JPH0335008A - Production of propylene-olefin block copolymer - Google Patents

Abstract

PURPOSE:To obtain a propylene-olefin block copolymer having excellent balance of rigidity and impact resistance in copolymerizing propylene with an olefin except propylene at two stages by using specific preliminarily activated catalyst. CONSTITUTION:(A) A titanium-containing solid catalytic component (preferably titanium trichloride composition) is blended with (B) an organoaluminum compound (e.g. trimethylaluminum) and optionally (C) an electron donor (e.g. dimethyl ether), 0.01-100g straight-chain olefin (preferably ethylene) is polymerized based on 1g of the component A and then 0.001-100g, preferably 0.01-100g non-straight-chain olefin (preferably vinylcyclopropane) is polymerized based on 1 g of the component A to give a preliminarily activated catalyst. The preliminarily activated catalyst is used and 60-95wt.% based on whole amount of propylene is polymerized, then 40-5wt.% based on the whole amount of propylene and an olefin except propylene are copolymerized to give a propylene- olefin block copolymer having 3-30wt.% olefin content.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a propylene-olefin block copolymer. More specifically, the present invention relates to a method for producing a propylene-olefin block copolymer with a good balance between rigidity and impact resistance using a specific preactivated catalyst.

[Prior art and its issues] Although crystalline polypropylene has high rigidity, hardness, tensile strength, heat resistance, etc., it has insufficient impact resistance.

In general, rigidity, hardness, etc. and impact resistance of plastic materials are incompatible, and it is often extremely difficult to simultaneously improve the former and the latter.In order to expand the use of crystalline polypropylene, it is necessary to It is desired to further improve not only the impact resistance but also the rigidity.

As a method for improving the impact resistance of polypropylene, there is a method of homopolymerizing propylene and then block copolymerizing propylene with an olefin other than propylene. However, the block copolymer has lower ffr resistance than crystalline polypropylene. Although the II properties are significantly improved, the rigidity is reduced. ! ! have.

In order to improve the above-mentioned problem, a propylene-olefin block copolymer is produced using a catalyst that has been preactivated by polymerizing a small amount of non-linear olefin such as 4,4-dimethylpentene-1 or allyltrimethylsilane. method (Japanese Patent Application Laid-Open No. 63-68.621,
No. 11,822) has been proposed, but when the present inventors produced block copolymerization according to the proposed method, not only did the polymerization activity decrease, but also the formation of bulk polymers and the polymerization vessel This method cannot be used in industrial long-term continuous polymerization methods, especially gas phase polymerization methods, because it causes operational problems such as scale adhesion to walls and poor controllability of the polymerization reaction.

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

The present inventors have conducted intensive research on a method for producing a propylene-olefin block copolymer with a good balance between impact resistance and rigidity, which solves the problems faced by the above-mentioned conventional techniques. As a result, it has been found that when a propylene-olefin block copolymer is produced using a specific preactivated catalyst, the production and crystallinity problems of the prior art described above can be solved, and the present invention reached.

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 with a good balance of stiffness and impact resistance.

[Means to solve the problem] The present invention has the following configuration.

(1) Combine a titanium-containing solid catalyst component, an organoaluminum compound (A1), and, if necessary, an electron donor (B11), and add the linear olefin to the titanium-containing solid catalyst component. After carrying out the polymerization reaction of 0.01 to lo [1g1t per tg, 1) using a preactivated catalyst obtained by polymerizing 0.001 to 100g of non-linear olefin per 1g of the titanium-containing solid catalyst component. Then, in the first stage of yg, 60% to 95% by weight of propylene of the total polymerization amount is polymerized, and then in the second stage, 40% to 5% of the total polymerization amount of propylene and olefin other than propylene are copolymerized. A method for producing a propylene-olefin block copolymer, characterized in that the olefin content in the resulting block copolymer is 3% to 30% by weight.

(2) The manufacturing method according to item N1 above, in which a titanium trichloride composition is used as the titanium-containing solid catalyst component.

(3) The production method according to item 1 above, in which a supported titanium-containing catalyst component containing titanium, magnesium, halogen, and an electron donor (B2) as essential components is used as the titanium-containing solid catalyst component.

(4) As the organic aluminum compound (Al), the general formula: AIR'pR2p・X5-1p**・+ (in the formula, R
1, Rp' represents a hydrocarbon group or alkoxy group such as an alkyl group, cycloalkyl group, or aryl group, X represents a halogen, and p and p' represent any number in the range of 0<pep'≦31) The manufacturing method according to item 1 above, using an organoaluminum compound represented by:

(5) As a non-linear olefin, the following formula, CH2FCH-
R' (wherein R3 represents a saturated cyclic hydrocarbon group having 3 to 18 carbon atoms which may contain silicon and which has a saturated cyclic structure of a hydrocarbon which may contain silicon); The manufacturing method according to item 1 above, using a saturated cyclic hydrocarbon monomer.

(B) As a non-linear olefin, the following formula, (wherein R4 represents a chain hydrocarbon group having 1 to 3 carbon atoms which may contain silicon, or silicon,
, R8, and R7 represent a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon; however, any one of R5, R11% and R2 may be hydrogen. The manufacturing method according to item 1 above, which uses olefins.

(In the formula, n is either 0, 1.m is 1.2, and B
6 represents a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, R9 represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen, or halogen; , ■ is 2, each R@ may be the same or different.

) The manufacturing method according to item 1 above, using an aromatic monomer represented by:

As the titanium-containing solid catalyst component used in the present invention, any known titanium-containing solid catalyst component for producing stereoregular polyolefins can be used. Titanium trichloride compositions containing titanium trichloride as a main component obtained by the methods described in Japanese Patent Publication No. 28.573, Japanese Patent Publication No. 17,104/1983, and Japanese Patent Publication No. 104,810/1981, Kaisho 82-404,
Titanium tetrachloride is supported on the magnesium compound described in JP-A No. 811, JP-A No. 82-104,812, etc.
A titanium-supported solid catalyst component containing titanium, magnesium, halogen, and an electron donor as essential components is used.

