JPH06104702B2 - Method for producing granular thermoplastic elastomer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a granular thermoplastic elastomer. More specifically, it relates to a novel method for producing a granular olefinic thermoplastic elastomer. The thermoplastic elastomer contains a soft segment showing a rubber-like property in the polymer and a hard segment which is regarded as a pseudo-crosslinking point, and behaves like a crosslinked rubber at a use temperature, and a thermoplastic resin at a processing temperature. Shows similar behavior.

Among various thermoplastic elastomers, olefin-based thermoplastic elastomers are particularly excellent in weather resistance and have appropriate heat resistance, and are therefore mainly used as resin modifiers in the fields of automobiles, home appliances and the like.

<Prior Art> Conventionally, a method for producing an olefin-based thermoplastic elastomer is produced by separately producing polypropylene or another olefin resin and an olefin-based copolymer rubber such as ethylene-propylene rubber in advance, and blending these. Has been done. However, in such a method, an olefin-based copolymer rubber is generally disadvantageous in cost because it is produced by a solution polymerization method, and it is necessary to add strong kneading to a blend with an olefin resin. This is a well-known fact because it requires a lot of energy and is disadvantageous in terms of manufacturing cost.

On the other hand, a method for directly producing the above-mentioned thermoplastic elastomer by a slurry two-step polymerization method under specific conditions is disclosed in JP-A-55-80.
No. 418 or JP-A No. 57-61012, and the like. However, even in such a method, the random copolymer of ethylene and propylene dissolves in a large amount in a solvent, so that the viscosity of the system increases, and it becomes difficult to remove the heat of polymerization,
There has been a problem that the adhesion of polymer particles remarkably increases and stable production becomes difficult. Random copolymerization of ethylene and propylene at 80 ℃
It is also proposed to carry out at the following extremely low temperature,
There is a problem in that the catalytic activity is lowered, and a large refrigerating facility is required to remove the heat of polymerization, which is economically disadvantageous.

Further, JP-A-59-105008 proposes a method for producing a thermoplastic elastomer by gas-phase two-step polymerization. In the invention, the use of an inorganic oxide such as silica gel as the carrier for the solid catalyst component is intended to reduce the adhesive force of the polymer particles, but the improvement effect is still unsatisfactory.

<Problems to be Solved by the Invention> Under the present circumstances, the problems to be solved by the present invention, that is, the object of the present invention is to separately produce polypropylene and an olefin-based copolymer rubber such as ethylene-propylene rubber in advance separately. , A conventional technique of blending these, or a method for producing a thermoplastic elastomer by a slurry two-step polymerization method at a low temperature, and a thermoplastic elastomer by a gas-phase two-step polymerization method using a catalyst with an inorganic oxide as a carrier. It is intended to provide a method for improving the production technique and efficiently producing a granular olefinic thermoplastic elastomer having excellent performance.

A polymer containing a large amount of a low crystalline polymer such as ethylene-propylene rubber generally has remarkably large adherence of polymer particles, and it is difficult to perform stable gas phase polymerization.

That is, as the gas phase polymerization reactor of α-olefin, a stirring and mixing tank reactor, a fluidized bed reactor, a fluidized bed reactor with a stirrer, etc. have been proposed, but the adhesive force of polymer particles increases. Then, in the reactor for stirring, extremely large power is required to achieve a constant stirring rotation number, which causes great difficulty in designing the equipment. Further, in such a situation, it becomes difficult to achieve uniform mixing, so that the high temperature region is localized, a part of the polymer is agglomerated, and the agglomerate causes a stirrer and a thermometer inside the reactor. It is difficult to remove the polymer particles from the reactor by using pipes.

On the other hand, the slugging phenomenon is likely to occur in the reactor in which the unreacted monomer is polymerized in a fluidized state, and the amount of scattered polymer particles to the gas circulation line is significantly increased.
Adhesion to the line and blockage occur.

Further, under such circumstances, uniform mixing is difficult, and a problem arises that a part of the polymer is agglomerated.

Further, when the adhesive force of the polymer particles is large, clogging of the pipe for transferring the particles easily occurs. In addition, there is a problem that bridging occurs in the lower part of the cyclone or in the hopper, which makes it difficult to stably withdraw.

Therefore, although the gas phase polymerization method has an advantage that a liquid medium that dissolves the low crystalline polymer is not used, it is extremely difficult to produce a polymer containing a large amount of the low crystalline polymer in reality. It was.

In a further improved gas-phase polymerization method, the catalyst system used has a high degree of stereoregularity and polymerization because it does not substantially remove the catalyst residue and removes the physically detrimental atactic polypropylene. It is necessary to use those with improved activity.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have efficiently obtained a granular olefinic thermoplastic elastomer having excellent performance by combining a specific catalyst system and a gas phase polymerization method. It was found that the present invention has been achieved.

<Means for Solving Problems> In the present invention, (A) a catalyst component composed of at least titanium, magnesium, chlorine and an ester compound having an average particle size of 5 to 1,000 is used.
Pore volume is 0.1c at μm and pore radius 100-5,000Å
Using a catalyst system comprising a solid catalyst component impregnated in an organic porous polymer carrier of c / g or more, (B) an organoaluminum compound and (C) an electron donating compound,
After the isotactic polypropylene is obtained by polymerization in liquefied propylene and / or in the gas phase in the step, a random copolymer of ethylene and α-olefin is formed in the step in the gas phase in the second step. The ethylene content of the copolymer is 15 to 90 mol%, the intrinsic viscosity at 135 ° C of tetralin is 0.5 to 15, and the copolymer produced in the step is 60 to 97% by weight based on the total polymerization amount. The present invention relates to a method for producing a granular thermoplastic elastomer, which is obtained by polymerizing the above.

Hereinafter, the present invention will be described in detail.

(A) Solid catalyst component The solid catalyst component (A) used in the present invention is a catalyst component composed of at least titanium, magnesium, chlorine and an ester compound, having an average particle size of 5 to 1,000 μm and a pore radius of 100.
It is impregnated with an organic porous polymer carrier having a pore volume of 0.1 cc / g or more at ˜5,000 liters.

The performance required for the catalyst of the present invention is that it has high activity and stereoregularity when a polymer mainly made of polypropylene is produced in the first step, and that it is a random mixture of ethylene and α-olefin in the second step. Examples thereof include producing a copolymer rubber having sufficient activity in copolymerization and good physical properties, and forming polymer particles having good particle properties.

According to the study by the present inventors, the amount of the total polymer produced is 5 × 10 ⁴ g or more, preferably 7.5 × 10 ⁴ or more, and particularly preferably 10 × 10 ⁴ g or more per 1 g of titanium atom in the solid catalyst component. When a solid catalyst component having high catalytic activity is used, it is advantageous because a thermoplastic elastomer can be produced without substantially deashing the catalyst residue.

