JPH06102707B2 - Method for producing propylene-olefin block copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a propylene-olefin block copolymer. More specifically, it relates to a method for producing a propylene-olefin block copolymer having both high rigidity and high impact resistance using a specific catalyst.

[Conventional technology and its problems] Crystalline polypropylene has high rigidity, hardness, tensile strength,
Although it has heat resistance and the like, the impact resistance is insufficient.

Generally, the rigidity, hardness, etc. of a plastic material are incompatible with impact resistance, and it is often extremely difficult to improve and improve the former and the latter at the same time. In order to expand the applications of crystalline polypropylene, it is required to further improve not only the above-mentioned impact resistance but also the rigidity.

As a method of improving the impact resistance of polypropylene,
Homopolymerization of Propylene Subsequently, there is a method of block copolymerizing propylene and an olefin other than propylene. However, the block copolymer has a problem that the impact resistance is significantly improved as compared with the crystalline polypropylene, but the rigidity is reduced.

In order to improve the above-mentioned problems, a propylene-olefin block copolymer is produced using a catalyst that is pre-activated by polymerizing a small amount of a non-linear olefin such as 4,4-dimethylpentene-1 or allyltrimethylsilane. (JP-A-63-68,621, JP-A-63-68,622) has been proposed, but when the present inventors produced a block copolymer according to the method of the proposal, Not only the activity decreases, but also operational problems such as formation of bulk polymer, scale adhesion to the wall of the polymerization vessel, and poor controllability of the polymerization reaction occur. It was a method that could not be adopted in the polymerization method.

Further, when the obtained block copolymer was processed into a molded product, although a certain improvement was found in the balance between rigidity and impact resistance, it was still insufficient, and further improvement is desired.

In addition, as a similar technique utilizing a non-linear olefin,
A propylene homocopolymer is produced using the catalyst component produced by adding a non-linear olefin polymer obtained by separately polymerizing a non-linear olefin during the production of a transition metal catalyst component for propylene polymerization. A method (Japanese Patent Laid-Open No. 63-69,809) has been proposed, but since the method of the proposal requires a separate step for producing a non-linear olefin polymer,
Not only is it industrially disadvantageous, but the resulting polymer is a propylene homocopolymer, so the impact resistance is extremely low.

Further, even when the present inventors produce a propylene-olefin block copolymer using the transition metal catalyst component obtained according to the proposed method, the balance of rigidity and impact resistance of the obtained block copolymer. Was inadequate.

On the other hand, the applicant has already produced a propylene-ethylene block copolymer having both high rigidity and impact resistance by using a catalyst composed of a specific titanium trichloride composition, an organoaluminum compound, and an aromatic carboxylic acid ester. Although a method (Japanese Patent Publication No. 62-4,402, hereinafter sometimes referred to as a prior invention) has been proposed, further improvement in rigidity and impact resistance is desired.

The present inventors have diligently studied a method for producing the propylene-olefin block copolymer having both high rigidity and impact resistance superior to those of the prior invention by solving the problems of the above-mentioned conventional technology.

As a result, a titanium trichloride composition containing a non-linear olefin polymer was found by a specific method, and a catalyst obtained by combining the titanium trichloride composition, an organoaluminum compound, and a specific amount of an aromatic carboxylic acid ester was prepared. In the case of producing a propylene-olefin block copolymer using the same, it was found that the problems of the above-mentioned prior art and prior inventions were solved, and the present invention was achieved.

As is apparent from the above description, an object of the present invention is to provide a method for stably producing a propylene-olefin block copolymer having both high rigidity and high impact resistance without causing operational problems. is there. Another object is to provide a propylene-olefin block copolymer having both high rigidity and high impact resistance.

[Means for Solving the Problems] The present invention has the following configurations.

(1) A solid product (II) obtained by reacting titanium tetrachloride with an organoaluminum compound (A ₁ ) or a reaction product (I) of an organoaluminum compound (A ₁ ) and an electron donor (B ₁ ). ) Is polymerized with a non-linear olefin, or a linear olefin and a non-linear olefin, and the electron donor (B ₂ ) and the electron acceptor are reacted to obtain a titanium trichloride composition (III). And an organoaluminum compound (A ₂ ) and an aromatic carboxylic acid ester (E) are combined to prepare the aromatic carboxylic acid ester (E) and the titanium trichloride composition (III) (converted to the number of Ti atoms, the same applies hereinafter). The molar ratio is (E) / (III) = 0.1 to 10.0, and the molar ratio of the organoaluminum compound (A ₂ ) to the titanium trichloride composition (III) is (A ₂ ) / (III) = 0.1 to 200. Using the catalyst A block copolymer obtained by polymerizing 60% by weight to 95% by weight of the propylene, and then copolymerizing 40% by weight to 5% by weight of the total amount of propylene with an olefin other than propylene in the second stage Content of olefins other than propylene in polymer is 3% to 30% by weight
The method for producing a propylene-olefin block copolymer, comprising:

(2) The general formula of the organoaluminum compound (A ₁ ) is
AlR ¹ _p R ² _{p ′} X _{3- (p + p ′)} (wherein R ¹ and R ² represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, and X represents a halogen; The manufacturing method according to claim 1, wherein an organoaluminum compound represented by p and p'represents an arbitrary number of 0 <p + p'≤3.

(3) As the non-linear olefin, CH ₂ ═CH—R ³ (wherein R ³ has a saturated cyclic structure of a hydrocarbon that may contain silicon, and a carbon that may contain silicon) Number 3
It represents a saturated ring hydrocarbon group from 1 to 18. The manufacturing method as described in said 1st item using the saturated ring hydrocarbon monomer shown by these.

(4) As the non-linear olefin, (In the formula, R ⁴ has 1 to 3 carbon atoms which may contain silicon.
Represents a chain hydrocarbon group up to, or silicon, R ⁵ ,
R ⁶ and R ⁷ represent a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and any one of R ⁵ , R ⁶ and R ⁷
The individual may be hydrogen. The manufacturing method of said 1st item using the branched chain olefin shown by these.

(5) As the non-linear olefin, the following formula: (In the formula, n is 0, 1 or m is 1, 2 and R ⁸
Represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen or halogen. , M is 2, each R ⁹ may be the same or different. The manufacturing method of the said 1st term using the aromatic-type monomer shown by these.

(6) The production method according to the above item 1, wherein a dialkylaluminum monohalide is used as the organoaluminum compound (A ₂ ).

(7) In place of the titanium trichloride composition (III), the titanium trichloride composition (III) is combined with an organoaluminum compound, and a catalyst component pre-activated by reacting a small amount of olefin is used. The manufacturing method described in.

The structure of the present invention will be described in detail below.

The production of the titanium trichloride composition (III) used for producing the propylene-olefin block copolymer of the present invention is as follows.

First, a reaction product (I) is obtained by reacting an organoaluminum (A ₁ ) with an electron donor (B ₁ ) and a solid product (I) obtained by reacting the reaction product (I) with titanium tetrachloride ( II), or the solid product (II) obtained by reacting the organoaluminum compound (A ₁ ) with titanium tetrachloride, is polymerized with a non-linear olefin, or a linear olefin and a non-linear olefin, and further, As the final solid product obtained by reacting the electron donor (B ₂ ) with the electron acceptor, the titanium trichloride composition (III) used in the present invention is produced.

In the present invention, "polymerizing" means to polymerize a linear olefin or a non-linear olefin by contacting the solid product (II) with a linear olefin or a non-linear olefin under conditions capable of polymerizing. Say. By this polymerization treatment, the solid product (II) is in a state of being coated with the polymer.

The reaction between the organoaluminum compound (A ₁ ) and the electron donor (B ₁ ) described above is carried out in a solvent (D ¹ ) at −20 ° C. to 200 ° C., preferably −10 ° C. to 100 ° C. for 30 seconds to 5 hours. Do. There is no limitation on the addition order of the organoaluminum compound (A ₁ , (B ₁ ), (D ₁ ), and the amount ratio used is 0.1 mol to an electron donor (B ₁ ) to 1 mol of the organoaluminum compound (A ₁ ). 8 mol, preferably 1-4 mol, solvent 0.5 L-5 L, preferably
It is 0.5L-2L. Thus, the reaction product (I) is obtained. The reaction product (I) can be subjected to the next reaction in a liquid state (may be referred to as a reaction product liquid (I)) after completion of the reaction without separation.

A solid product (II) obtained by reacting the reaction product (I) with titanium tetrachloride or the organoaluminum compound (A ₁ ) with titanium tetrachloride is treated with a non-linear olefin or a linear olefin and As a method of polymerizing with a non-linear olefin, a non-linear olefin or a linear olefin and a linear olefin can be used in an arbitrary process of the reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride. Solid product (I
I) is polymerized, and after the reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride is completed, a non-linear olefin or a linear olefin and a non-linear olefin are added. A method for polymerizing the solid product (II), and after the reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride is completed, and then the liquid portion is separated and removed by filtration or decantation. There is a method in which the obtained solid product (II) is suspended in a solvent, an organoaluminum compound is further added, and then a non-linear olefin, or a linear olefin and a non-linear olefin are added to carry out a polymerization treatment.