Further, as the organoaluminum compound (R1), the general formula is AIR'J", Xs-+t*p・+ (wherein, R1,
R2 represents a hydrocarbon group or an alkoxy group represented by an alkyl group, a cycloalkyl group, an aryl group, X represents a halogen, and p and p' represent any number in the range of 0<pep'≦3. Organoaluminum compounds are used.

Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n
-butylaluminum, tri-l-butylaluminum,
Trialkylaluminums such as tri-n-hexylaluminum, tri-hexylaluminum, tri-2-methylpentylaluminum, tri-n-octylaluminum, tri-n-decylaluminum, diethylaluminium monochloride, moro-propylaluminum monochloride, di-i - Dialkyl aluminum monohalides such as butyl aluminum monochloride, diethylaluminium monofluoride, diethylaluminium monobromide, diethylaluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, methyl aluminum sesquichloride, ethyl aluminum sesquichloride Alkylaluminum sesquihalides such as chloride, monoalkylaluminum cybalides such as ethylaluminum dichloride and i-butylaluminum dichloride, and monoethoxydiethylaluminium,
Alkoxyalkylaluminums such as jetoxymonoethylaluminum can also be used. These organoaluminum compounds are 2f! It is also possible to mix and use more than one type.

Furthermore, as the electron donor (Bl) used as necessary,
During normal propylene polymerization, a known electron donor is used for the purpose of improving stereoregularity.

Those used as electron donors are organic compounds having any of oxygen, nitrogen, sulfur, and phosphorus atoms, that is,
Ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, These include hydrogen sulfide, thioethers, thioalcohols, silanols, and organosilicon compounds having a 5t-oc bond.

Specific examples include dimethyl ether, diethyl ether, di-n-propyl ether, di-n-butyl ether, di-l-amyl ether, di-n-pentyl ether, di-n-hexyl ether, di-m-hexyl ether, Ethers such as di-n-octyl ether, di-mi-octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, methanol, ethanol, propanol,
Alcohols such as butanol, pentanol, hexanol, octanol, 2-ethylhexanol, allyl alcohol, 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, benzoic acid Ethyl, propyl benzoate, butyl benzoate, octyl benzoate, 2-benzoate
Ethyl xyl, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, propyl anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, naphthoate Monocarboxylic acid esters such as 2-ethylhexyl acid and ethyl phenylacetate, aliphatic polycarboxylic acid esters such as diethyl succinate, diethyl methylmalonate, diethyl butylmalonate, dibutyl maleate, diethyl butylmalonate, and phthalate. monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, mono-n-phthalate
Butyl, di-n-butyl phthalate, sheet butyl phthalate, di-n-heptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, Aromatic polycarboxylic acid esters such as di-2-ethylhexyl isophthalate, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, di-l-butyl naphthalenedicarboxylate, aldehydes such as acetaldehyde, propionaldehyde, benzaldehyde, formic acid , acetic acid, propionic acid,
Carboxylic acids such as butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, valeric acid, benzoic acid, acid anhydrides such as benzoic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as benzophenone, nitriles such as acetonitrile and benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β(N
, N-dimethylamino)ethanol, pyridine, quinoline, α-picoline, 2.4.6-trimethylpyridine,
2.2', 8.6-titramethylpiveridine, 2.2,
5.5-Tetramethylpyrrolidine, N, N, N'.

No-Tetramethylethylenecyan, aniline, dimethylaniline, etc., formamide, hexamethylphosphoric acid triamide, N,
N, N', N', N'-he: / Ta, +l f k-H
'-13-C, +l fAmides such as aminomethylphosphoric acid triamide, octamethylpyrophosphoramide, N
, N,N',N'-tetramethylurea and other ureas, phenyl isocyphnate, toluyl isocyanate and other isocyanates, azobenzene and other azo compounds, ethylphosphine, triethylphosphine, tri-n-octylphosphine, triphenylphosphine , phosphines such as triphenylphosphine oxyto, phosphites such as dimethyl phosphite, di-n-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, triphenyl phosphite, ethyl diethyl phosphinite, ethyl Phosphinites such as butyl phosphinite and phenyl diphenyl phosphinite, thioethers such as diethyl thioether, diphenyl thioether and methyl phenyl thioether, thio alcohols and thiophenol such as ethyl thio alcohol, n-propyl thio alcohol and thiophenol. silanols such as trimethylsilanol, triethylsilanol, triphenylsilanol, trimethylmethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, trimethyl Ethoxysilane, dimethyljethoxysilane, diphenyljethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane,
Examples include organic silicones having a 5t-oc bond such as butyltriethoxysilane, phenyltriethoxysilane, ethyltri-I-propoxysilane, and vinyltriacetoxysilane.

The above-mentioned (1) titanium-containing solid catalyst component, (2) an organic alkunium compound (A1), and optionally (3) an electron donor (B+) are combined, and [4] linear olefin is added to the titanium. 0.01 per gram of solid catalyst component contained
After reacting g~100g1, further add 0.001g of non-linear olefin per 1g of the titanium-containing solid catalyst component.
g to 100 g is polymerized and preactivated in two stages to obtain a preactivated catalyst used in the present invention.

In the first stage activation using a linear olefin, an organoaluminum compound (
A+) 0.005g to 500g, electron donor (at)
O~500g, solvent 0~50IL, hydrogen 0~1.000
1, and straight olefin 0.01g~s, 00
Use 0g.

The first stage activation by the olefin is performed at 0°C ~ 1
At a temperature of 00° C. and a pressure of atmospheric pressure to 50 kg/c1G, 0.01 g to 100 g of straight-chain olefin is polymerized per 1 g of the titanium-containing solid catalyst component over a period of 1 minute to IQ. Polymerization reaction amount per 1g of titanium-containing solid catalyst component is 0
．． If the amount is less than 100 g, the effect of improving driveability and improving the balance of rigidity and impact resistance of the obtained block copolymer will be insufficient, and if it exceeds 100 g, the improvement will not be significant, resulting in operational disadvantages. becomes.