Further, when homopolymerization of propylene is carried out, the stereoregularity of the obtained polypropylene is such that the 20 ° C xylene-soluble part (atactic polypropylene production amount) contained in the polypropylene is 10% by weight or less, preferably 7%. It is preferable from the viewpoint of the physical properties of the thermoplastic elastomer to use a catalyst system of not more than 5% by weight, particularly preferably not more than 5% by weight.

Further, the average particle size of the solid catalyst component is an important factor for producing an ethylene copolymer having good particle properties. That is, the average particle size of the solid catalyst component is 5 to 1,000 μm, preferably 10 to 600 μm, and particularly preferably 15 to 5400 μm.

When the average particle size is smaller than 5 μm, the adhesive force of the polymer particles increases, and in the fluidized bed type gas phase reactor,
Problems such as scattering of catalyst and polymer particles occur. On the other hand, when the average particle size is larger than 1,000 μm, it becomes difficult to obtain a stable fluidized state in the fluidized bed type gas phase reactor because the minimum fluidization rate is remarkably increased, and the polymer particles are agglomerated. Problem occurs.

The fixed catalyst component will be described more specifically.

Examples of the organic porous polymer carrier used as the component (A) of the present invention include polystyrene-based, polyacrylic acid ester-based, polymethacrylic acid ester-based, polyacrylonitrile-based, polyvinyl chloride-based, and polyolefin-based porous materials. Examples thereof include polymer beads. Specifically, polystyrene, styrene-divinylbenzene copolymer, styrene-N, N'-alkylenedimethacrylamide copolymer, styrene-ethylene glycol dimethacrylate, polymethyl acrylate, ethyl polyacrylate, methyl acrylate- Divinylbenzene copolymer, ethyl acrylate-
Divinylbenzene copolymer, polymethylmethacrylate,
Methyl methacrylate-divinylbenzene copolymer, polyethylene glycol methyl dimethacrylate, polyacrylonitrile, acrylonitrile-divinylbenzene copolymer, polyvinyl chloride, polyvinylpyrrolidine, polyvinylpyridine, ethylvinylbenzene-divinylbenzene copolymer, polyethylene, Examples thereof include ethylene-methyl acrylate copolymer and polypropylene.

Of these organic porous polymer carriers, preferably polystyrene-based, polyvinyl chloride-based, polyolefin-based,
Polyacrylonitrile-based porous polymer beads are used, more preferably styrene-divinylbenzene copolymer and polyvinyl chloride are used, and particularly preferably styrene-divinylbenzene copolymer is used.

The average particle size of the organic porous polymer carrier is 5 to 1,000 μm,
The thickness is preferably 10 to 600 μm, particularly preferably 15 to 500 μm. And the pore volume at a pore radius of 100 to 5,000Å
0.1 cc / g or more, preferably 0.2 cc / g or more, particularly preferably
0.25cc / g or more. When the pore volume of the organic porous polymer carrier is small, the catalyst component cannot be effectively impregnated. Moreover, the pore volume of the organic porous polymer carrier is 0.1 cc / g.
Even if it is above, unless it exists in the pore radius of 100 to 5,000Å, the catalyst component cannot be effectively impregnated.

Next, a catalyst component containing at least titanium, a magnesium ester compound, and chlorine to be contained in the organic porous polymer carrier will be specifically described.

In the catalyst component of the present invention, the atomic ratio of titanium / magnesium is 0.01 to 0.8, preferably 0.02 to 0.2. The chlorine / magnesium atomic ratio is 1.8 to 10, preferably 2.0.
~ 5.0.

As a method for producing such a catalyst component, for example, Japanese Patent Publication Sho
35-495, JP-A-46-4393, JP-B-46-31330, JP-A-47-42283, JP-A-49-86483, JP-B-57-2436
No. 1, Japanese Patent Application No. 60-139951, Japanese Patent Publication No. 39-12105, Japanese Patent Publication No.
43-13050, JP-B-46-34092, JP-B-46-34098
The methods disclosed in JP-B No. 47-41676, JP-B No. 55-23561 and the like can be mentioned.

Next, as a method of impregnating the organic porous polymer carrier with the catalyst component, a mechanical method such as pulverization or a chemical method in a slurry state is used, but the latter method is preferable from the viewpoint of particle properties.

Specific examples of such a method include, for example, JP-A-52-42585.
JP-A-54-148093, JP-A-56-47407, JP-A-5
The method of impregnating a porous carrier such as silica gel with a catalyst component disclosed in JP-A No. 9-230006, JP-A No. 61-37803, and Japanese Patent Application No. 61-228963 can be applied.

Examples of these methods include (1) a method in which a porous carrier is treated with an organomagnesium compound such as a Grignard reagent and then TiCl ₄ or the like, and (2) a porous carrier is treated with an organomagnesium compound such as a Grignard reagent. And then reacting with a halogenating agent and / or alcohols and treating with a titanium compound such as TiCl ₄ , (3) Dissolving the magnesium halide compound and / or alkoxy magnesium compound with various donors such as alcohols and ethers And then complexing with TiCl ₄ etc. and impregnating it into a porous carrier, (4) After dissolving the magnesium halide compound and / or the alkoxy magnesium compound with various donors such as alcohols and ethers, Impregnate a porous carrier,
Further, a method of treating with a titanium compound such as TiCl ₄ (5) In the presence of a porous carrier, the alkoxytitanium compound is reduced with an organomagnesium compound such as a Grühl reagent, and then treated with a mixture of an ether compound and titanium tetrachloride. A method such as the method can be illustrated. Of these methods, the method exemplified in (5) is preferable, and more preferably, in the coexistence of an organosilicon compound having a Si—O bond and an organic porous polymer carrier, an alkoxytitanium compound is used as an organomagnesium compound such as a Grignard reagent. It is possible to use a method in which the solid product obtained by reduction with is treated with a mixture of an ether compound and titanium tetrachloride.

The amount of the catalyst component impregnated in the organic porous polymer carrier is 1 to 70% by weight, preferably 3 to 60% by weight, particularly preferably 5 to 55% by weight, as the content in the solid catalyst component. If the amount of the catalyst component impregnated in the organic porous polymer carrier is too large, the polymer particle properties will deteriorate. On the contrary, if the amount is too small, the activity per solid catalyst decreases.

The titanium compound used in the synthesis of the catalyst component used in the present invention has the general formula Ti (OR ¹ ) _a X _b (R ¹ has ¹ to 20 carbon atoms.
Hydrocarbon group, X is a halogen atom, a and b are 0 ≦ a ≦
4, a number represented by 0 ≦ b ≦ 4 and a + b = 3 or 4. ) Is represented. Specifically, titanium trichloride, ethoxy titanium dichloride, butoxy titanium dichloride, titanium tetrachloride, ethoxy titanium trochloride, butoxy titanium trichloride, phenoxy titanium trichloride,
Dibutoxy titanium dichloride, diphenoxy titanium dichloride, tributoxy titanium chloride, tetraethoxy titanium, tetrabutoxy titanium, tetraphenoxy titanium and the like can be preferably used.

