JPH03210308A - Production of polypropylene - Google Patents

Abstract

PURPOSE:To obtain a polypropylene containing a specified amount of boiling n-heptane insolubles and gives a molding excelling in melt flow and rigidity by polymerizing propylene in the presence of a catalyst containing a titanium- containing solid catalyst component obtained by a specified preparative method and an organoaluminum compound. CONSTITUTION:In the course of producing a titanium-containing solid catalyst component, it is treated by the polymerization of an olefin component essentially consisting of a nonlinear olefin (e.g. 3-methylbutene-1) and subjected to the subsequent processes to produce a titanium-containing solid catalyst component containing 0.01-99wt.% nonlinear olefin polymer (block). A catalyst comprising this component, an organoaluminum compound and optionally an electron donor is produced. Propylene is polymerized in the presence of this catalyst to obtain a polypropylene containing 70-95wt.% boiling n-heptane insolubles.

Description

[Detailed description of the invention] [! Business field of use] The present invention relates to a method for producing polypropylene.

More specifically, the present invention relates to a method for producing polypropylene that has excellent processability and relatively low stereoregularity, yet has rigidity equivalent to that of ordinary polypropylene, and has excellent impact resistance and transparency.

[Conventional technology and its issues]

Hitherto, isotactic polypropylene with well controlled stereoregularity having a boiling n-heptane insoluble fraction of more than 95% by weight has been produced commercially, and this is also combined with aluminum salts of aromatic carboxylic acids and dipropylene. Compositions with improved rigidity and transparency by adding various nucleating agents such as benzylidene sorbitol are also used in various fields of molded products.

However, due to the high stereoregularity of polypropylene (isotactic pentad fraction (P) of 0.92 to 0.416), the polypropylene and its compositions require high energy and high molding during processing. Processability may be insufficient due to the need for pressure, or the resulting molded product may have high rigidity but low impact resistance or transparency.
It had a problem.

On the other hand, compared to the above-mentioned isotactic polypropylene and its composition, stereoregular polypropylene with a low boiling point insoluble portion in heptane of about 20% to 80% by weight (
Special Publication No. 32-10,598, Special Publication No. 39-12,
No. 105, Japanese Patent Publication No. 53-48,799, Japanese Patent Application Laid-open No. 102-214, etc.) are known.

Since the polypropylene requires less energy during processing than isotactic polypropylene, it is expected to be used in the field of film molding, which is different from that of ordinary isotactic polypropylene. However, these polypropylenes are composed of a boiling 1n-heptane soluble portion with extremely low stereoregularity and a boiling an-heptane insoluble portion with relatively high stereoregularity, so when made into molded products, , as a result of the extremely low stereoregularity bleeding onto the surface, JP-A-57-47.
As seen in Publication No. 371, only molded products with surface tackiness can be obtained.

In order to improve this point, 5 compositions in which dibenzylidene sorbitol and zeolite are added to the polypropylene (Japanese Unexamined Patent Publication No. 80-118,727) and compositions in which dibenzylidene sorbitol and the like are added to the polypropylene are used. Technology for rapidly cooling the film and for forming a film into a specific crystal structure
No. 39, JP-A No. 59-43.044) have been proposed, but boiling n-
The improvement effect was still insufficient because the heptane soluble portion was relatively large.

Furthermore, the purpose of molded articles obtained using the polypropylene or composition is to have low rigidity.

The present inventors have created a polypropylene that combines the advantages of isotactic polypropylene and low stereoregularity polypropylene described above.
We conducted extensive research on a method for producing polypropylene that is easy to process, has excellent rigidity, impact resistance, and transparency, and is free from problems such as bleeding.

As a result, we found that the above problems can be solved when using polypropylene with relatively low stereoregularity produced under specific polymerization conditions using a titanium-containing solid catalyst component obtained by a specific method. The present invention was completed based on the findings.

As is clear from the above description, an object of the present invention is to provide a method for producing polypropylene that is easy to process, has excellent rigidity, impact resistance, and transparency, and is free from problems such as bleeding. It is in.

[Means for solving problems] The present invention has the following configuration.

+11 Propylene is polymerized using a catalyst consisting of a titanium-containing solid catalyst component, an organoaluminum compound (A2), and, if necessary, an electron donor (Bl), so that the boiling n-heptane insoluble portion is 70% by weight. %〜
In the method for producing polypropylene having a content of 95% by weight, a non-linear olefin, or a straight chain olefin and a non-linear olefin are used as the titanium-containing solid catalyst component under polymerization conditions during the production of the titanium-containing solid catalyst component. It is characterized by using a titanium-containing solid catalyst component containing 0.01% to 99% by weight of a non-linear olefin polymer or a non-linear olefin polymer block obtained through a polymerization treatment and further subsequent steps. A method for producing polypropylene.

(2) As a non-linear olefin, the following formula, CH2-C)I
-R' (wherein, the pass has a saturated cyclic structure of a hydrocarbon that may contain silicon, and has a carbon number of 3 that may contain silicon)
The manufacturing method according to item 1 above, using a saturated ring-containing hydrocarbon monomer represented by ), which represents a saturated ring-containing hydrocarbon group from to 18.

(3) As a non-linear olefin, the following formula, CH
-R''-R' s (wherein, R2 represents a quenched hydrocarbon group having 1 to 3 carbon atoms which may contain silicon, or silicon, and Ra
, R4 and R8 have 1 to 6 carbon atoms and may contain silicon.
(Rs%R4, any one of R may be hydrogen). The manufacturing method described in Section J1.

(4) As a non-linear olefin, the following formula, (where n is 0
．． 1, chicken is either 1 or 2, R6 represents a chain hydrocarbon group having 1 to 6 carbon atoms that may contain silicon, and R? represents a hydrocarbon group having 1 to 12 carbon atoms that may contain silicon, hydrogen, or halogen; when - is 2, each 87 may be the same or different;
) The manufacturing method according to item 1 above, using an aromatic monomer represented by:

(5) Instead of the titanium-containing solid catalyst component, the titanium-containing solid catalyst component is combined with an organoaluminum compound (A), and this is reacted with an olefin of 1 g to 2008 O per 18 of the titanium-containing solid catalyst component, The manufacturing method according to item 1 above, which uses a preactivated catalyst component.

(6) The isotactic pentad fraction CP) of the obtained polypropylene is 0.70 to 0.91, and the isotactic pentad fraction (P r ) of the boiling n-heptane insoluble portion of the polypropylene The manufacturing method according to item 1 or 5, wherein in relation to (P) above, satisfies the formula o<(P, )-(P)≦0.1.

The configuration of the present invention will be explained in detail below.

The titanium-containing solid catalyst component used in the method for producing polypropylene of the present invention may be polymerized using a non-linear olefin, or a linear olefin and a non-linear olefin under polymerization conditions during the production of the titanium-containing solid catalyst component. Then, a titanium-containing solid catalyst component obtained through subsequent steps is used.

To specifically explain in detail the method for producing such a titanium-containing solid catalyst component, for example, an organoaluminum compound (A1) and an electron donor (B, ) are reacted to obtain a reaction product (1), A solid product (I+) obtained by reacting this (1) with titanium tetrachloride, or a solid product (I+) obtained by reacting an organoaluminum compound (A3) with titanium tetrachloride, is The final solid product obtained by polymerizing a chain olefin, a straight chain olefin, and a non-linear olefin, and further reacting an electron donor (BS) with an electron acceptor is referred to as (II!), and the titanium-containing A solid catalyst component is produced.

In the present invention, ``polymerization treatment'' refers to ``polymerization treatment'' in which straight-chain olefins or non-linear olefins are brought into contact with a solid product (I or (IV) described below) under conditions that allow polymerization. This polymerization process, which refers to the polymerization of chain olefins, produces solids (I+) or (IV
) becomes coated with polymer.

The above organoaluminum compound (A3) and an electron donor (
The reaction with B) is carried out at -20°C to 200°C in a solvent (DI).
The organic aluminum compounds (A, ), (B, ), (
There is no restriction on the order of addition of the electron donor (B
,) 0.1 mol to 8 mol, preferably 1 to 4 mol, solvent 0.5 L to 5 L, preferably 0.5 L to 2 L.

In this way, reaction product (1) is obtained. The reaction product (reaction product) can be used in the next reaction with the liquid R (sometimes referred to as reaction product liquid (1)) that remains after the reaction is completed without separation. can.

A solid product (11) obtained by reacting this reaction product (1) with titanium tetrachloride or an organoaluminum compound (A) with titanium tetrachloride is used as a non-linear olefin or a linear olefin. As a method for polymerizing with non-linear olefins, ■ Reaction product (1) or organoaluminum compound (
A method of polymerizing a solid product (11) by adding a non-linear olefin, or a straight-chain olefin and a non-linear olefin in any step of the reaction of A.) with titanium tetrachloride, 0 reaction products (1) or organoaluminum compound (
After the reaction between AS) and titanium tetrachloride is completed, a non-linear olefin, or a linear olefin and a non-linear olefin are added to polymerize the solid product (11) in multiple stages; 1) or organoaluminum compound (
After the reaction between A. There is a method in which a non-linear olefin, or a straight-chain olefin and a non-linear olefin are added and polymerized.

