JPH06102706B2 - Process 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 pre-activated 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,
Following homopolymerization of propylene, there is a method of block copolymerizing propylene and an olefin other than propylene. However, the block copolymer is significantly improved in impact resistance as compared with crystalline polypropylene,
There is a problem that the rigidity decreases.

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.

On the other hand, the present inventors have already produced a propylene-olefin block copolymer having both high rigidity and impact resistance using a catalyst composed of a specific titanium trichloride composition, an organoaluminum compound, and a specific organosilicon compound. A method (Japanese Patent Application No. 1-7,428, which may hereinafter be referred to as a prior invention) has been proposed, but further improvement is desired.

MEANS TO SOLVE THE PROBLEM These artificers solved the problems which the above-mentioned prior art has, and earnestly researched about the method of manufacturing the propylene-olefin block copolymer which has both high rigidity and high impact resistance superior to the invention of prior application. . As a result, in the case of producing a propylene-olefin block copolymer by using a catalyst that has been subjected to a specific pre-activation treatment by combining the same catalyst components as those used in the invention of the prior application, it has already been described. The inventors have found that the problems in manufacturing and quality of the prior art are solved, and have reached the present invention.

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) Titanium trichloride composition (III), organoaluminum compound (A ₁ ), and Si—O—C bond and / or
Alternatively, in a method for producing a propylene-olefin block copolymer by copolymerizing propylene and an olefin other than propylene using a catalyst composed of an organosilicon compound (S) having a mercapto group, a titanium trichloride composition (III) As a solid product (II) obtained by reacting an organoaluminum compound (A ₂ ) or a reaction product (I) of an organoaluminum compound (A ₂ ) with an electron donor (B ₁ ) with titanium tetrachloride. Using a titanium trichloride composition (III) obtained by further reacting an electron donor (B ₂ ) and an electron acceptor with or without polymerization treatment with olefin. The composition (III) is combined with the organoaluminum compound (A ₁ ), and a linear olefin is added thereto in an amount of 0.01 g to 100 g per 1 g of the titanium trichloride composition (III).
After the polymerization reaction, 1 g of the non-linear olefin was continuously added to the titanium trichloride composition (III).
Therefore, 0.001 g to 100 g of a pre-activated catalyst component obtained by a polymerization reaction, an additional organoaluminum compound (A ₁ ) if necessary, and an organosilicon compound having a Si—O—C bond and / or a mercapto group ( S) in combination with the organosilicon compound (S) having the Si—O—C bond and / or mercapto group and the titanium trichloride composition (II
The molar ratio of (I) (based on the number of Ti atoms, the same applies hereinafter) is (S) / (I
II) = 1.0 to 10.0 and a catalyst having a molar ratio of the organoaluminum compound (A ₁ ) to the titanium trichloride composition (III) of (A ₁ ) / (III) = 0.1 to 200, The first step is to polymerize 60% to 95% by weight of the total polymerization amount of propylene, and the second step is to copolymerize 40% to 5% by weight of the total polymerization amount of propylene with olefins other than propylene. A method for producing a propylene-olefin block copolymer, characterized in that the olefin content in the obtained block copolymer is 3% by weight to 30% by weight.

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

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

(4) 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 the said 1st item using the saturated ring hydrocarbon monomer shown by these.

(5) As the non-linear olefin, 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 ,
R ⁷ represents 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 may be hydrogen. The manufacturing method of said 1st item using the branched chain olefin shown by these.

(6) 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 item which uses the aromatic type monomer shown by these.

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

The titanium trichloride composition (III) used in the present invention is produced as follows. First, a reaction product (I) is obtained by reacting organoaluminum (A ₂ ) with an electron donor (B ₁ ), and a solid product (I) obtained by reacting this reaction product with titanium tetrachloride ( II) or a solid product (II) obtained by reacting an organoaluminum compound (A ₂ ) with titanium tetrachloride
Polymerized with or without olefin,
Further, as the final solid product (III) obtained by reacting the electron donor (B ₂ ) with the electron acceptor, the titanium trichloride composition (III) used in the present invention is produced.

First, the reaction between the organoaluminum compound (A ₂ ) and the electron donor (B ₁ ) to obtain the reaction product (I) is carried out in the solvent (D) at −20 ° C. to 200 ° C., preferably −10 ° C. At ~ 100 ° C
Do 30 seconds to 5 hours. (A ₂ ), (B ₁ ), (D) There is no limitation on the ignition sequence, and the quantity ratio used is 1 organoaluminum.
The electron donor is 0.1 to 8 mol, preferably 1 to mol.
4 mol, 0.5 to 5 l of solvent, preferably 0.5 to 2 l are suitable. Aliphatic hydrocarbons are preferred as the solvent. Thus, the reaction product (I) is obtained. The reaction product (I) can be subjected to the next reaction in a liquid state as it is after completion of the reaction (sometimes referred to as reaction product (I)) without separation.

Next, the reaction between the reaction product (I) or the organoaluminum compound (A ₂ ) and titanium tetrachloride (C) is 0 to 200
C., preferably 10 to 90.degree. C., for 5 minutes to 8 hours. Although it is preferable not to use a solvent, an aliphatic or aromatic hydrocarbon can be used. The mixing of (A ₂ ) or (I), (C) and the solvent may be carried out in any order, and it is preferable that the mixing of the entire amount be completed within 5 hours. The amount of each used in the reaction is 1 mol of titanium tetrachloride, and the solvent is 0 to
3,000 ml of organoaluminum compound (A ₂ ) or reaction product (I) is the ratio of the number of Al atoms in (A ₂ ) or (I) to the number of Ti atoms in titanium tetrachloride (Al / Ti ) At 0.05
-10, preferably 0.06-0.3.