Next, the following compounds are used as the magnesium compound.

Examples of the compound having a reducing ability having a magnesium-carbon bond or a magnesium-hydrogen bond include, for example, diethyl magnesium, dibutyl magnesium, dihexyl magnesium, ethyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride,
Butyl ethoxy magnesium, butyl magnesium hydride and the like are preferably used. These magnesium compounds may be used in the form of a complex compound with an organoaluminum compound. On the other hand, as the magnesium compound having no reducing ability, magnesium dichloride, magnesium dihalide such as magnesium dibromide, methoxy magnesium chloride, ethoxy magnesium chloride, butoxy magnesium chloride, phenoxy magnesium chloride, diethoxy magnesium, dibutoxy magnesium, diphenoxy. Alkoxy magnesium compounds such as magnesium and magnesium carboxylates such as magnesium laurate and magnesium stearate are preferably used.

These magnesium compounds having no reducing ability may be those which are synthesized by a known method from magnesium compounds having reducing ability in advance or at the time of preparing the solid catalyst.

The ester compound used in the present invention is a mono- or polyvalent carboxylic acid ester, and an aliphatic carboxylic acid ester, an olefin carboxylic acid ester, an alicyclic carboxylic acid ester, or an aromatic carboxylic acid ester is used. . Specific examples include methyl acetate, ethyl acetate, phenyl acetate, methyl propionate, ethyl propionate, ethyl butyrate, ethyl valerate, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl benzoate, butyl benzoate, toluyl. Methyl acid, ethyl toluate, ethyl anisate, diethyl succinate, dibutyl succinate, diethyl malonate, dibutyl malonate,
Dimethyl maleate, dibutyl maleate, diethyl itaconate, dibutyl itaconate, monoethyl phthalate,
Dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate,
Examples thereof include di-n-heptyl phthalate, di-n-octyl phthalate, and diphenyl phthalate.

Among these ester compounds, methacrylic acid ester,
Olefin carboxylic acid esters such as maleic acid esters and phthalic acid esters are preferred, and phthalic acid diesters are particularly preferred.

(B) Organoaluminum compound In the present invention, the organoaluminum compound (B) used in combination with the above-mentioned solid catalyst component (A) has at least one Al-carbon bond in the molecule.
A typical one is shown below by a general formula.

R ² _c AlY _3-c R ³ R ⁴ Al-O-AlR ⁵ R ⁶ Here, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are hydrocarbon groups having 1 to 8 carbon atoms, and Y is halogen. , Hydrogen or an alkoxy group. C
Is a number represented by 2 ≦ C ≦ 3.

Specific examples of the organic aluminum compound, triethyl aluminum, triisobutyl aluminum, trialkyl aluminum such as trihexyl aluminum, diethyl aluminum halide, dialkyl aluminum halide such as diisobutyl aluminum halide, a mixture of trialkyl aluminum and dialkyl aluminum halide, tetraethyl di Examples thereof include alkylalumoxane such as alumoxane and tetrabutyl dialumoxane. Of these organoaluminum compounds, trialkylaluminums, mixtures of trialkylaluminums and dialkylaluminum halides, alkylalumoxanes are preferred, especially triethylaluminum, triisobutylaluminum, mixtures of triethylaluminum, diethylaluminum and diethylaluminum chloride and tetraethyldiamine. Alumoxane is preferred.

The amount of the organoaluminum compound used can be selected within a wide range such as 1 to 1,000 mol per 1 mol of titanium atom in the solid catalyst, but the range of 5 to 600 mol is particularly preferable.

(C) Electron-donating compound The electron-donating compound used in the polymerization in the present invention is a Si-OR ⁷ bond (R ⁷ is a hydrocarbon group having 1 to 20 carbon atoms) or Si-N-C. It is selected from organic silicon compounds having a bond, aromatic carboxylic acid ester compounds and sterically hindered amines.

As the organosilicon compound, a compound represented by the general formula R ⁸ _d Si (OR ⁷ ) _4-d
(R ⁷ and R ⁸ are hydrocarbon groups having 1 to 20 carbon atoms, d is 0 ≦
Represents a number d ≦ 8. An alkoxysilane compound represented by the formula (4) is preferably used.

As the aromatic carboxylic acid ester compound, methyl benzoate, ethyl benzoate, n-propyl benzoate, isopropyl benzoate, n-butyl benzoate, phenyl benzoate, methyl toluate, ethyl toluate, methyl anisate, Ethyl anisate, monoethyl phthalate, dimethyl phthalate, methyl ethyl phthalate, diethyl phthalate, di-n-propyl phthalate, diisopropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, Examples thereof include di-n-octyl phthalate and diphenyl phthalate.

Examples of the sterically hindered amines include 2,6-substituted piperidines, 2,5-substituted pyrrolidines, and substituted methylenediamine compounds such as N, N, N ′, N′-tetramethylmethylenediamine. it can.

Of these electron-donating compounds, the general formula R ⁸ _d Si (O
The alkoxysilane compounds represented by R ⁷ ) _4-d give favorable results.

Specific examples of the alkoxysilane compound include tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, phenylmethyldimethoxysilane, tetraethoxysilane, methyltriethoxysilane, and ethyltriethoxy. Examples thereof include silane, vinyltriethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, butyltriethoxysilane, tetrabutoxysilane, vinyltributoxysilane and diethyldiethoxysilane.

The amount of the electron-donating compound used is 0.01 mol per 1 mol of aluminum atom of the organoaluminum compound which is the component (B).
-5 mol, preferably 0.03-3 mol, particularly preferably 0.03 mol.
It is from 05 to 1.0 mol.

(D) Polymerization Method The present invention proposes a method for producing a granular thermoplastic elastomer, which comprises substantially two steps using the above catalyst system.

The first step of the polymerization process of the present invention is carried out in liquefied propylene and / or in the gas phase in the presence of the above catalyst system. That is, the effect of the present invention is achieved by any of the method of carrying out the polymerization in liquefied propylene, the method of carrying out the polymerization in liquefied propylene and then the method of carrying out the polymerization in the gas phase, or the method of carrying out the polymerization in the gas phase. be able to.

More specific embodiments of the polymerization in the first step are shown below.

For the polymerization, propylene can be polymerized alone,
It is possible to perform copolymerization by adding propylene and ethylene as a comonomer or an α-olefin having 4 to 6 carbon atoms. In this case, the comonomer content in the polymer formed in the step is preferably 6 mol% or less, and most preferably 4 mol% or less.