Further, the above-mentioned non-linear olefin, or the polymerization treatment with the linear olefin and the non-linear olefin may be a polymerization treatment with the non-linear olefin alone. Polymerization with an olefin followed by polymerization with a non-linear olefin gives the resulting titanium trichloride composition (II
It is a preferred method from the viewpoints of improving the polymerization operability during use of I) and the rigidity and impact resistance of the resulting propylene-olefin block copolymer.

Further, the polymerization treatment is performed by using the linear olefin and the non-linear olefin once each as described above, and two or more times, for example, the linear olefin is added after the polymerization treatment of the non-linear olefin to perform polymerization. It is also possible to perform processing.

The reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride can be carried out at −10 ° C. or higher with or without addition of a linear olefin and a non-linear olefin in any process of the reaction. 200 ° C, preferably 0 ° C to 100 ° C
5 minutes to 10 hours.

Although it is preferable not to use a solvent, an aliphatic or aromatic hydrocarbon can be used. The reaction product (I) or the organoaluminum compound (A ₁ ), titanium tetrachloride, and the solvent may be mixed in any order, and the linear olefin and the non-linear olefin may be added at any stage.

Mixing of the reaction product (I) or the organoaluminum compound (A ₁ ), titanium tetrachloride, and the solvent is preferably completed within 5 hours, and the reaction is performed during the mixing. It is preferable to continue the reaction within 5 hours after mixing the whole amount.

The amount of each used in the reaction is 1 to 1 mol of titanium tetrachloride, the solvent is 0 to 3,000 ml, and the reaction product (I) or the organoaluminum compound (A ₁ ) is the (I) or the organoaluminum compound (A ₁ ), The ratio of the number of Al atoms in Ti) to the number of Ti atoms in titanium tetrachloride (Al / Ti) is 0.05 to 10, preferably
0.06 to 0.3.

The non-linear olefin, or the polymerization treatment with the linear olefin and the non-linear olefin, the non-linear olefin in any process of the reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride, Alternatively, when a linear olefin and a non-linear olefin are added and after the reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride, the non-linear olefin or the non-linear olefin and the non-linear olefin When a linear olefin is added, the reaction temperature is 0 ° C. to 90 ° C. for 1 minute to 10 hours, and the reaction pressure is atmospheric pressure (0 kgf / cm ² G) in any polymerization treatment with a linear olefin or a non-linear olefin. ~ 10kg
0.1 g to 100 kg of linear olefin and 0.01 of non-linear olefin per 100 g of solid product (II) under the condition of f / cm ² G
~ 100 kg, so that the content of the non-linear olefin polymer in the final titanium trichloride composition (III) is 0.01 wt% to 99 wt% in the case of non-linear olefin homopolymerization treatment. In the case of using a linear olefin and a non-linear olefin, the content of the linear olefin polymer block is 0.1% by weight to 49.5% by weight, and the content of the non-linear olefin polymer block is 0.01% by weight. Polymerize to ~ 49.5 weight.

If the content of the non-linear olefin polymer is less than 0.01% by weight, the effect of improving the rigidity of the propylene-olefin block copolymer produced using the obtained titanium trichloride composition (III) is insufficient. Further, if it exceeds the above range, the improvement of the effect is not remarkable, which is disadvantageous in terms of operation and economy.

As described above, it is preferable to use not only the non-linear olefin but also the linear olefin in the polymerization treatment. In this case, the weight ratio of the linear olefin polymer block to the non-linear olefin polymer block is Considering the balance between the effect of improving drivability and the effect of improving rigidity and impact resistance, it is preferably 98/2 or less.

After completion of the reaction between the reaction product (I) or the organoaluminum compound (A ₁ ) and titanium tetrachloride, the non-linear olefin, or the polymerization treatment with the linear olefin and the non-linear olefin is separated by filtration or decantation to form a liquid. When the solid product (II) thus obtained is suspended in a solvent after separation and removal, a solid product (II) can be obtained by any polymerization treatment with a linear olefin or a non-linear olefin. For 100 g, in the presence of 100 ml to 5,000 ml of solvent and 0.5 g to 5,000 g of organoaluminum compound, the reaction temperature is 0 ° C to
1 minute to 10 hours at 90 ℃, reaction pressure is atmospheric pressure (0kgf / cm ² G)
The final titanium trichloride composition (III) using 0.1 g to 10 kg of a linear olefin and 0.01 g to 100 kg of a non-linear olefin per 100 g of the solid product (II) under the condition of -10 kgf / cm ² G. In the case of the non-linear olefin homopolymerization treatment, the content of the non-linear olefin polymer should be 0.01% by weight to 99% by weight, and in the case of using the linear olefin and the non-linear olefin, , The content of the linear olefin polymer block is 0.1% to 49.5% by weight, the content of the non-linear olefin polymer block is 0.01% to 49.5% by weight,
Polymerization is performed so that the weight ratio of the linear olefin polymer block to the non-linear olefin polymer block is 98/2 or less.

In any of the above-mentioned polymerization treatments, the reaction mixture can be used as it is for the next-stage polymerization treatment after the completion of the polymerization treatment in each step with the linear olefin or the non-linear olefin. Further, coexisting solvent, unreacted linear olefin or non-linear olefin, and organoaluminum compound etc. are removed by filtration or decantation, etc., and the solvent and organoaluminum compound are added again, and the next step of non-linear You may use it for the polymerization process by an olefin or a linear olefin.

The solvent used during the polymerization treatment is preferably an aliphatic hydrocarbon,
The organoaluminum compound may be the same as that used in obtaining the reaction product (I) or the one used in the reaction with titanium tetrachloride directly without reacting with the electron donor (B ₁ ), It can be different.

After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and after further repeating washing with a solvent, the obtained solid product subjected to polymerization treatment (hereinafter referred to as solid product (II-A) (May be said) may be used in the next step while being suspended in the solvent, or may be dried and taken out as a solid to be used.

The solid product (II-A) is then reacted with an electron donor (B ₂ ) and an electron acceptor (F). This reaction can be carried out without using a solvent, but using an aliphatic hydrocarbon gives preferable results.

The amount used is 100 g of solid product (II-A),
(B ₂ ) 0.1 g to 1,000 g, preferably 0.5 g to 200 g, (F) 0.
1g-1,000g, preferably 0.2g-500g, solvent 0-3,000m
l, preferably 100-1,000 ml.

As a reaction method, a solid product (II-A) is reacted with an electron donor (B ₂ ) and an electron acceptor (F) at the same time, and after (II-A) is reacted with (F), ( a method of reacting B _2), was reacted with (B ₂₎ to (II-a),
There are a method of reacting (F) and a method of reacting (B ₂ ) with (F) and then reacting with (II-A), but any method may be used.

The reaction conditions are 40 ° C. to 20 ° C. in the above method.
It is desirable to carry out the reaction at 0 ° C., preferably 50 ° C. to 100 ° C. for 30 seconds to 5 hours, and in the method of (II-A) and (B ₂ ) the reaction is performed at 0 ° C. to 50 ° C. for 1 minute to 3 hours. After the reaction, (F) is reacted under the same conditions as described above.

In the other method, (B ₂ ) and (F) are heated at 10 ℃ to 100 ℃.
After reacting for 30 minutes to 2 hours, cool to 40 ° C or lower (II
After the addition of -A), the reaction is carried out under the same conditions as above.

After the reaction of the solid products (II-A), (B ₂ ) and (F) is completed, the liquid portion is separated and removed by filtration or decantation, and the washing with a solvent is repeated to obtain the final solid product. , A titanium trichloride composition used in the present invention (II
I) is obtained.

The organoaluminum compound (A ₁ ) used in the production of the titanium trichloride composition (III) used in the present invention has a general formula of AIR ¹ _p R ² _{p ′} X _{3- (p + p ′)} (wherein R ¹ , R ² represents a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, X represents a halogen, and p and p ′ represent any number of 0 <p + p ′ ≦ 3). The organoaluminum compounds represented are used.

Specific examples thereof include trimethyl aluminum, triethyl aluminum, tri n-propyl aluminum, tri n-butyl aluminum, tri i-butyl aluminum, tri n-hexyl aluminum, tri i-hexyl aluminum, tri 2-methylpentyl aluminum,
Trialkylaluminums such as tri-n-octylaluminum and tri-n-decylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, di-butylaluminium monochloride, diethylaluminum monofluoride, diethylaluminum monobromide, Dialkyl aluminum monohalides such as diethyl aluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, i-butyl aluminum dichloride, etc. Monoalkyl aluminum dihalides of Monoethoxy diethylaluminum, alkoxyalkyl aluminum such as diethoxy monoethyl aluminum can also be used to. Two or more kinds of these organoaluminum compounds may be mixed and used.

