JPH0780974B2 - 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 a good balance of rigidity and impact resistance by using a specific preactivated catalyst.

[Prior Art and Its Problems] Although crystalline polypropylene has high rigidity, hardness, tensile strength, heat resistance, etc., its 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.

To improve the above-mentioned problems, a propylene-olefin block copolymer is prepared by using a catalyst preliminarily activated by a small amount of non-linear olefin such as 4,4-dimethylpentene-1 or allyltrimethylsilane. Manufacturing method (JP-A-63-68,621, JP-A-63-68,622)
However, when the inventors of the present invention produced a block copolymer according to the method proposed, not only the polymerization activity is lowered, but also the formation of a lump polymer and the adhesion of scale to the wall of the polymerization vessel, This is a method that cannot be used in industrial long-term continuous polymerization methods, particularly in gas phase polymerization methods, because operational problems such as poor controllability of the polymerization reaction occur.

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.

The present inventors have earnestly studied a method for producing a propylene-olefin block copolymer having a good balance of impact resistance and rigidity, which solves the problems associated with the above-mentioned conventional techniques. As a result, when producing a propylene-olefin block copolymer using a specific pre-activated catalyst, it was found to solve the above-mentioned problems in production and quality of the prior art, the present invention I arrived.

As is clear from the above description, an object of the present invention is to provide a method for stably producing a propylene-olefin block copolymer having a good balance of rigidity and impact resistance without causing operational problems. It is in. Another object is to provide a propylene-olefin block copolymer having a balance of rigidity and impact resistance.

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

(1) A titanium-containing solid catalyst component, an organoaluminum compound (A ₁ ) and, if necessary, an electron donor (B ₁ ) are combined, and a linear olefin is added to the titanium-containing solid catalyst component 1 g. Hit
After the polymerization reaction of 0.01 to 100 g, a non-linear olefin represented by the following formula [I], [II] or [III] is further added to 0.1 g of the titanium-containing solid catalyst component.
Using a pre-activated catalyst obtained by polymerizing 001 to 100 g, 60% to 95% by weight of the total polymerization amount of propylene is polymerized as the first stage, and then 40% of the total polymerization amount is used as the second stage. Propylene-olefin block copolymer, characterized in that the olefin content in the resulting block copolymer is 3% to 30% by weight by copolymerizing propylene with 5% to 5% by weight and olefin other than propylene. Method for producing polymer.

As the non-linear olefin, the following formula: CH ₂ ═CH—R ³ ...... [I] (In the formula, R ³ has a saturated cyclic structure of a hydrocarbon which may contain silicon, and may contain silicon. Good carbon number 3
It represents a saturated ring hydrocarbon group from 1 to 18. ) 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 ,
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. ) A branched chain olefin, or 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. ) An aromatic monomer represented by.

(2) The production method according to (1) above, wherein a titanium trichloride composition is used as the titanium-containing solid catalyst component.

(3) The above-mentioned (1), wherein a titanium-containing supported catalyst component containing titanium, magnesium, halogen, and an electron donor (B ₂ ) as essential components is used as the titanium-containing solid catalyst component.
The manufacturing method according to item.

(4) The general formula for the organoaluminum compound (A ₁ ) is Al
R ¹ _p R ² _{p ′} X _{3- (p + p ′)} (In the formula, 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; , p 'is 0
<P + p ′ ≦ 3 represents an arbitrary number. The manufacturing method of said 1st item using the organoaluminum compound represented by these.

As the titanium-containing solid catalyst component used in the present invention, any known titanium-containing solid catalyst component for producing stereoregular polyolefin can be used, but in industrial production, it is preferable to use JP-B-59- 28,573, JP-A-58-17,1
Titanium trichloride composition containing titanium trichloride as the main component obtained by the method described in JP-A-04, etc., JP-A-62-104,810, JP-A-62-104,811 and JP-A-62-104,812. A titanium-containing supported catalyst component containing titanium tetrachloride supported on a magnesium compound as described in JP-A No. 1993-135, and containing titanium, magnesium, a halogen, and an electron donor as essential components is used.

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

Specific examples include trimethyl aluminum, triethyl aluminum, tri n-propyl aluminum, and tri n.
-Butylaluminum, tri-i-butylaluminum,
Tri-n-hexylaluminum, tri-i-hexylaluminum, tri-2-methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, and other trialkylaluminums, diethylaluminum monochloride, di-n-propylaluminum monochloride, Dialkyl aluminum monohalides such as di-butyl aluminum monochloride, diethyl aluminum monofluoride, diethyl aluminum monobromide, diethyl aluminum monoiodide, etc., dialkyl aluminum hydrides such as diethyl aluminum hydride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride Alkyl aluminum sesquihalides such as chloride, ethyl aluminum dichlora De, i- butyl aluminum dichloride monoalkyl aluminum dihalides such as chloride, etc. and the like, other can also be used alkoxyalkyl aluminum such as monoethoxy diethylaluminum diethoxy monoethyl aluminum. Two or more kinds of these organoaluminum compounds may be mixed and used.