In addition, the above-mentioned polymerization treatment using a non-linear olefin or a straight-chain olefin and a non-linear olefin may be performed using a non-linear olefin alone; A method of polymerizing with a chain olefin, followed by polymerization with a non-linear olefin is preferred from the viewpoint of polymerization operability when using the obtained titanium-containing solid catalyst component and purchasing of the obtained polypropylene. .

Furthermore, in addition to the above-mentioned method in which a linear olefin and a non-linear olefin are used at least once each, the polymerization treatment can be carried out two or more times, for example, after the polymerization treatment of a non-linear olefin, a linear olefin is further added. It is also possible to carry out a polymerization treatment.

Reaction product (1) or organoaluminum compound (A
The reaction between the
It is carried out at 00°C for 5 minutes to 10 hours.

Although it is preferred not to use a solvent, aliphatic or aromatic hydrocarbons can be used. The organic aluminum compound (XS), titanium tetrachloride 5 and the solvent may be mixed in any order, and the straight chain olefin and non-straight chain olefin may be added at any stage.

It is preferable to complete the mixing of the total amount of the organic aluminum compound (A), titanium tetrachloride, and the solvent within 5 hours, and the reaction is carried out during the mixing.After the total amount is mixed, the reaction is continued for another 5 hours. It is preferable to continue.

The amount of each used in the reaction is 1 mole of titanium tetrachloride, the solvent is O ~ 3,000 mA, and the reaction product (1)
Or the organoaluminum compound (AS) is (1)
Alternatively, the number of ^1rX molecules in the (AS) and τl in titanium tetrachloride [the ratio of tens (At/τI) is 0.05 to IQ, preferably 0.06 to 0.3.

Polymerization treatment with non-linear olefins, or straight-chain olefins, and non-linear olefins can be performed in any process of the reaction of the reaction product (or organoaluminum compound fAs) with titanium tetrachloride. When adding olefins and non-linear olefins, and when adding reaction products (1) or organoaluminum compounds (
After the reaction between A3) and titanium tetrachloride, when adding a non-linear olefin, or a linear olefin and a non-linear olefin, the reaction temperature is 0 in any polymerization treatment using a linear olefin or a non-linear olefin. ℃～90℃
for 1 minute to 10 hours, the reaction pressure was atmospheric pressure (Okgf/cm
Under the conditions of ``G)~lOkgf/cs''G, the solid product <It) 1(1(per Ig, straight olefin 0.
18-100 kg, and non-linear olefin 0.01
3~! The final titanium trichloride composition (
In the case of non-linear olefin homopolymerization treatment in III'), the content of the non-linear olefin polymer is 0.01% by weight.
9g% by weight, and in the case of using a straight chain olefin and a non-linear olefin, the content of the straight chain olefin polymer block is Q, lll weight% to 49.5I
1% by weight and the content of the non-linear olefin polymer block is 0.01% by weight to 49.5% by weight.

When the content of the straight olefin polymer block is less than 0.01% by weight, the obtained titanium trichloride composition (III
) The rigidity of the polypropylene produced using the above-mentioned polypropylene is insufficient, and if the above range is exceeded, the improvement in effectiveness is not significant, resulting in operational and economical disadvantages.

In addition, as mentioned above, it is preferable to use a non-linear olefin in the polymerization treatment, and in this case, the weight ratio of the straight-chain olefin polymer block to the non-linear olefin polymer block has the effect of improving driveability, It is preferable to set the ratio to 98/2 or less, taking into consideration both the effect of increasing the purchase price of polypropylene per unit.

After the polymerization treatment using a non-linear olefin, a straight-spun olefin, and a non-linear olefin is completed, the liquid portion is removed by filtration or decantation after the reaction of the reaction product (or organoaluminum compound (A3)) with titanium tetrachloride. If the solid product (11) obtained after separation and removal is suspended in a solvent, the solid product C11') will be On the other hand, 100 servings of solvent 1~
5,000 layer 1, organoaluminum compound 0.5g ~
In the presence of 6,000 g, reaction temperature is 0°C to 90°C for 1 minute
For 10 hours, the reaction pressure was atmospheric pressure (Okgf/cm”G)
Under conditions of ~10 kgf/cm”G, the solid product (II
) 0.1g to 100 linear olefins per 100g
kg, and non-linear olefins 0.01 g to 1 (IQ
g, and in the case of non-linear olefin homopolymerization treatment in the titanium trichloride composition (III), the content of the non-linear olefin polymer is 0.0! When using a straight chain olefin and a non-straight chain olefin, the content of the straight chain olefin polymer block should be 0.5% by weight to 99% by weight.
1 dish amount% to 4g, 5% by weight, the content of non-linear olefin polymer block is 0.01% to 49.5% by weight, and the content of the non-linear olefin polymer block to the non-linear olefin polymer block Polymerization is carried out so that the weight ratio is 9872 or less.

In any of the multi-stage polymerization treatments described above, after each stage of polymerization treatment using a linear olefin or non-linear olefin is completed, the reaction mixture can be used as it is in the next stage polymerization treatment. In addition, the coexisting solvent, unreacted linear olefin or non-linear olefin, and organoaluminum compound, etc. are removed by filtration or decantation, and the solvent and organoaluminum compound are added again. It may also be used for polymerization treatment with chain olefins or straight chain olefins.

The solvent used during the polymerization treatment is preferably an aliphatic hydrocarbon;
Even if the organoaluminum compound is the same as the one used to obtain the reaction product (1) or the one used in the direct reaction with titanium tetrachloride without reacting with the electron donor (Ba), it may be different. It may also be something you have.

After the reaction is completed, the liquid portion is separated and removed by filtration or decantation, and then washed with a solvent repeatedly.
The obtained polymerized solid product (hereinafter sometimes referred to as solid product (II-A)) may be used in the next step while suspended in a solvent, or it may be further dried to form a solid product. You may take it out and use it as an object.

The solid product (■-A) is then treated with an electron donor (
B,) and an electron acceptor (F) are reacted.

Although this reaction can be carried out without using a solvent, preferable results are obtained using an aliphatic hydrocarbon.

The amount used is 0.1 g to 1,0001.0 g of (Bs) per 100 g of solid product (II-A). Preferably 0.
58-200g, (F) 0.1g-1. OOQg,
Preferably 0.2g to 500g, solvent O to 3,000g
s, Q, preferably 100 to t, 000s, Q.

As for the reaction method, ■ Solid product <11-A'')
A method in which an electron donor (BS) and an electron acceptor (F) are reacted simultaneously, ■ A method in which (F) is reacted with (II-A) and then (Bs) is reacted, ■ A method in which (Bs) is reacted with (II-A).
') is reacted with (!Is) and then (F) is reacted.

There is a method of reacting @(h) and (F) and then reacting (II-A), but any method may be used.

The reaction conditions are 40°C to
It is desirable to react at 200°C, preferably 50°C to 100°C for 30 seconds to 5 hours.
II-A) and (Bs) are reacted at 0°C to 50°C for 1 minute to 3 hours, and then reacted with (F) under the same conditions as in (1) and (2) above.

In addition, in method (■), (BS) and (F) are heated at 10°C to 1
After reacting at 00°C for 30 minutes to 2 hours, the mixture is cooled to 40°C or below, and (n-A) is added, followed by reaction under the same conditions as in (1) and (2) above.

The solid products (II-A), (as), and (F
After the reaction of ) is completed, the liquid portion is separated and removed by filtration or decantation, and washing with a solvent is repeated to obtain titanium trichloride composition CIII), which is the titanium-containing solid catalyst component used in the present invention.

The organoaluminum compound (A3) used in the production of the titanium-containing solid catalyst component has a general formula of AIR'l
R@1-Xs-1I*L・+ (wherein, R6 and R9 represent a hydrocarbon group or alkoxy group represented by 7A/kyl group, cycloalkyl group, or aryl group, X represents a halogen, and 1, An organoaluminum compound represented by (1° represents an arbitrary number of o<, c+x'≦3) is used.

Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, trinibutylaluminum, tri-n-hexylaluminum, tri-hexylaluminum, tri-2-methylpentylaluminum, tri-n-octylaluminium. , trialkylaluminums such as tri-n-decylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, cytobutylaluminum monochloride, diethylaluminum monofluoride, diethylaluminum monochloride, diethylaluminium monoiodide, etc. Dialkyl aluminum monohalides, dialkyl aluminum halides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, monoalkyl aluminum cybarides such as ethyl aluminum dichloride, I-butyl aluminum dichloride, etc. In addition, alkoxyalkylaluminums such as monoethoxydiethylaluminum and jetoxymonoethylaluminum can also be used.

Two or more types of these organoaluminum compounds can also be used in combination.

As the electron donor used to produce the titanium trichloride composition (■) which is the titanium-containing solid catalyst component used in the present invention, there are various electron donors shown below, including (B,)
, (B,), it is preferable to mainly use ethers, and to share the other electron donors with the ethers.

Those used as electron donors are organic compounds 2 having any of oxygen, nitrogen, sulfur, and phosphorus atoms, i.e.,
Ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, sulfides Hydrogen, thioethers, thioalcohols, etc.