When polymerizing in liquefied propylene, it is preferable to carry out in a temperature range of 40 ° C to 90 ° C and a pressure range of 17 to 50 kg / cm ² , while when polymerizing in a gas phase, the polymer melts. Temperature below, preferably in the temperature range of 40 ℃ ~ 100 ℃, normal pressure ~ 4
It is preferable to carry out under conditions where the monomer does not liquefy in the polymerization tank within a pressure range of 0 kg / cm ² . Further, in this step, it is preferable to add a molecular weight modifier such as hydrogen and polymerize for the purpose of improving the melt fluidity of the final product.

The second polymerization step is carried out subsequent to the first polymerization step. That is, random copolymerization of ethylene and α-olefin is performed in the gas phase. Examples of the α-olefin copolymerized with ethylene include propylene, butene-1, pentene-
1, hexene-1, 4-methylpentene-1, 3-methylbutene-1 and the like can be mentioned. Propylene and butene-1 are particularly preferred.

In the copolymerization of the present invention, ethylene, α-olefin and polyene can be copolymerized. Specific examples of such polyene include butadiene, dicyclopentadiene, 1,4-hexadiene, 1,8,7-octatriene, vinylcyclohexane, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene and the like. Can be mentioned. Of these, non-conjugated dienes are particularly preferable.

Due to the physical properties of the thermoplastic elastomer, the ethylene content in the copolymer of ethylene and α-olefin is 15 to 90 mol%, preferably 20 to 85 mol%. If the ethylene content of the resulting copolymer exceeds the above range, rubbery properties are impaired, which is not preferable. Further, even when the amount is small, the low temperature characteristics and the rubber properties are impaired, which is not preferable.

Further, in the present invention, the step can be carried out in two or more steps by changing the ethylene concentration. The polymerization conditions are not higher than the temperature at which the polymer melts, preferably 20 to 85 ° C, particularly preferably 40.
It is preferable to carry out the reaction in a temperature range of ˜75 ° C. and a pressure range of normal pressure˜40 kg / cm ² under conditions where the monomer does not liquefy in the polymerization tank. Further, in this step, for the purpose of adjusting the melt fluidity of the final product, it is preferable to add a molecular weight modifier such as hydrogen and polymerize.

The molecular weight of the random copolymer of ethylene and α-olefin produced in the second step is 0.5 to 15 in terms of intrinsic viscosity [η] at 135 ° C. of tetralin, preferably 1.0 to 10 and particularly preferably 1.5 to 7. If [η] is too small, sufficient tensile strength cannot be obtained. On the other hand, if [η] is too large, the moldability will be significantly deteriorated.

The copolymer produced in the second step of the present invention has a total polymerization amount of 60%.
~ 97% by weight, preferably 70-95% by weight, particularly preferably
75 to 90% by weight. The larger the amount produced in the second step, the richer the rubber-like property, and conversely, when the amount is small, the behavior of plastic is exhibited.

By carrying out the polymerization method of the present invention, the adhesive force is usually
A granular thermoplastic elastomer having a particle property of 6.0 g / cm ² or less can be obtained.

The gas phase polymerization reactor for carrying out the present invention is not particularly limited, and a known stirring and mixing tank type reactor, a fluidized bed type reactor, a fluidized bed type reactor with a stirrer and the like can be used.

The polymerization of the present invention may be carried out by a method of continuously connecting two or more reactors in series, a batch polymerization in one or more reactors, or a combination of both. It can be carried out.

<Examples> The method of the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

In addition, the physical-property value in an Example is measured by the following method.

Intrinsic viscosity (hereinafter abbreviated as [η]): 135 in tetralin solvent
It was measured at ° C.

[Η] P ... indicates the intrinsic viscosity of the polymer produced in the first step.

[Η] T ... indicates the intrinsic viscosity of all polymers.

[Η] EP: shows the limit of the polymer produced in the second step.

 [Η] EP was calculated by the following method.

(P) ・ ・ ・ Proportion of the amount of polymerization in the first step (weight fraction) (EP) ・ ・ Proportion of the amount of polymerization in the second step (weight fraction) Ethylene content measurement: Using infrared absorption spectrum Quantification was performed using a known absorption band.

The obtained ethylene content was in good agreement with the value obtained from the mass balance.

Adhesion of polymer particles: Width 30 mm, length 53 mm, height 12 mm, made of aluminum plate shear test cells, adhered one on top of the other,
Put polymer particles to be measured inside and preload for 30 seconds under a preconsolidation load of 1,000 g and then as a vertical load of 50 g, 100 g, 2
00g, 300g and 400g are applied and a one-sided shear test is performed at room temperature at a take-up speed of 100 mm / min to measure the shear stress for each vertical load. The measured values of vertical load and shear stress were linearly approximated by the method of least squares, and the shear stress when extrapolated to a vertical load of 0 g was taken as the adhesive force.

20 ℃ xylene soluble part (abbreviated as CXS below): 1g of polymer is dissolved in 200ml of boiling xylene, then 5
The polymer is gradually cooled to 0 ° C., then immersed in ice water, cooled to 20 ° C. with stirring, and allowed to stand at 20 ° C. for 3 hours, and then the precipitated polymer is separated. Xylene is evaporated from the liquid, and the polymer soluble in xylene at 20 ° C. is recovered by vacuum drying at 60 ° C.

Pore volume: Measurement model: Micromeritics Poisizer 9310 (Porosimeter) Mercury injection method, Pore radius 40
Pore volumes in the range of ~ 75,000Å were measured.

Average particle size of solid catalyst: determined by optical microscope observation.

Example 1 (A) Synthesis of organomagnesium compound After a flask having an inner volume of 1 equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was replaced with argon, 32.0 g of milled magnesium for Grignard was charged.

A dropping funnel was charged with 120 g of n-butyl chloride and 500 ml of di-n-butyl ether, and about 30 ml was added dropwise to magnesium in the flask to start the reaction. After the reaction was started, the dropping was continued at 50 ° C for 4 hours, and after the dropping was completed, the dropping was continued at 60 ° C for another 1 hour.
The reaction continued for an hour. Then, the reaction solution was cooled to room temperature,
Solids were separated.

When n-butylmagnesium chloride in di-n-butyl ether was hydrolyzed with 1N sulfuric acid and the concentration was determined by back titration with 1N aqueous sodium hydroxide solution (phenolphthalein was used as an indicator), the concentration was 2.0. Mol /
It was l.

(B) Synthesis of solid product A flask having an internal volume of 200 ml equipped with a stirrer and a dropping funnel was replaced with argon, and then Chromosolve 101 manufactured by Johns Manville Co., a porous polymer composed of a copolymer of styrene and divinylbenzene. The average particle diameter of beads is 200 μm, and as a result of porosimeter measurement, the pore volume (cc / g) (hereinafter abbreviated as dVp) in the pore radius of 100 to 5,000 Å is dVp = 0.
92cc / g) was vacuum dried at 80 ℃ for 0.5 hours 5.0
After adding 20 g of g and n-butyl ether, 14.0 ml of the organomagnesium compound synthesized in (A) was added dropwise from the dropping funnel over 10 minutes while maintaining the temperature in the flask at 80 ° C while stirring, and at the same temperature. The treatment was carried out for 1 hour. Then, washing with n-butyl ether (20 ml) twice and n-heptane (20 ml) was repeated twice, followed by drying under reduced pressure to obtain 5.0 g of an organomagnesium-treated product.

Next, after replacing the flask having an internal volume of 100 ml equipped with a stirrer and a dropping funnel with argon, 5.0 g of the organomagnesium-treated product synthesized above, 25 ml of n-heptane, 0.44 g (1.3 mmol) of tetrabutoxytitanium and tetraethoxysilane. Four.
5 g (21.6 mmol) was added and the mixture was stirred at 30 ° C for 30 minutes.

Then, add 4.6 ml of the organomagnesium compound synthesized in (A) from the dropping funnel while maintaining the temperature in the flask at 5 ° C.
It dripped over time. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and further at room temperature for 1 hour, and then washed with 25 ml of n-heptane 3 times repeatedly and dried under reduced pressure to obtain 6.2 g of a brown solid product.

The solid product contained 0.4 wt% titanium atoms and 3.9 wt% magnesium atoms.

(C) Synthesis of solid catalyst component After replacing a flask having an internal volume of 100 ml with argon,
6.0 g of a solid product synthesized by the reduction reaction of (B), 30.0 ml of monochlorobenzene and 0.41 of diisobutyl phthalate.
ml (1.5 mmol) was added and the reaction was carried out at 80 ° C. for 1 hour.

After the reaction, solid-liquid separation was carried out, and the mixture was washed twice with 30 ml of n-heptane.

After washing, add 30.0 ml of monochlorobenzene to the flask.
-Butyl ether (0.53 ml, 3.1 mmol) and titanium tetrachloride (9.6 ml, 87.3 mmol) were added, and the reaction was carried out at 80 ° C for 3 hours. After completion of the reaction, solid-liquid separation was carried out at 80 ° C., and then washed with 30 ml of monochlorobenzene at the same temperature twice. The above-mentioned treatment with the mixture of n-butyl ether and titanium tetrachloride was carried out again for 1 hour, and then n-heptane 30 was added.
After repeatedly washing twice with ml, the solid was dried under reduced pressure to obtain 5.4 g of a brown solid catalyst component.

The solid catalyst component contained 0.5% by weight of titanium atom, 4.3% by weight of magnesium atom, and 0.7% by weight of phthalate ester.

The average particle size of this solid catalyst component was 200 μm, and the pore volume was dVp = 0.75 cc / g.

(D) Polymerization Using an autoclave equipped with a stirrer with an internal volume of 5 l, homopolymerization of propylene was carried out in the first step, and random copolymerization of ethylene and propylene was carried out in the second step.

The autoclave was dried at 80 ° C. for 1 hour, then depressurized with a vacuum pump, charged with 0.5 g of triethylaluminum, 0.13 g of phenyltrimethoxysilane and 564.0 mg of the solid catalyst component prepared in (C) above, and 0.53 kg / cm ² Hydrogen corresponding to a partial pressure of was added.

Then, 1.3 kg of liquefied propylene was pressed into the autoclave and the temperature was raised to 75 ° C. After homopolymerization of propylene at 75 ° C. for 15 minutes, unreacted monomer was purged and a small amount of polymer was sampled to measure [η] p and CXS. Then hydrogen 0.075 kg / cm ² was supplied, after that is pressurized by propylene up to 8 kg / cm ² G, ethylene 10 kg / cm ²
The pressure was raised to G and the temperature was adjusted to 70 ° C. to start the polymerization in the second step.

Then, a mixed gas of ethylene / propylene = 50/50 vol% was fed so as to keep the total pressure at 10 kg / cm ² G, and ethylene / propylene copolymerization was carried out in the gas phase for 420 minutes.

After the polymerization was completed, unreacted monomers were purged to obtain 643 g of a granular thermoplastic elastomer having a fine powder and free of coarse particles.

As a result of open inspection of the autoclave, no polymer was attached to the inner wall of the autoclave and the stirrer.

The production amount (g / g) (hereinafter abbreviated as PP / Ti) of all polymers per 1 g of titanium atom in the solid catalyst component was PP / Ti = 228,000. The CXS of the P part of the propylene homopolymer (hereinafter abbreviated as P) in the first step was 3.8 wt%.

In addition, 85 wt% of the ethylene / propylene copolymer (hereinafter abbreviated as EP) in the second step was contained in all the polymers. The ethylene content in EP was 48 wt%. The molecular weight was [η] P = 1.7, [η] EP = 3.8, and [η] T = 3.5.

The adhesive force of the obtained polymer particles was 2.8 g / cm ² .

The polymerization conditions and the polymerization results are shown in Table 1 and Table 2, respectively.

Comparative Example 1 (A) Synthesis of solid product After replacing a flask with an internal volume of 200 ml equipped with a stirrer and a dropping funnel with argon, Fuji Debison Chemical Co., Ltd. Super Microbeads silica gel ID type average particle size was 40μ.
m and also (dVp = 0.84cc / g) at 100 ° C for 2
Vacuum dried for 15.0g and n-butyl ether 46ml
Was charged, and while stirring, 42.0 ml of the organomagnesium compound synthesized in (A) of Example 1 was heated to the temperature in the flask.
While maintaining the temperature at 30 ° C., the mixture was added dropwise from the dropping funnel over 10 minutes and further treated at the same temperature for 2 hours. Then, washing with 20 ml of n-butyl ether twice and 40 ml of n-heptane was repeated twice, followed by drying under reduced pressure to obtain 14.8 g of an organomagnesium-treated silica gel product.

After replacing the flask with an internal volume of 300 ml equipped with a stirrer and a dropping funnel with argon, 13.8 g of the organomagnesium-treated silica gel synthesized above, 69 ml of n-heptane, 0.77 g (2.3 mmol) of tetrabutoxytitanium and tetraethoxysilane. 8.04 g (38.6 mmol) was added and the mixture was stirred at 30 ° C for 30 minutes.

Next, 22.6 ml of the organomagnesium compound synthesized in (A) of Example 1 was added dropwise from the dropping funnel over 1 hour while maintaining the temperature in the flask at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 1 hour and then at room temperature for 1 hour, and then n-heptane 60 ml.
Repeatedly washed 3 times with vacuum drying under reduced pressure to give a brown solid product 2
I got 1.1g.