After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and the solid product (II) thus obtained is further washed with a solvent, and the obtained solid product (II) is suspended in the solvent to the next step. It may be used, or may be dried and taken out as a solid to be used.

It is also possible to polymerize a solid product (II) obtained by reacting the organoaluminum compound (A ₂ ) or the reaction product (I) with titanium tetrachloride, and use it for the next reaction. Is.

In the present invention, "polymerizing" means that the olefin is polymerized by bringing the solid product (II) into contact with the solid product (II) under a condition in which a small amount of olefin can be polymerized. By this polymerization treatment, the solid product (II) is in a state of being coated with the polymer.
As a method of polymerizing with an olefin, (1) an olefin is added at any stage of the reaction between the organoaluminum compound (A ₂ ) or the reaction product (I) and titanium tetrachloride to give a solid product (II). (2) a method of polymerizing, a method of polymerizing the solid product (II) by adding an olefin after the reaction of the organoaluminum compound (A ₂ ) or the reaction product (I) with titanium tetrachloride is completed, 3) After completion of the reaction between the organoaluminum compound (A ₂ ) or the reaction product (I) and titanium tetrachloride, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product (II) is obtained. There is a method of suspending in a solvent, further adding an organoaluminum compound and an olefin, and polymerizing.

The organoaluminum compound (A ₂₎ or the reaction product when adding olefins any process and an organoaluminum compound in the reaction of (I) and titanium tetrachloride (A ₂₎ or the reaction product (I) with titanium tetrachloride When the olefin is added after the reaction with, the reaction temperature is 30 to 90 ° C for 5 minutes to 10 hours, and the olefin is passed at atmospheric pressure or 10 kg / cm ³ G
Add to the pressure below. Regarding the amount of olefin added, it is desirable to polymerize 0.05 g to 1,000 g using 10 to 5,000 g of olefin per 100 g of the solid product (II).

After the completion of the reaction of the organoaluminum compound (A ₂ ) or the reaction product (I) with titanium tetrachloride in the polymerization treatment with an olefin, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product is obtained. When (II) is suspended in a solvent, 100 g of solid product (II) to 2,000 ml of solvent and 0.5 g of organoaluminum compound are added to 100 g of solid product (II).
~ 5,000 g, reaction temperature 0 ~ 90 ° C for 5 minutes ~ 10 hours, olefin 0 ~ 10 kg / cm ² G 10 ~ 5,000 g, 0.05 ~
It is desirable to polymerize 1,000 g.

The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound may be the same as or different from that used for (A ₂ ). After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and after further washing with a solvent, the obtained solid product subjected to polymerization treatment (hereinafter referred to as solid product (II-A) (Sometimes called) may be used in the next step in the state of being suspended in the solvent, and may be dried and taken out as a solid to be used.

The solid product (II) or (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 to be used is (B ₂ ) 0.1 g to 1,000 g, preferably 0.5 g to 200 g, based on 100 g of the solid product (II) or (II-A),
(F) 0.1 g to 1,000 g, preferably 0.2 g to 500 g, solvent 0
It is 3,000 ml, preferably 100 to 1,000 ml.

As a reaction method, a solid product (II) or (II-
A method in which an electron donor (B ₂ ) and an electron acceptor (F) are simultaneously reacted with A), and (F) is added to (II) or (II-A).
And then reacting with (B ₂ ), (II) or (II-A) with (B ₂ ) and then reacting with (F), (B ₂ ) and (F ₂ ), Then (II)
Alternatively, there is a method of reacting (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. In the method of (II) or (II
After reacting the reaction of (A) with (B ₂ ) at 0 ° C to 50 ° C for 1 minute to 3 hours, the reaction with (F) is performed 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 below, and
After adding I) or (II-A), the reaction is carried out under the same conditions as above.

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

The organoaluminum compound (A ₂ ) used in the production of the titanium trichloride composition (III) used in the present invention has 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, 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, nityl 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, isopropylbenzene, 2-ethylnaphthalene, alkyl-substituted compounds such as 1-phenylnaphthalene, monochlorobenzene, chlorotoluene, Halides such as chlorxylene, chloroethylbenzene, dichlorobenzene, and brombenzene are shown.

As the olefin used in the polymerization treatment, ethylene,
Propylene, butene-1, pentene-1, hexene-
1, straight chain monoolefins such as 1, heptene-1, and branched chain monoolefins such as 4-methyl-pentene-1, 2-methyl-pentene-1 are used. These olefins may be used as a mixture of two or more kinds.

The titanium trichloride composition (III) obtained as described above is combined with an organoaluminum compound (A ₁ ), and a straight chain olefin is added to the titanium trichloride composition (III) 1
After a polymerization reaction of 0.01 g to 100 g per g, subsequently, a non-linear olefin is added to the titanium trichloride composition (III) 0.001 g to 100 g per 1 g of the titanium trichloride composition (III). Accordingly, an additional organoaluminum compound (A ₁ ) and an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group (hereinafter sometimes abbreviated as organosilicon compound (S)). And is used as a catalyst used in the present invention.

The first stage pre-activation with a linear olefin is carried out by adding 0.005 g to 500 g of an organoaluminum compound (A ₁ ) to ₁ g of the titanium trichloride composition (III), 0 to 50 l of a solvent, 0 to 1,000 ml of hydrogen,
And 0.01 g to 5,000 g of linear olefin, 0 ° C to 1
At a temperature of 00 ° C, atmospheric pressure ~ 50 kg / cm ² G, 1 minute ~
0.01g per 1g of titanium trichloride composition (III) over 10 hours
100 g of linear olefin are polymerized. When the amount of the polymerization reaction per 1 g of the titanium trichloride composition (III) is less than 0.01 g, the improvement of the runnability and the rigidity and impact resistance of the obtained propylene-olefin block copolymer are insufficient, and
Even if it exceeds 100 g, the improvement of various effects is not remarkable, which is disadvantageous in operation.