After the first stage pre-activation is completed, the reaction mixture can be directly used in the second stage pre-activation reaction. In addition, coexisting solvents, unreacted linear olefins,
and the organoaluminum compound (AI), etc. are removed by filtration or decantation, and a granular material or a solvent is added to the granular material to form a suspended state, and to this, an additional organoaluminum compound (AI), and If necessary, an electron donor (B+) may be added to perform the second preactivation C using a non-linear olefin.

In the second stage catalyst activation using a non-linear olefin, under the same reaction conditions as the first stage catalyst activation, 0.00 g per tg of titanium-containing solid catalyst component was used instead of the linear olefin.
0.001 g to 100 g per 1 g of titanium-containing solid catalyst component using 1 g to 5,000 g of non-linear olefin,
It is preferable to polymerize 0.01g to t6og.If the polymerization reaction amount is less than 0.0013, the effect of improving the balance between rigidity and impact resistance of the block copolymer obtained will be insufficient, and if it exceeds 100g, the effect will be reduced. The improvement becomes less noticeable and becomes economically disadvantageous.

For the first and second stage preactivation treatments, it is essential to first perform the preactivation treatment with a straight chain olefin, and then perform the preactivation treatment with a non-linear olefin, in accordance with the above method. However, if the order of the pre-activation process is reversed, the effects of the present invention cannot be obtained.

In addition, after the completion of the second-stage preactivation treatment, it is also possible to additionally carry out a third-stage preactivation treatment using a straight-quenching olefin in a reaction amount of 100 g or less per 1 g of the titanium-containing solid catalyst component.

Preactivation can also be performed in a hydrocarbon solvent such as n-pentane, n-hexane, n-hebutane, toluene, etc., and hydrogen may be present in the preactivation.

After the preactivation reaction is completed, the preactivated catalyst component can be used as it is for propylene-olefin block copolymerization, or the coexisting solvent, unreacted non-linear olefin, and organoaluminum compound ( A1
) is removed by filtration or decantation, and a powder or a solvent is added to the powder to create a suspended state, and an additional organoaluminum compound (A2) and, if necessary, an electron donor are added to the powder. (B2) as a catalyst and subjecting it to propylene-olefin block copolymerization, or removing the coexisting solvent and unreacted non-linear olefin by evaporation by vacuum distillation or an inert gas stream, etc. Add a solvent to the granular material or the granular material to form a suspended state, add an organoaluminum compound (A1) to this as necessary, and further combine with an electron donor (B1) as necessary. It is also possible to use it as a catalyst in propylene-olefin block copolymerization.

As the straight chain olefin used in the first stage preactivation treatment of the present invention, straight chain olefins such as ethylene, propylene, butene-1, pentene-1, hexene-11 octene-1, etc. are used, and especially ethylene, propylene is preferably used. One or more types of these straight chain olefins are used.

The non-linear olefin used in the second stage preactivation treatment of the present invention has the following formula: A saturated ring-containing hydrocarbon monomer represented by >, which represents a saturated ring-containing hydrocarbon group having 3 to 18 carbon atoms which may contain Represents a suitable hydrocarbon group having 1 to 3 carbon atoms, or silicon, and R8
,R11,R? represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, but 3! .

Any one of R6 and R7 may be hydrogen. Branched olefins represented by 1), (where n is 0, 1, m
is either 1.2, R6 represents a decomposed hydrocarbon group having 1 to 6 carbon atoms which may contain silicon,
Rp' represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen, or a halogen; when m is 2, each R@ may be the same or different; It is a family monomer.

To be more specific, examples of the saturated ring-containing hydrocarbon monomer (1) include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, 3-methylvinylcyclopentane, vinylcyclohexane, 2-methylvinylcyclohexane, 3- In addition to vinylcycloalkanes such as methylvinylcyclohexane, 4-methylvinylcyclohexane, and vinylcycloheptane, allylcycloalkanes such as allylcyclopentane and allylcyclohexane, cyclotrimethylenevinylsilane, cyclotrimethylenemethylvinylsilane, and cyclotetramethylene. Vinylsilane, cyclotetramethylenemethylvinylsilane, cyclopentamethylenevinylsilane, cyclopentamethylenemethylvinylsilane, cyclopentamethyleneethylvinylsilane, cyclohexamethylenevinylsilane, cyclohexamethylenemethylvinylsilane, cyclohexamethyleneethylvinylsilane, cyclotetramethyleneallylsilane, cyclotetramethylene Saturated ring hydrocarbon monomers having a silicon atom in the saturated ring structure such as methylallylsilane, cyclopentamethyleneallylsilane, cyclopentamethylenemethylallylsilane, cyclopentamethyleneethylallylsilane, cyclobutyldimethylvinylsilane, cyclopentyldimethylvinylsilane, cyclopentyl Ethylmethylvinylsilane, cyclopentyldiethylvinylsilane, cyclohexylvinylsilane, cyclohexyldimethylvinylsilane, cyclohexylethylmethylvinylsilane, cyclobutyldimethylallylsilane, cyclopentyldimethylallylsilane, cyclohexylmethylallylsilane, cyclohexyldimethylallylsilane, cyclohexylethylmethylallylsilane,
Examples include saturated ring-containing hydrocarbon monomers containing silicon in addition to the saturated ring structure, such as cyclohexyldiethylallylsilane, 4-trimethylsilylvinylcyclohexane, and 4-trimethylsilylallylcyclohexane.

Examples of the branched olefins (3) include 3-methylbutene-1,3-methylpentene-1,3-ethylpentene-
1st class 300 million branched chain olefin, 4-ethylhexene-1,
400 million branched chain olefins such as 4,4-dimethylpentene-1,4,4-dimethylhexene-1, vinyltrimethylsilane, vinyltriethylsilane, vinyltri-n-butylsilane, allyltrimethylsilane, allylethyldimethylsilane, allyldiethylmethyl silane, alkenylsilanes such as allyltriethylsilane, allyltri-n-propylsilane, 3-butenyltrimethylsilane, 3-butenyltriethylsilane, dimethyldiallylsilane,
Examples include diallysilanes such as ethylmethyldiallylsilane and diethyldiallylsilane.