Specific examples include diethyl ether, di-n-propyl ether, di-n-butyl ether, diisoamyl ether, di-n-pentyl ether, di-n-hexyl ether,
Diisoamyl ether, Moro-octyl ether, Diisoamyl ether, Moro-dodecyl ether, Diphenyl ether, Ethylene glycol monoethyl ether,
Ethers such as tetrahydrofuran, methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, phenol, cresol,
Alcohols or phenols such as xylenol, ethylphenol, naphthol, methyl methacrylate,
Ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate , esters such as methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate, acetaldehyde, Aldehydes such as benzaldehyde, fatty acids such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, aromatic acids such as benzoic acid, ketones such as methyl ethyl ketone, methyl isobutyl ketone, benzophenone, Nitriles such as acetonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β(N,N-dimethylamino)ethanol, pyridine, quinoline, α-picoline, 2,4.6-
Trimethylpyridine, N, N.

Amines such as N', N'-tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N'.

Amides such as N', N-pentamethyl-No-β-dimethylaminomethylphosphate triamide and octamethylpyrophosphoramide, ureas such as N, N, N", No-tetramethylurea, phenyl isocyanate, toluyl Isocyanates such as isocyanate, azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxyto, dimethylphosphine, di-n - Phosphites such as octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, triphenyl phosphite, phosphites such as ethyl diethyl phosphinite, ethyl butyl phosphinite, phenyl diphenyl phosphinite, diethyl Other examples include thioethers such as thioether, diphenylthioether, methylphenylthioether, ethylene sulfide and propylene sulfide, and thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol.

These electron donors can also be used in combination.
Each of the electron donors (B, ), solid product (II) or CIt-A) to be reacted (B3) to obtain the reaction product (1) may be the same or different.

As the linear olefin used in polymerization 1A31, linear olefins such as ethylene, propylene, butene-11pentene-1, hexene-11octene-1, etc. are used, and ethylene and propylene are particularly preferably used. One or more types of these straight chain olefins are used.

The non-linear olefin used in the polymerization treatment has the following formula 5, CH2-0H-R' (wherein R+ has a saturated cyclic structure of a hydrocarbon that may contain silicon, and may contain silicon. A saturated ring-containing hydrocarbon carmer represented by ) representing a saturated ring-containing hydrocarbon group having 3 to 18 carbon atoms; represents a chain hydrocarbon group having 1 to 3 carbon atoms which may contain silicon, or silicon; R3
, R4, R' represent a chain hydrocarbon group having from 1 to 6 carbon atoms which may contain silicon, but R', R4, R'
Branched olefins represented by ) or (where n is 0.1 and m is 1.2
R' represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R' represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon. represents a group, hydrogen, or halogen, and when m is 2, each R7 may be the same or different. ) is an aromatic monomer represented by

Specifically, examples of the saturated ring-containing hydrocarbon carmer in (2) include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, 3-methylvinylcyclopentane, vinylcyclohexane, 2-methylvinylcyclohexane, and 3-methylvinylcyclopentane. In addition to vinylcycloalkanes such as methylvinylcyclohexane, 4-methylvinylcyclohexane, and vinylcyclohebutane, allylcycloalkanes such as allylcyclopentane and allylcyclohexane, cyclotrimethylenevinylsilane, cyclotrimethylenemethylvinylsilane, and cyclotetramethylene Vinylsilane, cyclotetramethylenemethylvinylsilane, cyclopentamethylenevinylsilane, cyclopentamethylenemethylvinylsilane, cyclopentamethyleneethylvinylsilane, cyclohexamethylenevinylsilane, cyclohexamethylenemethylvinylsilane, cyclohexamethyleneethylvinylsilane, cyclotetramethyleneallylsilane, Saturated hydrocarbon monomers having a silicon atom in the saturated cyclic structure such as cyclotetramethylenemethylallylsilane, cyclopentamethyleneallylsilane, cyclopentamethylenemethylallylsilane, cyclopentamethyleneethylallylsilane, cyclobutyldimethylvinylsilane, cyclopentyldimethyl Vinyl Cylil, Cyclopenyl Ethyl Ethyl Vinyl Cylil, Cyclopenyl Julbinyl Silan, Cyclohexylvinyl Silan, Cyljemethyl Vinyl Silan, Cyclohexyl Eettlumethyl Vinyl Silan, Cyclobicyl Jemethyl Lyluslan, Cyclopentiljiruslan, Cyclo Pennil Jillyl. Rohexylmethylluslan, to Cyclro, Kisirujemethylal Lylan, Cyclohexyleett Lemethylluslan,
Examples include saturated ring-containing hydrocarbon monomers containing a silicon atom 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 3-position branched olefin, 4-ethylhexene-1,
4-position branched olefin such as 4,4-dimethylpentyne-1,4,4-dimethylhexene-1, vinyltrimethylsilane, vinyltriethylsilane, vinyltri-n-butylsilane, allyltrimethylsilane, allylethyldimethylsilane, allyldiethyl Alkenylsilanes such as methylsilane, allyltriethylsilane, allyltri-n-probylsilane, 3-butenyltrimethylsilane, 3-butenyltriethylsilane, dimethyldiallylsilane,
Examples include diallysilanes such as ethylmethyldiallylsilane and diethyldiallylsilane.

In addition, as the aromatic monomer (2), styrene, its derivatives such as 0-methylstyrene, alkylstyrenes such as pt-butylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, etc. , 34-dimethylstyrene, dialkylstyrenes such as 3,5-dimethylstyrene, 2-methyl-4-fluorostyrene, 2-ethyl-4-chlorostyrene, 0-fluorostyrene, p-
Halogen-substituted styrenes such as fluorostyrene, trialkylsilylstyrenes such as p-trimethylsilylstyrene, 1-triethylsilylstyrene, p-ethyldimethylsilylstyrene, allyltoluenes such as O-allyltoluene and p-allyltoluene, 2 - Allylxylenes such as allyl-p-xylene, 4-allyl-0-xylene, 5-allyl-1-xylene, vinyldimethylphenylsilane, vinylethylmethylphenylsilane, vinyldiethylphenylsilane, allyldimethylphenylsilane, allyl Examples include alkenylphenylsilanes such as ethylmethylphenylsilane, 4-(〇-tolyl)-butene-1 and 1-vinylnaphthalene, and one or more of these non-linear olefins may be used.

The electron acceptor (F) reacted with the solid product (II-A') is typified by halides of elements of groups I11 to II of the periodic table. Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, and antimony pentachloride. , these can also be used in combination. Most preferred is titanium tetrachloride.

The following solvents (DI) are used.

Examples of aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, l-octane, etc. Carbon tetrachloride, chloroform Halogenated hydrocarbons such as , dichloroethane, trichloroethylene, and tetrachloroethylene can also be used. As an aromatic compound,
Aromatic hydrocarbons such as naphthalene, alkyl-substituted derivatives thereof such as mesitylene, dielene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, l-phenylnaphthalene, monochlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, dichlorobenzene, etc. Examples include halides such as chlorobenzene and brombenzene.

Titanium trichloride composition obtained as above (l)
In addition, for example, a solid product (IV
) is polymerized with a non-linear olefin or a straight-chain olefin and a non-linear olefin in the presence of an organoaluminum compound (A4) to obtain a solid product (V), and a halogen is added to the solid product (V). The titanium-containing supported catalyst component (Vl) obtained by reacting the titanium oxide compound (T2) can also be used as the titanium-containing solid catalyst component used in the present invention.

The method for producing the titanium-containing supported catalyst component (Vl) is shown below.

In addition, "liquefaction of a magnesium compound" as used in the present invention refers to cases in which the magnesium compound itself becomes a liquid, cases in which the magnesium compound itself becomes soluble in a solvent and forms a solution, or cases in which it reacts with other compounds. , or as a result of forming a complex, it may be solubilized in a solvent to form a solution, and the solution may be in a state where it is completely dissolved or contains colloidal or semi-dissolved substances. I don't mind.

The magnesium compound to be converted into a liquid may be any compound that can be in the above-mentioned liquefaction state, such as magnesium cybaride, alkoxymagnesium halide, aryloxymagnesium halide, dialkoxymagnesium, dialkoxymagnesium Magnesium, magnesium oxyhalide, magnesium oxide, magnesium hydroxide, magnesium carboxylate,
In addition to dialkylmagnesium, alkylmagnesium halide, etc., metal magnesium can also be used.

A known method can be used to liquefy a magnesium compound. For example, a magnesium compound can be liquefied with alcohol,
A method of liquefying with an aldehyde, amine, or carboxylic acid (JP-A-56-811, etc.), a method of liquefying with an orthotitanate ester (JP-A-54-40,293, etc.)
(Japanese Unexamined Patent Publication No. 1983), liquefaction method using a phosphorus compound (Japanese Unexamined Patent Application Publication No. 1983)
1-19,307, etc.), as well as methods combining these methods.

Regarding organomagnesium compounds having a C-Mg bond, which cannot be applied to the above-mentioned method, since they are soluble in ether, dioxane, pyridine, etc., they can be used as a solution of these or reacted with an organometallic compound. −
The formula is M, yg, R+6. R11 (M is aluminum,
Zinc, boron, or beryllium atoms, RIOlRll
is a hydrocarbon residue, p, 9, ``, S〉0, and V is the complementary valence, forming a complex compound represented by ``bow vP ÷ 2q.'' 139,885, etc.), it can be dissolved in a hydrocarbon solvent and liquefied.