As the electron donor used in the present invention, various ones shown below are shown. As (B ₁ ) and (B ₂ ), ethers are mainly used, and other electron donors are shared with ethers. Is preferred.

What is used as an electron donor is an organic compound having any atom of oxygen, nitrogen, sulfur and phosphorus, that is, ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines. And amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, hydrogen sulfide or thioethers, and thioalcohols.

Specific examples include diethyl ether, di-n-propyl ether, di-n-butyl ether, diisoamyl ether, di-n-pentyl ether, di-n-hexyl ether, di-hexyl ether, di-n-octyl ether, di-i-. Ethers such as octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol,
Alcohols such as cresol, xylenol, ethylphenol, naphthol, or phenols, methyl methacrylate, ethyl acetate, butyl formate, amyl acetate,
Vinyl butyrate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, Propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, esters such as ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, formic acid, acetic acid , Fatty acids such as propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, aromatic acids such as benzoic acid, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as benzophenone, nitriles such as acetonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, 2,4,6-trimethyl Amines such as pyridine, N, N, N ′, N′-tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N ′, N ′, N ″ -pentamethyl-N ′ -Β
-Dimethylaminomethyl phosphoric acid triamide, amides of octamethylpyrophosphoramide, ureas such as N, N, N ', N'-tetramethylurea, isocyanates such as phenyl isocyanate and toluyl isocyanate, azo such as azobenzene Compounds, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxide, dimethylphosphite, di-n-octylphosphite, triethylphosphite, trin -Phosphites such as butyl phosphite and triphenyl phosphite, phosphinites such as ethyl diethyl phosphite, ethyl dibutyl phosphinite and phenyl diphenyl phosphanite, diethyl thioacetate Tell, diphenyl thioether,
Methyl phenyl thioether, ethylene sulfide,
Examples thereof include thioethers such as propylene sulfide, thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol.

These electron donors can also be used as a mixture.
The electron donor (B ₁ ) for obtaining the reaction product (I) and (B ₂ ) reacted with the solid product (II-A) may be the same or different.

The electron acceptor (F) used in the present invention is represented by the periodic table III to V.
It is represented by halides of Group I elements. Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, antimony pentachloride and the like. These can also be used as a mixture. Most preferred is titanium tetrachloride.

The following solvents are used. Examples of the aliphatic hydrocarbon include n-pentane, n-hexane, n-heptane, n-octane, i-octane and the like, and carbon tetrachloride, chloroform instead of or together with the aliphatic hydrocarbon. It is also possible to use halogenated carbon hydrogen such as dichloroethane, trichloroethylene, and tetrachloroethylene.

As aromatic compounds, aromatic hydrocarbons such as benzene and naphthalene, and their derivatives such as mesitylene, durene, ethylbenzene, isoprolbenzene, 2-ethylnaphthalene, alkyl-substituted compounds such as 1-phenylnaphthalene, monochlorobenzene and chlorotoluene. , Halogen chlorides such as chloroxylene, chloroethylbenzene, dichlorobenzene, and bromobenzene.

As the linear olefin used in the polymerization treatment, linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, octene-1 are used, and ethylene and propylene are particularly preferably used.
One or more kinds of these linear olefins are used.

The non-linear olefin used in the polymerization treatment has the following formula: CH ₂ = CH-R ³ (wherein R ³ has a saturated ring structure of a hydrocarbon that may contain silicon, and may contain silicon. Carbon number 3
To 18 saturated cyclic hydrocarbon groups. ) A saturated ring hydrocarbon monomer represented by the following formula, (In the formula, R ⁴ has 1 to 3 carbon atoms which may contain silicon.
Represents a chain hydrocarbon group up to, or silicon, R ⁵ ,
R ⁶ and R ⁷ represent a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and any one of R ⁵ , R ⁶ and R ⁷
The individual may be hydrogen. ) Branched-chain olefins represented by the following formula, (In the formula, n is 0, 1 or m is 1, 2 and R ⁸
Represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen or halogen, and m When is 2, each R ⁹ may be the same or different. )
It is an aromatic monomer represented by. Specifically,
Examples of the saturated ring hydrocarbon monomer include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, 3-methylvinylcyclopentane, vinylcyclohexane, 2-methylvinylcyclohexane, 3-methylvinylcyclohexane, 4-methyl. In addition to vinylcycloalkanes such as vinylcyclohexane and vinylcycloheptane, allylcycloalkanes such as allylcyclopentane and allylcyclohexane, cyclotrimethylenevinylsilane, cyclotrimethylenemethylvinylsilane, cyclotetramethylenevinylsilane, cyclotetramethylenemethylvinylsilane , Cyclopentamethylene vinyl silane, cyclopentamethylene methyl vinyl silane, cyclopentamethylene ethyl vinyl silane, cyclohexamethylene vinyl silane Silicon atom in the saturated cyclic structure of cyclohexane, cyclohexamethylenemethylvinylsilane, cyclohexamethyleneethylvinylsilane, cyclotetramethyleneallylsilane, cyclotetramethylenemethylallylsilane, cyclopentamethyleneallylsilane, cyclopentamethylenemethylallylsilane, cyclopentamethyleneethylallylsilane, etc. Saturated ring hydrocarbon monomer having, cyclobutyldimethylvinylsilane, cyclopentyldimethylvinylsilane, cyclopentylethylmethylvinylsilane, cyclopentyldiethylvinylsilane, cyclopentyldiethylvinylsilane, cyclohexylvinylsilane, cyclohexyldimethylvinylsilane, cyclohexylethylmethylvinylsilane, cyclobutyldimethylallylsilane , Cyclopen Saturated ring hydrocarbons containing silicon outside the saturated ring structure such as dimethylallylsilane, cyclohexylmethylallylsilane, cyclohexyldimethylallylsilane, cyclohexylethylmethylallylsilane, cyclohexyldiethylallylsilane, 4-trimethylsilylvinylcyclohexane, and 4-trimethylsilylallylcyclohexane. The body is raised.

Examples of the branched chain olefins include 3-methylbutene-1,3-methylpentene-1,3-ethylpentene-
3-position branched olefin such as 1, 4-ethylhexene-1,
4,4-dimethylpentene-1,4,4-dimethylhexene-
4-position branched olefin such as 1, vinyltrimethylsilane,
Alkenylsilanes such as vinyltriethylsilane, vinyltri-n-butylsilane, allyltrimethylsilane, allylethyldimethylsilane, allyldiethylmethylsilane, allyltriethylsilane, allyltrin-propylsilane, 3-butenyltrimethylsilane, 3-butenyltriethylsilane. And diallylsilanes such as dimethyldiallylsilane, ethylmethyldiallylsilane, and diethyldiallylsilane.

As the aromatic monomer, styrene, and alkylstyrenes such as o-methylstyrene and pt-butylstyrene, which are derivatives thereof, 2,4-dimethylstyrene, 2,5-dimethylstyrene, Dialkylstyrenes such as 3,4-dimethylstyrene and 3,5-dimethylstyrene, 2-methyl-4-fluorostyrene, 2-ethyl-
Halogen-substituted styrenes such as 4-chlorostyrene, o-fluorostyrene, p-fluorostyrene, p-trimethylsilylstyrene, m-triethylsilylstyrene,
Trialkylsilylstyrenes such as p-ethyldimethylsilylstyrene, o-allyltoluene, allyltoluenes such as p-allyltoluene, 2-allyl-p-xylene, 4-allyl-o-xylene, 5-allyl-m. -Allylxylenes such as xylene, vinyldimethylphenylsilane, vinylethylmethylphenylsilane, vinyldiethylphenylsilane, allyldimethylphenylsilane,
Alkenylphenylsilanes such as allylethylmethylphenylsilane, and 4- (o-tolyl) -butene-1
And 1-vinylnaphthalene, and one or more kinds of these non-linear olefins are used.

A catalyst for use in the present invention, which is obtained by combining the titanium trichloride composition (III) obtained as described above, an organoaluminum compound (A ₂ ) and an aromatic carboxylic acid ester (E) in a predetermined amount described below. Or more preferably, it is used as a catalyst pre-activated by reacting an olefin.

The polymerization mode of the propylene-olefin block copolymer of the present invention using the above catalyst is not limited, and slurry polymerization,
In addition to liquid phase polymerization such as bulk polymerization, gas phase polymerization can be suitably performed. A catalyst obtained by combining a titanium trichloride composition (III) with an organoaluminum compound (A ₂ ) and an aromatic carboxylic acid ester (E) is sufficiently effective for slurry polymerization or bulk polymerization, but it is effective for gas phase polymerization. When used, the titanium trichloride composition (III) is replaced with a titanium trichloride composition (III) and an organoaluminum compound, and this is reacted with an olefin to preactivate it to obtain a higher activity. It is desirable to use a catalyst component.