Further, as the electron donor (B ₁ ) used if necessary, a known electron donor used for the purpose of improving stereoregularity in the ordinary propylene polymerization is used.

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. , Amides, urea or thioureas, isocyanates,
Examples thereof include azo compounds, phosphines, phosphites, phosphinites, hydrogen sulfide or thioethers, thioalcohols, silanols, and organosilicon compounds having a Si—O—C bond.

Specific examples include dimethyl ether, diethyl ether, di-n-propyl ether, di-n-butyl ether, di-i-amyl ether, di-n-pentyl ether, di-n-hexyl ether, di-i-hexyl ether. , Di-n-octyl ether, di-i-octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, ethers such as tetrahydrofuran, methanol, ethanol, propanol, butanol, pentanol, Hexanol, octanol, 2-ethylhexanol, allyl alcohol,
Alcohols such as benzyl alcohol, ethylene glycol, glycerin, phenols such as phenol, cresol, xylenol, ethylphenol, naphthol, methyl methacrylate, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, n-propyl acetate. , I-propyl acetate, butyl formate, amyl acetate, n-butyl acetate, octyl acetate, phenyl acetate, ethyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoic acid 2 −
Ethylhexyl, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, propyl anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, naphthoic acid 2 -Ethylhexyl, ethyl phenylacetate, and other monocarboxylic acid esters, diethyl succinate, diethyl methylmalonate, diethyl butylmalonate, dibutyl maleate, diethyl butylmaleate, and other aliphatic polycarboxylic acid esters, monomethyl phthalate , Dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, mono-n-phthalate
Butyl, di-n-butyl phthalate, di-i-butyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diethyl isophthalate, dipropyl isophthalate, Aromatic polycarboxylic acid esters such as dibutyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, di-i-butyl naphthalene dicarboxylate, acetaldehyde, propionaldehyde, benzaldehyde, etc. Aldehydes, formic acid, acetic acid, propionic acid,
Butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, valeric acid, carboxylic acids such as benzoic acid, benzoic anhydride, phthalic anhydride, anhydrides such as tetrahydrophthalic anhydride, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as benzophenone, acetonitrile, nitriles such as benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N,
N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, 2,4,6-trimethylpyridine, 2,2,
Amine such as 6,6-tetramethylpiperidine, 2,2,5,5-tetramethylpyrrolidine, N, N, N ', N'-tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide , N, N,
N ', N', N "-pentamethyl-N'-β-dimethylaminomethylphosphoric triamide, octamethylpyrophosphoramide, etc., N, N, N ', N'-tetramethylurea, etc. ureas, phenyl Isocyanates, isocyanates such as toluyl isocyanate, azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxide, dimethylphosphite, di-n-octylphosphite , Phosphites such as triethylphosphite, tri-n-butylphosphite and triphenylphosphite, phosphinites such as ethyldiethylphosphinite, ethyldibutylphosphinite and phenyldiphenylphosphinite, diethylthioether, diphenylphosphinite Thioethers such as phenylthioether and methylphenylthioether, thioalcohols and thiophenols such as ethylthioalcohol, n-propylthioalcohol and thiophenol, silanols such as trimethylsilanol, triethylsilanol and triphenylsilanol, trimethylmethoxysilane , Dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, methyltriethoxysilane,
Examples thereof include organic silicon having a Si—O—C bond such as ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltrii-propoxysilane, and vinyltriacetoxysilane.

The titanium-containing solid catalyst component described above is combined with an organoaluminum compound (A ₁ ) and, if necessary, an electron donor (B ₁ ), and a linear olefin is added to ₁ g of the titanium-containing solid catalyst component. , 0.01 g to 100 g of polymerization reaction, and then 0.001 g to 100 g of non-linear olefin per 1 g of the titanium-containing solid catalyst component to perform pre-activation in two steps to carry out pre-activation used in the present invention. Use as a catalyst.

The first stage pre-activation with a linear olefin is performed by adding 0.005 g to 500 g of an organoaluminum compound (A ₁ ), 0 to 500 g of an electron donor (B ₁ ) and 0 to 50 l of a solvent to ₁ g of a titanium-containing solid catalyst component. Hydrogen 0 to 1,000 ml, and linear olefin 0.01
Use g to 5,000 g.