After the completion of the first-stage pre-activation, the reaction mixtures can be used as they are in the subsequent second-stage pre-activation reaction. Further, the coexisting solvent, unreacted linear olefin, and organoaluminum compound (A ₁ ) are removed by filtration or decantation, and the powder or the powder is suspended by adding a solvent to the powder. Alternatively, an additional organoaluminum compound (A ₁ ) may be added to this product to be used for the pre-activation by the second stage non-linear olefin.

Under the same reaction conditions as in the first-stage pre-activation, the second-stage pre-activation with the non-linear olefin was replaced with the linear olefin by 0.001 g per 1 g of the titanium trichloride composition (III).
0.001 g to 100 g, preferably 0.01 g to 10 g per 1 g of the titanium trichloride composition (III) using 5,000 g of a non-linear olefin.
It is desirable to polymerize 0g. When the amount of polymerization reaction is less than 0.001 g, the effect of improving the rigidity and impact resistance of the resulting block copolymer is insufficient, and when it exceeds 100 g, the effect is not significantly improved, which is economically disadvantageous.

The above-mentioned first-stage and second-stage pre-activation treatments are indispensable according to the above method, first of all, a pre-activation treatment with a linear olefin and then a non-linear olefin. Therefore, the effect of the present invention cannot be obtained if the order of the preliminary activation treatment is reversed.

After the completion of the second stage pre-activation treatment, it is possible to additionally perform the third stage pre-activation treatment with a linear olefin at a reaction amount of 100 g or less per 1 g of the titanium trichloride composition (III). is there.

The preliminary activation can be carried out in a hydrocarbon solvent such as n-pentane, n-hexane, n-heptane or toluene, and hydrogen may be allowed to coexist during the preliminary activation.

After the pre-activation reaction is completed, the catalyst obtained by adding a predetermined amount of the organosilicon compound (S) to the pre-activation catalyst component slurry can be used as it is for the propylene-olefin block copolymer, or it can be used together. Solvent, unreacted olefin, and organoaluminum compound (A ₁ )
Is removed by filtration or decantation, and the powder or particles are suspended by adding a solvent to the powder and the organoaluminum compound (A ₁ ) and the organosilicon compound (S). A method of providing a propylene-olefin block copolymer by combining them as a catalyst, a coexisting solvent, and unreacted olefins are evaporated and removed by distillation under reduced pressure, or by an inert gas flow, and the like, or a granular material or the granular material. A solvent is added to prepare a suspended state, and an organoaluminum compound (A ₁ ) is added to this as needed, and further combined with an organosilicon compound (S) to serve as a catalyst for propylene-olefin block copolymerization. It is also possible to use.

During propylene-olefin block copolymerization,
Regarding the total amount of the titanium trichloride composition (III), the organoaluminum compound (A ₁ ) including the additional organoaluminum compound (A ₁ ), and the amount of the organosilicon compound (S) used, the organosilicon compound The molar ratio (S) / (III) of (S) and the titanium trichloride composition (III) is 1.0 to 10.
0, and the molar ratio (A ₁ ) / (III) of the organoaluminum compound (A ₁ ) to the titanium trichloride composition (III) is 0.1 to 200.
Use within the range.

If the addition amount of the organosilicon compound (S) is small, the stereoregularity of the polymer is insufficiently improved, so that the polymer does not have high rigidity, and if the addition amount is too large, the polymerization activity decreases and it 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).

As the linear olefin used in the first pretreatment of the present invention, linear olefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, octene-1 are used, and particularly ethylene, propylene. Is preferably used. One or more kinds of these linear olefins are used.

The non-linear olefin used in the second-stage pre-activation treatment of the present invention has the following formula: CH ₂ = CH-R ³ (wherein R ³ is a saturated cyclic structure of a hydrocarbon which may contain silicon). Having 3 carbon atoms which may contain silicon
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, 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. ) Is an aromatic monomer.

Specifically, examples of the saturated ring hydrocarbon monomer include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, 3-methylvinylcyclopentane, vinylcyclohexane, 2-methylvinylcyclohexane, 3-methyl. In addition to vinylcycloalkanes such as vinylcyclohexane, 4-methylvinylcyclohexane and vinylcycloheptane, allylcycloalkanes such as allylcyclopentane and allylcyclohexane,
Cyclotrimethylenevinylsilane, cyclotrimethylenemethylvinylsilane, cyclotetramethylenevinylsilane, cyclotetramethylenemethylvinylsilane, cyclopentamethylenevinylsilane, cyclopentamethylenemethylvinylsilane, cyclopentamethyleneethylvinylsilane, cyclohexamethylenevinylsilane, cyclohexamethylenemethylvinylsilane, Saturated ring hydrocarbons having a silicon atom in the saturated cyclic structure such as cyclohexamethylene retyl vinyl silane, cyclotetramethylene allyl silane, cyclotetramethylene methyl allyl silane, cyclopentamethylene allyl silane, cyclopentamethylene methyl allyl silane, and cyclopentamethylene ethyl allyl silane. Monomers, cyclobutyldimethylvinylsilane, cyclopen Le dimethylvinylsilane, cyclopentylethyl methylvinylsilane, white pentyl diethyl vinyl silane, cyclohexyl vinyl silane, cyclohexyl dimethyl vinyl silane, cyclohexylethyl methylvinylsilane, cyclobutyl dimethylallyl silane, cyclopentyl dimethylallyl silane, cyclohexyl methyl allyl silane, cyclohexyl dimethylallyl silane, cyclohexyl ethyl methyl allyl silane,
Examples thereof include saturated ring-containing hydrocarbon monomers containing silicon in addition to the saturated cyclic structure such as cyclohexyldiethylallylsilane, 4-trimethylsilylvinylcyclohexane, and 4-trimethylsilylallylcyclohexane.

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.

Dialkylaluminum monohalide is preferably represented by titanium trichloride composition (III) and combined with the organoaluminum compound (A _1), and the general formula AIR ¹⁰ as the organic aluminum compound (A ₁₎ used optionally R ¹¹ X .

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

Specific examples of the organosilicon compound (S) having a Si—O—C bond and / or a mercapto group, which is another component constituting the catalyst, include methyltrimethoxysilane, vinyltrimethoxysilane, and allyl. Trimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, triphenylmethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxylane, Propyltriethoxysilane, allyltriethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, n-octyltriethoxysilane, n-octadecyltriethoxysilane, - triethoxysilane 2-
Norbornene, dimethyldiethoxysilane, diethyldiethoxysilane, diphenylgetoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylethoxysilane, allyloxytrimethylsilane, methyltri i-propoxysilane, dimethyldi i-
Propoxysilane, trimethyl i-propoxysilane,
Tetra n-butoxysilane, methyltrin-butoxysilane, tetra (2-ethylbutoxy) silane, methyltriphenoxysilane, dimethyldiphenoxysilane, trimethylphenoxysilane, trimethoxysilane, triethoxysilane, triethoxychlorosilane, tri i-
Propoxychlorosilane, tri-n-butoxychlorosilane, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, methyldiacetoxysilane, diacetoxymethylvinylsilane, dimethyldiacetoxysilane, methylphenyldiacetoxysilane, diphenyl Diacetoxysilane, trimethylacetoxysilane, triethylacetoxysilane, phenyldimethylacetoxysilane, triphenylacetoxysilane, bis (trimethylsilyl) adipate, trimethylsilylbenzoate,
Organosilicon compounds having a Si—O—C bond such as triethylsilylbenzoate, mercaptomethyltrimethylsilane, 2-mercaptoethyltrimethylsilane, 3-
Mercaptopropyltrimethylsilane, 4-mercapto-n-butyltrimethylsilane, mercaptomethyltriethylsilane, 2-mercaptoethyltriethylsilane, 3-mercaptopropyltriethylsilane, 1-mercaptoethyltrimethylsilane, mercaptopropyldimethylphenylsilane, 3-mercapto Organosilicon compounds having a mercapto group such as propylethylmethylphenylsilane, 4-mercaptobutyldiethylphenylsilane and 3-mercaptopropylmethyldiphenylsilane, mercaptomethyltrimethoxysilane, mercaptomethyldimethylmethoxymethylsilane, mercaptomethyldimethoxymethyl Silane, mercaptomethyltriethoxysilane, mercaptomethyldiethoxymethylsilane, mercapto Chill dimethylethoxysilane, 2
-Mercaptoethyltrimethoxysilane, 3-mercaptotopyrtrimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 3-mercaptopropyltriethoxysilane, diethoxy-3-mercaptopropylmethylsilane, mercaptomethyldimethyl-2-phenylethoxy Organosilicon compounds having a Si—O—C bond and a mercapto group such as silane, 2-mercaptoethoxytrimethylsilane, 3-mercaptopropoxytrimethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Aminopropyldiethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 2-ami Ethylaminomethyltrimethoxysilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane, 2-aminoethylaminomethylbenzyloxydimethylsilane, 3- [2- (2-aminoethylaminoethylamino) propyl] trimethoxy An organosilicon compound having a Si—O—C bond and an amino group, such as silane, can be given.

The propylene-olefin block copolymerization of the present invention is carried out by using a catalyst composed of a combination of the thus obtained pre-activated catalyst component and, if necessary, an additional organoaluminum compound (A ₁ ) and an organosilicon compound (S). Polymerization of propylene is carried out as the first stage.

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 stereoregularity. The polymerization pressure is normal pressure to 50 kg / cm ² G and is usually carried out for about 30 minutes to 15 hours. At the time of polymerization, the addition of an appropriate amount of water for controlling the molecular weight is the same as the conventional polymerization method.

The block copolymerization of propylene and olefin of the present invention is carried out by slurry polymerization carried out in an inert solvent such as n-hexane or n-heptane, bulk polymerization carried out in liquefied propene, or gas phase polymerization carried out in gaseous propylene. It is possible to carry out by any of the formats, and it is also possible to combine these formats.

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 is polymerized in the first stage, the amount of olefin copolymerized in the second stage is limited to 30% by weight or less. For the above, propylene must be copolymerized.

Specific examples of the olefin other than propylene to be used by mixing with propylene in the second stage described above include ethylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1 and the like. Chain monoolefins, 4
-Methyl-pentene-1, 2-methyl-pentene-1,
Branched chain monoolefins such as 3-methylbutene-1 and styrene can be 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 two-step pre-activation treatment according to the present invention is a solid pre-activation catalyst component having a good shape and less likely to be crushed by the pre-activation treatment with a linear olefin in the first step. By forming, the good shape is maintained even during the pre-activation treatment with the non-linear olefin in the second stage. Therefore, when the pre-activated catalyst component is used for block copolymerization, stable continuous polymerization operation can be performed regardless of drying.

Further, as a result of stable polymerization operation, propylene-obtained
The quality of the olefin block copolymer is stable, and the linear olefin polymer block of the linear olefin-non-linear olefin block copolymer produced by the two-step preactivation treatment is a propylene-olefin block copolymer. Since it has compatibility with the non-linear olefin polymer block, the dispersibility of the non-linear olefin polymer block in the propylene-olefin block copolymer is highly improved. Therefore, it is presumed that the rigidity and impact resistance are improved.

Furthermore, although the detailed mechanism thereof is unknown, Si-O-C
Due to the high-rigidity polymer production performance possessed by the catalyst in which a predetermined amount of the organosilicon compound (S) having a bond and / or a mercapto group is combined, the propylene-olefin block copolymer obtained by the method of the present invention has the above-mentioned 2
Combined with the effect of the stage preliminary activation treatment, it is an excellent product that has both high rigidity and high impact resistance.

[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.

(4) Impact resistance: Izod impact strength: A test piece was prepared in the same manner as in (3), and the 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) Mixing 6 l of n-hexane, 5.0 mol of diethyl aluminum monochloride (DEAC), 12 mol of diisoamyl ether at 25 ° C. for 1 minute. Then, the reaction was carried out for 5 minutes at the same temperature to obtain a reaction product liquid (I) (diisoamyl ether / DEAC molar ratio 2.4). 40 mol of titanium tetrachloride was placed in a reactor purged with nitrogen, heated to 35 ° C., and the whole amount of the reaction product (I) was added dropwise to this in 30 minutes, and then kept at the same temperature for 30 minutes, and then to 75 ° C. The temperature was raised and the reaction was continued for another 1 hour, the mixture was cooled to room temperature, the supernatant was removed, 20 l of n-hexane was added and the supernatant was removed by decantation was repeated 4 times to obtain 1.9 k of solid product (II).
got g.

The whole amount of (II) was suspended in 30 l of n-hexane, 200 g of diethylaluminum monochloride was added, 1.0 kg of propylene was added at 30 ° C., and the mixture was reacted for 1 hour to obtain a solid product (II-A) subjected to polymerization treatment. ) Was obtained.
6kg). After the reaction, the supernatant liquid was removed, 30 l of n-hexane was added and the operation of removing by decantation was repeated twice, and 2.5 kg of the solid product (II-A) subjected to the above-mentioned polymerization treatment was added to n.
-Suspended in 6 liters of hexane, added 3.5 kg of titanium tetrachloride at room temperature for about 1 minute, and reacted at 80 ° C for 30 minutes,
Further, 1.6 kg of diisoamyl ether was added and the reaction was carried out at 80 ° C for 1 hour. After the reaction was completed, the supernatant was removed by decantation, 40 l of n-hexane was added, and the mixture was stirred for 10 minutes,
The operation of leaving still and removing the supernatant was repeated 5 times, and then dried under reduced pressure to obtain a titanium trichloride composition (III). The titanium content in 1 g of the titanium trichloride composition (III) was 192 mg.

(2) Preparation of pre-activated catalyst component A stainless steel reactor with an internal volume of 150 liter equipped with a stirrer with inclined blades was replaced with nitrogen gas, and then 100 liter of n-hexane, 260 g of diethylaluminum monochloride, and (1) above were used. 1.8 kg of the obtained titanium trichloride composition (III) was added at room temperature. Then, the temperature in the reactor was set to 40 ° C., 2.4 kg of propylene was added, and the first pre-activation treatment was performed at 40 ° C. for 1 hour (1.0 g of propylene per 1 g of the titanium trichloride composition (III)). g reaction).

After the reaction time had elapsed, the supernatant was removed by decantation, and the solid was washed twice with 80 l of n-hexane. Subsequently, after adding 100 liters of n-hexane and 260 g of diethylaluminum monochloride, the temperature inside the reactor was set to 40 ° C,
Add 2.8 kg of vinylcyclohexane, 2 hours at 40 ℃, 2
The preliminary activation treatment of the second stage was performed. (Vinylcyclohexane 1.0 g reaction per 1 g of titanium trichloride composition (III)). After completion of the reaction, it was washed with n-hexane, filtered and dried to obtain a preactivated catalyst component.

(3) Manufacture of block copolymer MFR30 polypropylene powder 30k in a horizontal first stage L / D = 4 polymerization vessel equipped with a nitrogen-substituted stirrer with an internal volume of 150 l
After adding g, n was added to the pre-activated catalyst component obtained in (2) above.
-Hexane was added to make a 4.0 wt% n-hexane suspension, and the suspension was converted to titanium atom at 9.0 mg / hr, and diethylaluminum monochloride and allyltriethoxysilane were added to titanium atom. Then, the catalyst was supplied from the same pipe so that the molar ratio was 7.0 and 1.9, respectively.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 15.5% by volume, and propylene was supplied so that the total pressure was maintained at 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 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 maintained at 7.2% 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 block copolymer withdrawn was then treated with nitrogen gas containing 0.2% by volume of propylene oxide at 95 ° C. for 30 minutes.
After the contact treatment for a minute, the contact treatment was performed with steam at 100 ° C. for 30 minutes. Further, it was dried with nitrogen gas at 100 ° C, and propylene-
An ethylene block copolymer was obtained. 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, and the ethylene content was
It was 8.5% by weight.

Comparative Example 1 In (2) of Example 1, the preliminary activation treatment with vinylcyclohexane in the second step was omitted, and only propylene was reacted to obtain a preactivated catalyst component. A propylene-ethylene block copolymer was prepared in the same manner as in (3) of Example 1 except that the preliminary activation component was supplied so that the total pressure in the first-stage polymerization vessel was 23 kg / cm ² G. Got

Comparative Example 2 In (2) of Example 1, the preliminary activation treatment with propylene in the first step was omitted, and only vinylcyclohexane was reacted to obtain a preactivated catalyst component. A propylene-ethylene block copolymer was prepared in the same manner as in (3) of Example 1 except that the preliminary activation component was supplied so that the total pressure in the first-stage polymerization vessel was 23 kg / cm ² G. As a result, the produced bulk polymer blocked the polymer withdrawing from the polymerization vessel and closed the pipe, so that propylene-
The ethylene block copolymer had to be stopped.

Comparative Example 3 In (2) of Example 1, the pre-activation treatments of the first and second steps were carried out in the reverse order, and after the reaction of vinylcyclohexane, propylene was reacted to obtain a pre-activated catalyst component. When block copolymerization was carried out in the same manner as in (3) of Example 1 except that the pre-activated catalyst component was used, the produced bulk polymer blocked the polymer withdrawal pipe from the polymerization vessel. The block copolymerization had to be stopped within 6 hours after the initiation of the polymerization.

Comparative Example 4 In (3) of Example 1, the catalyst comprising the diethylaluminum monochloride and the pre-activated catalyst component used in Comparative Example 1 as the pre-activated catalyst component was first supplied without supplying allyltriethoxysilane. Supply to the first-stage polymerization reactor so that the total pressure in the first-stage polymerization reactor is maintained at 23 kg / cm ² G, and adjust the hydrogen concentration in the gas phase in the first-stage polymerization reactor.
9.5% by volume, the hydrogen concentration in the gas phase in the second stage polymerization vessel
A propylene-ethylene block copolymer was prepared in the same manner except that the content was 4.0% by volume.

Comparative Example 5 A polypropylene was obtained in the same manner as in Example 1 (3) except that the second copolymerization of propylene and ethylene was omitted.

Comparative Example 6 and Examples 2 and 3 In (2) of Example 1, the amounts of propylene and vinylcyclohexane used were changed to obtain pre-activated catalyst components whose reaction amounts were as shown in the table. A propylene-ethylene block copolymer was prepared in the same manner as in (3) of Example 1 except that the preliminary activation component was supplied so that the total pressure in the first-stage polymerization vessel was 23 kg / cm ² G. Got

Example 4 (1) A titanium trichloride composition (III) was obtained in the same manner as in (1) of Example 1.

(2) In (2) of Example 1,
A preactivated catalyst component was obtained in the same manner except that 960 g and 6.2 kg of allyltrimethylsilane were used instead of vinylcyclohexane.

(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. At 8.7 mg atom / hr in terms of atom, the molar ratio of diethylaluminum monoclide and phenyltriethoxysilane to titanium atom is 7.0 each.
And 2.0 were continuously supplied as a catalyst from the same pipe.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was 6.7% by volume, and propylene was supplied so that the total pressure was kept at 23 kg / cm ² G, and the first-stage propylene polymerization was carried out 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 completion of the first-stage polymerization, the polymerization mixture consisting of the withdrawn catalyst and polymer 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 18% 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. In the above, copolymerization of ethylene and propylene was carried out.

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 MRF of the obtained block copolymer is 10.0,
The ethylene content was 6.0% by weight.

Comparative Example 7 In (2) of Example 4, the pre-activation treatment with allyltrimethylsilane in the second step was omitted, and only propylene was reacted to obtain a pre-activated catalyst component. Block copolymerization was carried out in the same manner as in (3) of Example 4 except that it was used.

Comparative Example 8 In (2) of Example 4, the pre-activation treatment with propylene in the first step was omitted, and only the allyltrimethylsilane was reacted to obtain the pre-activated catalyst component. When propylene-ethylene block copolymerization was carried out in the same manner as in (3) of Example 4 except that it was used, the produced bulk polymer blocked the polymer withdrawing pipe from the polymerization vessel, and thus the polymerization was initiated. After that, the block copolymerization had to be stopped in 12 hours.

Comparative Example 9 In the same manner as in (2) of Example 4 except that the order of the pre-activation treatments of the first step and the second step was reversed and propylene was reacted after the reaction of allyltrimethylsilane,
A preactivated catalyst component was obtained. Propylene-ethylene block copolymerization was carried out in the same manner as in (3) of Example 4 except that the pre-activated catalyst component was used. The produced bulk polymer blocked the polymer withdrawal pipe from the polymerization vessel. Therefore, the block copolymerization had to be stopped 15 hours after the initiation of the polymerization.

Example 5 (1) A titanium trichloride composition (III) was obtained in the same manner as in (1) of Example 1.

(2) A pre-activated catalyst component was obtained in the same manner as in (2) of Example 1 except that 1.2 kg of propylene was used and 2.6 kg of 3-methylbutene-1 was used instead of vinylcyclohexane. It was

(3) In the horizontal first-stage polymerization section 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. 7.8 mg atom / hr in terms of atom, diethyl aluminum monochloride and dimethoxy-3-
Mercaptopropylmethylsilane was continuously supplied as a catalyst to the titanium atom from the same pipe so that the molar ratio was 7.0 and 1.3, respectively.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was kept at 4.0% by volume, and propylene was supplied so that the total pressure was kept at 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 11.5% 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 10 to 12 In (3) of Example 5, the molar ratio of dimethoxy-3-mercaptopropylmethylsilane to titanium atom was changed as shown in the table, and each catalyst component was changed to the first stage. Propylene-ethylene block copolymerization was carried out in the same manner as in Example 5 except that the total pressure in the polymerization vessel was adjusted to 23 kg / cm ² G.