Furthermore, when metallic magnesium is used, it can be liquefied with alcohol and orthotitanate (such as JP-A-50-51587), or reacted with an alkyl halide in ether using the so-called Grignard reagent. It can be liquefied by the method of forming .

Among the above methods for liquefying a magnesium compound, for example, when magnesium chloride is dissolved in a hydrocarbon solvent (D) using a titanate ester and alcohol, , titanate ester from 0.1 mol to 2 mol, alcohol from 0.1 mol to 5 mol, solvent (0,) from 0.1 u to
5J2, mix each component in any order of addition, and heat the suspension at 40°C to 200°C, preferably 5°C while stirring.
Heat at 0°C to 150°C. The time required for the reaction and dissolution is 5 minutes to 7 hours, preferably 10 minutes to S hours.

Examples of titanate esters include orthotitanate esters represented by Tl(OR'')4, and all [0-
Ti (OR") + OR") ] t OR"i' table Wasarel phorititanate is mentioned. Here, RI
JIS, R14R111 and R111 have 1 to 2 carbon atoms
0 alkyl group or a cycloalkyl group having 3 to 20 carbon atoms, and (is a number of 2 to 2G).

Specifically, methyl orthotitanate, ethyl orthotitanate, n-propyl orthotitanate, orthotitanate i
-propyl, n-butyl orthotitanate, l-butyl orthotitanate, n-amyl orthotitanate, 2-ethylhexyl orthotitanate, n-octyl orthotitanate, phenyl orthotitanate, and cyclohexyl orthotitanate. Titanate ester, polymethyl titanate, polyethyl titanate, polyn-propyl titanate, polytitanate 1-propyl, polytitanate n-butyl, polytitanate l-butyl, polytitanium 1ln-amyl, polytitanate 2-ethylhexyl, polytitanate n
Polytitanate esters such as -octyl, phenyl polytitanate and cyclohexyl polytitanate can be used. The amount of polytitanate to be used may be converted into orthotitanate units and used as the orthotitanate equivalent.

As alcohols it is possible to use aliphatic saturated and unsaturated alcohols. Specifically, methanol, ethanol, n-propertool, 1-propertool, n-
Monohydric alcohols such as butanol, n-amyl alcohol, 1-amyl alcohol, n-hexanol, n-octanol, 2-ethylhexanol, and allyl alcohol, as well as polyhydric alcohols such as ethylene glycol, trimethylene glycol, and glycerin. can also be used. Among these, aliphatic saturated alcohols having 4 to 10 carbon atoms are preferred.

As the inert hydrocarbon solvent (B2), a solvent similar to the solvent (Dll) used in producing the titanium trichloride composition (Ill) described above can be used, but aliphatic hydrocarbons are particularly preferred.

The solid product (rV) is the above-mentioned liquefied magnesium compound, precipitating agent (Xi), halogen compound (x, ), and electron donor (B4)! 5 and a titanium compound (τl). As the precipitation agent (Xi), halogen, halogenated hydrocarbon, halogen-containing silicon compound, halogen-containing aluminum compound, halogen-containing titanium compound,
Examples include halogenating agents such as halogen-containing zirconium compounds and halogen-containing vanadium compounds.

Further, when the liquefied magnesium compound is the above-mentioned organomagnesium compound, a compound having active hydrogen, such as an alcohol or a polysiloxane having a 5I-H bond, can also be used. These precipitating agents (×,
) is used in an amount of 0.0% per mole of magnesium compound.
1 mol to 50 mol is used.

Further, as the halogen compound (x2), halogen and a compound containing halogen can be mentioned, and the same halogenating agent mentioned as an example of the precipitating agent can be used. When used, the halogen compound (x,) does not necessarily require new use, and the amount of the halogen compound (x2) used is 0.1 mol to 50 mol per mol of the magnesium compound.

As the electron donor (B4), the above-mentioned (B2) and (
In addition to those similar to Bs), aromatic polyvalent carboxylic acid esters and alkoxysilanes are used, and aromatic polyvalent carboxylic acid esters are particularly preferably used. One or more types of these electron donors (B4) are used, and the amount used is 0.01 mol to 5 mol per 1 mol of the magnesium compound.

Titanium compound (T1) required for the preparation of solid product (IV)
) is -Formula Ti(OR")4-1IXII (wherein R
The halogenated titanium compound represented by ``ltltfurkyl group, loalkyl group, or aryl group, x represents a halogen, and U is an arbitrary number of O<u≦4'', and the liquefaction of the above-mentioned magnesium compound. The orthotitanates and polytitanates mentioned above are used.

Specific examples of halogenated titanium compounds include titanium tetrachloride, titanium tetrabromide, methoxytitanium trichloride, ethoxytitanium trichloride, propoxytitanium trichloride, butoxytitanium trichloride, phenoxytitanium trichloride, ethoxytitanium tribromide, Butoxy titanium tribromide, titanium dimethoxy dichloride,
Jetoxytitanium dichloride, dipropoxytitanium dichloride,
Dibutoxytitanium dichloride, diphenoxytitanium dichloride,
Examples include jetoxytitanium tribromide, dibutoxytitanium tribromide, trimethoxytitanium chloride, triethoxytitanium chloride, tributoxytitanium chloride, and triphenoxytitanium chloride.

Examples of the orthotitanate ester and polytitanate ester include those mentioned above.

One or more types of these titanium compounds (T,) are used, but when a halogenated titanium compound is used as the titanium compound (T1), since it has a halogen, the precipitating agent (
xl) and the halogen compound (x2) are optional. Also, when titanate ester is used to liquefy magnesium compounds, titanium compounds (
Any new use of T11 is optional. Titanium compound (T,
) is used in an amount of 0 per mol of magnesium compound.
．． The amount is 1 mol to 100 mol.

The above liquefied magnesium compound, precipitation agent (x+)
A solid product (
IV). During contact, an inert hydrocarbon solvent (D
3) may be used, or each component may be diluted beforehand. Examples of the inert hydrocarbon solvent (D) to be used include those similar to the above-mentioned (D2). The amount used is O~5,0001 per mol of magnesium compound.
It is 1.

There are various methods of contact, for example, ■
Add (x1) to the liquefied magnesium compound to precipitate a solid, and add (x2), (B4), (T1) to the solid.
(1) is added to a solution in which the liquefied magnesium compound and (B4) are brought into contact with each other in any order, a solid is precipitated, and (x, ), (T,) are added to the solid. There are two methods: (1) bringing the liquefied magnesium compound into contact with (Tl), then adding (x1), and then contacting (B4) and (X2) in any order.

The amount of each component to be used is within the above-mentioned range, but these components may be used all at once or in several stages. Moreover, as mentioned above, if one component has atoms or groups that also characterize the other component, it is not necessarily necessary to newly use the other component. For example, when a titanate ester is used to liquefy a magnesium compound, (T1) is obtained, but when a halogen-containing titanium compound is used as a precipitating agent (×,), (×2) and (
When T, ) uses a halogenating agent as the precipitating agent (x1), (x2) becomes an optional component.

The contact temperature of each component is -40°C to ÷180°C, preferably 0°C to ◆150°C, and the contact time is 5 minutes to 8 hours for each step at a reaction pressure of atmospheric pressure to 10 kg/c1G. , preferably 10 minutes to 6 hours.

A solid product (rv) is obtained in the above catalytic reaction. The solid product (TV) may be subsequently subjected to the next reaction step, but it is preferably washed with the above-mentioned inert hydrocarbon solvent.

Next, the solid product (+V) obtained by the above method is
Polymerization treatment is performed with a non-linear olefin, or a straight chain olefin and a non-linear olefin in the presence of an organoaluminum compound (A4) to obtain a solid product (V).

The above-mentioned polymerization treatment using a non-linear olefin or a linear olefin and a non-linear olefin may be performed using a non-linear olefin alone as described above in the production of the titanium trichloride composition (II+). The method of first carrying out a polymerization treatment with a linear olefin and a non-linear olefin, followed by a polymerization treatment with a non-linear olefin, improves the polymerization operability when using the obtained titanium-containing solid catalyst component. This is preferable from the viewpoint of the quality of the polypropylene obtained.

In addition, the above polymerization treatment can be performed by using a straight chain olefin and a non-linear olefin at least once each, or by adding a straight chain olefin two or more times, for example, after the polymerization treatment of the non-linear olefin. It is also possible to do this.

The conditions for polymerization treatment are such that a solid product (IV) is produced in both polymerization treatment using linear olefins and non-linear olefins.
Inert hydrocarbon solvent (D4) 1001 for 100g
β~5,000m alternating, organoaluminum compound (Aa
) 0.5g to 5,000g was added, and the reaction temperature was 0°C to 90°C.
t for 1 minute to 10 hours, and the reaction pressure was atmospheric pressure (Okgf/c
s2G) ~ 10 kgf/cm'G, 0.1 g of linear olefin per 100 g of solid product (ll)
~100kg, and 0.01g of non-linear olefin
~ look, the final titanium-containing supported catalyst component (Vl) has a non-linear olefin polymer content of 0.01% by weight ~ 9 in the case of non-linear olefin homopolymerization treatment.
When linear olefin and non-linear olefin are used, the content of the linear olefin polymer block is 0.11% to 49.5% by weight, and the non-linear olefin polymer block content is 0.11% to 49.5% by weight. Polymerization is carried out so that the content of the combined block is from O,01% by weight to 495% by weight, and the weight ratio of the straight chain olefin polymer block to the non-linear olefin polymer block is 98/2 or less.