The first stage pre-activation with a linear olefin is 0 ° C to 10 ° C.
At a temperature of 0 ° C, atmospheric pressure to 50 kg / cm ² G, 1 minute to 1
From 0.01 g per 1 g of titanium-containing solid catalyst component over 0 hours
100 g of linear olefin are polymerized. When the polymerization reaction amount per 1 g of the titanium-containing solid catalyst component is less than 0.01 g, the effect of improving the runnability and improving the balance of rigidity and impact resistance of the resulting block copolymer is insufficient, and even if it exceeds 100 g, The improvement of the effect is not remarkable, which is disadvantageous in operation.

After the completion of the first stage pre-activation, the reaction mixture can be used as it is for the next second stage pre-activation reaction. In addition, coexisting solvent, unreacted linear olefin,
And the organoaluminum compound (A ₁ ) and the like are removed by filtration or decantation, and the powder or granules or a solvent is added to the powder to make a suspension, and the organoaluminum compound (A ₁ ) is added to this. , And, if necessary, an electron donor (B ₁ ) may be added and used for the pre-activation by the second stage non-linear olefin.

The second-stage pre-activation with a non-linear olefin is carried out under the same reaction conditions as in the first-stage pre-activation, in which 0.001 g to 5 per 1 g of titanium-containing solid catalyst component is substituted for the linear olefin.
It is desirable to polymerize 0.001 g to 100 g, preferably 0.01 g to 100 g, per 1 g of the titanium-containing solid catalyst component using 000 g of a non-linear olefin. If the polymerization reaction amount is less than 0.001 g, the effect of improving the balance between rigidity and impact resistance of the resulting block copolymer is insufficient, and if 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.

It is also possible to carry out the third pre-activation treatment with an additional linear olefin at a reaction amount of 100 g or less per 1 g of the titanium-containing solid catalyst component after the completion of the second pre-activation treatment.

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 completion of the pre-activation reaction, the pre-activation catalyst component can be used as it is for propylene-olefin block copolymerization, or a coexisting solvent, unreacted non-linear 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 or particles, and an organoaluminum compound (A ₂ ) and, if necessary, an electron donor ( B ₂₎ in combination with a catalyst, propylene - a method of subjecting the olefin block copolymer, the solvent coexisting, and non-linear olefins the vacuum distillation of unreacted or by a stream of inert gas such as, was evaporated off, A powder or granules or a solvent is added to the powder or granules to bring them into a suspended state, and an organoaluminum compound (A ₃ ) is added to the powder if necessary, and an electron donor (B ₃ ) is further added if necessary. It is also possible to combine the above as a catalyst and use it for propylene-olefin block copolymerization.

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 ,
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. ) Branched-chain olefins represented by (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 ring structure such as cyclohexamethyleneethylvinylsilane, cyclotetramethyleneallylsilane, cyclotetramethylenemethylallylsilane, cyclopentamethylenemethylallylsilane, cyclopentamethylenemethylallylsilane, and cyclopentamethyleneethylallylsilane. Polymer, cyclobutyldimethylvinylsilane, cyclopen Didimethylvinylsilane, cyclopentylethylmethylvinylsilane, cyclopentyldiethylvinylsilane, cyclohexylvinylsilane, cyclohexyldimethylvinylsilane, cyclohexylethylmethylvinylsilane, cyclobutyldimethylallylsilane, cyclopentyldimethylallylsilane, cyclohexylmethylallylsilane, cyclohexyldimethylallylsilane, cyclohexylethylmethylallylsilane, cyclohexyldiethylmethyl Allylsilane, 4-
Examples thereof include saturated ring hydrocarbon monomers containing silicon in addition to the saturated cyclic structure such as trimethylsilylvinylcyclohexane and 4-trimethylsilylallylcyclohexane.

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

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, etc., and one or more kinds of these non-linear olefins are used.

In the method for producing a propylene-olefin block copolymer of the present invention using the thus obtained pre-activated catalyst, propylene is polymerized as the first stage.

Usually, the polymerization temperature is 20 to 100 ° C, preferably 40 to 90 ° C. If the temperature is too low, the polymerization activity will be low, which is not practical, and if the temperature is high, it will be difficult to increase the rigidity of the block copolymer. Polymerization pressure is normal pressure ~ 50kg / c
It is usually carried out for 30 minutes to 15 hours at m ² G. At the time of 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 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 propylene, or gas phase polymerization carried out in gaseous propylene. It is also possible to implement by any of the formats, and it is also possible to combine these formats. In the first-stage propylene polymerization, as long as the block copolymer obtained can maintain a good balance of rigidity and impact resistance,
For example, up to 5% by weight of olefins such as ethylene, butene-1, or 4-methylpentene-1 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 terms of the balance between the rigidity and impact resistance of the resulting block copolymer, the total amount of polymer (excluding soluble polymer) in the first stage polymerization is 60% by weight to
Polymerize 95% by weight of propylene. It is also possible to carry out the first-stage polymerization in multiple stages.