Example 7 (1) Preparation of titanium trichloride composition (III) 8 l of n-heptane, 16 mol of di-n-butylaluminum monochloride and 10 mol of di-n-butyl ether were mixed at 30 ° C for 10 minutes and reacted for 20 minutes. Then, a reaction product liquid (I) was obtained. The whole amount of this reaction product liquid (I) was added dropwise to a solution consisting of 5 liters of toluene and 64 mol of titanium tetrachloride kept at 45 ° C for 60 minutes, then heated to 85 ° C and further reacted for 2 hours. ,
The mixture was cooled to room temperature, the supernatant was removed, 30 l of n-heptane was added, and the operation of removing the supernatant by decantation was repeated twice to obtain 4.9 kg of a solid product (II).

The whole amount of this (II) was suspended in 30 l of n-heptane, 2.0 kg of di-n-butyl ether and 15 kg of titanium tetrachloride were added at room temperature for about 20 minutes, and the mixture was reacted at 90 ° C for 2 hours, cooled, and then decanted. After removing the supernatant by filtration, washing with n-heptane and drying were performed to obtain a titanium trichloride composition (III). The content of titanium atoms in 1 g of the titanium trichloride composition (III) was 255 mg.

(2) Preparation of pre-activated catalyst component In the reactor used in (2) of Example 1, n-hexane 10 was added.
Ol, 1.73 kg of diethylaluminum monochloride, and 0.9 kg of the titanium trichloride composition (III) obtained in (1) above were added at room temperature. The temperature in the reactor was set to 35 ° C., and 450 Nl of ethylene was supplied at the same temperature for 1 hour to perform the first stage pre-activation treatment (titanium trichloride composition (III) 1
0.5g ethylene per g reaction).

Then, unreacted ethylene was removed, 3.0 kg of 4,4-dimethylpentene-1 was added to the reaction mixture without washing the reaction mixture, and the mixture was heated at 40 °
The second stage pre-activation treatment was carried out for 2 hours (for 1 g of the titanium trichloride composition (III), 4,4-dimethylpentene-1
1.0 g reaction), a pre-activated catalyst component was obtained in a slurry state.

(3) Manufacture of block copolymer Into a polymerization vessel equipped with a stirrer and equipped with a 2-stage turbine blade with an internal volume of 150 l, which had been replaced with nitrogen, was added the slurry of the pre-activated catalyst component obtained in the above (2) 17.5 mg atom in terms of titanium atom
/ amino-triethoxysilane was supplied continuously at a molar ratio of 2.5 with respect to titanium atoms at a rate of / hr, and n-hexane was continuously fed at a rate of 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 14% by volume, and propylene was supplied so that the total pressure was maintained at 8 kg / cm ² G. 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 added to the polymerization reactor so that the concentration in the gas phase of the polymerization reactor was kept at 14% by volume.
Propylene was supplied so that the total pressure was maintained at 10 kg / cm ² G, and the propylene polymerization in the first stage and the second stage 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 slurry was taken out from the polymer, dried, and analyzed.
It was 0.0. After the first stage polymerization consisting of two stages is completed, the extracted polymerization mixture of the catalyst, n-hexane and polymer is continuously added to the second stage having the same internal volume of 100 liters as the first stage polymerizer. It was continuously introduced into the staged 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 inside the polymerization vessel was 11% by volume, and the molar ratio of ethylene and propylene in the vapor phase was maintained. But
Ethylene and propylene were continuously fed to the second-stage polymerization vessel so that the total pressure was kept at 0.45 and the total pressure was kept at 5.4 kg / cm ² G, and the copolymerization of ethylene and propylene was carried out at 60 ° C. Regarding the copolymer, the block copolymer slurry was continuously withdrawn from the polymerizer into a flash tank having an inner volume of 40 l so that the level of the block copolymer slurry retained 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 13 In (3) of Example 7, 0.9 kg of the titanium trichloride composition (III) obtained in (1) of Example 7 and 1.73 kg of diethylaluminum monochloride instead of the preactivated catalyst component slurry, And using a catalyst component slurry in which 40-liter of n-hexane was mixed, and supplying each catalyst component to the polymerization reactor so that the total pressure in the first stage first stage polymerization reactor was maintained at 8 kg / cm ² G. Was subjected to block copolymerization in the same manner.

Comparative Example 14 In the reaction for obtaining the solid product (II) in (1) of Example 7, 16 mol of diethylaluminum monochloride was used instead of the reaction product (I), and the reaction was performed at 0 ° C. instead of 45 ° C. In the same manner as (1) of Example 7, after dropping, the temperature was raised to 75 ° C., the mixture was further stirred and reacted for 1 hour, and then refluxed at the boiling temperature of titanium tetrachloride (about 136 ° C.) for 4 hours to change to purple, cooled, and filtered. After drying, titanium trichloride (RA) was obtained. Block copolymerization was carried out in the same manner as in Example 7 except that this titanium trichloride (RA) was replaced with the titanium trichloride composition (III) of Example 7.

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 the completion of dropping, the temperature was kept at the same temperature for 15 minutes for reaction, then the temperature was raised to 65 ° C over 1 hour, and the temperature was further increased to 1 ° C.
Reacted for hours. Next, the supernatant was removed, and 10 l of n-hexane was added.
Repeat 5 times by adding and removing by decantation.
Of 5.7 kg of the obtained solid product (II), 1.8 kg was suspended in 11 l of n-hexane, and 1.2 g of diisoamyl ether was added thereto.
1 and 0.4 l of ethyl benzoate were added. 3 this suspension
After stirring at 5 ° C for 1 hour, the solid was washed 5 times with 3 liters of n-hexyne 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 completion of the reaction, 20 l of n-hexane was used once to wash the solid obtained three times 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) A pre-activated catalyst component was obtained in the same manner except that 1.8 kg was used, the amount of propylene used was 1.3 kg, and p-trimethylsilylstyrene was used instead of vinylcyclohexane in an amount of 9.6 kg.