In addition, as the aromatic monomer (2), styrene and its derivatives such as 0-methylstyrene, alkylstyrenes such as pt-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, etc. , 3,4-dimethylstyrene, dialkylstyrenes such as 3,5-dimethylstyrene, 2-methyl-4-fluorostyrene, 2-ethyl-4-chlorostyrene, 0-fluorostyrene, p
-Halogen-substituted styrenes such as fluorostyrene, p-
Trialkylsilylstyrenes such as trimethylsilylstyrene, m-triethylsilylstyrene, p-ethyldimethylsilylstyrene, allyltoluenes such as 0-allyltoluene and p-allyltoluene, 2-allyl-p-xylene, 4-allyl- Allyl xylenes such as O-xylene and 5-allyl-xylene, alkenyl phenyl silanes such as vinyldimethylphenylsilane, vinylethylmethylphenylsilane, vinyldiethylphenylsilane, allyldimethylphenylsilane, allylethylmethylphenylsilane, and , 4-(o-tolyl)-butene-1! -vinylnaphthalene, etc., and these non-linear olefins are 11! The above are used.

In the propylene-olefin block copolymer of the present invention, propylene is polymerized in the first stage using the preactivated catalyst thus obtained.

Usually, the polymerization temperature is 20-100°C, preferably 40-90°C.
It is 0°C. If the temperature is too low, the polymerization activity will be low and it is not practical; if the temperature is too high, it will be difficult to increase the rigidity of the block copolymer. 0 Polymerization pressure is normal pressure to 5 Gkg/cm"G The polymerization process is usually carried out for about 30 minutes to 15 hours. During the polymerization, adding an appropriate amount of hydrogen to adjust the molecular weight is the same as in conventional polymerization methods.

The block copolymerization of propylene and olefin of the present invention can be carried out, for example, by slurry polymerization carried out in an inert solvent such as n-hexane or rhohebutane, bulk polymerization carried out in liquefied propylene, or gas phase polymerization carried out in gaseous propylene. It can be carried out in any format, or it can be carried out in combination of these formats. In the first stage propylene polymerization, as long as the resulting block copolymer maintains 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. On balance, in the first stage polymerization, propylene is polymerized in an amount of 60 to 95% by weight of the total polymer amount (note, excluding soluble polymers). This first stage polymerization can also be carried out in multiple stages.

In the second stage, following the first stage polymerization, copolymerization of propylene and an olefin other than propylene is carried out in one stage or in multiple stages under the same polymerization conditions as in the first stage. A stage of polymerization refers to a continuous or temporary feeding of monomer. In this second stage copolymerization, 40! Copolymerize i to 5% by weight of 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) is 3! ! The amount must be within the range of ~30% by weight, so in the first stage only propylene is
When polymerizing by weight%, the amount of olefin copolymerized in the second stage is limited to 30% by weight or less, so in that case, the remaining 10% by weight or more must be copolymerized with propylene. It won't happen.

Specific examples of olefins other than propylene that are mixed with propylene in the second stage described above include ethylene, butene-11pentene-11hexeno-11hebutene-11octene-1, etc. Olefins, 4
-methyl-pentene-1,2-methyl-pentene-1,
Examples include branched monoolefins such as 3-methylbutene-1 and styrene, and one or more of these may be used.

Thus, the propylene-olefin block copolymer obtained by the method of the present invention is a propylene-olefin block copolymer having a good balance of rigidity and impact resistance, and can be processed by known injection molding, vacuum forming, extrusion molding,
It is provided as various molded products using techniques such as blow molding.

[For production]

In conventional methods that use catalysts that have been preactivated with only non-linear olefins, the titanium-containing solid catalyst component becomes ultra-fine or swells during the reaction of non-linear olefins, resulting in a significantly deteriorated shape. do. Therefore, when the preactivated catalyst component is dried before being used in block copolymerization, it solidifies into lumps during drying.
If a lumpy polymer is produced, or if the preactivated catalyst component is used in a slurry state for block copolymerization, it may cause operational problems such as runaway polymerization and scale adhesion to the reactor wall. As a result, the obtained block copolymer also had insufficient improvement in the balance of rigidity and impact resistance.

In contrast to the above-mentioned conventional technology, the two-stage preactivation treatment according to the present invention is a solid titanium-containing solid catalyst that has a good shape and is less likely to be crushed by the first-stage preactivation treatment with a directly-quenched olefin. By forming these components, it maintains its good shape even during the second stage preactivation treatment with non-linear olefin. Therefore, when the preactivated catalyst is used in block copolymerization, stable and continuous polymerization operation is possible regardless of drying conditions.

In addition, as a result of stable polymerization operation, the propylene obtained
The quality of the olefin block copolymer is also stable, and the linear olefin polymer block of the linear olefin-non-linear olefin block copolymer produced by the two-stage preactivation treatment is a propylene-olefin block copolymer. As a result, the dispersibility of the non-linear olefin polymer block into the propylene-olefin block copolymer is highly improved, and the nucleation effect of the non-linear olefin polymer block is significantly demonstrated. As a result, the resulting propylene-olefin block copolymer has an excellent balance of rigidity and impact resistance.

(Example) The present invention will be explained below 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 72
10 According to condition 14 in Table 1. (Unit: g/lo min) (2) Olefin content: Based on infrared absorption spectroscopy.

(3) Tetrakis [methylene-3-〈3°, 5゛-di-t-
Butyl-4°-hydroxyphenyl)propionate comethane 0.1 part by weight, and calcium stearate 0
．． 1 part by weight, and the mixture was passed through a screw with a diameter of 40I.
Granulation was performed using an I11 extrusion granulator. Then, the granules were heated in an injection molding machine at a molten resin temperature of 230°C and a mold temperature of 50°C.
A JIS type test piece was prepared, and the test piece was left in a room with a humidity of 50% and a room temperature of 23° C. for 88 hours, and then its flexural modulus was measured in accordance with JIS K 7203.

