JPH03111404A - Highly stereoregular polypropylene - Google Patents

Abstract

PURPOSE:To prepare a highly stereoregular polypropylene having a wide mol.wt. distribution and giving a molded article excellent in the rigidity, transparency, and heat resistance by polymerizing propylene using a specific catalyst, thereby giving the resulting polymer specified physical properties. CONSTITUTION:An organoaluminum compd. (e.g. diethylaluminum monochloride) or a reaction product thereof with an electron donor (e.g. diisoamyl ether) is reacted with TiCl4 to give a solid product, which is subjected to the polymn. treatment in multisteps with a linear olefin (e.g. propylene) and a nonlinear olefin (e.g. vinylcyclohexane), each separately and each at least once, and then reacted with an electron donor and an electron acceptor (e.g. TiCl4) to give a titanium trichloride compsn. The resulting compsn., an organoaluminum compd. (e.g. diethylaluminum monochloride), and a third component comprising an arom. carboxylic acid ester (e.g. methyl p-toluate) or an organosilicon compd. contg. an SiO-C bond and/or an SH group, constitutes a catalyst component, which is used in polymerizing propylene, thereby giving a polypropylene having a melt flow rate, isotactic pentad fraction, mol.wt. distribution, and wt.-average mol.wt. each in a specified range.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to highly stereoregular polypropylene. More specifically, it has a wide molecular weight distribution and extremely stereoregularity, allowing molded products with outstanding transparency, rigidity, and durability to be obtained by ordinary molding methods without the addition of any special additives. Concerning high polypropylene.

[Prior art and its problems] Polypropylene has excellent heat resistance, chemical resistance, and electrical properties, and also has good rigidity, tensile strength, optical properties, and processability, and can be used for injection molding, extrusion molding, Widely used for hollow molding, etc.

However, known ordinary polypropylene has limitations in its uses due to limitations in physical properties and processability.To solve these problems, efforts have been made to improve the performance of polypropylene, particularly in maintaining rigidity and strength at high temperatures, improving durability, and improving the ability to form large molded products. Improvements in moldability, etc. are strongly desired.

In order to improve the above-mentioned properties, we can increase the stereoregularity of polypropylene to improve physical properties such as heat resistance, rigidity, and strength, and broaden the molecular weight distribution to improve strength and durability that depend on the high molecular weight portion. , efforts are being made to improve the moldability of extrusion molding, blow molding, etc.

The present applicant has already proposed highly stereoregular polypropylene having a wide molecular weight distribution in JP-A-59-22,913 and JP-A-63-191,809. Through the use of this polypropylene, molded products with significantly higher rigidity and durability than conventionally known polypropylenes have been obtained, making it possible to expand its use in certain fields of application; however, the polypropylene boils n- Although the stereoregularity of the hebutane-insoluble portion is high, the stereoregularity of the entire polymer is insufficient, and it is desired to further improve the stereoregularity as well as improve transparency.

Other techniques for providing polypropylene with relatively high stereoregularity include, for example, polypropylene obtained using a catalyst combining a titanium trichloride composition, an alkoxyaluminum compound, and an ester compound (Japanese Patent Publication No. 64-ff , No. 325), by prepolymerizing a non-linear olefin such as 4-methylpentene-1 using a catalyst consisting of a titanium trichloride composition and an organoaluminum compound, and then polymerizing propylene. Polypropylene (Japanese Unexamined Patent Publication No. 81-155,404), polypropylene obtained using a catalyst combining a titanium trichloride composition, an organoaluminum compound, an organometallic intramolecular coordination compound, and an electron donor (Japanese Unexamined Patent Application Publication No. 81-155,404) 62-100,
Polypropylene obtained using a titanium trichloride composition as a solid catalyst component such as SO5), a so-called supported solid catalyst component in which titanium tetrachloride is supported on a magnesium compound, an organoaluminum compound, and an organosilicon compound. Polypropylene obtained using combined catalysts (JP-A-54-83.006, JP-A-64-6
6.217 Publication) etc.

However, the polypropylene described in the above-mentioned Japanese Patent Publication No. 64-9jZS and Japanese Patent Application Laid-open No. 82-100,505 has insufficient stereoregularity as a polymer as a whole, so moldings obtained using the polypropylene are The rigidity, heat resistance, etc. of the product were insufficient. Also, JP-A-58-1
The polypropylenes described in JP-A No. 13.008, JP-A No. 61-155,404, and JP-A No. 64-6,621 have a certain degree of stereoregularity, but their durability is limited due to their narrow molecular weight distribution. The results were extremely inadequate. Furthermore, although the polypropylene described in JP-A No. 61-155,404 shows a certain degree of improvement in transparency, it is still insufficient;
JP-A-58-83,006, JP-A-62-100
, 505 and JP-A-64-8,821 have extremely insufficient transparency.