(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 by weight of n-Hekin, the suspension was converted into titanium atom at 17.9 mg atom / hr and diethylaluminium monoiodide and di-n-propylaluminum monochromate were used as the organoaluminum compound (A ₁ ). Catalyst from the same pipe so that the molar ratio of the equimolar mixture of titanium to titanium atom is 6.0 and mercaptomethyltrimethylsilane as the organosilicon compound (S) is 2.8 to titanium atom. Was continuously supplied as.

Also, hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was kept at 8.0% by volume, and propylene was supplied so that the total pressure was kept at 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 unit into the second-stage polymerization unit as described above, hydrogen and ethylene were added so that the concentration in the gas phase in the polymerization unit was kept at 25% 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 polymerization, 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 (2) of Example 8, the pre-activation treatment with p-trimethylsilylstyrene in the second stage was omitted, and only propylene was reacted to obtain a pre-activated catalyst component. (3) of Example 8 except that the pre-activated catalyst component was used and each catalyst component was supplied to the polymerization reactor so that the total pressure in the first polymerization reactor was maintained at 23 kg / cm ² G. Block copolymerization was carried out in the same manner as.

Example 9 A preactivated catalyst component was obtained in the same manner as in (2) of Example 1 except that 1.8 Nm ^{3 was} used instead of propylene. Then, a block copolymer was obtained in the same manner as in (3) of Example 1 using the pre-activated catalyst component.

Examples 10 and 11 Block copolymers were prepared in the same manner as in Examples 2 and 3 except that ethylene 18Nm ³ (Example 10) and 360Nl (Example 11) were used instead of propylene during preactivation. Obtained.

Example 12 A polypropylene was obtained in the same manner as in Example 4 except that 720 Nl of ethylene was used instead of propylene during the preliminary activation.

Examples 13 and 14 Preliminarily activated catalyst components were obtained in the same manner as in Examples 5 and 6 except that 900 Nl of ethylene was used instead of propylene. Subsequently, a block copolymer was obtained by using the pre-activated catalyst component in the same manner as in (5) of Examples 5 and 6.

Example 15 A preactivated catalyst component was obtained in the same manner as in Example 8 (2) except that 970 Nl of ethylene was used instead of propylene. Then, a block copolymer was obtained in the same manner as in (3) of Example 8 using the pre-activated catalyst component.

The table below shows the preliminary activation treatment 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 usual methods and block copolymerization methods obtained by the method of the invention of the prior application, it has good rigidity and impact resistance, and especially the rigidity is remarkably improved. (Examples 1 to 14, Comparative Examples 1, 4, 7, 13, 15
reference).

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, even when using a catalyst that has been pre-activated with a non-linear olefin,
If the preliminary activation treatment according to the method of the present invention is not carried out, operational problems will occur and continuous operation for a long period of time will be impossible. Further, the obtained block copolymer also has insufficient improvement in the balance between rigidity and impact resistance (see Comparative Examples 2, 3, 8, 9).

[Brief description of drawings]

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

Claims (6)

[Claims] 1. A catalyst comprising a titanium trichloride composition (III), an organoaluminum compound (A ₁ ) and an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group, In the method for producing a propylene-olefin block copolymer by copolymerizing propylene and an olefin other than propylene, in the titanium trichloride composition (III), an organoaluminum compound (A ₂ ) or an organoaluminum compound (A ₂ ) The solid product (II) obtained by reacting the reaction product (I) with the electron donor (B ₁ ) with titanium tetrachloride is subjected to a polymerization treatment with an olefin, or to a further electron donation. body (B ₂₎ and the titanium trichloride composition obtained by reacting an electron acceptor with (III), the titanium trichloride composition (III) and an organic aluminum compound (a ₁ Combining the door, this one, a linear olefins the titanium trichloride composition (III) 1 g per, 0.01G～100g
After the polymerization reaction, 1 g of the non-linear olefin was continuously added to the titanium trichloride composition (III).
Therefore, 0.001 g to 100 g of a pre-activated catalyst component obtained by a polymerization reaction, an additional organoaluminum compound (A ₁ ) if necessary, and an organosilicon compound having a Si—O—C bond and / or a mercapto group ( S) in combination with the organosilicon compound (S) having the Si—O—C bond and / or mercapto group and the titanium trichloride composition (II
The molar ratio of (I) (based on the number of Ti atoms, the same applies hereinafter) is (S) / (I
II) = 1.0 to 10.0 and a catalyst having a molar ratio of the organoaluminum compound (A ₁ ) to the titanium trichloride composition (III) of (A ₁ ) / (III) = 0.1 to 200, The first step is to polymerize 60% to 95% by weight of the total polymerization amount of propylene, and the second step is to copolymerize 40% to 5% by weight of the total polymerization amount of propylene with olefins other than propylene. A method for producing a propylene-olefin block copolymer, characterized in that the olefin content in the obtained block copolymer is 3% by weight to 30% by weight. 2. The method according to claim 1, wherein a dialkylaluminum monohalide is used as the organoaluminum compound (A ₁ ). Wherein the organoaluminum compound as the (A _2), the general formula in ^{_{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. 4. A non-linear olefin having the following formula: CH ₂ ═CH—R ³ (wherein R ³ has a saturated cyclic 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. 5. 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 ,
R ⁷ represents 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 may be hydrogen. The manufacturing method of Claim 1 which uses the branched chain olefins shown by these. 6. 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.