When performing gas phase polymerization following slurry polymerization or bulk polymerization, even if the catalyst initially used is the former, the latter catalyst will be the same since the reaction of propylene has already been carried out during gas phase polymerization. And an excellent effect can be obtained.

Pre-activation is based on 1 g of titanium trichloride composition (III),
Organoaluminum compound 0.005 g to 500 g, solvent 0 to 50 l,
0 to 1,000 ml of hydrogen and 0.01 to 5,000 g, preferably 0.05 g to 3,000 g of olefin are used at 0 ° C to 100 ° C for 1 minute to 20
The olefin is allowed to react for a time, and the titanium trichloride composition (II
I) It is desirable to polymerize 0.01 g to 2,000 g, preferably 0.05 to 200 g of olefin per 1 g.

The reaction of olefins for preactivation is n-pentane,
It can be carried out in an aliphatic or aromatic hydrocarbon solvent such as n-hexane, n-heptane, or toluene, or in a liquefied olefin such as liquefied propylene or liquefied butene-1 without using a solvent. The reaction can be carried out in a phase, or can be carried out in the presence of an olefin polymer and hydrogen in advance.

It is also possible to add the aromatic carboxylic acid ester (E) in advance in the preliminary activation.

Examples of the olefin used for preactivating include linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, 4-methyl-pentene-1. , 2-ethyl-
Branched chain mono-olefins such as benzene-1 are listed, and 1
More than one type of olefin is used. Further, as the organoaluminum compound, the same ones as the above-mentioned (A ₁ ) can be used, but a dialkylaluminum monohalide similar to the below-mentioned (A ₂ ) is preferably used.

After completion of the pre-activation reaction, the catalyst obtained by adding a predetermined amount of the aromatic carboxylic acid ester (E) to the pre-activation catalyst component slurry can be used as it is for propylene-olefin block copolymerization. The coexisting solvent, unreacted olefin and organoaluminum compound are removed by filtration or decantation, and dried powder or a suspension of the powder is added with a solvent. ₂ ) and the aromatic carboxylic acid ester (E) are used as a catalyst to provide a catalyst for propylene-olefin block copolymerization,
Coexisting solvent and unreacted olefin under reduced pressure distillation,
Or, by an inert gas flow or the like, it is evaporated to remove, and the powder or granules or the powder and granules in a suspended state by adding a solvent, to which the organoaluminum compound (A ₂ ) is added, if necessary, It is also possible to combine the aromatic carboxylic acid ester (E) into a catalyst and use it as a propylene-olefin block copolymer.

During propylene-olefin block copolymerization,
The above titanium trichloride composition (III), the total amount of the organoaluminum compound (A ₂ ) including the additional organoaluminum compound (A ₂ ), and the aromatic carboxylic acid ester (E)
With respect to the amount used, the molar ratio (E) of the aromatic carboxylic acid ester (E) and the titanium trichloride composition (III) is
/ (III) is 1.0 to 10.0, and the molar ratio (A ₂ ) of the organoaluminum compound (A ₂ ) to the titanium trichloride composition (III)
/ (III) is used in a range of 0.1 to 200, preferably 0.1 to 100.

If the amount of the aromatic carboxylic acid ester (E) added is small, the isotacticity of the polymer will not be sufficiently improved, so that the rigidity will not be high, and if it is too large, the polymerization activity will decrease, which is not practical. The number of moles of the titanium trichloride composition (III) refers to the number of Ti gram atoms substantially contained in (III).

Dialkylaluminum monohalide is preferably represented by titanium trichloride composition (III) and combined with the organoaluminum compound (A _2), and the general formula AIR ¹⁰ as the organic aluminum compound (A ₂₎ used if necessary R ¹¹ X .

In the formula, R ¹⁰ R ¹¹ represents a hydrocarbon group such as an alkyl group, an aryl group, an alkaryl group, a cycloalkyl group or an alkoxy group, X represents halogen, and specific examples thereof include diethylaluminum monochloride and di-n. -Propyl aluminum monochloride, di-butyl aluminum monochloride, di-n-butyl aluminum monochloride, diethyl aluminum monoiodide, diethyl aluminum monobromide and the like.

Specific examples which can be used as the aromatic carboxylic acid ester (E) which is another component constituting the catalyst include ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate,
Methyl toluate, ethyl toluate, toluic acid 2-
Ethylhexyl, methyl anisate, ethyl aniate, broth anisate, ethyl cinnamate, methyl naphthoate,
Propyl naphthoate, butyl naphthoate, naphthoic acid 2
-Ethylhexyl, ethyl phenylacetate and the like.

The propylene-olefin block copolymer of the present invention is subjected to propylene polymerization as the first stage using the catalyst thus combined.

Usually, the polymerization temperature is 20 ° C to 100 ° C, preferably 40 ° C to 85 ° C.
Is. If the temperature is too low, the polymerization activity becomes low, which is not practical, and if the temperature is high, it becomes difficult to increase the isotacticity. Polymerization pressure is normal pressure to 50 kg
/ cm ² G is usually carried out for about 30 minutes to 15 hours. During polymerization,
The addition of an appropriate amount of hydrogen for controlling the molecular weight is the same as the conventional polymerization method.

The block copolymerization of propylene and olefin of the present invention may be carried out by slurry polymerization carried out in an inert solvent such as n-hexane or n-heptane, bulk polymerization carried out in a liquefied monomer, or gaseous monomer as mentioned above. It is possible to carry out any of the forms of gas phase polymerization carried out in a monomer, and it is also possible to carry out a combination of these forms.

In the first-stage propylene polymerization, as long as the propylene-olefin block copolymer finally obtained can maintain high rigidity, for example, 5% by weight or less of ethylene, butene-1, or 4-methylpentene-1 is used. Such olefins can be used in combination with propylene.

However, in order to maintain high rigidity of the propylene-olefin block copolymer obtained by the method of the present invention, homopolymerization of propylene is desirable and easy to carry out. In addition, in order to balance the rigidity and impact resistance of the resulting block copolymer, the total amount of polymer (Note.
(Excluding the soluble polymer eluted in the solvent), 60 to 95% by weight of propylene is polymerized. It is also possible to carry out the first-stage polymerization in multiple stages.

Subsequent to the first-stage polymerization, the first-stage polymerization mixture was used to carry out copolymerization of propylene and an olefin other than propylene in the second-stage polymerization under the same range of polymerization conditions as in the first-stage polymerization. Perform in one step or multiple steps. The term "one step of polymerization" means a continuous or temporary supply of the monomer. In this second-stage copolymerization, 40% to 5% by weight of the total amount of the above-mentioned polymer is copolymerized with propylene and an olefin other than propylene.

However, the olefin content in the finally obtained block copolymer (note: excluding the soluble polymer eluted in the solvent) must be within the range of 3 to 30% by weight.

Therefore, when only 10% by weight of propylene was polymerized in the first stage, the amount of olefins copolymerized in the second stage was 30%.
Since it is limited to less than 10% by weight, propylene must be copolymerized for the remaining 10% by weight or more.

Specific examples of the olefin other than propylene to be used by mixing with propylene in the second step described above include linear chains such as ethylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1. Mono-olefins, 4
-Methylpentene-1,2-methylpentene-1,3-
Branched-chain monoolefins such as methylbutene-1 and styrene are mentioned, and one or more kinds thereof are used.

Thus, the propylene-olefin block copolymer obtained by the method of the present invention is a propylene-olefin block copolymer having both high rigidity and high impact resistance, and known injection molding, vacuum molding, extrusion molding and blow molding. It is provided as various molded products by the technique such as molding.

[Operation] In the method of the prior art which uses a catalyst preliminarily activated by only a non-linear olefin, the pre-activated catalyst component is pulverized or swelled during the reaction of the non-linear olefin, resulting in a shape Becomes significantly worse. Therefore, when the pre-activated catalyst component is dried and then used for block copolymerization, a solid polymer is produced as a result of solidification in the bulk during drying, and the pre-activated catalyst is also formed. When the components are used in the block copolymerization in a slurry state, they cause operational problems such as runaway of the polymerization reaction and adhesion of scale to the reactor wall. As a result, the obtained block copolymer also has insufficient improvement in the balance between rigidity and impact resistance.

In contrast to the above-mentioned conventional techniques, the titanium trichloride composition (III) used in the present invention has a non-linear olefin polymer introduced by the method of the present invention, which is a polymerization treatment from the production stage. In addition, a solid titanium trichloride composition (III) is formed, which does not deteriorate the shape of the catalyst component and is difficult to be crushed. Therefore, when the catalyst component is used for block copolymerization, stable and continuous polymerization operation becomes possible.

Further, as a result of stable polymerization operation, propylene-obtained
The quality of the olefin block copolymer is also stable.