Following the first stage polymerization, in the second stage, copolymerization of propylene and an olefin other than propylene is carried out in one stage or multiple stages under the same polymerization conditions as in the first stage. 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 weight described above
And olefin other than propylene are copolymerized. However, the content of the olefin in the finally obtained block copolymer (excluding the soluble polymer eluted in the solvent) must be within the range of 3 to 30% by weight. Therefore, 60% by weight of propylene alone in the first stage
When polymerized, the amount of olefin copolymerized in the second stage is limited to 30% by weight or less, and in that case, 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 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 good rigidity and impact resistance balance, known injection molding, vacuum molding, extrusion molding,
It is provided as various molded products by techniques such as blow molding.

[Action]

In the conventional method using a catalyst pre-activated with only a non-linear olefin, the titanium-containing solid catalyst component is extremely finely pulverized or swollen during the reaction of the non-linear olefin, and the shape is significantly deteriorated. To do. Therefore, when the pre-activated catalyst component is used for block copolymerization after drying, the result is that it solidifies into a mass during drying,
If a blocky polymer is produced, or if the pre-activated catalyst component is used in the block copolymerization in the slurry state, it may cause a runaway polymerization reaction or a scale adhesion on the reactor wall. Cause problems. 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 titanium-containing solid catalyst having a good shape and less likely to be crushed by the first-stage pre-activation treatment with a linear olefin. By forming the components, 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 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, the obtained propylene-olefin block copolymer is excellent in the balance between rigidity and impact resistance.

〔Example〕

Hereinafter, the present invention will be described with reference to examples. The definitions of terms used in Examples and Comparative Examples and the measuring methods are as follows.

(1) MFR: Melt flow rate JIS K 7210 Table 1 conditions
According to 14. (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: A test piece was prepared in the same manner as (3), and Izod impact strength was measured according to JIS K 7110. (Unit: kgf · cm / cm) Example 1 (1) Production of titanium-containing solid catalyst component n-hexane 6 l, diethylaluminum monochloride (DEAC) 5.0 mol, diisoamyl ether 12.0 mol 25
The mixture was mixed at 1 ° C for 1 hour and reacted at the same temperature for 5 minutes to obtain a reaction product solution (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 above reaction product solution (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 operation of removing the supernatant by decantation was repeated 4 times to obtain a solid product (II). It was

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 (Propylene reaction amount 60
0g). After the reaction, the supernatant liquid was removed, 30 ml 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 10 minutes, 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, the mixture was stirred for 10 minutes, allowed to stand, and the operation of removing the supernatant was repeated 5 times, then dried under reduced pressure. A titanium chloride composition was obtained.

(2) Preparation of pre-activated catalyst component After replacing the stainless reactor with an inclined blade with an internal volume of 80 l with nitrogen gas, n-hexane 40 l, diethylaluminum monochloride 200 g, and titanium-containing solid catalyst component in (1) were used. After adding 450 g of the obtained titanium trichloride composition at room temperature, the temperature in the reactor was set to 40 ° C., 600 g of propylene was added, and the first stage preactivation treatment was carried out at 40 ° C. for 1 hour (trichloride). Propylene 1.0 g reaction per 1 g of titanium composition).

After the reaction time had elapsed, the supernatant was removed by decantation, and the solid was washed twice with 40 l of n-hexane. Subsequently, after adding 40 liters of n-hexane and 200 g of diethylaluminum monochloride, the temperature inside the reactor was set to 40 ° C,
Add 0.7 kg of vinylcyclohexane, 2 hours at 40 ℃, 2
The pre-activation treatment of the second step was performed (titanium trichloride composition 1 g
Per vinylcyclohexane 1.0 g reaction). After the reaction,
It was washed with n-hexane, filtered and dried to obtain a preactivated catalyst component.

(3) Manufacture of block copolymer MFR10 polypropylene powder 30 kg in a horizontal first polymerization vessel of L / D = 4 equipped with a stirrer with an internal volume of 150 l and having nitrogen substitution
Is added to the pre-activated catalyst component obtained in (2) above.
Hexane was added to prepare a 4.0 wt% n-hexane suspension, and the suspension was converted to titanium atom at 5.1 mg atom / hr with diethylaluminum monochloride to titanium atom to give a molar ratio of 7.0. So that the catalyst was supplied from the same pipe.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was kept at 4.5% 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 extracted at 13.5 kg / hr so that When a part of the extracted polymer was collected and analyzed, the MFR was 19.
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 inside the polymerization vessel was kept at 12% 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 0.34 and the total pressure was kept at 3.7 kg / cm ² G, and the copolymerization of ethylene and propylene was carried out at 60 ° C. During the copolymerization, the block copolymer was continuously withdrawn from the polymerization vessel at 15 kg / hr so that the level of the retained block copolymer in the polymerization vessel was 44% by volume. The block copolymer extracted was followed by propylene oxide.
Contact treatment was carried out at 95 ° C. for 30 minutes using nitrogen gas containing 0.2% by volume to obtain a propylene-ethylene block copolymer. As described above, the propylene-ethylene block copolymer was continuously run for 168 hours, but no operational problem occurred and the propylene-ethylene block copolymer was stably produced. The MFR of the obtained copolymer was 1
The ethylene content was 5.0% by weight.