In any of the above-mentioned polymerization treatments, after each stage of polymerization treatment using a straight-chain olefin or a non-linear olefin is completed, the reaction mixture can be used as it is in the next stage of polymerization treatment. Further, the coexisting solvent, unreacted straight chain olefin or non-linear olefin, organoaluminum compound (A4), etc. are removed by filtration or decantation, and the solvent and organoaluminum compound (A4) are added again. It may also be used in the next step of polymerization treatment with non-linear olefins or linear olefins.

In addition, in the polymerization process step, electron It is also possible to coexist a donor. Their usage depends on the solid product (
rV) 90 to 5,000 g per 100 g.

Organoaluminum compound (A4) used in polymerization treatment
, the solvent (D4), the linear olefin, and the non-linear olefin are the same as the previously described (A3), (D,), linear olefin, and non-linear olefin, respectively.

The polymerization treatment using a non-linear olefin or a linear olefin and a non-linear olefin is performed as described above, and the solid product (V) is obtained by washing with the above-mentioned inert hydrocarbon solvent.

Subsequently, the solid product (V) is reacted with a halogenated titanium compound (T2) to obtain a titanium-containing supported catalyst component (M
l) is obtained. As the halogenated titanium compound (T2), one formula 1 (
OR'')4-X-f In the formula, R+7 represents a 7JL/kyl group, a cycloalkyl group, or an aryl group, X represents a halogen, and U is an arbitrary number satisfying O<u≦4. Although the same halogenated titanium compounds can be used as specific examples, titanium tetrachloride is most preferred.

The reaction of the solid product (V) with the halogenated titanium compound (T,
Using 1 mole or more of the halogenated titanium compound (T,) per mole, reaction temperature of 20 ° C. to 200 ° C., reaction pressure of atmospheric pressure to 10 kg/cm'G for 5 minutes to 6 hours, Preferably, the reaction is carried out for 10 minutes to 5 hours. In addition, during the reaction, an inert hydrocarbon solvent (Ds) and an electron donor (B1
It is also possible to carry out in the presence of 1), and specifically, the same inert solvents and electron donors as in (DI) to (D4) and (B4) described above are used. These usage amounts are
(Da) is O~5 for 100g of solid product (V)
,000 mJ2, solid product ((B,) is preferably in the range of 0 to 2 mol per 1 mol of magnesium compound in Ml.

After the reaction of the solid product (V) with the halogenated titanium compound (T2) and, if necessary, an electron donor, the solid is separated by filtration or decantation and washed with an inert hydrocarbon solvent to remove any unreacted By removing substances or by-products, the final titanium-containing supported catalyst component (■), that is, the titanium-containing solid catalyst component used in the present invention, is obtained.

As described above, the titanium-containing solid catalyst component used in the present invention can be obtained, but the method for producing the titanium-containing solid catalyst component is not limited to the above two methods, and various methods can be adopted.

For example, after reacting a solid containing Mg and trivalent Ti with an electron donor or without reaction, in the presence of an organoaluminum compound, and a non-linear olefin, or a straight olefin and a non-linear olefin. It is also possible to use a Mg-containing titanium trichloride composition obtained by polymerizing with , and then reacting an electron donor with an electron acceptor. 0.01% to 9% by weight of a non-linear olefin polymer or a non-linear olefin polymer block obtained by polymerization treatment using
Any titanium-containing solid catalyst component containing 9% by weight can be used.

The method for producing polypropylene of the present invention includes the above titanium-containing solid catalyst component, an organoaluminum compound (A),
And if necessary, using a catalyst consisting of an electron donor (B1), propylene is polymerized so that the insoluble portion in heptane is 70% by weight to 95% by weight! ! % of polypropylene.

Examples of the polymerization method for obtaining polypropylene having a boiling n-heptane insoluble portion of 70% to 95% by weight include known methods, for example, at a relatively high polymerization temperature (75°C to 95°C).
A method of polymerizing propylene in It is also possible to adopt a method of polymerizing propylene without using a third catalyst component as a stereoregularity improver represented by an organosilicon compound, but as a method that significantly exhibits the effects of the present invention, By selecting the polymerization conditions, the isotactic pentad fraction (P) is between 0.70 and 0.91, and the insolubility when extracted for 6 hours in boiling n-heptane using a Soxhlet extractor is determined. A method for obtaining polypropylene in which the isotactic pentad fraction (Pr) of the moiety satisfies the formula 0<(Pr)-(P)≦0.1 in relation to the above-mentioned (P) is mentioned.

Note that the isotactic pentad fraction in the present invention is -acrom according to Zambelli et al.

1ecules 8925 (1973), that is, the isotactic fraction in pentad units in a polypropylene molecule measured using 'sC-NMR.

In other words, the fraction means the fraction of the propylene monomer unit located at the center of a chain in which five consecutive propylene monomer units are meso-bonded. However, the method for determining the attribution of the above-mentioned NMR absorption peak is based on Macroolacules 86
87 (1975).

Examples of polymerization conditions for obtaining polypropylene satisfying the above physical properties include the following polymerization methods.

■Titanium trichloride composition CIII obtained by the method described above
) and dialkylaluminum monohalide (1m) and aluminoxane (80) as organoaluminum compound components (Al) in the presence of a catalyst.

(2) Organosilicon containing the titanium-containing solid catalyst component obtained by the above method and an organoaluminum compound (A7), and any bond or group selected from a P-0 bond, an isocyanate group, an acryloxy group, and a methacryloxy group. A method of polymerizing propylene in the presence of a catalyst in combination with compound (S).

The above method will be explained in detail.

Examples of the titanium-containing solid catalyst component used in the method (2) include the titanium trichloride composition (Ill) described above, dialkyl aluminum monohalide (AS
), specific examples include diethylaluminum monochloride, moro-propylaluminium monochloride, diisobutylaluminum monochloride, di-n-hexylaluminum monochloride, diethylaluminum monofluoride, diethylaluminium sonobromide, diethylaluminium monoiodide, etc. are mentioned, and one or more types of these are used.

In addition, as aluminoxane (A,), the following general formula (
a) and - aluminoxane represented by formula (b) or general formula (a) or - formula (b), RI
a~82° is partially substituted with a halogen atom such as chlorine or bromine, and the halogen content is 40! % or less, preferably 30! % or less of halogenated aluminoxane.

R"AI-t-0-^l±"0-^lR2ONOR+9 (wherein, HIS~B21 is an alkyl group having 1 to 8 carbon atoms, and stomach and stomach ° are integers from 1 to about 20 ) Such aluminoxanes are organoaluminum compounds (
It can be obtained by the reaction of A,) with water, and the following method can be exemplified, for example.

(1) Compounds containing adsorbed water or salts with water of crystallization, such as organoaluminum compounds (8) in suspension in a hydrocarbon medium such as copper sulfate hydrate, aluminum sulfate hydrate, magnesium chloride hydrate, etc. A method of adding and reacting.

(2) A method in which water is allowed to directly act on the organic aluminum compound (A7) in a medium such as benzene, toluene, or ethyl ether.

In the method of the present invention, it is of course possible to use the above-mentioned aluminoxane (80) alone, or to use a mixture of this (A,) and an unreacted organoaluminum compound (A,).

Examples of the organoaluminum compound (A) to be reacted with water when obtaining the above aluminoxane include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, tri-butylaluminum, Trialkylaluminums such as tri-n-hexylaluminum and tri-n-octylaluminium and dialkylaluminum monohalides used as the above-mentioned (A@) are used, and trimethylaluminum is particularly preferably used.

The amount of each catalyst component used is as follows: titanium trichloride composition (+0)
0.1 to 200 mol of dialkyl aluminum halide (8B) is used per 1 mol of titanium in the mixture, and aluminoxane (A6) is used at a ratio of aluminum to dialkyl aluminum monohalide (AS) ((A6
)/(8s)) is used within a range of 0.02 to 70.

The above-mentioned catalyst combined in the prescribed amount can be used as it is for propylene polymerization, but from the viewpoint of operability during propylene polymerization, a titanium-containing solid catalyst is used instead of the titanium-containing solid catalyst component. It is more desirable to use a catalyst component which has been preactivated by combining the component with an organoaluminum compound (A) and reacting this with an olefin.

Pre-activation is performed by adding 0.005g to 500g of organoaluminum compound (A) per 1g of titanium-containing solid catalyst component.
g, solvent O~50it, hydrogen 0~1,000mu, and olefin 0.05g~1,000g, at O℃
The olefin is reacted at ~100°C for 1 minute to 20 hours to produce o, o1g~20 per gram of titanium-containing solid catalyst component.
It is desirable to react 0 g of olefin.

The reaction of olefins for preactivation can be carried out in aliphatic or aromatic hydrocarbon solvents or in liquefied olefins such as liquefied propylene and liquefied butene-1 without using a solvent. It can also be reacted. Furthermore, it can also be carried out in the presence of an olefin polymer or hydrogen in advance.

The olefins used for preactivation include linear olefins such as ethylene, propylene, butene-1, pentene-11hexene-1, heptene-1, octene-1, and 4-
Examples include branched chain olefins such as methylpentene-1,2-methylpentene-1,3-methylbutene-1, and styrene. Further, as the organoaluminum compound (A2), the same compounds as those mentioned above (A,) can be mentioned.