On the other hand, as a technique for providing polypropylene with improved transparency, there is a method in which a non-linear olefin such as vinylcyclohexane is prepolymerized using a catalyst consisting of a titanium compound and an organoaluminum compound, and then propylene is polymerized ( Although the polypropylene obtained by this method shows a certain degree of improvement in transparency, it suffers from polymerization instability due to poor shape of the catalyst component after prepolymerization. The rigidity and durability were poor due to problems such as qualitative heterogeneity of the polymer, insufficient stereoregularity, and narrow molecular weight distribution.

In view of the above-mentioned current state of the known technology, the present inventors have discovered that a molded article with extremely high transparency, rigidity, and durability can be obtained by a normal molding method without adding any special additives. We conducted extensive research to find a polypropylene with a wide distribution and extremely high stereoregularity. As a result, the present invention was completed based on the knowledge that molding of a new polypropylene that satisfies the requirements of the present invention, which will be described later, would yield a molded product with outstanding transparency, rigidity, and durability.

As is clear from the above description, an object of the present invention is to provide a novel polypropylene that allows the production of molded articles with outstanding transparency, rigidity, and durability. Another objective is to expand the specific fields of use of polypropylene.

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

(1) ■ Solid product (II) obtained by reacting titanium tetrachloride with the reaction product (1) of the organoaluminum compound (A1) or the organoaluminum compound (AI) and the electron donor (B1). , after performing multistage polymerization treatment with straight chain olefin and non-linear olefin one or more times each,
Furthermore, a titanium trichloride composition (III) obtained by reacting an electron donor (B2) and an electron acceptor, ■organoaluminium compound (A2), and as a third component, ■aromatic carboxylic acid ester (E), Or Si-0
It is obtained by polymerizing propylene using a catalyst combined with an organosilicon compound (S) having a -C bond and/or a mercapto group, and has a melt flow rate (MFFt) of 0.1 to 100 (gzio min, 230t, load 12
．． 16 gf), isotactic pentad fraction (
P) is 0.975 to 0.991), the ratio of weight average molecular weight to number average molecular weight, weight average molecular weight/number average molecular weight (Q) is 7 to 30, and weight average molecular weight is 10
A highly stereoregular polypropylene having a molecular weight of 0,000 to 1,000,000.

(2) Instead of the titanium trichloride composition (m), a preactivated catalyst component obtained by combining the titanium trichloride composition (nt) and an organoaluminum compound and reacting this with an olefin is used. The polypropylene according to item 1 above.

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

Melt flow rate (MFR) of the polypropylene of the present invention
), when the load is 2.16 Kgf under the temperature condition of 230 ° C, is o, tg 710 minutes to 100 g 710 minutes,
Preferably it is 0.5 g 710 minutes to Box/lo minutes.

If the MFR is less than 0.1 g/10 minutes, the fluidity during melting will be insufficient, and if it exceeds 100 g/10 minutes, the strength of the molded product obtained will be insufficient.

Further, the isotactic pentad fraction (P), which is a measure of stereoregularity, which is the most characteristic physical property of the polypropylene of the present invention, is 0.975 to 0.990. here,
What is isotactic pentad fraction (P)?
Macromolecules6 by bell I et al.
925 (1973), i.e. 's
Isotactic fraction in pentad units within a polypropylene molecule measured using c-NMR. In other words, the fraction (P) means the fraction of the propylene monomer unit at the center of a chain of five consecutive meso-bonded propylene monomer units.

However, the above-mentioned method for determining the attribution of NMR absorption peaks is based on Ma
cromolecules F4 [7 (1975)].

Note that the value of the isotactic pentad fraction (P) in the present invention is the value of the stereoregular polypropylene obtained by polymerization as it is, and is not the value of the polypropylene after extraction, fractionation, etc.

If P is less than 0.975, the desired high rigidity and high heat resistance will not be achieved. There is no upper limit for P, but
Due to manufacturing constraints of polypropylene according to the present invention, P −
A value of about 0,990 is actually available at the present time of the present invention.

Furthermore, I! is a measure of molecular weight distribution, which is another characteristic physical property of the polypropylene of the present invention. Ratio of weight average molecular weight to number average molecular weight, weight average molecule f! The number average molecular weight (Q) is 7 to 30.

Regarding molecular weight distribution, the ratio of weight average molecular weight to number average molecular weight is generally used as a measure. ! The ratio weight average molecular weight/number average molecular weight Q) is used; the larger the ratio (Q), the wider the molecular weight distribution. If Q is less than 7, the durability of the obtained molded product will be poor, and if it exceeds 30, the processability will be poor. Moreover, the weight average molecular weight at this time is tGo, 000 N1,000,000.