Comparative Example 1 In (2) of Example 1, the pre-activation treatments of the first step and the second step were carried out in the reverse order, and after the reaction of vinylcyclohexane, propylene was reacted to obtain a pre-activated catalyst component,
(3) of Example 1 except that the pre-activating component was used.
When block copolymerization was carried out in the same manner as described above, the generated bulk polymer was taken out of the polymerizer and clogged the pipe, so the block copolymerization had to be stopped within 6 hours after the initiation of the polymerization. It was

Comparative Example 2 In (2) of Example 1, the pre-activation treatment with propylene in the first step was omitted, only vinyl cyclohexane was reacted to obtain a pre-activated catalyst component, and the pre-activated catalyst component was used. Block copolymerization was carried out in the same manner as in (3) of Example 1 except that the bulk polymer produced in the same manner as in Comparative Example 1 was withdrawn and blocked the piping.
The block copolymerization had to be stopped 4 hours after the initiation of the polymerization.

Comparative Example 3 In (2) of Example 1, the pre-activation treatment with vinylcyclohexane in the second step was omitted, only propylene was reacted to obtain a pre-activated catalyst component, and the pre-activated catalyst component was used. Block copolymerization was performed in the same manner as in (3) of Example 1 except for the above.

Comparative Example 4 A polypropylene was obtained in the same manner as in Example 1 except that the second-stage copolymerization was omitted in (3) of Example 1.

Comparative Example 5 and Examples 2 and 3 In (2) of Example 1, the amounts of propylene and vinylcyclohexane used for the preactivation were changed so that the reaction amounts of the preactivated catalyst components shown in the table were changed. Obtained. Thereafter, a block copolymer was obtained in the same manner as in (3) of Example 1.

Example 4 (1) Preparation of Titanium-Containing Solid Catalyst Component In a stainless reactor equipped with a stirrer, 3 l of decane,
480g anhydrous magnesium chloride, n-butyl orthotitanate
1.7 kg and 1.95 kg of 2-ethyl-1-hexanol were mixed and heated at 130 ° C. for 1 hour while stirring to dissolve them to obtain a uniform solution. The homogeneous solution was heated to 70 ° C., 180 g of diisobutyl phthalate was added with stirring, and after 1 hour, 5.2 kg of silicon tetrachloride was added dropwise over 2.5 hours to precipitate a solid.
Heated to 70 ° C. for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product (III).

The total amount of the solid product (III) was mixed with 15 liters of titanium tetrachloride dissolved in 15 liters of 1,2-dichloroethane, subsequently 360 g of diisobutyl phthalate was added, and the mixture was reacted at 100 ° C. for 2 hours while stirring, and then at the same temperature. In 1, the liquid phase part was removed by decantation, 15 l of 1,2-dichloroethane and 15 l of titanium tetrachloride were added again, and the mixture was stirred at 100 ° C. for 2 hours, washed with hexane and dried to obtain a titanium-containing supported catalyst component. .

(2) Preparation of pre-activated catalyst component After replacing a stainless steel reactor with an inclined blade with an internal volume of 30 l with nitrogen gas, 20 l of n-heptane, 400 g of diethylaluminum monochloride 400 g, triethylaluminum 90
g, 55 g of diphenyldimethoxysilane, and (1) above
After adding 100 g of the titanium-containing supported catalyst component obtained in the above step, 280 g of propylene was supplied and the first pre-activation treatment was carried out at 30 ° C. for 2 hours (1.8 g of propylene per 1 g of titanium-containing supported catalyst component). g reaction). Then, it was washed with n-heptane and then filtered to obtain a solid.

Subsequently, 20 l of n-heptane, 400 g of diethylaluminum monochloride, 90 g of triethylaluminum, 120 g of diphenyldimethoxysilane and 0.5 kg of allyltrimethylsilane were added, and a second pre-activation treatment was performed at 45 ° C for 2 hours (containing titanium). A 2.0 g reaction of allyltrimethylsilane per 1 g of the supported catalyst component) and a pre-activated catalyst component were obtained in a slurry state.