After preactivation, the solvent, organoaluminum compound (
A.), unreacted olefin can be removed by distillation under reduced pressure, etc., and it can be used in the polymerization as a dry powder, or it can be suspended in a solvent with a temperature not exceeding 80°C per 1 g of the titanium-containing solid catalyst component. Alternatively, after removing the solvent, unreacted olefin, and organoaluminum compound (8) by filtration or decantation, it can be dried and used as a powder.

Polymerization of propylene is carried out using the catalyst thus combined or the preactivated catalyst. The polymerization format for propylene is n-hexane, n-hexane,
Examples include slurry polymerization carried out in a hydrocarbon solvent such as -heptane, n-octane, benzene or toluene, bulb polymerization carried out in liquefied propylene, and gas phase polymerization carried out in the gas phase.

Polymerization temperature is usually 20°C to 100°C, preferably 30°C to
The temperature is 85°C. 1i joint force is reduced (Okgf/co+2
G)~50 kgf/c■ Polymerization is carried out at 2G and usually for a polymerization time of about 30 minutes to 15 hours. During the first polymerization, adding an appropriate amount of hydrogen to control the molecular weight is the same as in the conventional propylene polymerization method. Note that polymerization can be carried out by either batch polymerization or continuous polymerization.

In the method (2), various titanium-containing solid catalyst components manufactured according to the method of the present invention described above can be used. As the organoaluminum compound (A,), (A,) used when obtaining the titanium trichloride composition (II+) described above,
, ) can be used.

Also, P Tomio bond, isocyanate grave, acryloxy group,
Specific examples of organosilicon compounds (S) (hereinafter sometimes abbreviated as organosilicon compounds (S)) having any bond or group selected from methacryloxy and methacryloxy groups include tris(trimethylsilyl)phosphate. ]・Lis(ethyldimethylsilyl)phosphate, tris(triethylsilyl)phosphate, bis(tolylmethylsilyl)methylphosphate, bis(tolylmethylsilyl)ethylmethylphosphate, bis(tolylmethylsilyl)1-methylvinylphosphate, diethyl (trimeg-lucilylmethyl)phosphonate, diethyl(trimethylsilylethyl)phosphonate, diethyl(trimethylsiloxycarbonyl)methylphosphonate, bis(trimethylsilylmethyl)ethylphosphinate, bis(trimethylsilylmethyl)ethylphosphinate, bis(trimethylsilylethyl)ethylphosphinate, etc. Organosilicon compound having a P-0 bond of trimethylsilyl isocyanate, triethylsilyl isocyanate, ethyldimethylsilyl isocyanate, 3
- Organosilicon compounds having isocyanate groups such as incyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyldimethylchlorosilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropymethyldimethoxysilane, Organosilicon containing an acryloxy group such as 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltris(trimethylsiloxy)silane, 3-acryloxypropylmethylbis(trimethylsiloxy)silane, etc. Compound, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyljethoxysilane, 3-methacryloxypropyldimethylethoxysilane, 2- Examples include organosilicon compounds having a methacryloxy group such as methacryloxypropenyltrimethoxysilane, 3-methacryloxypropylbis(trimethylsiloxy)methylsilane, and 3-methacryloxypropyldimethyldichlorosilane, and one or more of these may be used.

The amounts of the titanium-containing solid catalyst component, organoaluminum compound (ladle), and silicon compound (S) used are based on 11 moles of T in the titanium-containing solid catalyst component.
0.1 mol to 200 mol of organoaluminum compound (A7)
0 mol, and 0.05 mol to 200 mol of the organosilicon compound (S).

The catalysts combined in the above-mentioned amounts can be used as they are for the polymerization of propylene, but
As in the case of (2) above, from the viewpoint of operability during propylene polymerization, instead of the titanium-containing solid catalyst component, a titanium-containing solid catalyst component and an organoaluminum compound (A2) were combined and this was reacted with the olefin. It is more desirable to use a catalyst component that has been preactivated.The preactivation conditions are the same as in (2).

Polymerization of propylene is carried out using the above-mentioned catalyst or a preactivated catalyst. The polymerization conditions for propylene are also the same as in the case (2) described above.

Thus, the polypropylene obtained by polymerizing propylene according to the method of the present invention can be treated with appropriate amounts of stabilizers and additives such as heat stabilizers, antioxidants, ultraviolet absorbers, anti-blocking agents, and color agents, as required. , Furthermore, after various synthetic resins etc. are blended and pelletized as necessary,
It can be used to make various molded products such as injection molded products, unstretched films, stretched films, and sheets using known techniques such as injection molding, extrusion molding, vacuum forming, and blow molding.

[Function] The polypropylene obtained by the method of the present invention has a difference between the stereoregularity of the boiling in-heptane insoluble part and the stereoregularity of the entire polypropylene, so that the boiling n-heptane soluble part can be molded. There is little bleeding to the surface of the product, and the overall stereoregularity of the polypropylene is relatively low, resulting in good processability, impact resistance, and transparency.

Furthermore, the polypropylene obtained by the method of the present invention contains non-linear olefin polymers or non-linear olefin polymer blocks resulting from the polymerization process during the production of the titanium-containing solid catalyst component used in the method of the present invention. Since it is dispersed, the polymer (block) exhibits a nucleating effect during molding of the olefin polymer, thereby improving the rigidity and transparency of the resulting molded product.

In particular, in the above polymerization process, if the polymerization treatment with a straight chain olefin is performed before the polymerization treatment with a nonlinear olefin, the straight chain olefin of the block copolymer is added to the produced crystalline straight chain olefin-nonlinear olefin. Due to the compatibility of the anti-olefin polymer block with polypropylene,
The non-linear olefin polymer block also has highly improved dispersibility in polypropylene.

Therefore, the homogeneity of the entire polypropylene is further improved, and the nucleation effect of the non-linear olefin polymer block is even more remarkable, so the homogeneity of molded products manufactured using the obtained polypropylene can be improved, e.g. It is presumed that this produces effects such as a reduction in the occurrence of voids, further improvement in transparency, and further improvement in rigidity in injection molded products in films.

(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.

(11MFR: Melt flow rate JIS 7210
According to condition 14 in Table 1. (Unit: glu minute) (2)
Isotactic bentad fraction: Measured using JEOL GX-270 manufactured by JEOL, based on the method described above.

(3) Boiling n-heptane insoluble portion: represents the solid residue after polypropylene is extracted with boiling an-heptane based on the method described above.

(4) Spiral flow: Tetrakis [methylene-3-(3',5-di-
t-butyl-4-'hydroxyphenyl)propinate] 0.1 parts by weight of methane, and 0.1 parts by weight of calcium stearate! The mixture was mixed with a screw diameter of 40 mm.
The mixture was extruded using an extrusion granulator, cooled with water, and then cut to obtain a granulated product. The granules were injected by an injection molding machine at a molten resin temperature of 220°C into a mold at 50°C with a semicircular cross section of 31111 and a ^rchl-sedes spiral in the length direction. PressureBOOKgf/cm'
The length of the resin inside the mold was measured when the resin was injected for 15 seconds. The longer the resin length, the better the melt fluidity of the resin and the better the processability.

(Unit: ce+) Flexural modulus: A JIS type test piece was prepared from the polypropylene granules obtained in the same manner as in (4) using an injection molding machine at a molten resin temperature of 220°C and a mold temperature of 50°C. After leaving the test piece in a room with a humidity of 50% and a room temperature of 23°C for 96 hours, JI
The bending elastic modulus was measured in accordance with S.7203.

(Unit: kgf/cm2) Izod impact strength - A test piece was prepared in the same manner as in (5), and the Izod impact strength was measured at 23°C in accordance with JIS K7203.

(Unit: kgf-am/cm) Internal haze: For a test piece with a thickness of 1 cm (8) obtained in the same manner as in (5), after applying liquid paraffin to both sides of the test piece, it was determined according to JIS 7105. The haze was measured in accordance with the above, and the transparency inside the test piece excluding the influence of the surface was evaluated.

(Unit: %) Plotting power: The polypropylene granules obtained in the same manner as (4) were processed using a T-die type film forming machine at a temperature of 230 mol.
After extruding at ℃ and pressing with a cooling roll at 20℃ to form an l-layer sheet, the sheet was heated with hot air at 140℃ for 60 seconds and stretched by a factor of 7 in both length and width directions using a biaxial stretching machine. A biaxially stretched film with a thickness of 20 μm was obtained. The same sides of the film of 2ci + (width) x 7c * (length) are connected to each other with a length of 2
After stacking the samples over a length of 250 gf/am2 and leaving them in an atmosphere at a temperature of 40°C and a relative humidity of 90% for 72 hours, the force required for shear peeling of the samples was measured using a tensile tester at a speed of 300 m+e/min. .

The lower the numerical value is, the less the boiling n-heptane soluble portion and other components bleed, and the better the locking resistance is.

(J1st place: GF/4C Ugly 2) Void: Observe the biaxial film obtained in the same manner as in (8) with an optical microscope, measure the number of voids with a diameter of 10μ or more, and calculate the number of voids per 1 cm2. Less than 10 pieces are shown as ○, 10 or more but less than 30 pieces are shown as Δ, and 30 or more pieces are shown as X.