(4) (Unit: kgf/crr?) Impact resistance: Prepare a test piece in the same manner as in (3),
Izot impact strength was measured in accordance with JIS 711G. (J# position: kgLcm/c+a) Example 1 (1) Production of titanium-containing solid catalyst component n-hexane 6°C, diethylaluminum monochloride (DEAC) 5.0 mol, diisoamyl ether 1
2.0 mol was mixed at 25°C for 1 minute and reacted at the same temperature for 5 minutes to form the reaction product liquid (■) (diisoamyl ether/
A molar ratio of DEAI: 2.4) was obtained. 40 mol of titanium tetrachloride was placed in a reactor purged with nitrogen and heated to 35°C.
After adding the entire amount of the reaction product liquid (1) dropwise to this over 30 minutes, the temperature was kept at the same temperature for 30 minutes, the temperature was raised to 75°C, and the temperature was further increased for 1 hour.
The reaction mixture was allowed to react for an hour, cooled to room temperature, the supernatant liquid was removed, 20 ft of n-hexane was added, and the supernatant liquid was removed by decantation, and this operation was repeated four times to obtain a solid product (II).

The entire amount of (II) was suspended in n-hexane 30J2, 200 g of diethylaluminum monochloride was added, and 1.0 kg of propylene was added at 30°C and reacted for 1 hour to obtain a polymerized solid product (n- A) was obtained (propylene reaction amount aoog). After the reaction, the supernatant was removed, and the operation of adding 300 mA of n-hexane and removing by decantation was repeated twice to obtain a solid product subjected to the above polymerization treatment. (II-A) 3.5 kg of titanium tetrachloride was prepared by suspending 2.5 kg in 6 fL of n-hexane.
was added at room temperature for about 10 minutes, reacted at 80°C for 30 minutes, further added 1.6 kg of diisoamyl ether, and reacted at 80°C for 1 hour. After the completion of the reaction, the supernatant was decanted. 40 It of n-hexane was added, the mixture was stirred for 10 minutes, left to stand, and the supernatant liquid was removed. The procedure was repeated five times, followed by drying under reduced pressure to obtain a titanium trichloride composition.

(2) Preparation of pre-activated catalyst component After purging a stainless steel reactor with inclined blades with internal volume aOU with nitrogen gas, 40 IL of n-hexane, 200 g of diethylaluminium monochloride, and (1) as the titanium-containing solid catalyst component were prepared. 450g of the obtained titanium trichloride composition
was added at room temperature, the temperature inside the reactor was raised to 40°C, 600 g of propylene was added, and the first preactivation treatment was performed at 40°C for 1 hour (titanium trichloride composition (III) I
per gram of propylene. Og reaction).

After the reaction time had elapsed, the supernatant was removed by decantation, and the solid was washed twice with n-hexane at 40°C. Subsequently, after adding 40 It of n-hexane and 200 g of diethylaluminium monochloride, the temperature inside the reactor was lowered to 4.
Bring to 0°C, add 0.7 kg of vinylcyclohexane, and
A second preactivation treatment was carried out at 0°C for 2 hours (vinylcyclohexane 1.0% per 1g of titanium trichloride composition).
g reaction) After the completion of the reaction, wash with n-hexane, and then
A preactivated catalyst component was obtained by filtration and drying.

(3) Production of block copolymer
After charging 30 kg of MFRto polypropylene powder into the first horizontal polymerization vessel of D-4, n-hexane was added to the preactivated catalyst component obtained in (2) above to form a 4.0% by weight n-hexane suspension. After making the suspension into a liquid, the molar ratio of diethylaluminum monochloride to titanium atoms was 7.1 milligram atoms/hr in terms of titanium atoms.
It was supplied as a catalyst from the same pipe so that the concentration was 0.

In addition, hydrogen was supplied so that the concentration in the gas phase of the polymerization reactor was maintained at 4.5% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg/cs"G, and the first stage propylene polymerization was carried out. It was carried out at 70°C.

During the polymerization, the polymer was extracted at a rate of 13.5 kg/hr so that the polymer retention level in the polymerization vessel was 45% by volume. When a part of the extracted polymer was collected and analyzed, the VFR was 19.0. After the first stage polymerization was completed, the extracted polymerization mixture consisting of the catalyst and polymer was continuously introduced into a horizontal second stage polymerization vessel having an internal volume of 1,501 cm, which was the same as the first stage polymerization vessel. .

While introducing the polymerization mixture into the second stage polymerization vessel as described above, hydrogen was added so that the concentration in the gas phase in the polymerization vessel was maintained at 12% by volume, and the molar ratio of ethylene and propylene in the gas phase was Ethylene and propylene are each continuously added to the
The mixture was supplied to the second stage polymerization vessel, and copolymerization of ethylene and propylene was carried out at 60°C. During the copolymerization, the block copolymer was continuously fed at 15 kg/hr from the polymerization vessel so that the retention level of the block copolymer in the polymerization vessel was 44% by volume.
I pulled it out. The extracted block copolymer was then contacted with nitrogen gas containing 0.2% by volume of propylene oxide at 95°C for 30 minutes to obtain a propylene-ethylene block copolymer as described above. The propylene-ethylene block copolymer was produced continuously for 168 hours, but no operational problems occurred and the propylene-ethylene block copolymer was stably produced. The VFR of the obtained copolymer was 15.0, and the ethylene content was 5.0% by weight.

Comparative Example 1 In (2) of Example 1, the first and second stage preactivation treatments were performed in the reverse order, and propylene was reacted after the vinylcyclohexane reaction to obtain a preactivated catalyst component.
(3) of Example 1 except that the preactivation component is used.
When block copolymerization was carried out in the same manner as above, the produced bulk polymer blocked the pipe for extracting the polymer from the polymerization vessel, so block copolymerization had to be stopped 6 hours after the start of polymerization. Ta.

Comparative Example 2 In (2) of Example 1, the first preactivation treatment with propylene was omitted, only vinylcyclohexane was reacted to obtain a preactivated catalyst component, and the preactivated catalyst component was used. When block copolymerization was carried out in the same manner as in Example 1 (3), the block copolymerization was performed in the same manner as in Comparative Example 1, and the extraction piping was blocked. The block copolymerization had to be stopped at

Comparative Example 3 In (2) of Example 1, the second preactivation treatment with vinylcyclohexane is omitted, only propylene is reacted to obtain a preactivated catalyst component, and the preactivated catalyst component is used. Block copolymerization was carried out in the same manner as in Example 1 (3) except for the above.