In particular, in the polymerization treatment during production of the titanium trichloride composition (III) according to the present invention, when a linear olefin is used in addition to the non-linear olefin, the linear olefin-non-produced by the multi-stage polymerization treatment is used. Since the linear olefin polymer block of the linear olefin block copolymer has compatibility with the propylene-olefin block copolymer, the non-linear olefin polymer block of propylene-
Since the dispersibility in the olefin block copolymer is highly improved, it is presumed that the nucleating action of the non-linear olefin polymer block is significantly exerted, and as a result, the rigidity of the resulting propylene-olefin block copolymer and It is presumed that the impact resistance is improved.

Furthermore, although the detailed mechanism thereof is unknown, the propylene-obtained by the method of the present invention is obtained by the high-rigidity polymer production performance possessed by the catalyst in which a predetermined amount of the aromatic carboxylic acid ester used in the present invention is combined. The olefin block copolymer is an excellent one having both high rigidity and high impact resistance in combination with the effect of the polymerization treatment during the production of the titanium trichloride composition (III) described above.

[Examples] Hereinafter, the present invention will be described with reference to Examples. Definitions of terms used in Examples and Comparative Examples and measurement methods are as follows.

(1) MFR: Melt flow rate JIS K 7210 Table 1 condition 1
According to 4. (Unit: g / 10 minutes) (2) Olefin content: Based on infrared absorption spectroscopy.

(3) Rigidity: Tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane based on 100 parts by weight of the block copolymer.
0.1 part by weight and 0.1 part by weight of calcium stearate were mixed, and the mixture was granulated using an extruder having a screw diameter of 40 mm. Then, the granulated product was made into a JIS type test piece at a molten resin temperature of 230 ° C. and a mold temperature of 50 ° C. with an injection molding machine, and the test piece was allowed to stand in a room at a humidity of 50% and room temperature of 23 ° C. for 88 hours. The flexural modulus was measured according to JIS K 7203. (Unit: kgf / cm ² ) (4) Impact resistance: Izod impact strength: A test piece was prepared in the same manner as (3), and Izod impact strength was measured according to JIS K 7210. (Unit: kgf · cm / cm) DuPont impact strength: A test piece was prepared in the same manner as in (3), and the DuPont impact strength was measured by the following method. The roundness (R) of the tip is a 0.25 inch hammer, the inner diameter of the hammer cradle is 1.5 inches, the load drop height is 1 m, and the load is 100 g to 5,000 g.
Using a DuPont impact tester consisting of, drop the load from a height of 1 m at a temperature of -20 ° C, find the load when 50% of the test piece is cracked, and multiply the load by the drop height (100 cm). Then, the impact strength was obtained. (Unit: kgf · cm) Example 1 (1) Preparation of titanium trichloride composition (III) n-hexane 6 l, diethylaluminum monochloride (DEAC) 5.0 mol, diisoamyl ether 12.0 mol 25 ° C
And mixed for 1 minute at room temperature and reacted at the same temperature for 5 minutes to obtain a reaction product solution (I) (diisoamyl ether / DEAC molar ratio 2.4).

Put 40 mol of titanium tetrachloride in a reactor purged with nitrogen and
After heating to ℃, the whole amount of the above reaction product liquid (I) was added dropwise over 18 minutes, kept at the same temperature for 60 minutes, heated to 80 ℃ and reacted for 1 hour, cooled to room temperature, Remove the supernatant,
The operation of adding 20 l of n-hexane and removing the supernatant by decantation was repeated 4 times to obtain a solid product (II).

The whole amount of this (II) was suspended in 30 l of n-hexane, 400 g of diethylaluminum monochloride was added, 1.5 kg of propylene was added at 30 ° C., and a polymerization treatment was carried out at the same temperature for 1 hour. After the elapse of the reaction time, the supernatant was removed by decantation, and the solid was washed twice with 30 l of n-hexane.

Subsequently, 30 liters of n-hexane and 400 g of diethylaluminum monochloride were added, the temperature was raised to 40 ° C., 1.9 kg of vinylcyclohexane was added, and polymerization was carried out at 40 ° C. for 2 hours. After the reaction was completed, the supernatant was removed and n-hexane 30l was added.
Was added and the operation of removing the supernatant liquid by decantation was repeated 4 times to obtain a solid product (II-A) which had been subjected to multi-stage polymerization treatment with propylene-vinylcyclohexane.

With the total amount of this solid product (II-A) suspended in 9 l of n-hexane, 3.5 kg of titanium tetrachloride was added at room temperature to about 10
After adding for 1 minute and reacting at 80 ° C. for 30 minutes, 1.6 kg of diisoamyl ether was further added and reacted at 80 ° C. for 1 hour. After the reaction was completed, the operation of removing the supernatant was repeated 5 times and then dried under reduced pressure to obtain a titanium trichloride composition (III).

In the obtained titanium trichloride composition (III), the content of propylene polymer block was 25.0% by weight, the content of vinylcyclohexane polymer block was 25.0% by weight, and the titanium content was 12.6% by weight.

(2) Preparation of pre-activated catalyst component After replacing a stainless reactor with an inclined blade with an internal volume of 150 l with nitrogen gas, 100 l of n-hexane, 114 g of diethylaluminum monochloride, and the titanium trichloride composition obtained in (1) After adding 1.8 kg of the compound (III) at room temperature and supplying 1.8 Nm ^{3 of} ethylene at 30 ° C. for 2 hours to cause a reaction (1 g of the titanium trichloride composition (III) reacts with 1.0 g of ethylene), Unreacted ethylene was removed, washed with n-hexane, filtered and dried to obtain a preactivated catalyst component.

(3) Manufacture of block copolymer MFR 30 polypropylene powder 30 in a horizontal first-stage polymerizer with L / D = 4 equipped with a stirrer with an internal volume of 150 L and nitrogen substitution
After adding kg, to the pre-activated catalyst component obtained in (2) above, n was added.
-Hexane was added to make a 4.0 wt% n-hexane suspension, and the suspension was converted into titanium atoms at 10.3 mg atom / hr, and diethyl aluminum monochloride and methyl p-toluate were added to the titanium atoms. On the other hand, a catalyst was supplied from the same pipe so that the molar ratio was 7.0 and 1.0, respectively.

Further, hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 18.3% by volume, and propylene was supplied so that the total pressure was maintained at 23 kgf / cm ² G. It was carried out in.

During the polymerization, the retention level of the polymer in the polymerization vessel was 45% by volume.
The polymer was extracted at 13.5 kg / hr so that When a part of the extracted polymer was collected and analyzed, the MFR was 70.
It was 0. After the first-stage polymerization was completed, the extracted polymerization mixture consisting of the catalyst and the polymer was continuously introduced into a horizontal second-stage polymerizer having the same internal volume of 150 l as the first-stage polymerizer. .

While introducing the polymerization mixture into the second-stage polymerization vessel as described above, hydrogen was added so that the concentration in the vapor phase in the polymerization vessel was 8.5% by volume, and the molar ratio of ethylene and propylene in the vapor phase was maintained. Was maintained at 0.38 and the total pressure was maintained at 5.5 kg / cm ² G, ethylene and propylene were continuously fed to the second-stage polymerizer, and ethylene and propylene were copolymerized at 60 ° C. . During the copolymerization, the block copolymer was continuously withdrawn at 15.7 kg / hr from the polymerization reactor so that the level of the block copolymer retained in the polymerization reactor was 44% by volume.

The extracted block copolymer was subsequently contact-treated with nitrogen gas containing 0.2% by volume of propylene oxide at 95 ° C. for 30 minutes, and then with 100 ° C. steam for 30 minutes.
Further, it was dried with nitrogen gas at 100 ° C. to obtain a propylene-ethylene block copolymer.

As described above, propylene-ethylene block copolymerization was continuously carried out for 168 hours, but no operational problems occurred and a propylene-ethylene block copolymer was stably produced. The MFR of the obtained copolymer was 25.0,
The ethylene content was 8.5% by weight.

Comparative Example 1 (1) In (1) of Example 1, the multistage polymerization of propylene and vinylcyclohexane for the solid product (II) was omitted, and the solid product (II) was replaced with the solid product (II-
A titanium trichloride composition was obtained in the same manner except that it was the equivalent of A).

(2) A pre-activated catalyst component was obtained in the same manner as in (2) of Example 1, except that the titanium trichloride composition obtained in (1) above was used in place of the titanium trichloride composition (III). .

(3) Propylene-ethylene block copolymerization was carried out in the same manner as in (3) of Example 1 except that the pre-activated catalyst component obtained in (2) above was used as the pre-activated catalyst component. An ethylene block copolymer was obtained.

Comparative Example 2 The titanium trichloride composition was obtained by omitting the second stage polymerization treatment of vinylcyclohexane on the solid product (II) in (1) of Example 1 and reacting only propylene. A titanium trichloride composition (II
(2) of Example 1 except that it is used instead of I),
Propylene-ethylene block copolymer was performed in the same manner as in (3) to obtain a propylene-ethylene block copolymer.