Example 1 (1) Preparation of titanium-containing solid catalyst component n-hexane 61. Diethylaluminum monochloride (DEAC) 5.0 mol, diisoamyl ether 1
2.0 mol was mixed at 25° C. for 5 minutes and reacted at the same temperature for 215 minutes to obtain a reaction product liquid (I) (diisoamyl ether/DEAC molar ratio 2.4).

Put 40 moles of titanium tetrachloride into a reactor purged with nitrogen,
The mixture was heated to 35°C, and the entire amount of the reaction product solution (1) was added dropwise thereto over 180 minutes, and then kept at the same temperature for 60 minutes.
The temperature was raised to 0°C, the reaction was further carried out for 1 hour, and the mixture was cooled to room temperature.
The operation of removing the supernatant liquid, adding n-hexane 2042, and removing the supernatant liquid by decantation was repeated four times to obtain a double product (11).

The entire amount of (II) was suspended in 30 fl of n-hexane, 400 g of diethylaluminium monochloride was added, 1.5 kg of propylene was added at 30°C, and polymerization was performed at the same temperature for 1 reaction time. After passage, the supernatant was removed by decantation, and the solid was washed twice with 30 ft of n-hexane. Subsequently, n-hexane 3
i. After adding 400g of diethylaluminum monochloride, the temperature was raised to 40°C, and vinylcyclohexane 1.
After the completion of the reaction, the supernatant liquid was removed, n-hexane 301 was added, and the supernatant liquid was removed by decantation, which was repeated 4 times to obtain propylene-9. A solid product (II-A) was obtained after a multi-stage polymerization treatment using vinylcyclohexane.

With the entire amount of this solid product suspended in n-hexane 91, 8 was added to 3.5 titanium tetrachloride at room temperature for about 10 minutes, and after reacting at 80°C for 30 minutes, further 1.6 kg of diisoamyl ether was added and reacted at 80°C for 1 hour. After the reaction was completed, the supernatant was removed 5 times, dried under reduced pressure, and titanium trichloride composition (Ill.
) was obtained and used as a titanium-containing solid catalyst component used in the present invention. The content of the propylene polymer block in the titanium trichloride composition (Ill) is 25.0% by weight, the content of the vinylcyclohexane polymer block is 25.0% by weight,
And the titanium content was 12.61% by weight.

(2) Preparation of preactivated catalyst components A stainless steel reactor equipped with a stirrer with inclined blades (inner volume 15Ofl) was replaced with nitrogen gas, and n-hexane
100j! , diethylaluminum monochloride 1
14 g, and the titanium trichloride composition obtained in +11 above (
III) 1.8Kg was added at room temperature. Subsequently, 30
After reacting by supplying 1.8N+e' of ethylene at ℃ for 2 hours (1.0g of ethylene reacted per 111g of titanium trichloride composition), unreacted ethylene was removed and n-
After washing with hexane, it was dried to obtain a preactivated catalyst component.

(3) Propylene polymerization Nitrogen replacement with internal volume 801 stirrer, /D
After charging 20 kg of polypropylene powder obtained by a known method with MF82.0 into the horizontal polymerization vessel of 4-3, n-hexane was added to the preactivated catalyst component obtained in (2) above,
After making a suspension in O-hexane of 0.01% by weight, the suspension was
6.1 milligram atoms/hr in terms of i atom, a 30% by weight n-hexane solution of diethylaluminium monochloride and tris(trimethylsilyl) phosphate was
They were continuously supplied so that the molar ratio to i atom was 7.0 and 2.2, respectively.

*9jli4-! Gas-phase polymerization of propylene was carried out by supplying propylene to each polymerization vessel so that the total pressure was maintained at 23 kg/Cm"G. The test was carried out continuously for 72 hours at 70°C.

During the polymerization period, the polymer retention level in the polymerization vessel was 60%.
Continuously LOk the polymer from the polymerization vessel so that the volume%
It was extracted at a rate of g/hr.

The extracted polymer was then treated with 0.0% propylene oxide.
A polypropylene powder was obtained by contact treatment with nitrogen gas containing 2% by volume at 65° C. for 30 minutes. The isotactic pentad fraction (P) of the polypropylene is 0.
6111, boil! The in-heptane insoluble portion was 85.5% by weight, and the isotactic pentad fraction (Pr) of the boiling 11n-heptane insoluble portion was 0.863.

Ratio 10 Example 1 (1) In Example 1 (1), solid product (11)
A titanium trichloride composition was obtained in the same manner, except that the multi-stage polymerization treatment with propylene and vinylcyclohexane was omitted, and the solid product (11) was used as the solid product CII-A).

(2) Preactivated catalyst in the same manner as in (2) of Example 1 except that 1.35 kg of the titanium trichloride composition obtained in (2) above was used in place of the titanium trichloride composition (Ill). Got the ingredients.

(3) In (3) of Example 1, the preactivated catalyst components obtained in (2) above were used as the preactivated catalyst components, and each catalyst component was heated to a total pressure of 23 g/cs' in the polymerization vessel. Propylene was polymerized and post-treated in the same manner except that it was fed to the polymerization vessel so as to maintain G, and polypropylene was obtained.

Comparative Example 2 (1) A titanium trichloride composition was obtained in the same manner as in Comparative Example 1 (1).

(2) Into the reactor used in Example 1 (2), add n-hexane 100J2. After adding 300 g of diethylaluminium monochloride and 1.8 g of the titanium trichloride composition obtained in (1) above at room temperature, 1.5 g of vinylcyclohexane was added and reacted at 40° C. for 2 hours. (0.5 vinylcyclohexane per 1g of titanium trichloride composition)
(g) Reaction) After 6 reaction hours, the supernatant was removed by decantation, washed with n-hexane, filtered and dried to obtain a preactivated catalyst component.

(3) Propylene polymerization was carried out in the same manner as in (3) of Example 1, except that the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component.
A sticky polymer was produced in the polymerization vessel, making it impossible to extract the polymer from the polymerization vessel, so the propylene polymerization had to be stopped 3 hours after the start of polymerization.

Comparative Example 3 (1) In (1) of Comparative Example 1, when reacting the reaction product liquid (1) with titanium tetrachloride, (1) of Comparative Example 1 was separately added.
) using 500 g of a titanium trichloride composition obtained in the same manner as described above and 120 g of diethylaluminium monochloride as a catalyst, gvA was reduced to 1.3 in n-hexane 10042.
After polymerizing the added vinyl cyclohexane at 60°C for 2 hours, the resulting vinyl cyclohexane polymer was washed with methanol and dried to give a volume of 950 g. A titanium trichloride composition containing 33.3% by weight of vinylcyclohexane polymer was prepared in the same manner except that it was ground in a vibration mill of No. 01 at room temperature for 5 hours and then suspended in the titanium tetrachloride. Obtained.

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

(3) Polypropylene was polymerized and post-treated in the same manner as in (3) of Comparative Example 1, except that the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component, and polypropylene was obtained. Ta.

Comparative Example 4 Polymerization and post-treatment of propylene were carried out in the same manner as in Comparative Example 1 (3) except that tris(trimethylsilyl) phosphate was not used to obtain ordinary polypropylene.

Comparative Example 5 Polypropylene was polymerized and post-treated in the same manner as in Comparative Example 4, except that an equimolar mixture of diethylaluminum monochloride and triethylaluminum was used instead of diethylaluminum monochloride during the polymerization of polypropylene. Ta.

Comparative Example 6 and Examples 2 and 3 In (1) of Example 1, the amounts of propylene and vinylcyclohexane used in the polymerization treatment were changed to create a titanium trichloride composition ( 11
Got a mouth. Thereafter, polypropylene was obtained in the same manner as in Example 1 (2) and (3).

Example 4 (1) Preparation of titanium-containing solid catalyst component In a stainless steel reactor equipped with a stirrer, decane 3J2
, 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 130° C. for 1 hour while stirring to dissolve and form a uniform solution. The homogeneous solution was
180 g of diisobutyl phthalate at 0°C with stirring.
After 1 hour had passed, 5.2 J 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 (IV).

After suspending the entire amount of the solid product (TV) in 1O1 hexane containing 450 g of triethylaluminum and 145 g of diphenyldimethoxysilane maintained at 30°C, 160 g of propylene was added, and polymerization was carried out at the same temperature for 1 hour while stirring. After one reaction time had elapsed, the supernatant liquid was removed by decantation, and the solid was washed twice with 6j2 n-hexane.

Subsequently, 1041 g of n-hexane, 450 g of triethylaluminum and 145 g of diphenyldimethoxydisilane were added under stirring, and then the temperature was raised to 30° C., 440 g of allyltrimethylsilane was added, and polymerization was carried out at 30° C. for 2 hours.

After the reaction, the supernatant was removed, n-hexane 61 was added, and the supernatant was removed by decantation, which was repeated 4 times.
A solid product (V) was obtained which was subjected to a polymerization treatment using propylene and allyltrimethylsilane.