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

Comparative Example 5 and Example 2.3 In (2) of Example 1, the amounts of propylene and vinylcyclohexane used for preactivation were changed to increase the reaction amount (preactivated catalyst components as shown in the table). A block copolymer was obtained in the same manner as in Example 1 (3).

Example 4 (1) Preparation of titanium-containing solid catalyst component In a stainless steel reactor equipped with a stirrer, decane 3I
L, anhydrous magnesium chloride 480g, orthotitanic acid n
1.7 kg of -butyl and 1.95 kg of 2-ethyl-1-hexanol were mixed and heated to NOC for 1 hour while stirring to dissolve and form a uniform solution. 70% of the homogeneous solution
℃ and without stirring, add 1110 g of diisobutyl phthalate.
After 1 hour had passed, 5.2 kg of silicon tetrachloride was added dropwise over 2.5 hours to precipitate a solid, and the mixture was further 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 entire amount of the solid product (III) was mixed with titanium tetrachloride 151 dissolved in 1,2-dichloroethane, and then 360 g of diisobutyl phthalate was added, and 1
After reacting at 00°C for 2 hours, the liquid phase was removed by decantation at the same temperature, and 1,2-dichloroethane 15j2 and titanium tetrachloride 151 were added again.
The mixture was stirred at 0° C. for 2 hours, washed with hexane, and dried to obtain a titanium-containing supported catalyst component.

(2) Preparation volume of preactivated catalyst component: 30j! After purging a stainless steel reactor with inclined blades with nitrogen gas, 20 g of n-hebutane, 400 g of diethyl aluminum monochloride, 90 g of triethyl aluminum, and 55 g of diphenyldimethoxysilane were added.
, and titanium-containing supported catalyst component 1 obtained in (1) above.
After adding 00g, feed 280g of propylene and add 30g of propylene.
A first stage preactivation treatment was carried out for 2 hours at 0.degree. C. (1.8 g of propylene was reacted per 1 g of the titanium-containing supported catalyst component).Then, the mixture was washed with n-hebutane and filtered to obtain a solid.

Next, 20j2 of n-heptane, 400g of diethylaluminum monochloride, ! - Add 90 g of ethylaluminum, 120 g of diphenyldimethoxysilane, and 0.5 kg of allyltrimethylsilane, and
A second preactivation treatment was carried out for 2 hours at a temperature of 2.5 g of allyltrimethylsilane per 1 g of the titanium-containing supported catalyst component.
0g reaction), a preactivated catalyst component was obtained in the form of a slurry.

(3) Manufacture of block copolymer
After charging 20 kg of IJFR10 polypropylene powder into the horizontal first-stage polymerization reactor (No. 3), the preactivated catalyst component slurry obtained in (2) above was added to 0.305 t in terms of titanium atoms.
In addition, triethylaluminum was continuously fed at 2.7 g/hr, and diphenyldimethoxysilane was continuously fed at O and SOg/hr from separate feed ports.

In addition, hydrogen was supplied so that the concentration in the gas phase of the polymerization reactor was maintained at 1.2% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg/cs"G, and the first stage of propylene polymerization was carried out. It was carried out at 70°C.

During the polymerization, the polymer was continuously extracted at a rate of 10.0 kg/hr so that the polymer retention level in the polymerization vessel was 60% by volume. When a part of the extracted polymer was collected and analyzed, the MFR was 15.0. After the first stage polymerization was completed, the polymerization mixture consisting of the extracted catalyst and polymer was continuously introduced into a horizontal second stage polymerization vessel of L/D-3 equipped with a stirrer and having an internal volume of 40 Jl. .

While introducing the polymerization mixture from the first stage polymerization vessel into the second stage polymerization vessel as described above, the concentration in the gas phase in the polymerization vessel was
．． Continuously feed hydrogen so as to maintain a concentration of 4% by volume, and continuously feed ethylene and propylene with a toothpick to maintain a molar ratio of ethylene and propylene in the gas phase of 0.21 and a total pressure of 13 J/cm'G in the polymerization vessel. is supplied to the second stage polymerization vessel,
Copolymerization of ethylene and propylene was carried out at 60°C. During the copolymerization, the block copolymer was continuously extracted from the second stage polymerization vessel at a rate of 11.5 kg/hr so that the retention level of the block copolymer in the second stage polymerization vessel was 36% by volume. . The extracted block copolymer was treated in the same manner as in Example 1, and a propylene-ethylene block copolymer was continuously produced for 188 hours.

During this period, 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 Example 4 (1).

(2) In (2) of Example 4, the order of the first and second stage preactivation treatments is reversed, and propylene is reacted after the reaction of allyltrimethylsilane. A catalyst component was obtained.

(3) In (3) of Example 4, a propylene-ethylene block was prepared in the same manner as in (3) of Example 4, except that the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component. When copolymerization was carried out, the block copolymerization had to be stopped 15 hours after the start of polymerization because the produced bulk polymers leaked out and clogged the piping.

Comparative Example 7 In (2) of Example 4, the first stage preactivation treatment with propylene was omitted, only allyltrimethylsilane was reacted to obtain a preactivated catalyst component, and the preactivated catalyst component was When block copolymerization was carried out in the same manner as in Example 4 (3) except for the use of Block copolymerization had to be stopped in time.

Comparative Example 8 In (2) of Example 4, the second-stage preactivation treatment with allyltrimethylsilane is omitted, only propylene is reacted to obtain a preactivated catalyst component, and the preactivated catalyst component is Block copolymerization was carried out in the same manner as in Example 4 (3) except for using the following.

Example 5 (1) Preparation of titanium-containing solid catalyst component
The mixture was mixed at 0° C. for 10 minutes and reacted for 20 minutes to obtain a reaction product solution (1). The total amount of this reaction product liquid (1) is 45
It was added dropwise over a period of 60 minutes to a solution consisting of 51 moles of toluene and 64 moles of titanium tetrachloride kept at ℃, the temperature was raised to 85℃ and the mixture was reacted for an additional 2 hours, then cooled to room temperature and the top film was added.
The solid product (
11) 4.9 kg was obtained. Let the total amount of this (n) be n-
Suspended in 30 ml of hebutane, di-n-butyl ether 2
．． 0 kg and 15 kg of titanium tetrachloride were added at room temperature for about 20 minutes, reacted at 90° C. for 2 hours, cooled, washed with n-heptane by decantation, and dried to obtain a titanium trichloride composition.