The solid product contained 0.5% by weight of titanium atoms and 5.9.% By weight of magnesium atoms.

(B) Synthesis of solid catalyst component After replacing a flask having an internal volume of 100 ml with argon,
5.6 g of a solid product synthesized by the reduction reaction of (A), 18.8 ml of toluene and 0.74 ml (2.8 mmol) of diisobutyl phthalate were added, and the reaction was carried out at 95 ° C for 1 hour.

After the reaction, solid-liquid separation was performed, and washing was performed twice with 20 ml of toluene.

After completion of washing, toluene 18.8 ml, n-butyl ether 0.65 ml (3.8 mmol) and titanium tetrachloride 11.4 m were placed in the flask.
l (104 mmol) was added and the reaction was carried out at 95 ° C. for 3 hours.
After completion of the reaction, solid-liquid separation was carried out at 95 ° C., followed by washing with 20 ml of toluene twice at the same temperature. The above-mentioned treatment with a mixture of n-butyl ether and titanium tetrachloride was carried out again for 1 hour, and the washing was repeated twice with 20 ml of n-heptane and then dried under reduced pressure to obtain 4.8 g of a brown solid catalyst component.

The solid catalyst component contained 1.1% by weight of titanium atoms, 7.8% by weight of magnesium atoms, and 1.5% by weight of phthalates.

The average particle size of this solid catalyst component is 40 μm,
The pore volume in the pore radius range of 75 to 5,000Å was 0.35 cc / g.

(C) Polymerization Using the solid catalyst component (297.0 mg) prepared in (B) above, P-EP block copolymerization was carried out under the same conditions as in (D) of Example 1. The polymerization conditions and the polymerization results are shown in Table 1 and Table 2, respectively.

In this case, since the silica gel was used as the carrier for the catalyst instead of the organic porous polymer, the obtained polymer was aggregated, and the particle property was remarkably bad and the adhesive force was 7.7 g / cm ² .

The polymerization conditions and the polymerization results are shown in Tables 1 and 2 together with Comparative Examples 2 to 4, respectively.

Comparative Example 2 (A) Synthesis of solid product A flask having an internal volume of 200 ml equipped with a stirrer and a dropping funnel was replaced with argon, and then 952 manufactured by Fuji Devison Chemical Co., Ltd.
8.25 g of grade silica gel calcined at 800 ° C. for 8 hours in a nitrogen atmosphere (dVp = 0.88 cc / g), n-heptane 41.3 ml, tetrabutoxy titanium 1.12 g (3.3 mmol), tetraethoxysilane 11.8. g (56.7 mmol) was added, and the mixture was stirred at room temperature for 30 minutes.

Next, 30.0 ml of the organomagnesium compound synthesized in (A) of Example 1 was dropped from the dropping funnel over 1 hour while maintaining the temperature in the flask at 5 ° C. After completion of dropping, the mixture was stirred at 5 ° C for 30 minutes and then at 30 ° C for 1 hour, and then n-heptane 40 ml.
Repeatedly washed twice with and dried under reduced pressure to give a brown solid product 1
7.5 g was obtained.

(B) Synthesis of solid catalyst component After replacing the flask having an internal volume of 100 ml with argon, 4.5 g of a solid product, 15.1 ml of toluene and 1.67 ml (6.2 mmol) of diisobutyl phthalate were added, and the reaction was carried out at 95 ° C for 1 hour. It was

After the reaction, solid-liquid separation was performed, and the solid was washed twice with 15 ml of toluene.

After completion of washing, toluene 15.1 ml, n-butyl ether 1.0 ml (5.7 mmol) and titanium tetrachloride 17.7 ml were added to the flask.
(161 mmol) was added and the reaction was carried out at 95 ° C for 3 hours.
After completion of the reaction, solid-liquid separation was carried out at 95 ° C., followed by washing with 15 ml of toluene twice at the same temperature. The above treatment with a mixture of n-butyl ether and titanium tetrachloride was carried out again for 1 hour, and the washing was repeated twice with 15 ml of n-heptane and then dried under reduced pressure to obtain 3.6 g of a brown solid catalyst component.

The solid catalyst component contained 1.9% by weight of titanium atoms, 9.0% by weight of magnesium atoms, and 2.3% by weight of phthalates. The pore volume was dVp = 0.25 cc / g.

(C) Polymerization Using 103.2 mg of the solid catalyst component synthesized in (B) above, block copolymerization of P-EP was carried out under the same conditions as in (D) of Example 1.

In this case, since the silica gel was used as the carrier for the catalyst instead of the organic porous polymer, the obtained polymer was agglomerated and the particle properties were remarkably poor and the adhesive force was 8.4 g / cm ² .

Comparative Example 3 (A) Synthesis of solid product After a flask having an inner volume of 500 ml equipped with a stirrer and a dropping funnel was replaced with argon, 150 ml of n-heptane, 7.6 g (22.4 mmol) of tetrabutoxytitanium and 78 g of tetraethoxysilane ( 378 mmol) was added to make a uniform solution. Next, 182 ml (400 mmol) of the organomagnesium compound synthesized in (A) of Example 1 was gradually added dropwise from the dropping funnel over 3 hours while maintaining the temperature in the flask at 5 ° C. After completion of dropping, the mixture was stirred at room temperature for 1 hour, solid-liquid separated at room temperature, washed with 300 ml of n-heptane three times, and dried under reduced pressure to give a brown solid product 62.0.
got g.

(B) Synthesis of solid catalyst component After replacing a flask having an internal volume of 200 ml with argon,
15 g of the solid product synthesized in (A), 75 ml of toluene and 8.1 ml of diisobutyl phthalate were added, and the reaction was carried out at 95 ° C for 1 hour.

After the reaction, solid-liquid separation was performed, and washing with 75 ml of n-heptane was performed three times.

Next, add 38 ml of toluene and n-butyl ether to the flask.
0 ml (88.5 mmol) and 88.5 ml (807 mmol) of titanium tetrachloride were added, and the reaction was carried out at 95 ° C for 3 hours.

After completion of the reaction, solid-liquid separation was carried out at 95 ° C., and then washed twice with 75 ml of toluene at the same temperature.

The above treatment with the mixture of n-butyl ether and titanium tetrachloride was carried out again for 1 hour, and then n-heptane was added.
After repeating washing twice with 75 ml, it was dried under reduced pressure to obtain 13 g of an ocher solid catalyst component.

This solid catalyst component contained 1.9% by weight of titanium atoms, 19.4% by weight of magnesium atoms and 5.0% by weight of phthalates. The solid catalyst component had an average particle diameter of 35 μm and a pore volume of dVp = 0.27 cc / g.

(C) Polymerization Using 31.8 mg of the solid catalyst component prepared in (B) above, block copolymerization of P-EP was carried out under the same conditions as in (D) of Example 1. The polymerization conditions and the polymerization results are shown in Table 1 and Table 2, respectively.

In this case, since the solid catalyst component was not impregnated in the porous carrier, the particle properties were remarkably poor although the pore volume was quite large. That is, as a result of the open inspection of the autoclave, the polymer particles adhered to the inner wall of the autoclave in layers and were half solidified.

Comparative Example 4 (A) Synthesis of solid catalyst component A solid catalyst component was synthesized in the same manner as in Example 5 of JP-A-61-287917.

That is, after a flask having an inner volume of 300 ml equipped with a stirrer and a dropping funnel was replaced with argon, (A) of Example 1 was used.
57.2 ml of the organomagnesium compound synthesized in 1. was added to the flask, and 12.8 ml of silicon tetrachloride was gradually dropped into n-butyl ether of n-butylmagnesium chloride over 1 hour while maintaining the internal temperature at 20 ° C. After completion of dropping, the mixture was stirred at 20 ° C. for another hour, the reaction solution was filtered and washed with 100 ml of hexane four times to synthesize a carrier.

Next, 70 ml of hexane was added to make a slurry, and then the internal temperature was kept at 60 ° C.

Next, a solution prepared by dissolving 4.2 g of phenol and 6.4 ml of ethyl benzoate was added to 100 ml of hexane and reacted at 60 ° C. for 30 minutes. After passing the reaction solution, hexane 15 at 60 ° C.
Washing was repeated 3 times with 0 ml.

Next, after adding monochlorobenzene 80 ml to make a slurry, And a solution consisting of 48 ml of monochlorobenzene,
The reaction was carried out at 100 ° C for 30 minutes. After completion of the reaction, the reaction solution was allowed to pass at 100 ° C, washed once with 150 ml of toluene at 100 ° C and 3 times with 100 ml of hexane, and then dried to 15.1 g.
The solid catalyst component of was synthesized.

This solid catalyst component contained 2.5% by weight of titanium atoms, 20.9% by weight of magnesium atoms, 1.7% by weight of phenol and 9.1% by weight of ethyl benzoate. The average particle size of this solid catalyst component is 30 μm, and the pore volume is dV.
It was p = 0.29cc / g.

(B) Polymerization Using 32.4 mg of the solid catalyst component synthesized in (A) above,
Block copolymerization of P-EP was carried out in the same manner as in (D) of Example 1 except that 0.2 g of methyl p-toluate was used instead of phenyltrimethoxysilane as the electron-donating compound of the component (C). It was

The polymerization conditions and the polymerization results are shown in Table 1 and Table 2, respectively. In this case, the change in catalyst activity over time was large,
During the random copolymerization of ethylene and propylene in the second step, the catalytic activity was completely lost, and the thermoplastic elastomer having the composition of the present invention could not be obtained.

Example 2 Using the solid catalyst component synthesized in Example 1, block copolymerization of P-EP was performed.

After drying in an autoclave at 80 ° C for 1 hour, the pressure was reduced by a vacuum pump, 0.5 g of triethylaluminum, 0.13 g of phenyltrimethoxysilane and 282.9 mg of the solid catalyst component prepared in Example 1 were charged, and the content of 0.53 kg / cm ^{2 was} measured. Hydrogen was added corresponding to the pressure.

Then, 1.3 kg of liquefied propylene was pressed into the autoclave and the temperature was raised to 75 ° C. After homopolymerization of propylene for 10 minutes at 75 ° C., unreacted monomers were purged, and a small amount of polymer was sampled to measure [η] P and CXS. Then supply 0.3 kg / cm ^{2 of} hydrogen,
After the pressure was increased to kg / cm ² G, the pressure was increased to 10 kg / cm ² G with ethylene, the temperature was adjusted to 70 ° C., and the polymerization in the second step was started.

Then, a mixed gas of ethylene / propylene = 80/20 vol% was fed so as to keep the total pressure at 10 kg / cm ² G, and ethylene / propylene copolymerization was performed in the gas phase for 540 minutes.

After the completion of the polymerization, unreacted monomers were purged to obtain 368 g of a granular thermoplastic elastomer having a good powder property free of fine powder and coarse particles.

As a result of open inspection of the autoclave, no polymer was attached to the inner wall of the autoclave and the stirrer.

The polymerization conditions and the polymerization results are shown in Table 1 and Table 2, respectively.

Example 3 377.0 mg of the solid catalyst component synthesized in Example 1 was used, except that the amount of hydrogen charged in the second step of the polymerization was 0.2 kg / cm ² .
Block copolymerization of P-EP was carried out under the same conditions as in (D) of Example 1. The polymerization conditions and the polymerization results are shown in Table 1 and Table 2, respectively.

Example 4 Using the solid catalyst component synthesized in Example 1, homopolymerization of propylene in the first step, ethylene and butene-1 in the second step
Random copolymerization was carried out.

After the autoclave was dried at 80 ° C. for 1 hour, the pressure was reduced with a vacuum pump, 0.5 g of triethylaluminum, 0.13 g of phenyltrimethoxysilane and 372.4 mg of the solid catalyst component prepared in Example 1 were charged, and 0.53 kg / cm ² Hydrogen corresponding to partial pressure was added.

Then, 1.3 kg of liquefied propylene was pressed into the autoclave and the temperature was raised to 75 ° C. After homopolymerization of propylene at 75 ° C for 10 minutes, unreacted monomers were purged and [η] P
And a small amount of polymer was sampled to measure CXS. Next, hydrogen is supplied at 0.075 kg / cm ² and the total pressure is 4 kg.
ethylene / butene-1 = 80 / 20vol% to keep at / cm ² G
Was mixed, and ethylene / butene-1 copolymerization was performed in the gas phase at 75 ° C. for 420 minutes. After the polymerization is completed, unreacted monomers are purged and the thermoplastic elastomer has good particle properties.
Obtained 260 g.

As a result of open inspection of the autoclave, no polymer was attached to the inner wall of the autoclave and the stirrer.

The amount of all polymers produced per 1 g of titanium atom was PP / Ti 140,000. Ethylene / butene-1 from the second step in all polymers
The copolymer (hereinafter abbreviated as EB) was contained at 73 wt%.
The ethylene content in EB was 77 wt%.

The molecular weight is [η] P = 2.2, [η] EB = 4.1, [η] T = 3.
Was 6. The adhesive force of the obtained polymer particles is 2.4 g / m ²
Met.

