claim 11 and thereafter polymerizing the alpha-olefin in the presence of the catalyst component and organo aluminum compound.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14116574A JPS5168490A (en) | 1974-12-10 | 1974-12-10 | Arufua orefuin jugoyo shokubai seibun no seizoho |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1079485A true CA1079485A (en) | 1980-06-17 |
Family
ID=15285634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA241,208A Expired CA1079485A (en) | 1974-12-10 | 1975-12-08 | Titanium trichloride catalyst component |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPS5168490A (en) |
| BE (1) | BE836501A (en) |
| CA (1) | CA1079485A (en) |
| DE (1) | DE2555165A1 (en) |
| FR (1) | FR2294187A1 (en) |
| IT (1) | IT1050322B (en) |
Families Citing this family (2)
| 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 |
| NL185455C (en) * | 1976-09-08 | 1990-04-17 | Sumitomo Chemical Co | PROCESS FOR PREPARING A FIXED TITANIC TRICHLORIDE CATALYST AND PROCESS FOR PREPARING OLEGIN POLYMERS. |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE789227A (en) * | 1971-09-24 | 1973-03-26 | Hoechst Ag | ALPHA-OLEFINS POLYMERIZATION PROCESS |
| BE791728A (en) * | 1971-11-24 | 1973-05-22 | Shell Int Research | PROCESS FOR THE PREPARATION OF A FORMATION CONSTITUENT OF A CATALYST |
| JPS5130593A (en) * | 1974-09-09 | 1976-03-15 | Mitsubishi Chem Ind | KOTAISANENKACHITANSHOKUBAI NO SEIZOHO |
| JPS5130591A (en) * | 1974-09-10 | 1976-03-15 | Mitsubishi Chem Ind | Arufua orefuinjugoyoshokubai no seizohoho |
| JPS5132493A (en) * | 1974-09-13 | 1976-03-19 | Mitsubishi Chem Ind | Arufua orefuinjugoyoshokubai no seiho |
-
1974
- 1974-12-10 JP JP14116574A patent/JPS5168490A/en active Granted
-
1975
- 1975-12-08 CA CA241,208A patent/CA1079485A/en not_active Expired
- 1975-12-08 DE DE19752555165 patent/DE2555165A1/en not_active Withdrawn
- 1975-12-09 IT IT3011475A patent/IT1050322B/en active
- 1975-12-09 FR FR7537603A patent/FR2294187A1/en active Granted
- 1975-12-10 BE BE162631A patent/BE836501A/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| BE836501A (en) | 1976-06-10 |
| DE2555165A1 (en) | 1976-06-24 |
| FR2294187A1 (en) | 1976-07-09 |
| JPS5168490A (en) | 1976-06-14 |
| FR2294187B3 (en) | 1979-09-21 |
| IT1050322B (en) | 1981-03-10 |
| JPS5731562B2 (en) | 1982-07-06 |
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