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

(3) Production of block copolymer N-hexane was added to the preactivated catalyst component obtained in (2) above into a polymerization reactor equipped with a stirrer and a two-stage turbine blade with an internal volume of 150 ft, which was purged with nitrogen. Obtained, 4, oM amount%
A suspension of n-hexane was added as a catalyst at a rate of 10.9 milligram atoms/hr in terms of titanium atoms, and diethylaluminum monochloride was added as a catalyst at a molar ratio of 3.0 to titanium atoms from the same pipe and from a separate pipe. N-hexane was continuously supplied at 24 kg/hr.

Furthermore, the concentration in the gas phase of the polymerization vessel is 1! Hydrogen was supplied so as to maintain the volume %, and propylene was supplied so as to maintain the total pressure at 8 kg/cm'G, and the first stage of propylene polymerization was carried out at 70°C.

During the polymerization, the polymer slurry was continuously extracted so that the polymer retention level in the polymerization vessel was 80% by volume.

The extracted polymer slurry was then continuously introduced into a first stage second stage polymerization vessel having an internal volume of 150 ft similar to that used in the first stage. Hydrogen was further supplied to the polymerization vessel so that the concentration in the gas phase of the polymerization vessel was maintained at 9.6% by volume, and propylene was supplied so that the total pressure was maintained at 10 kg/cm''6. The second stage propylene polymerization was carried out at 70°C.

During the polymerization, the polymer slurry was continuously extracted as a polymer at a rate of 13.8 kg/hr so that the retention level of the polymer slurry in the polymerization vessel was 68% by volume.

A portion of the extracted slurry was sampled, dried, and analyzed, and the VFR was found to be 50.0. The first stage consists of two stages.
After the stage polymerization is completed, the extracted polymerization mixture consisting of the catalyst, n-hexane, and polymer is continuously transferred to a second stage polymerization vessel of the same type as the first stage polymerization vessel and having an internal volume of 100j2. C was introduced.

While introducing the polymerization mixture into the second stage polymerization vessel as described above, hydrogen was added to the gas phase of ethylene and propylene so that the concentration in the gas phase in the polymerization vessel was maintained at 7.5% by volume. The molar ratio is maintained at 0.45, and the total pressure is 5.4 kg/c+a”
Ethylene and propylene were each continuously supplied to the second stage polymerization vessel so as to maintain G, and copolymerization of ethylene and propylene was carried out at 60°C. During the copolymerization, the block copolymer slurry was continuously supplied from the polymerization vessel to an internal volume of 40 J! so that the retention level of the block copolymer slurry in the polymerization vessel was 62% by volume. was taken out into a flash tank.

While reducing the pressure in a flash tank to remove unreacted hydrogen, ethylene, and propylene, methanol was added to 1 k
It was supplied at a rate of g/hr and contact treatment was carried out at 10°C. Subsequently, the slurry is centrifuged to separate the solvent, and then dried.
Propylene-ethylene block copolymer 15kg/h
It was obtained continuously for 168 hours at r. During the production of the block copolymer, no operational problems occurred and the production was extremely stable. In addition, the VFR of the obtained copolymer was 30
．． 0. The ethylene content was 4.6% by weight.

Comparative Example 9 Block copolymerization was carried out in the same manner as in Example 5 (3), except that the titanium trichloride composition obtained in Example 5 (1) was used instead of the preactivated catalyst component. Ta.

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

In a stainless steel reactor equipped with a stirrer, 6 It of purified decane, 1.0 kg of magnesium-containing solid, 3.4 kg of n-butyl orthotitanate, and 3.9 kg of 2-ethyl-l-hexanol were mixed and heated at 130°C with stirring.
The mixture was heated for 2 hours to dissolve and form a uniform solution.

The solution was brought to 70°C and Gl-)ethyl ruylate 02k
After adding g and reacting for 1 hour, diisobutyl phthalate 0
．． After adding 4 kg of silicon tetrachloride and reacting for an additional 1 hour, 10.4 kg of silicon tetrachloride was added dropwise over 2 hours without stirring to precipitate a solid, and the mixture was further stirred at 70°C for 1 hour. The solid was separated from the solution and washed with purified hexane to yield a solid product (Hl).
I got it.

To the entire amount of the solid product (Ill), 0.4 kg of diisobutyl phthalate was added together with 101 1 of 1,2-dichloroethane and 10 ml of titanium tetrachloride, and 100 kg of diisobutyl phthalate was added while stirring.
After reacting at ℃ for 2 hours, the liquid phase was removed by decantation at the same temperature, and 1,2-dichloroethane 1
01, 10j2 of titanium tetrachloride, and 0.4 kg of diisobutyl phthalate were added and reacted at 100°C for 2 hours with stirring.The solid portion was collected by hot filtration, washed with purified hexane, and heated at 25°C under reduced pressure. After drying for 1 hour, a titanium-containing supported catalyst component was obtained.

(2> Preparation of preactivated catalyst component In the reactor used in Example 4 (2), add 2
0ft! - 1.5 kg of ethylaluminum, 270 g of diisobutyldimethoxysilane, and 200 g of the titanium-containing supported catalyst component obtained in (1) above were added at room temperature.The temperature in the reactor was brought to 35°C, and at the same temperature, A first stage preactivation treatment was performed by supplying 100 NJI of ethylene over a period of 1 hour (1.0 g of ethylene reacted per 1 g of the titanium-containing supported catalyst component).

Next, unreacted ethylene was removed, and 450 g of 3-methylbutene-1 was added without washing the reaction mixture.
A second preactivation treatment was performed at 5° C. for 2 hours (1.5 g of 3-methylbutene-1 was reacted per tg of the titanium-containing supported catalyst component) to obtain a preactivated catalyst in the form of a slurry.