The total amount of the solid product (V) was converted into 51% of 1,2-dichloroethane.
1110 g of diisobutyl phthalate was added, and while stirring, the mixture was mixed with 51 g of titanium tetrachloride dissolved in
After reacting at 0°C for 2 hours, the liquid phase was removed by decantation at the same temperature, 1,2-dichloroethane 51 and titanium tetrachloride 51 were added again, and the mixture was heated to 100°C for 2 hours.
The mixture was stirred for a period of time, washed with hexane, and dried to obtain a titanium-containing supported catalyst component (iv), which was used as a titanium-containing solid catalyst component for use in the present invention.

The titanium-containing supported catalyst component (IV) has a nearly spherical particle shape, a propylene polymer block content of 1000% by weight, an allyltrimethylsilane polymer block content of 40.0% by weight, and a titanium-containing supported catalyst component (IV). The content is 1
．． It was 51% by weight.

(2) Preparation of preactivated catalyst components After purging a stainless steel reactor with a stirrer with an internal volume of 3i with nitrogen gas, 20 j2 n-hexane, 150 g triethylaluminum, and 45 g diphenyldimethoxysilane were added.
g and the titanium-containing supported catalyst component obtained in (1) above (
After adding 200 g of [V], 300 g of propylene was supplied, and a preactivation reaction was carried out at 30° C. for 2 hours (1.5 g of propylene per Ig of titanium-containing supported catalyst component (IV)).
og reaction) After 0 reaction time, the solid part was washed with n-hexane and further dried to obtain a preactivated catalyst component. As a catalyst component, the preactivated catalyst component obtained in (2) above was used at a concentration of 0.45 milligram atom/hr in terms of T1 atom, and triethylaluminum and 3-tris(trimethylsilyl) monochloride were used in place of diethylaluminum monochloride and tris(trimethylsilyl)phosphate. The molar ratio of isocyanatepropyltriethoxysilane to Ti atoms is 200 and 50, respectively.
Polypropylene was obtained in the same manner except that the hydrogen concentration in the gas phase in the polymerization vessel was 0.2% by volume. The isotactic pentad fraction (P) of the polypropylene is 0.850, the boiling n-heptane insoluble portion is 88.3% by weight, and the isotactic pentad fraction (Pr) of the boiling n-heptane insoluble portion is 0.
It was 883.

Comparative Example 7 In (1) of Example 4, the multi-stage polymerization treatment with propylene and allyltrimethylsilane for the solid product (TV) was omitted, and the solid product (rV) was converted into the solid product (
V) A titanium-containing supported catalyst component was obtained in the same manner except that the equivalent product was used. Thereafter, polypropylene was obtained in the same manner as in Example 4 (2), H) using the titanium-containing supported catalyst component.

Example 5 (1) In Example 4 (1), the solid product (IV
) in the polymerization process by replacing propylene and allyltrimethylsilane with 100Nu of ethylene.

and using 0.7 g of 3-methylbutene-1,
In addition, after the first stage of ethylene polymerization treatment, after removing unreacted ethylene, 3-methylbutene-1 was added without washing the solid phase with a solvent, and the second stage of polymerization was carried out! A titanium-containing supported catalyst component (Vl) was prepared in the same manner except that filling A was performed.
I got it.

(2) Preactivation was carried out in the same manner as in (2) of Example 4, except that the titanium-containing supported catalyst component (Vl) obtained in the above (1) was used as the titanium-containing supported catalyst component (Vl). A catalyst component was obtained.

(3) In (3) of Example 4, the preactivated catalyst component obtained in the above (2) was used as the preactivated catalyst component,
In addition, 3-acryloxypropyltrimethoxysilane was used instead of 3-isocyanatepropyltriethoxysilane so that the molar ratio to TI was 30, and each catalyst component was added so that the total pressure in the polymerization vessel was 23 g/c Polypropylene was obtained in the same manner except that it was fed to the polymerization vessel so as to maintain 2G.

Comparative Example 8 In (1) of Example 5, the multi-stage polymerization treatment with ethylene and 3-methylbutene-1 for the solid product (rv) was omitted, and the solid product (IV) was converted into the solid product (V).
A titanium-containing supported catalyst component was obtained in the same manner except that the equivalent product was used. Thereafter, polypropylene was obtained in the same manner as in Example 5 (2) and (3) using the titanium-containing supported catalyst component.

Example 6 (1) Preparation of titanium-containing solid catalyst component In Example 1 (1), the polymerization treatment for solid product (II) was replaced with propylene and vinylcyclohexane, and styrene (g) was used instead of styrene (g) and styrene alone (1). A titanium trichloride composition (I+) was obtained in the same manner except that the step polymerization treatment was performed.

(2) Preparation of preactivated catalyst component In (2) of Example 1, titanium trichloride composition (I
The titanium trichloride composition (HT
) A preactivated catalyst component was obtained in the same manner except that the following was used.

(3) Preparation of aluminoxane After purging a stainless steel reactor equipped with a stirrer with an internal volume of 300 ml with nitrogen, 37 kg of sulfuric acid steel pentahydrate and dehydrated toluene SQJ! After cooling to 10℃, add trimethylaluminum 500 diluted with toluene under stirring while controlling the internal temperature to maintain 15℃.
mol was added over 4 hours.

After the addition, the reaction was continued at 15° C. for 48 hours, and then the solids were removed, and a portion of the toluene was distilled off under reduced pressure at room temperature to obtain a toluene solution 401 containing methylaluminoxane.

(4) Polymerization of propylene In (3) of Example 1, toluene was added to the preactivated catalyst component obtained in (2) above as a preactivated catalyst component, and a 4.0% by weight toluene suspension was prepared. Using the preactivated catalyst component prepared above, in addition to diethylaluminum monochloride, a toluene solution of methylaluminoxane obtained in (3) above was added so that the molar ratio to diethylaluminum monochloride was 1.0 in terms of aluminum atoms. In addition, tris(trimethylsilyl) phosphate should not be used, and the hydrogen concentration in the gas phase of the polymerization reactor should be kept at 0.
5% by volume, and the total pressure inside the polymerization vessel is 23kg/c+
Polypropylene was obtained by polymerization and post-treatment of propylene in the same manner except that each catalyst component was supplied so as to maintain a2G. The isotactic pentad fraction (P) of the obtained polypropylene was 0.832, the boiling n-heptane insoluble portion was 83.8% by weight, and the isotactic pentad fraction (P) of the boiling n-heptane insoluble portion was 0.832. ) is 0.
It was 889.

Comparative Example 9 In (1) of Example 6, the polymerization treatment with styrene for the solid product port V) was omitted, and the solid product (rV)
A titanium-containing supported catalyst component was obtained in the same manner except that the solid product (V) was used as the solid product (V). Thereafter, using the titanium-containing supported catalyst component, (2) of Example 6, +
3) Polypropylene was obtained in the same manner as in (4).

Regarding the above Examples and Comparative Examples, the composition of the titanium-containing solid catalyst component, the physical properties of the obtained polypropylene, and the evaluation results are shown in the table.

[Effects of the Invention] As is clear from the examples described above, when polypropylene obtained by the production method of the present invention is processed into molded products, it has excellent fluidity during melting, resulting in energy savings and productivity improvements. Contributes to sexual improvement. Moreover, the molded product obtained is rigid,
Since it has excellent blocking resistance, Sgx resistance, and transparency, it can be widely used in various fields of application.

[Brief explanation of drawings]

Figure 1 shows Preparation for detailed description of the invention Process diagram (flow sheet) It is. Below

Claims (1)

[Claims] (1) Using a catalyst consisting of [1] a titanium-containing solid catalyst component, [2] an organoaluminum compound (A_2), and, if necessary, [3] an electron donor (B_1). In a method for producing polypropylene having a boiling n-heptane insoluble portion of 70% to 95% by weight by polymerizing propylene, a titanium-containing solid catalyst component is used during the production of the titanium-containing solid catalyst component under polymerization conditions. Polymerization treatment using a linear olefin, or a linear olefin and a non-linear olefin, and obtained through subsequent steps,
A method for producing polypropylene, comprising using a titanium-containing solid catalyst component containing 0.01% to 99% by weight of a non-linear olefin polymer or a non-linear olefin polymer block. (2) The non-linear olefin has the following formula, CH_2=CH-R^1 (wherein, R^1 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). (3) Non-linear olefins include the following formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^2 is a chain hydrocarbon group with 1 to 3 carbon atoms that may contain silicon, or represents silicon, R
^3, R^4, R^5 have a carbon number of 1 and may contain silicon
represents a chain hydrocarbon group from to 6, R^3, R^
Any one of 4 and R^5 may be hydrogen. ) Claim 1 using branched olefins represented by
The manufacturing method described in section. (4) As a non-linear olefin,
The following formula, ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, n is either 0 or 1, m is either 1 or 2, and R
^6 represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R^7 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^7 may be the same or different. ) The manufacturing method according to claim 1, using an aromatic monomer represented by: (5) Instead of the titanium-containing solid catalyst component, combine the titanium-containing solid catalyst component with an organoaluminum compound (A_2), react 0.01 g to 200 g of olefin per 1 g of the titanium-containing solid catalyst component, and prepare the The manufacturing method according to claim 1, which uses an activated catalyst component. (6) The isotactic pentad fraction (P) of the obtained polypropylene is 0.70 to 0.91, and the isotactic pentad fraction (P_r) of the boiling n-heptane insoluble portion of the polypropylene The manufacturing method according to claim 1 or 5, wherein in relation to (P), satisfies the formula 0<(P_r)-(P)≦0.1.