Example 5 (B) Synthesis of solid catalyst component A flask with an internal volume of 3 l equipped with a stirrer and a dropping funnel was replaced with argon, and then porous polymer beads (dVp = 1.77 cc) made of a copolymer of styrene and divinylbenzene were replaced. /
g, average particle size 156 μm) were vacuum dried at 80 ° C., 234 g, toluene 2.34 l, tetrabutoxytitanium 15 ml (44 mmol) and tetraethoxysilane 150 ml (673 mmol) were added and stirred at 30 ° C. for 45 minutes.

Next, 339 ml of the organomagnesium compound synthesized in (A) of Example 1 was added dropwise from the dropping funnel while keeping the temperature in the flask at 5 ° C for 1 hour. After completion of dropping, the mixture was stirred at 5 ° C. for 1 hour and further at room temperature for 1 hour, and then washed with 200 ml of toluene 3 times repeatedly to obtain a brown solid product.

(C) Synthesis of solid catalyst component After replacing the flask having an internal volume of 3 l with argon, the whole solid product synthesized by the reduction reaction of (B), toluene 658 m
l and diisobutyl phthalate 105.4 ml (394 mmol)
Was added and the reaction was carried out at 95 ° C for 30 minutes. After the reaction, solid-liquid separation was performed, and washing was performed twice with 1.65 l of toluene.

After washing, add 658 ml of toluene, 10.5 ml (62 mmol) of n-butyl ether and 1317 ml of titanium tetrachloride to the flask.
(12 mol) was added and the reaction was carried out at 95 ° C for 3 hours. After the reaction was completed, solid-liquid separation was performed at 95 ° C, and the temperature was adjusted to 1650 with toluene.
It was washed twice with ml. The above treatment with a mixture of n-butyl ether and titanium tetrachloride was carried out again for 1 hour, and washing with 1650 ml of n-hexane was repeated twice, followed by vacuum drying to obtain 283 g of a brown solid catalyst component.

The solid catalyst component contained 0.3% by weight of titanium atom and 2.83% by weight of phthalate ester. The average particle size of this solid catalyst component was 156 μm.

(D) Polymerization Using an autoclave equipped with a stirrer with an internal volume of 5 l, homopolymerization of propylene was carried out in the first step, and random copolymerization of ethylene and propylene was carried out in the second step.

The autoclave was dried at 80 ° C for 1 hour and then depressurized with a vacuum pump to give 0.5 g of triethylaluminum, 2,2,6,
0.11 ml of 6-tetramethylpiperidine and 90.5 mg of the solid catalyst component prepared in the above (C) were charged, and hydrogen corresponding to a partial pressure of 600 mmHg was added.

Then, 1.3 kg of liquefied propylene was pressed into the autoclave and the temperature was raised to 75 ° C. After homopolymerization of propylene at 75 ° C. for 15 minutes, unreacted monomers were purged, and a small amount of polymer was sampled to measure [η] P and CXS. Then, supply 0.3 kg / cm ^{2 of} hydrogen, and add 5% of propylene.
After the pressure was increased to kg / cm ² G, the pressure was increased to 10 kg / cm ² G with ethylene, the temperature was adjusted to 70 ° C., and the polymerization in the second step was started.

Then, a mixed gas of ethylene / propylene = 50/50 vol% was fed so as to keep the total pressure at 10 kg / cm ² G, and ethylene / propylene copolymerization was carried out in the gas phase for 30 minutes.

After the polymerization was completed, unreacted monomers were purged to obtain 111 g of a granular thermoplastic elastomer having a fine powder and free of coarse particles. As a result of open inspection of the autoclave,
No polymer was attached to the inner wall of the autoclave and the stirrer.

The production amount (g / g) of all polymers per 1 g of titanium atom in the solid catalyst component was PP / Ti = 527,000. The CXS of the propylene homopolymer P part in the first step was 3.0 wt%.

In addition, the EP part of the ethylene / propylene copolymer in the second step was contained in the entire polymer in an amount of 60 wt%. The ethylene content in EP was 23.5 wt%.

The molecular weight is [η] P = 1.8, [η] EP = 1.8, [η] T =
It was 1.8.

The adhesive force of the obtained polymer particles was 3.2 g / m ² .

The polymerization conditions and the polymerization results are shown in Table 1 and Table 2, respectively.

Example 6 All the examples except that 97.4 mg of the solid catalyst component and 0.234 ml of diisobutyl phthalate were used instead of 2,2,6,6-tetramethylpiperidine, and ethylene / propylene copolymerization was performed in the gas phase for 50 minutes. P / EP block copolymerization was carried out in the same manner as in 5. The polymerization conditions and the polymerization results are shown in Table 1 and Table 2, respectively.

<Effects of the Invention> As described above, the following effects can be obtained by combining the specific catalyst system of the present invention with the gas phase polymerization method.

(1) A granular olefinic thermoplastic elastomer can be produced economically and stably, and the production cost can be greatly reduced as compared with the conventional method.

(2) Since the catalytic activity per titanium atom is very high, halogen atoms and titanium atoms, which are closely related to the coloring, stability and corrosion resistance of the polymer, do not have to be subjected to any special catalyst residue removal operation. Very low content. That is, the equipment for removing the catalyst residue is not required, and the production cost can be reduced.

(3) Since the thermoplastic elastomer is obtained in the form of particles, it can be easily handled and molded.

[Brief description of drawings]

FIG. 1 is a flow chart for facilitating the understanding of the present invention. This flowchart is a representative example of the embodiment of the present invention, and the present invention is not limited to this.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiyoshi Kawai 5-1 Anezaki Kaigan, Ichihara-shi, Chiba Sumitomo Chemical Co., Ltd. (56) Reference JP-A-63-178112 (JP, A) Japanese Patent Publication -57685 (JP, B2)

Claims (1)

[Claims] 1. (A) At least titanium, magnesium,
A solid catalyst component obtained by impregnating a catalyst component composed of chlorine and an ester compound into an organic porous polymer carrier having an average particle size of 5 to 1,000 μm and a pore volume of 0.1 cc / g or more at a pore radius of 100 to 5,000 Å. , (B) an organoaluminum compound, and (C) an Si-OR ⁷ bond (R ⁷ is a hydrocarbon group having 1 to 20 carbon atoms) or an Si-NC bond-containing organosilicon compound, aromatic After obtaining isotactic polypropylene by polymerization in the first step in liquefied propylene and / or in the gas phase, using a catalyst system consisting of the carboxylic acid ester compound of 1) and an electron donating compound selected from sterically hindered amines Then, in the second step, ethylene and α-in the gas phase
Random copolymer with olefin, ethylene content of the copolymer produced in the step is 15 ~ 90 mol%, tetralin
Granular thermoplastic resin having an intrinsic viscosity of 0.5 to 15 at 135 ° C. and obtained by polymerizing the copolymer produced in the step so as to be 60 to 97% by weight based on the total polymerization amount. Method for producing elastomer.