(3) Production of block copolymer MFR was installed in the horizontal first stage polymerization vessel used in Example 4 (3).
After adding 20 kg of polypropylene powder, the preactivated catalyst component slurry obtained in (2) above was continuously fed at a rate of 0.335 milligram atoms/hr in terms of titanium atoms.

In addition, hydrogen was supplied so that the concentration in the gas phase of the polymerization reactor was maintained at 0.9% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg/c1G, and the first stage propylene polymerization was carried out at 70°C. It was carried out in

During the polymerization, the polymer was continuously extracted at a rate of 10.0 kg/h so that the polymer retention level in the polymerization vessel was 60% by volume. A portion of the extracted polymer was collected and analyzed. As a result, the VFR was found to be IOJ. After the first stage polymerization was completed, the polymerization mixture consisting of the extracted catalyst and polymer was transferred to the horizontal second stage used in Example 4 (3).
It was continuously introduced into a stage polymerization vessel.

While introducing the polymerization mixture from the 1-stage multi-stage vessel into the second stage polymerization vessel as described above, hydrogen was introduced so that the concentration in the gas phase in the polymerization vessel was maintained at 1.6% by volume. In addition, ethylene and propylene were continuously polymerized in the second stage so that the molar ratio of ethylene and propylene in the gas phase was maintained at 0.42, and the total pressure in the polymerization vessel was maintained at 7 kg/cs"G. ethylene and propylene were copolymerized at 110°C.During the copolymerization, the block copolymer was added so that the level of block copolymer in the second stage polymerization vessel was 35% by volume. continuously from a 342-stage polymerization vessel to 75 kg/
I extracted it in hr. The extracted block copolymer was subjected to the same post-treatment as in Example 1, and a propylene-ethylene block copolymer was continuously produced for 168 hours.

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

Comparative Example 10 In (2) of Example 6, the second stage preactivation treatment with 3-methylbutene-1 was omitted, and only ethylene was reacted to obtain a preactivated catalyst component. Block copolymerization was carried out in the same manner as in Example 6 (3) except that the components were used.

Example 7 <1) A titanium trichloride composition was obtained in the same manner as in Example 1 (1).

(2) In (2) of Example 1, the amount of propylene used was 300 g, and P-
A preactivated catalyst component was obtained in the same manner except that 2.0 kg of trimethylsilylstyrene was used.

(3) In (3) of Example 1, the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component, and butane was further added as an 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 amount of 0.01 was supplied.

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

The preactivation conditions and results of the above Examples and Comparative Examples are shown in the table.

[Effects of the Invention] As is clear from the examples described above, the propylene-olefin block copolymer obtained by the method of the present invention has the following properties:
Compared to known block copolymers obtained by conventional methods, it has a better balance of rigidity and impact resistance (see Examples 1 to 7 and Comparative Examples 3.8 to 11), and therefore can be used in various molding methods. It can be widely applied in various fields, especially in the injection molding field, to demonstrate its characteristics.

On the other hand, even if a catalyst that has been preactivated with a non-linear olefin is used, if the preactivation treatment is not performed according to the method of the present invention, operational problems will occur, and long-term continuous operation will not be possible. It's impossible. In addition, the obtained block copolymer also has insufficient improvement in the balance between rigidity and impact resistance (Comparative Example 1
, 2, 6.7).

[Brief explanation of drawings]

Figure 's1 is a manufacturing process diagram (flow sheet) for explaining the present invention in detail. Below

Claims (7)

[Claims] (1) [1] A titanium-containing solid catalyst component, [2] an organoaluminum compound (A_1), and if necessary, [3] an electron donor (B_1) are combined, and this is combined with [4] directly. Add chain olefin to 1 g of the titanium-containing solid catalyst component.
After the polymerization reaction of 0.01 to 100 g per unit, [5] the non-linear olefin is added to the titanium-containing solid catalyst component 1.
Using a preactivated catalyst obtained by polymerization reaction of 0.001 to 100 g per gram, propylene in an amount of 60 to 95% by weight of the total polymerization amount is polymerized in the first stage, and then in the second stage. It is characterized by copolymerizing propylene and an olefin other than propylene in an amount of 40% to 5% by weight of the total polymerization amount, so that the olefin content in the obtained block copolymer is 3% to 30% by weight. A method for producing a propylene-olefin block copolymer. (2) The manufacturing method according to claim 1, in which a titanium trichloride composition is used as the titanium-containing solid catalyst component. (3) The manufacturing method according to claim 1, in which the titanium-containing solid catalyst component is a titanium-containing supported catalyst component containing titanium, magnesium, halogen, and an electron donor (B_2) as essential components. (4) As the organoaluminum compound (A_1), the general formula is AlR^1_pR^2_p・X_3_-_(_p_
+_p_′_) (wherein, R^1 and R^2 are alkyl groups,
A hydrocarbon group such as a cycloalkyl group or an aryl group or an alkoxy group, X represents a halogen, and p and p' represent any number satisfying 0<p+p'≦3. ) The manufacturing method according to claim 1, using an organoaluminum compound represented by: (5) The non-linear olefin has the following formula, CH_2=CH-R^3 (wherein, R^3 has a saturated cyclic structure of a hydrocarbon that may contain silicon, and may contain silicon. The manufacturing method according to claim 1, which uses a saturated ring-containing hydrocarbon monomer represented by (representing a saturated ring-containing hydrocarbon group having 3 to 18 carbon atoms). (6) Non-linear olefins include the following formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^4 is a chain hydrocarbon group with 1 to 3 carbon atoms that may contain silicon, or represents silicon, R
^5, R^6, R^7 have a carbon number of 1 and may contain silicon
represents a chain hydrocarbon group from to 6, R^5, R^
Any one of 6 and R^7 may be hydrogen. ) Claim 1 using branched olefins represented by
The manufacturing method described in section. (7) Non-linear olefins include the following formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is either 0 or 1, m is either 1 or 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 It represents halogen, and when m is 2, each R^9 may be the same or different. ) The manufacturing method according to claim 1, using an aromatic monomer represented by: