JPH083255A - Method for producing propylene block copolymer - Google Patents

Abstract

PURPOSE:To stably and efficiently prepare a propylene block copolymer which has a high m.p., comprises a rubber-like propylene/alpha-olefin copolymer component having a high mol.wt. and possesses excellent rigidity and impact resistance. CONSTITUTION:In a first stage polymn., polymn. of either propylene or propylene and other alpha-olefin is carried out in the presence of a catalyst comprising a titanium-contg. solid catalyst component, an organoaluminum compd. component, and t-butylethyldimethoxysilane, and, subsequently, in a second-stage polymn, gas-phase copolymn. of propylene with an alpha-olefin other than propylene is carried out without deactivating the catalyst system.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a propylene block copolymer having high rigidity and excellent impact strength.

[0002]

2. Description of the Related Art Crystalline polypropylene is used in various molded products that require physical properties such as rigidity and heat distortion resistance. However, it has a drawback that it cannot be used in applications where rigidity, thermal deformation resistance, impact resistance, and especially properties at low temperatures are required at the same time. In order to improve the balance of the above-mentioned properties of crystalline polypropylene, propylene is homopolymerized or propylene and another α-olefin are copolymerized in the preceding stage to prepare a stereoregular (co) polymer of propylene, and then ) A method of producing a propylene block copolymer by subjecting propylene and another α-olefin to gas phase copolymerization in the latter stage in the presence of the polymer is known. The product obtained here is a homogenous mixture of the polymers or copolymers produced in each stage, but is generally called a propylene block copolymer.

As a propylene block copolymer, in addition to being excellent in the above-mentioned rigidity and low-temperature characteristics, it has a high melting point and the like, the ethylene composition is in an appropriate range, and propylene produced by post-stage polymerization and other It is necessary that the molecular weight of the copolymer with α-olefin is relatively large.
With respect to these points, various improved methods relating to polymerization catalysts and polymerization methods have been proposed, but in recent years, the demands on the physical properties of propylene block copolymers have become more stringent, and the copolymers having a better balance of physical properties have been proposed. Polymers are desired.

From the viewpoint of the polymerization process, the activity sustainability of the latter-stage polymerization catalyst is the most important requirement. Further, a major problem in the latter gas phase polymerization method is that the viscosity increases and the fluidity deteriorates, which causes clogging or scaling of the reactor or line, or the monomer concentration is low, and There has been a strong demand for improvement of these problems, since the productivity is remarkably reduced.

In stereoregular polymerization of propylene, the polymerization activity of what is usually called a supported catalyst is
Although it shows high activity in the early stage, it has poor activity persistence, and when producing a propylene block copolymer, the copolymerization activity in the latter stage becomes low, making it difficult to produce the copolymer in high yield. Met. The following means can be considered as a method of increasing the ratio of the copolymer in the latter stage.

(1) A method of shortening the polymerization time in the first stage to suppress the polymerization activity of the polymerization catalyst in the first stage and relatively increase the amount of the copolymer in the second stage. However, in this method, the catalyst efficiency as a whole is lowered and the catalyst residue in the copolymer is increased, which is a problem in terms of product quality.

(2) A method of relatively increasing the amount of copolymer in the latter stage by lowering the polymerization temperature in the former stage and suppressing deactivation of the polymerization catalyst. However, with this method,
Since the catalyst efficiency as a whole is lowered and the stereoregularity of the copolymer is lowered, the rigidity of the product is lowered and the amount of catalyst residue in the product is increased.

(3) A method of increasing the copolymerization amount in the latter stage by increasing the copolymerization temperature in the latter stage. However, with this method, although it is possible to increase the amount of the copolymer in the latter stage, the improvement rate of impact resistance is small because the molecular weight of the rubber component produced is low, and the copolymers are It has the drawback of sticking easily.

(4) A method of increasing the copolymerization amount in the latter stage by increasing the copolymerization pressure in the latter stage. However, in this method, there is a problem in that there are restrictions on the apparatus, and if the equipment is used to increase the pressure resistance, the equipment cost will increase, which in turn will lead to an increase in the cost of the product.

(5) A method of increasing the copolymerization time in the latter stage. However, in this method, since the polymerization rate in the latter stage is lower than the polymerization rate in the former stage, it is not desirable to prolong the copolymerization time because the productivity as a whole decreases.

(6) A method in which ethylene is used in a larger amount than propylene in the latter mixing ratio of ethylene and propylene. However, this method is not preferable because the production rate of the random copolymer is lowered, the ethylene homopolymer is easily produced, and the effect of improving the impact resistance of the propylene block copolymer is lowered.

(7) A method of adding a specific compound at the time of copolymerization in the latter stage. However, in this method, for example,
When an organoaluminum compound is added, lumps may be formed due to the adhesion of polymers in the reactor, which may cause a trouble in operation (JP-A-53-30686). Further, a method of adding aluminum alkoxide has been proposed, but there is a problem that the stereoregularity is remarkably lowered and the polymers adhere to each other.

A technique using alkyllithium or alkylmagnesium for the purpose of preventing the adhesion of polymers to each other has been disclosed, but the copolymerization activity is remarkably reduced (Japanese Patent Laid-Open Nos. 62-132912 and 62-62). -135509 bulletin,
JP-A-2-117905).

As a method for preventing the adhesion of polymers to each other and improving the copolymerization activity, a method has been proposed in which both titanium alkoxide and hydrocarbon are coexistingly added using a titanium trichloride catalyst system. (Kaisho No. 58-213012), it is clarified that, in the absence of this requirement, these effects are not exhibited at all.

As a method for improving the fluidity of the block copolymer, a method of adding a metal alkoxide (Japanese Patent Laid-Open No. 61-61160).
-69823), a method of adding a compound having a Si-O-C bond (JP-A-61-215613), a method of adding siloxanes (JP-A-63-146914), and a silicon compound. Method of addition (JP-A-3-292311, JP-A-4-29
No. 136010) has been proposed, but there are some problems such as reduced activity or reduced stereoregularity.

On the other hand, as a method of reducing the production of by-products and improving the processability of the block copolymer, a technique of adding a special electron donor has also been proposed (JP-A-56-151).
713, JP 60-59139, JP 6169821, JP 61-69822, JP 61-69823,
JP-A-63-43915). Further, JP-A-4-331219 proposes a method of supplying saturated hydrocarbon having 3 to 5 carbon atoms. However, there are disadvantages that the polymerization activity or the molecular weight of the produced polymer is lowered and the amount of the additive used is large, resulting in high cost.

[0017]

OBJECT OF THE INVENTION The object of the present invention is to improve the above-mentioned problems of the prior art and to provide a technology capable of stably producing a block copolymer having a good balance of physical properties with high activity. That is.

[0018]

DISCLOSURE OF THE INVENTION The present invention comprises the steps of: (A) a titanium-containing solid catalyst component; (B) an organoaluminum compound component; and (C) a catalyst containing t-butylethyldimethoxysilane. Polymerization of propylene or propylene with other α-olefin is carried out, and subsequently, gas phase copolymerization of propylene and α-olefin other than propylene is carried out at a later stage without deactivating the above catalyst system. And a method for producing a propylene block copolymer, characterized in that

Examples of the titanium-containing solid catalyst as the component (A) of the present invention include supported high activity catalysts.
Here, a catalyst solid component containing magnesium, titanium, a halogen element and an electron donor as essential components can be used. The method for producing the catalyst solid component is not particularly limited,
For example, JP-A-54-94590, JP-A-56-55405,
56-45909, 56-163102, 57-63310, 57-115408, 58-83006, 58-830
16, gazette 58-138707 gazette, gazette 59-149905 gazette,
60-23404, 60-32805, 61-18330, 61-55104, JP2-77413, 2-11
The method proposed in Japanese Patent No. 7905 can be adopted. As a typical production method, (1) a method in which a magnesium compound such as magnesium chloride, an electron donor, and a titanium halide compound such as TiCl ₄ are co-ground, (2) a magnesium compound and an electron donor are dissolved in a solvent. A method in which a titanium halide compound is added to this solution to precipitate a catalyst solid can be mentioned.

In the present invention, the catalyst solid components described in JP-A-60-152511, JP-A-61-31402 and JP-A-62-81405 are particularly preferable for achieving the effects of the present invention. According to these production methods, an aluminum halide is reacted with an organosilicon compound, and then a Grignard compound is reacted to precipitate a solid. As the aluminum halide that can be used in the above reaction, anhydrous aluminum halide is preferable, but it is difficult to use completely anhydrous aluminum halide due to hygroscopicity, and aluminum halide containing a trace amount of water should also be used. You can Specific examples of aluminum halides include aluminum trichloride, aluminum tribromide and aluminum triiodide, with aluminum trichloride being particularly preferred.

Specific examples of the organosilicon compound used in the above reaction include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, methyltriethoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltributoxysilane, Examples thereof include methoxysilane compounds and dimethoxysilane compounds such as dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, trimethylmonoethoxysilane, and trimethylmonobutoxysilane. Particularly, tetraethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane and dimethyldiethoxysilane are preferable.

The amount of the compound used in the reaction between the aluminum halide and the organosilicon compound is determined by the element ratio (Al / Si).
Is usually in the range of 0.4 to 1.5, preferably 0.7 to 1.3, and it is preferable to use an inert solvent such as hexane or toluene in the reaction. Reaction temperature is usually 10-100
℃, preferably 20 ~ 80 ℃, the reaction time is usually 0.2 ~
5 hours, preferably 0.5 to 3 hours.

Specific examples of the Grignard compound used in the above reaction include ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, octyl magnesium chloride, ethyl magnesium bromide, propyl magnesium bromide, butyl magnesium bromide, ethyl. Organic magnesium halides such as magnesium iodide may be mentioned. As the solvent of the Grignard compound, for example, diethyl ether,
Aliphatic ethers such as dibutyl ether, diisopropyl ether and diisoamyl ether, and aliphatic cyclic ethers such as tetrahydrofuran can be used.

The amount of the Grignard compound used is usually 0.5 to 3, preferably 1.5 to 2.3 in terms of the element ratio (Mg / Al) to the aluminum halide used in the preparation of the reaction product of the above-mentioned aluminum halide and organosilicon compound. It is a range. The reaction temperature is usually -50 to 100 ° C, preferably-
20 to 50 ° C, reaction time is usually 0.2 to 5 hours, preferably 0.
5 to 3 hours.

The white solid obtained in the reaction between the aluminum halide and the organosilicon compound and then the reaction with the Grignard compound is contact-treated with an electron donor and a titanium halide compound. Alternatively, the solid is contact-treated with an electron donor and then with a titanium halide compound. As the contact treatment, a conventionally well-known method can be adopted. For example, the above solid is dispersed in an inert solvent and the electron donor or / and the titanium halide compound is dissolved therein, or an electron donor or / and a liquid titanium halide compound is used without using an inert solvent. Disperse the solid in. In this case, the contact treatment between the solid and the electron donor or / and the titanium halide compound is stirred, and the temperature is usually
50 to 150 ℃, contact time is not particularly limited, but usually 0.2 to 5
Can be done in time. Further, this contact treatment can be performed multiple times.

Titanium halide compounds that can be used in the contact treatment include tetrachlorotitanium, tetrabromotitanium, trichloromonobutoxytitanium, tribromomonoethoxytitanium, trichloromonoisopropoxytitanium,
Examples thereof include dichlorodiethoxy titanium, dichlorodibutoxy titanium, monochlorotriethoxy titanium, monochlorotributoxy titanium and the like. Particularly, tetrachlorotitanium and trichloromonobutoxytitanium are preferable.

The electron donor used in the above contact treatment is preferably an aromatic ester, of which orthophthalic acid diester is particularly preferable. Specific examples of the diester include diethyl orthophthalate, diisobutyl orthophthalate, dipentyl orthophthalate, dihexyl orthophthalate, di-2-ethylhexyl orthophthalate, di-n-heptyl orthophthalate, and di-n-octyl orthophthalate. .

After the above-mentioned catalytic treatment, the treated solid is generally separated from the treated mixture and thoroughly washed with an inert solvent, and the obtained solid can be used as the catalyst solid component (A) of the present invention.

As the organoaluminum compound as the component (B) in the present invention, halogenoalkylaluminum, trialkylaluminum and the like can be used.

Specific examples of the halogenoalkyl aluminum include diethyl aluminum monochloride, dibutyl aluminum monochloride, dinormalpropyl aluminum monochloride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, butyl aluminum sesquibromide and the like. Can be mentioned.

Specific examples of the trialkyl aluminum include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum and the like.

Any of the above organoaluminum compounds can be used as a mixture. Further, polyaluminoxane obtained by the reaction of alkylaluminum and water can be used as well.

When a catalyst solid that essentially contains magnesium, titanium, a halogen element and an electron donor is used as the catalyst (A) component, trialkylaluminum is preferably used as the organoaluminum compound of the catalyst (B) component. The amount of trialkylaluminum used is such that the element ratio of aluminum to titanium (A in the catalyst solids that essentially contains magnesium, titanium, halogen elements and electron donors
l / Ti), preferably 20 to 1000, particularly preferably 150 to
500.

As the catalyst (C) component, t-butylethyldimethoxysilane is used.

The amount of t-butylethyldimethoxysilane used is 0.01 to 5 mol, especially 0.1 to 1 mol, per mol of the component (B).
It is preferably molar.

The first-stage polymerization may be either homopolymerization of propylene or copolymerization of propylene with another α-olefin. As the α-olefin, ethylene, butene-1, 3-methylbutene-1, 3-methylpentene-1, 4-methylpentene-1, hexene-1, 4-methylhexene-1, octene-1, styrene, 2 -Acyclic monoolefins such as methylstyrene, 3-methylstyrene, 4-methylstyrene, vinylcyclohexane, vinylcyclopentane, 2-vinylnaphthalene, 9-vinylanthracene, cyclopentene,
Cyclohexene, cyclic monoolefins such as norbornene, dicyclopentadiene, 5-ethylidene norbornene
Examples thereof include diolefins such as -2,4-vinylcyclohexene and 1,5-hexadiene.

The proportion of α-olefin other than propylene in the crystalline polymer obtained in the first step is preferably an amount that does not impair the characteristics of polypropylene, for example, 10% by weight or less. When the proportion of α-olefin other than propylene in the crystalline polymer exceeds 10% by weight, the amount of low crystalline polymer by-products increases.

If necessary, hydrogen may be added as a chain transfer agent in order to adjust the molecular weight of the produced polymer.

In the first stage, after producing a crystalline polymer by homopolymerization of propylene or copolymerization of propylene with other α-olefins, the catalyst system described above is not deactivated and subsequently the second Propylene and non-propylene α in stages
To produce a propylene block copolymer by vapor phase copolymerization with an olefin.

The ratio of the rubbery copolymer of propylene and the α-olefin other than propylene obtained in the second step is
The proportion of α-olefin other than propylene in the rubbery copolymer, which is usually 3 to 40% by weight, more preferably 5 to 30% by weight, based on the total amount of the block copolymer is preferably 10 to 40% by weight.

As the polymerization mode of the present invention, bulk polymerization in which a monomer in a liquid state is used as a solvent for polymerization is carried out in the first step, and vapor phase polymerization in which the monomer is brought into contact with a catalyst in a gaseous state is carried out in the second step. be able to.

The bulk polymerization is preferably carried out under conditions of temperature and pressure at which propylene or a mixed monomer of propylene and another α-olefin can be kept in a liquid state. The polymerization temperature is usually 30 to 90 ° C, preferably 50 to 80 ° C. The polymerization time is usually 5 minutes to 5 hours.

The gas phase polymerization is carried out under conditions of temperature and pressure at which a gas phase state can be maintained by introducing propylene or a mixed monomer of propylene and another α-olefin. α-
As the olefin, ethylene, butene-1,3-methylbutene-1,3-methylpentene-1,4-methylpentene-1, hexene-1,4-methylhexene-1, octene-1, styrene, 2-methyl Acyclic monoolefins such as styrene, 3-methylstyrene, 4-methylstyrene, vinylcyclohexane, vinylcyclopentane, 2-vinylnaphthalene, 9-vinylanthracene, cyclopentene, cyclohexene, norbornene and other cyclic monoolefins, dicyclopentadiene, Mention may be made of a diolefin such as 5-ethylidene norbornene-2,4-vinylcyclohexene or 1,5-hexadiene.

The copolymerization pressure is usually from atmospheric pressure to 20 Kg / cm ² ,
Preferably from atmospheric pressure to 10 Kg / cm ² , the polymerization temperature is usually 30 ~
The temperature is 95 ° C, preferably 40 to 70 ° C. Polymerization time is usually 30
Minutes to 10 hours, preferably 1 to 5 hours.

When a solid catalyst component (A) is a catalyst solid containing magnesium, titanium, a halogen element and an electron donor as an essential component, before the first stage polymerization,
It is also possible to pre-polymerize a limited amount of propylene using the solid catalyst component (A) in the presence of the organoaluminum component (B) and t-butylethyldimethoxysilane component (C). By using the prepolymerized solid or the solid washed after the prepolymerization for the main polymerization, the polymerization activity per solid catalyst and the stereoregularity of the polymer can be improved.

In the present invention, when the prepolymerized solid is used as the solid catalyst component in the main polymerization, the component (C) can be omitted in the main polymerization.

The prepolymerization in the present invention can be carried out by a gas phase method, a slurry method, a bulk method or the like. The solid obtained in the prepolymerization can be separated and then used in the main polymerization, or the main polymerization can be continuously carried out without separation.

The prepolymerization time is usually 0.1 to 10 hours,
It is preferable to continue the prepolymerization until 0.1 to 100 g of the prepolymer is produced per 1 g of the solid catalyst component. Solid catalyst component
If it is less than 0.1 g per 1 g, the main polymerization activity will be insufficient and the catalyst residue will be large, and the stereoregularity of polypropylene will be insufficient. If it exceeds 100 g, the crystallinity of polypropylene tends to decrease. The prepolymerization temperature is 0 to 100 ° C,
It is preferably carried out at 5 to 60 ° C in the presence of each catalyst component. 50 ° C
When the prepolymerization is carried out at a temperature as high as above, it is preferable to reduce the propylene concentration or shorten the polymerization time. Otherwise 0.1 to 10 per 1 g of solid catalyst component
It is difficult to control the production of 0 g of the prepolymer, and the crystallinity of the polypropylene obtained by the main polymerization is lowered.

The amount of the organoaluminum component used in the prepolymerization is usually 0.5 to 1000, preferably 1 to 500, in the Al / Ti element ratio with respect to the titanium atom of the solid catalyst component. The amount of silicate compound used is usually 0.01 to 60% Si / Al element ratio with respect to the aluminum atoms of the organoaluminum compound component.
1, preferably 0.1 to 0.5. In the preliminary polymerization, hydrogen can be allowed to coexist if necessary.

[0050]

According to the present invention, a propylene block copolymer having a high melting point, a rubber-like copolymer component of propylene and α-olefin having a high molecular weight, and having excellent rigidity and impact resistance. The coalesced product can be produced stably and efficiently.

[0051]

Embodiments of the present invention will be described below.

In the examples, the copolymer yield is the weight ratio of the polymer in the second stage in the total polymer (polymer yield in the second stage / total polymer yield × 100%).