The method for producing highly stereoregular polypropylene of the present invention that satisfies the above requirements will be explained as follows.

First, to produce the highly stereoregular polypropylene of the present invention,
Titanium trichloride composition (■ri and organoaluminum compound (
AI) and a titanium trichloride composition (I
A catalyst is used in which an aromatic carboxylic acid ester (E) or an organosilicon compound (S) having a 5t-oc bond and/or a mercapto group is combined in a specific molar ratio with respect to II). These basic aspects are disclosed in Japanese Patent Application No. 1-156,042 and Japanese Patent Application No. 1-1-1 filed by the present applicant.
Although it is similar to No. 180,270, there is a specific difference in that the molar ratio of (E) or (S) is individually selective.

The above-mentioned titanium trichloride composition (III) is produced as follows. First, organoaluminum (A1) and electron donor (B+) are reacted to obtain a reaction product (l), and this (I) and Solid product (II) obtained by reacting with titanium tetrachloride or organoaluminum compound (A1)
A solid product obtained by reacting titanium tetrachloride with
As a final solid product obtained by polymerizing 1) in multiple stages, one or more times each with a linear olefin and a non-linear olefin, and then reacting an electron donor CB1) with an electron acceptor. , a titanium trichloride composition (■■) used in the production of polypropylene of the present invention is produced.

In the present invention, "to polymerize" means to polymerize the linear olefin or non-linear olefin by bringing it into contact with the solid product (11) under conditions that allow polymerization of the linear olefin or non-linear olefin. In this polymerization treatment, the solid product (II) becomes coated with the polymer.

The above-mentioned organoaluminum compounds (eight electron donors)
The reaction with B1) is carried out in a solvent (c++) at -20°C to 20°C.
It is carried out at 0°C, preferably -10°C to 100°C for 30 seconds to 5 hours. There is no restriction on the order of addition of (Al), (B+), and (D1), and the ratio of the amounts used is that of the organoaluminum compound (A+).
) per 1 mol of electron donor (B+) 0.1 mol to 8 mol, preferably 1 mol to 4 mol, solvent (B+) 0.5
L~5L.

Preferably it is 0.5L to 2L.

Thus, reaction product (I) is obtained.0 reaction product (1
) can be used in the next reaction as a liquid R (sometimes referred to as reaction product liquid (1)) without separation.

A solid product (1 summer) obtained by reacting this reaction product (I) with titanium tetrachloride, or an organoaluminum compound (Al) with titanium tetrachloride, is used as a linear olefin and a non-linear olefin. As a method for polymerizing chain olefins in multiple stages, there is the following method: A method of polymerizing a solid product (n) in multiple stages by adding
reaction product N) or organoaluminum compound (A1
) with titanium tetrachloride, linear olefins and non-linear olefins were added in multiple stages to form a solid product (1
) and a method for multistage polymerization IA treatment of 0 reaction products (
1) Or after the reaction between the organoaluminum compound (Al) and titanium tetrachloride, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product (
There is a method of suspending II) in a solvent, further adding an organoaluminum compound, and then adding a straight chain olefin and a non-straight chain olefin in multiple stages for polymerization treatment.

In addition, regarding the order of multistage polymerization using linear olefins and non-linear olefins, linear olefins,
Any of the non-linear olefins may be used first, but from the viewpoint of polymerization operability when using the final titanium trichloride composition (III) obtained and the performance of the obtained polypropylene, the non-linear olefins should be selected first. It is preferable to perform a polymerization treatment with a non-linear olefin, followed by a polymerization treatment with a non-linear olefin. Through this multi-stage polymerization, a linear olefin-non-linear olefin block copolymer is formed, and the pro-block copolymer forms a solid Product (II) becomes coated.

Furthermore, in the multi-stage polymerization process, as described above, the titanium trichloride composition (III) that achieves the object of the present invention can be obtained by using the linear olefin and the non-linear olefin at least once each. As mentioned above, for example, after the polymerization treatment of the non-linear olefin, it is also possible to further add the straight chain olefin and carry out the polymerization treatment.

Reaction product (1) or organoaluminum compound (A
1) with titanium tetrachloride, with or without the addition of linear and non-linear olefins at any step of the reaction, at temperatures ranging from -10°C to 200°C, preferably from 0°C to 1°C.
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. (I) or organoaluminum compound (81), titanium tetrachloride, and the solvent may be mixed in any order, and the linear olefin and non-linear olefin may be added at any stage.

Reaction product (1) or organoaluminum compound (A
1), titanium tetrachloride, and the solvent are preferably mixed in total within 5 hours, and the reaction continues during the mixing. It is preferable to continue the reaction for an additional 5 hours after mixing the entire amount.