(3) Manufacture of block copolymer 20 kg of polypropylene powder of MFR10 in a horizontal first-stage polymerizer of L / D = 3 equipped with a stirrer with an internal volume of 80 l, which was replaced with nitrogen.
, The pre-activated catalyst component slurry obtained in the above (2) was 0.305 mg atom / hr in terms of titanium atom, 2.7 g / hr of triethylaluminum and 0.50 g / hr of diphenyldimethoxysilane. Was continuously supplied from the supply port.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was 1.2% 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 60% by volume.
The polymer was continuously extracted at 10.0 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 1st stage polymerization, the polymerization mixture consisting of the extracted catalyst and polymer was continuously introduced into a horizontal 2nd stage polymerizer of L / D = 3 equipped with a stirrer with an internal volume of 40 liters. did.

While introducing the polymerization mixture from the first-stage polymerization reactor into the second-stage polymerization reactor as described above, the concentration in the gas phase in the polymerization reactor was 5.
Continuously maintain hydrogen at 4% by volume and ethylene and propylene at a molar ratio of ethylene and propylene in the gas phase of 0.21 and total pressure of 13 kg / cm ² G in the polymerization vessel. Then, it was fed to the second-stage polymerization reactor and copolymerized with ethylene and propylene at 60 ° C. During the copolymerization, the holding level of the block copolymer in the second stage polymerization vessel is
The block copolymer was continuously withdrawn at a rate of 11.5 kg / hr from the second-stage polymerizer so that the content of the block copolymer was 36% by volume. The extracted block copolymer was treated in the same manner as in Example 1,
The propylene-ethylene 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 was 10.
0, the ethylene content was 6.0% by weight.

Comparative Example 6 (1) A titanium-containing supported catalyst component was obtained in the same manner as in (4) of Example 4.

(2) Preliminary activation was performed in the same manner as in (4) of Example 4 except that the order of the pre-activation treatments of the first and second steps was reversed and propylene was reacted after the reaction of allyltrimethylsilane. A chemical conversion catalyst component was obtained.

(3) A propylene-ethylene block was prepared in the same manner as in (3) of Example 4 except that the pre-activated catalyst component obtained in (2) above was used as the pre-activated catalyst component in (3) of Example 4. When the copolymerization was carried out, the generated bulk polymer clogged the pipe as a subject, and therefore the block copolymerization had to be stopped 15 hours after the initiation of the polymerization.

Comparative Example 7 In (2) of Example 4, the pre-activation treatment with propylene in the first step was omitted, and only allyltrimethylsilane was reacted to obtain a pre-activated catalyst component. When block copolymerization was carried out in the same manner as in (3) of Example 4 except that it was used, the bulk polymer produced in the same manner as in Comparative Example 6 extracted and clogged the piping. The block copolymerization had to be stopped in time.

Comparative Example 8 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.

Example 5 (1) Preparation of titanium-containing solid catalyst component n-heptane 8l, di-n-butylaluminum monochloride 16mol, di-n-butyl ether 10mol were mixed at 30 ° C for 10 minutes and reacted for 20 minutes to react. A 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. ,
After cooling to room temperature and removing the supernatant, the operation of adding 30 l of n-heptane and 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. It was washed with n-heptane and dried to obtain a titanium trichloride composition.

(2) Preparation of pre-activated catalyst component In (2) of Example 1, 450 g of the titanium trichloride composition obtained in (1) above as a titanium-containing solid catalyst component,
A preactivated catalyst component was obtained in the same manner except that the amount of propylene used was 300 g and 1.5 kg of 4,4-dimethylpentene-1 was used instead of vinylcyclohexane.

(3) Manufacture of block copolymer A n-hexane was added to the pre-activated catalyst component obtained in (2) above in a stirrer-equipped polymerization vessel equipped with a 2-stage turbine blade having an internal volume of 150 l and having nitrogen substituted. The obtained 4.0 wt% n-hexane suspension was converted into titanium atom at 10.9 mg atom / h.
n-hexane was continuously fed at 24 kg / hr from the same pipe as a catalyst so that the molar ratio of diethylaluminum monochloride to titanium atom was 3.0 at r as a catalyst.

Furthermore, hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 11% by volume, and propylene was supplied so that the total pressure was maintained at 8 kg / cm ² G, respectively. Was carried out at 70 ° C.

During the polymerization, the retention level of the polymer in the polymerization vessel was 80% by volume.
The polymer slurry was continuously extracted so that The polymer slurry withdrawn was continuously introduced into a second-stage polymerization reactor of the first stage having an internal volume of 150 l similar to that used in the first stage. The polymerization vessel was further charged with hydrogen so that the concentration in the gas phase of the polymerization vessel was 9.6% by volume, and the total pressure was 1
Propylene was supplied so as to maintain 0 kg / cm ² G, and propylene polymerization in the first stage and 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. When a part of the extracted slurry was collected, dried and analyzed, the MFR was 50.0. 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 in the polymerization vessel was 7.5% 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, the slurry was centrifuged to separate the solvent and then dried to obtain a propylene-ethylene block copolymer continuously at 15 kg / hr for 168 hours. During the production period of the block copolymer, no operational problems occurred and the production was extremely stable. In addition,
The copolymer obtained had an MFR of 30.0 and an ethylene content of 4.6% by weight.