The melting point of the produced copolymer was raised to 230 ° C. under a nitrogen stream using a Shimadzu thermal analyzer (DSC-50), then lowered to 40 ° C., and again raised to 230 ° C. 2 of the hour
The value of the nd peak was taken as the melting point.

The ethylene content in the produced copolymer is measured by
The procedure was as follows. Add the sample on the hot plate of the hot press.
After melting by heat, cooling under pressure, quenching in a water bath, about 30μ
Was formed into a film. This film is an infrared spectrophotometer
At 974cm ^-1And 720 cm^-1Peaks are measured and created in advance
The ethylene content was calculated based on the obtained calibration curve.

The intrinsic viscosity [η] of the rubber component was measured as follows. Weigh accurately 20 mg of sample, place in a 25 mL volumetric flask, then 20 mL of decalin containing 0.3% BHT.
Add. Dissolve the sample completely at 135 ° C, and then use a thermostat set at 135 ° C in a viscometer.
The intrinsic viscosity [η] of the rubber component was measured by using the viscosity formula by transferring 5 mL and measuring the transit time between designated marked lines.

Example 1 (1) Preparation of solid catalyst component (A) 15 mmol of anhydrous aluminum chloride was added to 50 mL of toluene, and 15 mmol of methyltriethoxysilane was further added dropwise thereto at 25 ° C. with stirring. The reaction was carried out at the same temperature for 1 hour. This reaction product was cooled to −5 ° C., 20 mL of a diisoamyl ether solution containing 30 mmol of butylmagnesium chloride was added dropwise to the reaction product over 30 minutes with stirring, and the temperature was maintained at the same temperature for 30 minutes, then to 25 ° C. The temperature was raised in 30 minutes. After reacting at the same temperature for 1 hour, the precipitated solid was filtered off, washed with toluene and heptane, dispersed in 30 mL of toluene, and 150 mL of titanium tetrachloride and di-n-heptyl phthalate were dispersed.
4.0 mmol and 4.0 mmol of di-n-butyl phthalate were added and reacted at 90 ° C. for 1 hour. Separate the solid at the same temperature, wash with toluene and heptane, then disperse the solid again in 30 mL of toluene, add 150 mL of titanium tetrachloride,
The catalyst solid was separated by contact for 1 hour at ℃, and washed thoroughly with toluene and heptane. The catalyst solid was dried under a nitrogen atmosphere at 30 ° C., and then the titanium content was measured to obtain a value of 2.7 wt%.

(2) Prepolymerization After weighing a 2 L stainless steel autoclave with a stirrer, 2 mL of an n-hexane solution of triethylaluminum in nitrogen was weighed.
3.3 mL (0.3 mmol) of a t-butylethyldimethoxysilane solution diluted with (1.8 mmol) and n-heptane, 7.0 kg / cm ^{2 of} hydrogen at a gauge pressure, and 900 mL of liquid propylene were charged in an autoclave, and the mixture was stirred at 10 The temperature was set to 10 ° C for a minute. Next prepared catalyst solid 8.0 mg (titanium content
2.7 wt%) was injected and propylene was prepolymerized at the same temperature for 10 minutes.

(3) Polymerization reaction in the first stage liquid propylene Immediately after the completion of prepolymerization, the autoclave was placed in another bath 60
The mixture was heated to 0 ° C., and bulk polymerization of propylene was carried out at the same temperature for 50 minutes while stirring. Then, the unreacted gas was discharged to the outside of the system, and the pressure of the autoclave was maintained at 0.20 Kg / cm ² with a gauge pressure, the weight was measured, and the yield of polypropylene was calculated from the empty weight difference of the autoclave. there were.