The amount of each solvent used in the reaction is 0 to 3,000 mJ per mole of titanium tetrachloride! , reaction product (1)
Or the organoaluminum compound (A1) is the organic aluminum compound (I)
Alternatively, the ratio of the number of A1 atoms in (A1) to the number of TI atoms in titanium tetrachloride (Al/Tl) is 0.05 to 1O1, preferably 0.06 to 0.3.

The polymerization treatment using linear olefins and non-linear olefins is as follows: (1) Adding linear olefins and non-linear olefins in any process of the reaction of reaction product (1) or organoaluminum compound (Al) with titanium tetrachloride. and ■ When adding a straight olefin and a non-linear olefin after the reaction between the reaction product (I) or the organoaluminum compound (A1) and titanium tetrachloride, the addition of a straight olefin and a non-linear olefin In any polymerization process, the reaction temperature is 0°C to 90°C for 1 minute to 10 hours, and the reaction pressure is atmospheric pressure (Okgf/cm"G) to 10kgf/c.
m"G, using 0.1 g to 100 kg of straight chain olefin and 0.013 to 1 look of non-linear olefin per 100 g of solid product (II) to produce the final solid product (■), i.e. The content of the linear olefin polymer block in the titanium trichloride composition (III) used for producing the polypropylene of the present invention is 0.11i% by weight
49.5! ! ! %, and the content of the non-linear olefin polymer block is 0.01% by weight to 49.51i, and the weight ratio of the linear olefin polymer block to the non-linear olefin polymer block is 2798. ~9
The weight is multi-staged so that the ratio is 8/2.

The content of the straight-line olefin polymer block is 0, Ili
If the amount is less than %, the operability when using the obtained titanium trichloride composition and the homogeneity of the obtained polypropylene will be insufficient, resulting in poor appearance and insufficient improvement in strength or rigidity when molded. Become. Furthermore, if the amount exceeds 49.5%, the effect will not be significant, resulting in operational and economical disadvantages.

Furthermore, the content of the non-linear olefin polymer block is 0.
If the amount is less than 1% by weight, the effect of improving the stereoregularity of the obtained polypropylene and the transparency when formed into a molded product will be insufficient, and if it exceeds 49.5% by weight, the improvement in the effect will not be significant, resulting in operational and It becomes an economic disadvantage.

The weight ratio of the straight chain olefin polymer block to the non-straight chain olefin polymer block is preferably 2/98 to 98/2 in view of the balance of the various improvement effects described above.

The multi-stage polymerization treatment using linear olefins and non-linear olefins is carried out by (1) After the reaction of the reaction product (or organoaluminum compound (AI) and titanium tetrachloride is completed, the liquid portion is separated and removed by filtration or decantation. ,
If the obtained solid product (11) is suspended in a solvent and then carried out, the solid product (11) 10 can be obtained in any polymerization treatment using a linear olefin or a non-linear olefin.
0g, in the presence of 100sIt~S of solvent, OOOmjl, and 0.58~5.000g of organoaluminum compound, reaction temperature is 0℃~90℃, 1 minute~1O time, reaction pressure is atmospheric pressure (Okgf/cm''G). ) ~10kgf/cm'
Under the conditions of G, per long solid product (II),
Straight chain olefin 0.1g~100kg.

and 100 kg of non-linear olefin 0.013 N to prepare the final solid product (III), i.e. the titanium trichloride composition (III
) in which the content of linear olefin polymer blocks is 0.
1% to 49.5% by weight, and the content of non-linear olefin polymer block is 0.0! The weight ratio of the straight chain olefin polymer block and the non-linear olefin polymer block is 2/98 so that the weight is 4965% by weight.
The weight is multi-staged so that the ratio is ~98/2.

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 olefins or direct olefins.

The solvent used during the polymerization treatment is preferably an aliphatic hydrocarbon;
Even if the organoaluminum compound is the same as that used to obtain the reaction product (I) or the one used directly in the reaction with titanium tetrachloride without reacting with the electron donor (Bl), 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 (II-A) is then reacted with an electron donor (B) and an electron acceptor (F).

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 1,000 g, preferably 0.5 g of (Ih) per 100 H of solid product (II-A).
g~200g.

(F) 0.1g~t, 000g, preferably 0.2
8 to 51) Og, solvent θ to 3,000*J, preferably 100 to 1,000*J2.

The reaction methods include: (1) reacting the solid product (TI-A) with an electron donor (B2) and an electron acceptor (F) at the same time; (2) reacting (F) with (II-A); A method of reacting (B2), ■ A method of reacting (F) after reacting (B1) with (II-A), ■
There is a method of reacting (II - A >) after reacting (B1) with (F), 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.
- Reaction of A) and (B1) at 0°C to 50°C for 1 minute to 3 minutes.
The 3-hour reaction (F) is carried out under the same conditions as in (2) above.