Comparative Example 9 Block copolymerization was performed in the same manner as in Example 5 (3) except that the titanium trichloride composition obtained in Example 5 (1) was used in place of the pre-activated catalyst component. It was

Example 6 (1) Preparation of solid catalyst component containing titanium 4.0 kg of aluminum trichloride (anhydrous) and 1.2 kg of magnesium hydroxide were reacted with each other while being pulverized in a vibration mill at 250 ° C. for 3 hours to generate hydrogen chloride gas. The reaction took place with. After the heating was completed, it was cooled in a nitrogen stream to obtain a magnesium-containing solid.

In a stainless reactor equipped with a stirrer, refined decane
6l, magnesium-containing solid 1.0kg, orthotitanic acid n-
Butyl 3.4 kg and 2-ethyl-1-hexanol 3.9 kg
Were mixed and heated at 130 ° C. for 2 hours with stirring to dissolve them to obtain a uniform solution. The solution is heated to 70 ° C., 0.2 kg of ethyl p-toluate is added and reacted for 1 hour, 0.4 kg of diisobutyl phthalate is added and reacted for another 1 hour, and 10.4 kg of silicon tetrachloride is added dropwise over 2 hours while stirring. Then, a solid was precipitated and further stirred at 70 ° C. for 1 hour. The solid is separated from the solution and washed with purified hexane to give a solid product (III)
Got

The total amount of the solid product (III) was 10 l of 1,2-dichloroethane.
And titanium tetrachloride with 10 l diisobutyl phthalate
After adding 0.4 kg and reacting at 100 ° C for 2 hours with stirring, the liquid phase part was removed by decantation at the same temperature,
Again, 1,2-dichloroethane 10 l and titanium tetrachloride 10 l
l, add 0.4 kg of diisobutyl phthalate, and stir 10
After reacting at 0 ° C. for 2 hours, the solid portion was collected by hot filtration, washed with purified hexane, and dried at 25 ° C. under reduced pressure for 1 hour to obtain a titanium-containing supported catalyst component.

(2) Preparation of pre-activated catalyst component In the reactor used in (4) of Example 4, n-hexane 20 was added.
1, triethylaluminum 1.5 kg, diisobutyldimethoxysilane 270 g, and the titanium-containing supported catalyst component 200 g obtained in the above (1) were added at room temperature. The temperature inside the reactor was set to 35 ° C., and 180 Nl of ethylene was supplied over 1 hour at the same temperature to carry out the first stage preactivation treatment (1.0 g of ethylene reaction per 1 g of titanium-containing supported catalyst component). .

Then, unreacted ethylene was removed, 450 g of 3-methylbutene-1 was added to the reaction mixture without washing the reaction mixture, and a second pre-activation treatment was performed at 35 ° C. for 2 hours (titanium-containing supported catalyst component 1 g Then, 1.5 g of 3-methylbutene-1 reacted), and a pre-activated catalyst was obtained as a slurry.

(3) Production of block copolymer MFR10 was added to the horizontal first-stage polymerization vessel used in (3) of Example 4.
After adding 20 kg of polypropylene powder, the pre-activated catalyst component slurry obtained in the above (2) was converted into titanium atom.
It was continuously fed at 335 mg atom / hr.

Hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was 0.9% by volume, and propylene was supplied so that the total pressure was 23 kg / c ² G. It was carried out in.

During the polymerization, the retention level of the polymer in the polymerization vessel was 60% by volume.
The polymer was continuously extracted at 10.0 kg / hr so that When a part of the extracted polymer was collected and analyzed, the MFR was 10.5. 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 4.

While introducing the polymerization mixture from the first-stage polymerization reactor into the second-stage polymerization reactor as described above, the concentration in the gas phase in the polymerization reactor was 1.
Continuously maintain hydrogen at 6% by volume, ethylene and propylene at a molar ratio of ethylene and propylene in the gas phase of 0.42, and total pressure in the polymerization vessel of 7 kg / cm ² G respectively. Then, it was fed to the second-stage polymerization reactor and copolymerized with ethylene and propylene at 60 ° C. During the copolymerization, the holding level of the block copolymer in the second stage polymerization vessel is
The block copolymer was continuously withdrawn at a rate of 10.75 kg / hr from the second-stage polymerizer so that the content of the block copolymer was 35% 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, the ethylene content was 4.3% by weight.