Comparative Example 3 (1) A titanium trichloride composition was obtained in the same manner as in (1) of Comparative Example 1.

(2) In the reactor used in (2) of Example 1, 100 l of n-hexane, 300 g of diethylaluminum monochloride,
And 1.8) kg of the titanium trichloride composition obtained in (1) above at room temperature, and then 1.5 kg of vinylcyclohexane.
The reaction was carried out at 0 ° C. for 2 hours (0.5 g of vinylcyclohexane was reacted per 1 g of the titanium trichloride composition). After the elapse of the reaction time, the supernatant was removed by decantation, washed with n-hexane, filtered and dried to obtain a preactivated catalyst component.

(3) Propylene-ethylene block copolymerization was performed in the same manner as in Example 1 (3) except that the pre-activated catalyst component obtained in the above (2) was used as the pre-activated catalyst component. Since the bulk polymer blocked the polymer withdrawing from the polymerization vessel, after the start of polymerization,
The propylene-ethylene block copolymer had to be stopped in 4 hours.

Comparative Example 4 (1) Titanium trichloride composition obtained in the same manner as in Comparative Example 1 (1) when the reaction product liquid (I) was reacted with titanium tetrachloride in (1) of Comparative Example 1. Using 500 g of the product and 120 g of diethylaluminum monochloride as a catalyst, 1.3 kg of vinylcyclohexane added in 100 l of n-hexane was polymerized at 60 ° C for 2 hours, washed with methanol and dried to obtain vinylcyclohexane. United 95
A titanium trichloride composition containing 33.3% by weight of a vinylcyclohexane polymer in the same manner except that 0 g was pulverized in a vibrating mill having a capacity of 10 l at room temperature for 5 hours and then suspended in the titanium tetrachloride. Got

(2) A preactivated catalyst component was obtained in the same manner as in (2) of Example 1 except that the titanium trichloride composition obtained in the above (1) was used instead of the titanium trichloride composition (III). .

(3) Block copolymerization was carried out in the same manner as in (3) of Example 1 except that the pre-activated catalyst component obtained in (2) above was used as the pre-activated catalyst component. Got united.

Comparative Example 5 4 l of n-hexane and 10 mol of titanium tetrachloride were placed in a reactor purged with nitrogen and kept at 0 ° C. 4 l of an n-hexane solution containing 8 mol of diisoaluminum monochloride was added dropwise to 80 ° C. The temperature was raised and the reaction was continued for 1 hour. After the reaction was completed, the mixture was cooled to room temperature, the supernatant was removed, and then the produced solid was washed with n-hexane. Subsequently, the total amount of the solid was suspended in 30 liters of n-hexane, 400 g of diethylaluminum monochloride was added, 1.5 kg of propylene was added at 30 ° C., and then polymerization was carried out at the same temperature for 1 hour.

After the elapse of the reaction time, the supernatant was removed by decantation, and the solid was washed twice with 30 l of n-hexane. Next, after adding 30 liters of n-hexane and 400 g of diethylaluminum monochloride, the temperature was raised to 40 ° C., 1.9 kg of vinylcyclohexane was added, and a polymerization treatment was carried out at the same temperature for 2 hours. After the polymerization treatment, the supernatant was removed, and then 5 liters of n-hexane
Repeat the operation of adding and removing by decantation three times,
The solid product obtained by the polymerization treatment was added with 9 l of n-hexane.
Suspended in. Subsequently, 3.5 kg of titanium tetrachloride was added at room temperature and reacted at 90 ° C for 1 hour. After the reaction is completed, n
-Washing with hexane gave a titanium trichloride composition.

Block copolymerization was carried out in the same manner as in Example 1 except that the titanium trichloride composition (III) was used instead of the titanium trichloride composition (III) to obtain a block copolymer.

Comparative Example 6 In (3) of Example 1, the catalyst comprising diethyl aluminum monochloride and the pre-activated catalyst component used in Comparative Example 2 as the pre-activated catalyst component was supplied without supplying methyl p-toluate. The total pressure in the first stage polymerization vessel is
Supply to the first-stage polymerization reactor so as to maintain 23 kg / cm ² G, and adjust the hydrogen concentration in the gas phase in the first-stage polymerization reactor to 9.5.
Volume%, the hydrogen concentration in the gas phase in the second stage polymerization vessel is 4.0
Propylene-ethylene block copolymerization was carried out in the same manner except that the volume% was used.

Comparative Example 7 A polypropylene was obtained in the same manner as in (3) of Example 1 except that the copolymerization of propylene and ethylene in the second stage was omitted.

Comparative Example 8 and Examples 2 and 3 In (1) of Example 1, the amounts of propylene and vinylcyclohexane used were changed to obtain titanium trichloride compositions (III) whose contents were as shown in the table. It was A propylene-ethylene block copolymer was obtained in the same manner as in (2) and (3) of Example 1 except that the titanium trichloride composition (III) was used.

Example 4 (1) In (1) of Example 1, the amount of propylene used in the polymerization treatment of the solid product (II) was 0.6 kg,
Further, a titanium trichloride composition (III) was obtained in the same manner except that 6.1 kg of allyl trimethyl sila was used instead of vinylcyclohexane.

(2) In the same manner as in (2) of Example 1, except that the titanium trichloride composition (III) obtained in (1) above is used as the titanium trichloride composition (III), a preactivated catalyst is similarly prepared. The ingredients are obtained.

(3) For the horizontal first-stage polymerization vessel used in (3) of Example 1
After adding 30 kg of MFR 10 polypropylene powder, n-hexane was added to the pre-activated catalyst component obtained in (2) above to make a 4.0 wt% n-hexane suspension, and the suspension was made of titanium. Diethyl aluminum monochloride and methyl p-toluate were continuously supplied as catalysts from the same pipe at a molar ratio of 7.0 and 1.0 with respect to titanium atom at 9.5 mg atom / hr in terms of atom.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was 7.9% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg / cm ² G, and the first-stage propylene polymerization was conducted at 70 ° C. Carried out.

During the polymerization, the retention level of the polymer in the polymerization vessel was 45% by volume.
The polymer was continuously extracted at 13.5 kg / hr so that When a part of the extracted polymer was collected and analyzed, the MFR was 15.0. After the 1st stage polymerization was completed, the polymerization reaction mixture consisting of the extracted catalyst and polymer was continuously introduced into the horizontal type 2nd stage polymerizer used in (3) of Example 1.

While introducing the polymerization reaction mixture from the first-stage polymerization reactor into the second-stage polymerization reactor as described above, hydrogen and ethylene were added so that the concentration in the air in the polymerization reactor was maintained at 22% by volume. Ethylene and propylene were continuously fed to the second-stage polymerization reactor so that the molar ratio of propylene in the gas phase was maintained at 0.29 and the total pressure in the polymerization reactor was maintained at 5.0 kg / cm ² G. Was copolymerized with ethylene and propylene.

During the copolymerization, the block copolymer was continuously withdrawn at a rate of 15.5 kg / hr from the second-stage polymerizer so that the level of the retained block copolymer in the second-stage polymerizer was 44% by volume. . The extracted block copolymer was subjected to the same post-treatment as in Example 1 to continuously produce a propylene-ethylene block copolymer for 168 hours.

During this period, the operation was stable and no manufacturing problems occurred. The MFR of the obtained block copolymer is 10.0,
The ethylene content was 6.0% by weight.

Comparative Example 9 In (1) of Example 4, the solid product (II) was omitted from the multistage polymerization treatment with propylene and allyltrimethylsilane, and the solid product (II) was replaced with the solid product (II-
A titanium trichloride composition was obtained in the same manner except that it was the equivalent of A). Block copolymerization was carried out in the same manner as in (2) and (3) of Example 4 except that the titanium trichloride composition was used instead of the titanium trichloride composition (III).

Comparative Example 10 (1) A titanium trichloride composition was obtained in the same manner as in (1) of Comparative Example 1.

(2) In the reactor used in (2) of Example 1, 100 l of n-hexane, 300 g of diethylaluminum monochloride,
And 1.8 kg of the titanium trichloride composition obtained in (1) above was added at room temperature, and then 4.3 kg of allyltrimethylsilane was added.
The reaction was carried out at 0 ° C for 2 hours. After the reaction was completed, the supernatant was removed by decantation, and the solid was washed with n-hexane.

Subsequently, 100 l of n-hexane and 300 g of diethylaluminum monochloride were added at room temperature, and then propylene 0.5 k
g was added and reacted at 30 ° C. for 1 hour. After the elapse of the reaction time, the supernatant was removed by decantation, washed with n-hexane, filtered and dried to obtain a preactivated catalyst component.

(3) Propylene-ethylene block copolymerization was carried out in the same manner as in Example 3 (3) except that the pre-activated catalyst component obtained in the above (2) was used as the pre-activated catalyst component. Since the block polymer blocked the polymer withdrawing pipe from the polymerization vessel,
The propylene-ethylene block copolymer had to be stopped in 15 hours.