In addition, in method (■), (B1) and (F) are 10t~1
After reacting at 00°C for 30 minutes to 2 hours, cooling to 40°C or lower, adding (II-A), and reacting under the same conditions as in (1) and (2) above.

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

The organoaluminum compound (A1) used in the production of the titanium trichloride composition (m) has the general formula ^IR'p
R"p+Xs-+**p'+ (wherein, R1%R2 represents a hydrocarbon group or alkoxy group such as a haalkyl group, cycloalkyl group, or aryl group, X represents a halogen, and p and p' represent O< 1) representing any number 1149'≦3
An organoaluminum compound represented by is used.

Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-l-butylaluminum, tri-n-hexylaluminum, tri-l-hexylaluminum, tri-2-methylpentylaluminum,
Trialkyl aluminums such as tri-n-octyl aluminum and tri-n-decyl aluminum, diethylaluminum monochloride, di-n-propyl aluminum monochloride, di-l-butyl aluminum monochloride, diethylaluminium monofluoride, diethylaluminium monobromide, Dialkyl aluminum monohalides such as diethyl aluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, ■-butyl aluminum dichloride, etc. Examples include monoalkylaluminum cybarides, and alkoxyalkylaluminums such as monoethoxydiethylaluminum and jetoxymonoethylaluminum can also be used. These organoaluminum compounds can also be used in combination with Z fills or more.

As the electron donor used in the production of titanium (III) trichloride, various ones are shown below, but (at)
, (112), it is preferable to mainly use ethers and to share the other electron donors with ethers.

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, sulfides Hydrogen, thioethers, thioalcohols, etc.

Specific examples include diethyl ether, moro-propyl ether, moro-butyl ether, diisoamyl ether, di-n-pentyl ether, moro-hexyl ether,
Diisoamyl ether, moro-octyl ether, diisoamyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether,
Ethers such as tetrahydrofuran, methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, phenol, cresol,
Alcohols such as xylenol, ethylphenol, naphthol, or phenols, methyl methacrylate, ethyl acetate, butyl formate, amyl acetate, vinyl butyrate,
Vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, propyl anisate , esters such as ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, naphtho-fi2-ethylhexyl, 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, and maleic acid, aromatic acids such as benzoic acid, and ketones such as methyl ethyl ketone, methyl isobutyl ketone, and benzophenone. nitrites 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 of N', N-pentamethyl-N'-β-dimethylaminomethylphosphoric acid triamide, octamethylpyrophosphoramide, ureas such as N, N, N', N'-tetramethylurea, phenyl isocyanate, Isocyanates such as toluyl isocyanate, azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxyto, dimethylphosphite, mole - phosphites such as cutyl phosphite, triethyl phosphite, tri-n-butyl phosphite and triphenyl phosphite; phosphinites such as ethyl diethyl phosphinite, ethyl butyl phosphinite and phenyl diphenyl phosphinite; Other examples include thioethers such as diethylthioether, 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.
The electron donor (at) for obtaining the reaction product (1) and (B1) with which the solid product (II-A') is reacted may be the same or different.

Electron acceptor used in the production of titanium trichloride (II!)
(F) is represented by a halide of an element in 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,
Examples include vanadium tetrachloride and antimony pentachloride.
These can also be used in combination. Most preferred is titanium tetrachloride.

The following solvents are used. Examples of aliphatic hydrocarbons include lopentane, n-hexane, n-hebutane, n-octane, l-octane, etc. In addition, instead of or together with aliphatic hydrocarbons, carbon tetrachloride,
Chloroform, dichloroethane, trichlorethylene,
Hydrocarbon halides such as tetrachloroethylene can also be used.

As aromatic compounds, aromatic hydrocarbons such as naphthalene,
and its derivatives such as alkyl substituted products such as mesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, and l-phenylnaphthalene, and halogens such as monochlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, dichlorobenzene, and bromobenzene. Chemical substances, etc. are shown.

Directly cut olefins used in polymerization include ethylene,
Propylene, butene! , pentene-1, hexene-1
Directly cut olefins such as 1. In particular, ethylene and propylene are preferably used. These linear olefins are used in an amount of 1 fff1 or more.