Example 10 In (2) of Example 6, the pre-activation treatment with 3-methylbutene-1 in the second step was omitted, and only ethylene was reacted to obtain a pre-activated catalyst component. Block copolymerization was performed in the same manner as in (6) of Example 6 except that the components were used.

Example 7 (1) A titanium trichloride composition 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 the amount of propylene used was 300 g and p-trimethylsilylstyrene was used instead of vinylcyclohexane in an amount of 2.0 kg.

(3) In (3) of Example 1, using the pre-activated catalyst component obtained in (2) above as the pre-activated catalyst component, and further adding butene as the olefin during the second stage copolymerization. The molar ratio of -1 to propylene in the gas phase is 0.
Block copolymerization was carried out in the same manner except that the supply was 01.

Comparative Example 11 In (2) of Example 7, a pre-activated catalyst component was obtained without performing the second pre-activation treatment with p-trimethylsilylstyrene, and the pre-activated catalyst component was used thereafter. Block copolymerization was carried out in the same manner as in Example.

Example 8 A pre-activated catalyst component was obtained in the same manner as in (2) of Example 1 except that 450 Nl of ethylene 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.

Example 9 A block copolymer was obtained in the same manner as in Example 2 except that ethylene 4500Nl was used instead of propylene in the pre-activation.

Example 10 A polypropylene was obtained in the same manner as in Example 4, except that 160 Nl of ethylene was used in place of propylene during the preliminary activation.

Example 11 A preactivated catalyst component was obtained in the same manner as in Example 5 (2) except that 230 Nl of ethylene was used instead of propylene. Then, using the pre-activated catalyst component, a block copolymer was obtained in the same manner as in (5) of Example 5.

Example 12 A preactivated catalyst component was obtained in the same manner as in Example 7 (2) except that 230 Nl of ethylene was used instead of propylene. Subsequently, a block copolymer was obtained in the same manner as in (3) of Example 7 using the preactivated catalyst component.

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

[Effects of the Invention] As is clear from the above-mentioned Examples, the propylene-olefin block copolymer obtained by the method of the present invention is
It has a good balance of rigidity and impact resistance as compared with a known block copolymer obtained by a usual method (see Examples 1 to 7 and Comparative Examples 3 and 8 to 11). Therefore, it can be widely applied to the field of various molding methods, especially the field of injection molding, and can exhibit its characteristics.

On the other hand, even if a catalyst that has been subjected to a pre-activation treatment with a non-linear olefin is used, unless the pre-activation treatment according to the method of the present invention is performed, operational problems will occur and long-term continuous operation will not be possible. It is impossible. The obtained block copolymer also has insufficient improvement in the balance between rigidity and impact resistance (Comparative Example 1,
See 2, 6, 7).

[Brief description of drawings]

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

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08F 230: 08) (C08F 210/06 212: 04)

Claims (4)

[Claims] 1. A titanium-containing solid catalyst component, an organoaluminum compound (A ₁ ), and, if necessary, an electron donor (B ₁ ) in combination with a linear olefin. Per 1g of ingredient,
After the polymerization reaction of 0.01 to 100 g, a non-linear olefin represented by the following formula [I], [II] or [III] is further added to 0.1 g of the titanium-containing solid catalyst component.
Using a pre-activated catalyst obtained by polymerizing 001 to 100 g, 60% to 95% by weight of the total polymerization amount of propylene is polymerized as the first stage, and then 40% of the total polymerization amount is used as the second stage. Propylene-olefin block copolymer, characterized in that the olefin content in the resulting block copolymer is 3% to 30% by weight by copolymerizing propylene with 5% to 5% by weight and olefin other than propylene. Method for producing polymer. As the non-linear olefin, the following formula: CH ₂ ═CH—R ³ ...... [I] (In the formula, R ³ has a saturated cyclic structure of a hydrocarbon which may contain silicon, and may contain silicon. Good carbon number 3
It represents a saturated ring hydrocarbon group from 1 to 18. ) 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 ,
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. ) A branched chain olefin, or 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. ) An aromatic monomer represented by. 2. The method according to claim 1, wherein a titanium trichloride composition is used as the titanium-containing solid catalyst component. 3. Titanium as a solid catalyst component containing titanium,
The production method according to claim 1, wherein a supported titanium-containing catalyst component containing magnesium, halogen, and an electron donor (B ₂ ) as essential components is used. 4. An organoaluminum compound (A ₁ ) having a general formula of AlR ¹ _p R ² _{p ′} X _{3- (p + p ′)} (wherein R ¹ and R ² are alkyl groups, cycloalkyl groups, aryl groups, etc.). A hydrocarbon group or an alkoxy group, wherein X represents halogen, and p and p'represent any number of 0 <p + p'≤3). The manufacturing method described in.