Note: Descriptions are shown in the official language in which they were submitted.
10794~
1 FIELD OF THE INVENTION
__
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.
11 DESCRIPTION OF THE PRIOR ART
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
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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.
18 SUMMARY OF THE INVENTION
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.
:
.~ .
0 79 48 5
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.
19 PREFERRED EMBODIMENTS
; 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 -
~'
107948S
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-
.
?
- 1079485
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
-- 7 --
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)
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~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
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~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
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~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
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
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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
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.
1079485
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
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~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
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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
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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
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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
14 E 1960 1620 1990 1650 1360
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.
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Table 6
Comparative Example No. _ 1011 12 Grade AA
Titanium Tetrachloride
Vol. % 40 40 15 5
E 1410 1210 1160 950 430
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
E 1510 1840 1620 1720 1680
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
.
.
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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
E 1980 1927
HI 97.6 99.2
MFR 4.0 3.5
Percent of 5 Microns Or Less 10 ll
:`
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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
19 E 520 210 510
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
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