The non-linear olefin used in the polymerization treatment has the following formula: CH, -C)I-R' (wherein R3 has a saturated cyclic structure of a hydrocarbon that may contain silicon, even if it contains silicon) good carbon a
A saturated ring-containing hydrocarbon JII polymer represented by 1) representing a saturated ring-containing hydrocarbon having 3 to 18 carbon atoms; represents a hydrocarbon group or silicon, n@
, R11 and R7 have 1 carbon number and may contain silicon
represents a chain hydrocarbon group from 6 to 6, but BS, H8
,R? Any one of them may be hydrogen, and branched olefins represented by 1) or the zero-order formula, (where n is 0.1 and +a is 1.2,
na represents a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, Rg represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen, or halogen, and m is 2 In this case, each 89 is an aromatic monomer represented by 1), which may be the same or different.

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 vinylcyclohebutane, allylcycloalkanes such as allylcyclopentane and allylcyclohexane, cyclotrimethylenevinylsilane, cyclotrimethylenemethylvinylsilane, and cyclotetramethylene Vinylsilane, cyclotetramethylenemethylvinylsilane, cyclopentamethylenevinylsilane, cyclopentamethylenemethylvinylsilane, cyclopentamethyleneethylvinylsilane, cyclohexamethylenevinylsilane, cyclohexamethylenemethylvinylsilane, cyclohexamethyleneethylvinylsilane, cyclotetramethyleneallylsilane, Saturated ring hydrocarbon monomers having a silicon atom in the saturated ring structure such as cyclotetramethylenemethylallylsilane, cyclopentamethyleneallylsilane, cyclopentamethylenemethylallylsilane, cyclopentamethyleneethylallylsilane, cyclobutyldimethylvinylsilane, cyclopentyldiethylvinylsilane , cyclopentylethylmethylvinylsilane, cyclopentyldiethylvinylsilane, cyclohexylvinylsilane, cyclohexyldimethylvinylsilane, cyclohexylethylmethylvinylsilane, cyclobutyldimethylallylsilane, cyclopentyldimethylallylsilane, cyclohexylmethylallylsilane, cyclohexyldimethylallylsilane, cyclohexylethylmethylallylsilane,
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 3rd branch daughter olefin, 4-ethylhexene-1,
4-position branched chain olefin 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.

Further, the aromatic monomer ((2)) is styrene and its rust conductor. - Alkylstyrenes such as methylstyrene and pt-butylstyrene, dialkylstyrenes such as 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, and 3,5-dimethylstyrene, 2 -Methyl-4-fluorostyrene, 2-ethyl-4-chlorostyrene, 0-fluorostyrene, p
-Halogen-substituted styrenes such as fluorostyrene, 11
-Trimethylsilylstyrenes such as +1-triethylsilylstyrene, p-ethyldimethylsilylstyrene, 0-allyltoluene, p-
Allyltoluene etc.

Dilltoluenes, allylxylenes such as 2-allyl-p-xylene, 4-allyl-0-xylene, 5-allyl-kasumi-xylene, vinyldimethylphenylsilane, vinylethylmethylphenylsilane, vinyldiethylphenylsilane, allyl Examples include alkenylphenylsilanes such as dimethylphenylsilane and allylethylmethylphenylsilane, as well as 4-(o-tolyl)-butene-1 and l-vinylnaphthalene, and one or more of these non-linear olefins used.

The titanium trichloride composition (Ill
), an organoaluminum compound (A2), and an aromatic carboxylic acid ester (E) or an organosilicon compound having a 5t-oc bond and/or a mercapto group (S
) in a predetermined amount as described below to form a catalyst for use in producing the polypropylene of the present invention, or more preferably, to use it as a preactivated catalyst by reacting an olefin.

Preactivation is performed using 0.005g to 500g of an organoaluminum compound and 0g of solvent to titanium (III) trichloride Ig.
~50j2, hydrogen 0-1.00041 and olefin 0
．． 01g to 5.000g, preferably 0.05g to 3,
000g of titanium trichloride composition (i■) Ig
0.01g to 1.00041 preferably 0.05 per
g ~200g17) It is desirable to polymerize olefins.

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

Further, in the preactivation, it is also possible to add in advance an aromatic carboxylic acid ester (E) or an organosilicon compound (S) having an Si-0-C bond and/or a mercapto group.

Examples of the olefin used for preactivation include ethylene, propylene, butene-1, and pe.

Nten! , hexene-11 heptene-1, octene-
1 grade straight monoolefins, 4-methyl-pentene-
Examples include branched monoolefins such as 1,2-methyl-pentene-1, and olefins of the iffi class or higher are used. Further, as the organoaluminum compound, the same compounds as the above-mentioned (AI) can be used, but dialkylaluminum monohalides similar to the below-mentioned (A1) are preferably used.