Example 5 (1) In (1) of Example 1, the amount of propylene used in the polymerization treatment of the solid product (II) was 0.75 kg,
Also, instead of vinylcyclohexane, 3-methylbutene-
A titanium trichloride composition (III) was obtained in the same manner except that 2.7 kg of 1 was used.

(2) The titanium trichloride composition (I) obtained in the above (1) as the titanium trichloride composition (III) in (2) of Example 1
II) A preactivated catalyst component was obtained in the same manner except that it was used.

(3) For the horizontal first-stage polymerization vessel used in (3) of Example 1
After adding 30 kg of MFR 10 polypropylene powder, n-hexane was added to the pre-activated catalyst component obtained in (2) above to make a 4.0 wt% n-hexane suspension, and the suspension was made of titanium. Diethyl aluminum monochloride and methyl p-toluate were continuously supplied as catalysts from the same pipe at a molar ratio of 7.0 and 0.5 with respect to titanium atom at 6.5 mg atom / hr in terms of atom.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was 4.4% by volume, and propylene was supplied so that the total pressure was 23 kg / cm ² G. It was carried out in.

During the polymerization, the retention level of the polymer in the polymerization vessel was 45% by volume.
The polymer was continuously extracted at 13.5 kg / hr so that A part of the extracted polymer was collected and analyzed, and the MFR was 10.0. After the completion of the first-stage polymerization, the polymerization reaction mixture consisting of the catalyst and the polymer withdrawn was continuously introduced into the horizontal second-stage polymerization vessel used in (3) of Example 1.

While introducing the polymerization reaction mixture from the first-stage polymerization reactor into the second-stage polymerization reactor as described above, hydrogen and ethylene were added so that the concentration in the gas phase in the polymerization reactor was maintained at 12.5% by volume. Ethylene and propylene were continuously supplied to the second-stage polymerization reactor so that the molar ratio of propylene in the gas phase was maintained at 0.40 and the total pressure in the polymerization reactor was maintained at 3.0 kg / cm ² G, and the temperature was maintained at 60 ° C. In the above, copolymerization of ethylene and propylene was carried out.

During the copolymerization, the block copolymer was continuously withdrawn at a rate of 14.5 kg / hr from the second-stage polymerizer so that the level of the block copolymer held in the second-stage polymerizer was 44% by volume. The extracted block copolymer was subjected to the same post-treatment as in Example 1 to continuously produce a propylene-ethylene block copolymer for 168 hours.

During this period, the operation was stable and no manufacturing problems occurred. The MFR of the obtained block copolymer was 8.0 and the ethylene content was 4.3% by weight.

Example 6 and Comparative Examples 11 to 13 In (3) of Example 5, changing the molar ratio of methyl p-toluate to titanium atom as shown in the table.
In addition, the total pressure of each catalyst component in the first stage polymerization vessel was 23 kg / cm ²
Propylene-ethylene block copolymerization was performed in the same manner as in Example 5 except that the amount of G was supplied.

Example 7 (1) Preparation of titanium trichloride composition (III) n-heptane 4l, ethylaluminum monochloride 5.
The reaction solution obtained by reacting 9.0 mol of 0 mol diisoamyl ether and 5.0 mol of di-n-butyl ether at 18 ° C for 30 minutes was added dropwise to 27.5 mol of titanium tetrachloride at 40 ° C over 300 minutes, and then at the same temperature. After reacting for 1.58 hours, the temperature was raised to 65 ° C and the reaction was carried out for 1 hour. The supernatant was removed and n-hexane was added.
The operation of adding 20 L and removing by decantation was repeated 6 times, and 1.8 kg of the obtained solid product (II) was added to 40 L of n-hexane.
Suspended in diethyl aluminum monochloride 50
0 g was added, and 1.1 Nm ^{3 of} ethylene was supplied at 30 ° C. for 1 hour to carry out the first-stage polymerization treatment.

After the reaction time passed, unreacted ethylene was removed, and 4,4-dimethylpentene-1 was further added without washing the reaction mixture.
3.0 kg was added and reacted at 40 ° C. for 2 hours to carry out a second stage polymerization treatment to obtain a solid product (II-A) which was subjected to a multi-stage polymerization treatment with ethylene-4,4-dimethylpentene-1. It was

After the reaction, the supernatant liquid was removed, 20 l of n-hexane was added, and the operation of removing by decantation was repeated twice. The solid product (II-A) subjected to the above-mentioned polymerization treatment was suspended in 7 l of n-hexane. Turbid, 1.8 kg of titanium tetrachloride, n-butyl ether
1.8 kg was added and reacted at 60 ° C. for 3 hours. After the reaction,
After removing the supernatant liquid by decantation, 20 l of n-hexane was added, the mixture was stirred for 5 minutes and allowed to stand, and the operation of removing the supernatant liquid was repeated 3 times, followed by vacuum drying to obtain a titanium trichloride composition ( III) was obtained.

(2) Preparation of pre-activated catalyst component In the same manner as in (2) of Example 1 except that the titanium trichloride composition (III) obtained in (1) above was used as the titanium trichloride composition (III). To obtain a preactivated catalyst component.

(3) Manufacture of Block Copolymer A n-hexane was added to the pre-activated catalyst component obtained in the above (2) in a stirrer-equipped polymerization vessel equipped with a 2-stage turbine blade having an internal volume of 150 l and having nitrogen substitution, After preparing a 4.0 wt% n-hexane suspension, the suspension was converted into titanium atom at 19.0 mg / hr and diethylaluminum monochloride and methyl p-toluate were used in a molar ratio of 3.0 to titanium atom, respectively. And from the same pipe to 1.0
In addition, n-hexane was continuously supplied at 24 kg / hr from another pipe.

Furthermore, hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 18% by volume, and propylene was supplied so that the total pressure was maintained at 8 kg / cm ² G, respectively. The polymerization was carried out at 70 ° C.

During the polymerization, the retention level of the polymer slurry in the polymerization vessel is
The polymer slurry was continuously withdrawn so that the volume became 80% by volume. The polymer slurry that was extracted was subsequently used, and the second stage of the first stage with the same internal volume of 150 l as used in the first stage was used.
It was continuously introduced into the staged polymerizer.

Hydrogen was further supplied to the polymerization vessel so that the concentration in the gas phase of the polymerization vessel was kept at 15% by volume, and propylene was supplied so that the total pressure was kept at 10 kg / cm ² G, respectively. Two-stage propylene polymerization was carried out at 70 ° C.

During the polymerization, the retention level of the polymer slurry in the polymerization vessel is
The polymer slurry was used as a polymer so as to be 68% by volume.
It was continuously extracted at 3.8 kg / hr. A part of the extracted polymer slurry was collected, dried and analyzed, and the MFR was 50.
It was 0. The first-stage polymerization consisting of two stages is completed,
The polymerization mixture consisting of the withdrawn catalyst, n-hexane and polymer was subsequently continuously introduced into a second-stage polymerizer having an internal volume of 100 l in the same manner as the first-stage polymerizer.

While introducing the polymerization mixture into the second stage polymerization vessel as described above, hydrogen was added so that the concentration in the vapor phase in the polymerization vessel was 15.5% by volume, and the molar ratio of ethylene and propylene in the vapor phase was maintained. Was maintained at 0.45 and the total pressure was maintained at 5.4 kg / cm ² G, ethylene and propylene were continuously fed to the second-stage polymerization vessel, and ethylene and propylene were copolymerized at 60 ° C. . During the copolymerization, the block copolymer slurry was continuously withdrawn from the polymerizer into a flash tank having an internal volume of 40 l so that the retained level of the block copolymer slurry in the polymerizer was 62% by volume.

Reduce pressure in the flash tank to remove unreacted hydrogen, ethylene, and propylene while adding 1 kg / hr of methanol.
And contact treatment was performed at 70 ° C. Subsequently, after neutralization with an aqueous solution of sodium hydroxide, the polymer was washed with water, separated, and dried to obtain a propylene-ethylene block copolymer at 15 kg / hr for 168 hours continuously. During the production period of the block copolymer, no operational problems occurred and the production was extremely stable. The MFR of the obtained copolymer was 3
0.0, the ethylene content was 4.6% by weight.

Comparative Example 14 In (7) of Example 7, the solid product (II) was replaced with the solid product (II) by omitting the multi-stage polymerization treatment of ethylene and 4,4-dimethylpentene-1.
-A) A titanium trichloride composition was obtained in the same manner except that it was the equivalent. Block copolymerization was carried out in the same manner as in (2) and (3) of Example 7 except that the titanium trichloride composition was used instead of the titanium trichloride composition (III).