(4) Second-stage gas phase copolymerization reaction The temperature of the autoclave was maintained at 40 ° C. after the bulk polymerization in which the system was kept at a gauge pressure of 0.20 Kg / cm ² and the mixed gas of ethylene and propylene was mixed. Was continuously supplied to the autoclave at a volume ratio of 1: 2 (100 Ncc / min. And 200 Ncc / min. Respectively), and the copolymerization pressure was 2.0 Kg / cm as a gauge pressure.
Adjusted to ² . When carrying out the copolymerization reaction at the same temperature and the same pressure for 4 hours, the unreacted gas was discharged to the outside of the system so that the polymerization pressure was kept at 2.0 Kg / cm ² as a gauge pressure, and the copolymerization reaction was performed at 40 ° C for 4 hours. I went. Next, when the inside of the autoclave was observed by opening the lid, no adhesion of the polymer was observed on the wall or the stirring blade, and the fluidity of the polymer particles was also very good. The obtained copolymer was dried under reduced pressure at 60 ° C. for 20 hours, and the weight was measured. As a result, the yield was 286 g. Therefore, the amount of the polymer obtained in the second stage gas phase copolymerization reaction was 14 g, and the copolymer yield was 4.9 wt%.

(5) Preparation of rubber component 5.0 g of ethylene-propylene block copolymer was precisely weighed, transferred to a container containing 500 mL of p-xylene, and heated to dissolve the copolymer. Next, the solution was left to stand at room temperature for a whole day and night, and the released solid was separated by centrifugation, transferred to 1000 mL of acetone, and left standing for 1 hour while stirring at room temperature. The rubber-like precipitated solid was collected with a glass filter and dried under reduced pressure at 60 ° C. for 20 hours to obtain 0.20 g of a rubber component.

Tables 1 and 2 show the results of polymerization and the characteristics of the resulting copolymer.

Example 2 A propylene block copolymer was produced in the same manner as in Example 1 except that the hydrogenation amount was changed to 4.0 kg / cm ² .
Tables 1 and 2 show the polymerization results and the characteristics of the produced copolymer.

Example 3 A propylene block copolymer was produced in the same manner as in Example 1 except that the hydrogenation amount was changed to 1.0 kg / cm ² .
Tables 1 and 2 show the polymerization results and the characteristics of the produced copolymer.

Example 4 A propylene block copolymer was produced in the same manner as in Example 1 except that the copolymerization pressure was changed to 4.0 kg / cm ² · G. Tables 1 and 2 show the polymerization results and the characteristics of the produced copolymer.

Example 5 A propylene block copolymer was produced in exactly the same manner as in Example 1 except that the amount of t-butylethyldimethoxysilane used as the catalyst (C) component was increased to 0.6 mmol. Tables 1 and 2 show the polymerization results and the characteristics of the produced copolymer.

Example 6 A propylene block copolymer was produced in the same manner as in Example 1 except that the copolymerization temperature was raised to 50 ° C. Table 1
And Table 2 shows the polymerization results and the characteristics of the produced copolymer.

Comparative Example 1 A propylene block copolymer was produced in the same manner as in Example 1 except that t-butylethyldimethoxysilane as the component of the catalyst (C) was not used at all. In Table 3 and Table 4,
The results of the polymerization and the characteristics of the resulting copolymer are shown.

Comparative Example 2 A propylene block copolymer was produced in exactly the same manner as in Example 1 except that phenyltriethoxysilane was used instead of t-butylethyldimethoxysilane as the component of the catalyst (C). Tables 3 and 4 show the polymerization results and the characteristics of the produced copolymer.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

[Table 4]

[Brief description of drawings]

FIG. 1 is a flow chart showing a preparation process and a polymerization process of a catalyst of the present invention.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Zenpei Hosoyama 8-1 Goi Minamikaigan, Ichihara City, Chiba Ube Industries Ltd. Chiba Petrochemical Factory

Claims (1)

[Claims] 1. A solid catalyst component containing titanium (A), and (B)
In the presence of a catalyst containing an organoaluminum compound component and (C) t-butylethyldimethoxysilane, propylene or propylene and another α-olefin are polymerized in the preceding step, and then the above catalyst system is deactivated. A method for producing a propylene block copolymer, characterized in that the vapor phase copolymerization of propylene and an α-olefin other than propylene is carried out at a later stage without being carried out.