After the preactivation reaction is completed, a predetermined amount of aromatic carboxylic acid ester (E) or organosilicon compound (S) having a 5t-oc bond and/or mercapto group is added to the preactivated catalyst component slurry. The added catalyst can be used as it is for the polymerization of propylene, or the coexisting solvent, unreacted olefin, and organoaluminum compound can be removed by filtration or decantation, and the dried powder or granules can be mixed with a solvent. is added to form a suspended state, and this is combined with organoaluminum compound (A1) and (E) or (S) to serve as a catalyst and subjected to polymerization of propylene, coexisting solvent, and unreacted olefin. is removed by evaporation by vacuum distillation or inert gas flow, etc., and a granular material or a solvent is added to the granular material to form a suspended state, and if necessary, an organoaluminum compound (A snow) is added to this material. It is also possible to add and further combine with (E) or (S) to form a catalyst and use it for propylene polymerization.

When polymerizing propylene, the above titanium trichloride composition (III), organoaluminum compound (A2)
, further aromatic carboxylic acid ester (E) or 5t-
Regarding the usage amount of the organosilicon compound (S) having an oc bond and/or a mercapto group, when using an aromatic carboxylic acid ester (E) as the third component of the catalyst, The molar ratio (E)/(nt) of the titanium composition (Ill) is 0.2 to 10.0, and 5t-o-
When using an organosilicon compound (S) having a c bond and/or a mercapto group, the (S) and the (III
) molar ratio (S)/(Ill) 1.5-1O90
, and in any case, the molar ratio (A2)/(Ill) of the organoaluminum compound (A1) and the titanium trichloride composition (III) is 0.
It is used in a range of 2 to 200 G, preferably 0.2 to 10 G.

It should be noted that the highly stereoregular polypropylene of the present invention may not necessarily be obtained if the molar ratio of each catalyst component is within the above-mentioned molar ratio range. It is necessary to confirm the specific type of S) and the molar ratio to (III).

Also, the number of moles of titanium trichloride composition (III) is
Refers to the number of 71 gram atoms substantially contained in (III).

Titanium trichloride composition (Ill) during polymerization of propylene
The organoaluminum compound (A1) to be combined with is preferably a dialkyl aluminum monohalide represented by the formula ^IRIORIIX.

In the formula, R16 and R1' represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, an alkaryl group, or an alkoxy group, and X represents a halogen.

Specific examples include diethylaluminum monochloride,
Examples include moro-propyl aluminum monochloride, dialkyl aluminum monohalide, moro-butyl aluminum monochloride, diethylaluminum monoiodide, diethylaluminium monobromide, and the like.

Specific examples of the aromatic carboxylic acid ester (E) that can be used as the third component constituting the catalyst include ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, and toluic acid. Methyl, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate can be given.

A specific example of an organosilicon compound (S) having a 5t-oc bond and/or a mercapto group that can be used as the third component of the catalyst in place of the aromatic carboxylic acid ester (E) is methyldiacetoxysilane. , vinyltrimethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, triphenylmethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane Ethoxylan, vinyltriethoxysilane, propyltriethoxysilane, allyltriethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, n-octyltriethoxysilane, n-
octadecyltriethoxysilane, 6-dryethoxysilane-2-norbornene, dimethyljethoxysilane,
Diethyljethoxysilane, diphenyljethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylethoxysilane, allyloxytrimethylsilane, methyltril-propoxysilane, dimethyldil-propoxysilane, trimethylacetoxysilane, tetra n-butoxysilane, Methyltri-n-butoxysilane, tetra(2-ethylbutoxy)silane, methyltriphenoxysilane, dimethyldiphenoxysilane, trimethylphenoxysilane, trimethoxysilane, triethoxysilane, triethoxychlorosilane, trinipropoxychlorosilane, tri-n-butoxy Chlorosilane, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, methyldiacetoxysilane, diacetoxymethylvinylsilane, dimethyldiacetoxysilane, methylphenyldiacetoxysilane, diphenyldiacetoxysilane, trimethylacetoxy Organosilicon compounds having a 5i-oc bond such as silane, triethylacetoxysilane, phenyldimethylacetoxysilane, triphenylacetoxysilane, bis(trimethylsilyl)adipate, trimethylsilylbenzoate, triethylsilylbenzoate, mercaptomethyltrimethylsilane, 2 -Mercaptoethyltrimethylsilane, 3-mercaptopropyltrimethylsilane, 4-mercapto-n-butyltrimethylsilane, mercaptomethyltriethylsilane, 2-mercaptoethyltriethylsilane, 3-mercaptobrobyltriethylsilane, l
- Organosilicon compounds having a mercapto group such as mercaptoethyltrimethylsilane, 3-mercaptobropyldimethyphenylsilane, 3-mercaptopropylethylmethylphenylsilane, 4-mercaptobutyldiethylphenylsilane, 3-mercaptopropylmethyldiphenylsilane, Also, mercaptomethyltrimethoxysilane, mercaptomethyldimethylmethoxymethylsilane,
Mercaptomethyldimethoxymethylsilane, mercaptomethyltriethoxysilane, mercaptomethyljethoxymethylsilane, mercaptomethyldimethylethoxysilane, 2-mercaptoethyltrimethoxysilane, 3-
Mercaptopropyltrimethoxysilane, dimethoxy-
Si such as 3-mercaptopropylmethylsilane, 3-mercaptopropyltriethoxysilane, jetoxy-3-mercaptopropylmethylsilane, mercaptomethyldimethyl-2-phenylethoxysilane, 2-mercaptoethoxytrimethylsilane, 3-mercaptopropoxytrimethylsilane, etc. -Organosilicon compounds having a -0-C bond and a mercapto group, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-aminopropyljethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 2-aminoethylaminomethyltrimethoxysilane, 3-(2-aminoethylaminopropylene) 2-aminoethylaminomethylbenzyloxydimethylsilane, 3-[2-(2
Examples include organosilicon compounds having a 5i-0-C73 compound and an amino group, such as -aminoethylaminoethylamino)probilcotrimethoxysilane.