Example 8 (1) Preparation of titanium trichloride composition (III) 27.0 mol of titanium tetrachloride was added to 12 liters of n-hexane and the temperature was 1 ° C.
After cooling to 1, 22.5 l of n-hexane containing 27.0 mol of diethylaluminum monochloride was further added dropwise at 1 ° C over 4 hours. After completion of the dropping, the reaction was carried out at the same temperature for 15 minutes, then the temperature was raised to 65 ° C. over 1 hour, and the reaction was further performed at the same temperature for 1 hour.

Next, the procedure of removing the supernatant liquid, adding 10 liters of n-hexane, and removing by decantation was repeated 5 times. Of 5.7 kg of the obtained solid product (II), 1.8 kg was suspended in 50 liters of n-hexane. Then, 350 g of diethylaluminum monochloride was added, and 6.9 kg of p-trimethylsilylstyrene was further added, and polymerization treatment was carried out at 40 ° C. for 2 hours.

After the polymerization treatment, the supernatant was removed, 30 l of n-hexane was added, and the operation of removing by decantation was repeated twice.
The total amount of the obtained solid product (II-A) subjected to the multi-stage polymerization treatment was suspended in 11 l of n-hexane, and 1.2 l of diisoaluminum ether and 0.4 l of ethyl benzoate were added thereto.
The suspension was stirred at 35 ° C for 1 hour and then mixed with 3 liters of n-hexane.
It was washed twice to obtain a treated solid.

The treated solid obtained was suspended in 6 l of an n-hexane solution containing 40% by volume of titanium tetrachloride and 10% by volume of silicon tetrachloride.

This suspension was heated to 65 ° C. and reacted at the same temperature for 2 hours. After the reaction was completed, 20 l of n-hexane was used once and 3
The solid thus obtained was washed and then dried under reduced pressure to obtain a titanium trichloride composition (III).

(2) Preparation of pre-activated catalyst component In (2) of Example 1, the titanium trichloride composition (II
The titanium trichloride composition (I) obtained in (1) above as I)
II) 1.8 kg is used, and propylene 2.5 is used instead of ethylene.
A preactivated catalyst component was obtained in the same manner except that kg was used.

(3) Manufacture of block copolymer MFR 15 was added to the horizontal first-stage polymerizer used in (3) of Example 1.
After adding 30 kg of the polypropylene powder mentioned above, n-hexane was added to the pre-activated catalyst component obtained in (2) above to obtain 4.0
After preparing a suspension of n-hexane in a weight percentage of 14.9 mg / hr in terms of titanium atom, the suspension was converted to diethylaluminium monoiodide and di-n-propylaluminum monochromate as an organoaluminum compound (A ₂ ). The equimolar mixture of the rides was adjusted to a molar ratio of 6.0 with respect to the titanium atom, and p-
Ethyl anisate was continuously supplied as a catalyst from the same pipe so that the molar ratio to titanium atom was 1.0.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was 9.0% by volume, and propylene was supplied so that the total pressure was 23 kg / cm ² G. It was carried out in.

During the polymerization, the retention level of the polymer in the polymerization vessel was 45% by volume.
The polymer was continuously extracted at 13.5 kg / hr so that When a part of the extracted polymer was collected and analyzed, the MFR was 20.0. After the first-stage polymerization was completed, the polymerization reaction mixture consisting of the catalyst and the polymer withdrawn was continuously introduced into the horizontal second-stage polymerization vessel used in (3) of Example 1.

While introducing the polymerization reaction mixture from the first-stage polymerization reactor into the second-stage polymerization reactor as described above, hydrogen and ethylene were added so that the concentration in the gas phase in the polymerization reactor was kept at 31% by volume. The molar ratio of propylene in the gas phase was 0.34, the molar ratio of butene-1 and propylene in the gas phase was 0.01, and the total pressure in the polymerization vessel was
Ethylene, butene-1 and propylene were continuously fed to the second-stage polymerization vessel so as to maintain 4.0 kg / cm ² G at 60 ° C.
In, ethylene, butene-1 and propylene were copolymerized.

During the copolymerization, the block copolymer was continuously withdrawn from the second-stage polymerizer at 15.8 kg / hr so that the retained level of the block copolymer in the second-stage polymerizer was 44% by volume. The extracted block copolymer was subjected to the same post-treatment as in Example 1, and the block copolymer was continuously produced for 168 hours.

During this period, the operation was stable and no manufacturing problems occurred. The MFR of the obtained block copolymer is 15.0,
The total content of ethylene and butene-1 was 5.3% by weight.

Comparative Example 15 In (8) of Example 8, the solid product (II) was omitted from the polymerization treatment with p-trimethylsilylstyrene, and the solid product (II) was used as the solid product (II-A) equivalent. A titanium trichloride composition was obtained in the same manner except for the above.
Using the titanium trichloride composition instead of the titanium trichloride composition (III), a block copolymer was obtained in the same manner as in Example 8, (2) and (3).

The table below shows the catalyst conditions and results of the above Examples and Comparative Examples.

[Effect of the Invention] The main effect of the present invention is that a propylene-olefin block copolymer having both high rigidity and high impact resistance can be stably obtained without causing any problems in production.

As is apparent from the above-mentioned Examples, the propylene-olefin block copolymer obtained by the method of the present invention has
Compared with known block copolymers obtained by ordinary methods and block copolymerization methods obtained by the method of the invention of the prior application, it has good rigidity and impact resistance, and in particular, the rigidity is remarkably improved. (Examples 1-8, Comparative Examples 1,2,7,9,14,1
See 5).

Therefore, it can be widely applied to the field of various molding methods, especially the field of injection molding, and its characteristics can be exhibited.

On the other hand, according to the method of the prior art in which the non-linear olefin polymer is introduced into the block copolymer by a method other than the present invention, operational problems occur and continuous operation for a long period of time is impossible. Also, the block copolymer obtained is insufficient in improving the balance between rigidity and impact resistance (see Comparative Examples 3, 4, and 10).

[Brief description of drawings]

FIG. 1 is a manufacturing process diagram (flow sheet) for explaining the method of the present invention.

Claims (7)

[Claims] 1. A solid product obtained by reacting an organoaluminum compound (A ₁ ) or a reaction product (I) of an organoaluminum compound (A ₁ ) with an electron donor (B ₁ ) with titanium tetrachloride. A titanium trichloride composition obtained by polymerizing (II) with a non-linear olefin, or a linear olefin and a non-linear olefin, and further reacting an electron donor (B ₂ ) with an electron acceptor ( III) in combination with an organoaluminum compound (A ₂ ) and an aromatic carboxylic acid ester (E), the aromatic carboxylic acid ester (E) and the titanium trichloride composition (III) (converted to the number of Ti atoms, the same applies hereinafter). The molar ratio of (E) / (III) = 0.1 to 10.0, and the molar ratio of the organoaluminum compound (A ₂ ) to the titanium trichloride composition (III) is (A ₂ ) / (III) = 0.1. Using the catalyst of ~ 200, To polymerize 60% to 95% by weight of the total polymerization amount of propylene, and then copolymerize 40% to 5% by weight of the total polymerization amount of propylene with an olefin other than propylene in the second stage. Content of olefin other than propylene in the block copolymer to be used is 3% to 30% by weight
The method for producing a propylene-olefin block copolymer, comprising: 2. An organoaluminum compound (A ₁ ) having a general formula of AlR ¹ _p R ² _{p ′} X _{3- (p + p ′)} (wherein R ¹ , R ²
Represents a hydrocarbon group such as an alkyl group, a cycloalkyl group or an aryl group or an alkoxy group, and X represents a halogen,
Further, p and p'represent an arbitrary number of 0 <p + p'≤3. The manufacturing method of Claim 1 which uses the organoaluminum compound represented by these. 3. A non-linear olefin having the following formula: CH ₂ ═CH—R ³ (wherein R ³ has a saturated ring structure of a hydrocarbon which may contain silicon; Good carbon number 3
It represents a saturated ring hydrocarbon group from 1 to 18. The manufacturing method of Claim 1 which uses the saturated ring hydrocarbon monomer shown by these. 4. A non-linear olefin having the following formula: (In the formula, R ⁴ has 1 to 3 carbon atoms which may contain silicon.
Represents a chain hydrocarbon group up to, or silicon, R ⁵ ,
R ⁶ and R ⁷ represent a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and any one of R ⁵ , R ⁶ and R ⁷
The individual may be hydrogen. The manufacturing method of Claim 1 which uses the branched chain olefins shown by these. 5. A non-linear olefin having the following formula: (In the formula, n is 0, 1 or m is 1, 2 and R ⁸
Represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen or halogen. , M is 2, each R ⁹ may be the same or different. The manufacturing method of Claim 1 which uses the aromatic type monomer shown by these. 6. The production method according to claim 1, wherein a dialkylaluminum monohalide is used as the organoaluminum compound (A ₂ ). 7. A catalyst component prepared by combining the titanium trichloride composition (III) with an organoaluminum compound instead of the titanium trichloride composition (III) and reacting a small amount of an olefin to pre-activate the catalyst component. The manufacturing method according to item 1 of the above.