Polymerization of propylene is carried out using the catalyst thus combined or the preactivated catalyst. Polymerization methods for propylene include slurry polymerization conducted in a hydrocarbon solvent such as n-hexane, rhohebutane, n-octane, benzene, or toluene, bulk polymerization conducted in liquefied propylene, and gas phase polymerization conducted in a gas phase. Phase polymerization may be mentioned, but slurry polymerization is most preferred.

The polymerization temperature is usually 20°C to 75°C, preferably 40°C to 6°C.
Relatively low temperatures of 5°C, particularly preferably between 40°C and 60°C are suitable. I! If the degree of polymerization is too high, it will be difficult to increase the stereoregularity of the resulting polypropylene, and if the polymerization temperature is too low, the polymerization rate of propylene will be slow, and the impractical 0 polymerization pressure will be lower than normal pressure ( o Kgf/c
m”G) ~50 to gf/cm2G usually 30 minutes to 15
During zero polymerization, which is carried out for a polymerization time of about 1 hour, adding an appropriate amount of hydrogen to adjust 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. After completion of polymerization, a known catalyst deactivation step,
After a post-treatment process such as a catalyst residue removal process, the highly stereoregular polypropylene of the present invention is obtained.

The polypropylene of the present invention obtained by the novel method described above is a novel polypropylene having both a wide molecular weight distribution and high stereoregularity, and if necessary, an appropriate amount of a heat stabilizer and an antioxidant is added. , UV absorbers, anti-blocking agents, stabilizers and additives such as colorants, as well as nucleating agents, inorganic fillers, various synthetic resins, etc. are added, and if necessary, after being pelletized, known It is used for various molded products using techniques such as injection molding, extrusion molding, and blow molding.

[Function] Since the polypropylene of the present invention has extremely high stereoregularity, molded articles obtained using the polypropylene of the present invention are extremely excellent in heat resistance, rigidity, and strength. Furthermore, since it has a wide molecular weight distribution, it has extremely high durability. Furthermore, the molded article has a high degree of crystallinity and exhibits a fine spherulite morphology, so it is also excellent in transparency.

The characteristic physical properties of the polypropylene of the present invention, which contribute to the excellent performance of molded products obtained using the polypropylene of the present invention, are as described above. Although the details of the manufacturing effect are not clear, it is presumed as follows.

The titanium trichloride composition (Ill) according to the production of polypropylene of the present invention is a polypropylene composition having a higher isotactic pentad fraction than conventionally known titanium trichloride compositions, as will be clear from the examples described below. The manufacturing performance of the titanium trichloride composition (Ill'
) A linear olefin-non-linear olefin block copolymer produced by a multi-stage polymerization process during the production of (), especially one in which the non-linear olefin polymer block imparts a high degree of stereospecificity to the polymerization active site. it is conceivable that.

Further, the aromatic carboxylic acid ester (E) or the organosilicon compound (S) having a 5t-oc bond and/or a mercapto group as the third component of the catalyst for producing polypropylene of the present invention has a wide molecular weight distribution. High stereoregularity is imparted to the polypropylene of the present invention.

Furthermore, the aforementioned straight olefin-non-linear olefin block copolymer derived from the titanium trichloride composition (Ill) according to the present invention is dispersed in the polypropylene of the present invention; As the linear olefin polymer block of the copolymer has compatibility with polypropylene, the non-linear olefin polymer block also has highly improved dispersibility in polypropylene. Therefore, since the nucleation effect of the non-linear olefin polymer block is significantly exhibited, molded products manufactured using the resulting polypropylene have a high degree of crystallinity and a fine spherulite morphology, resulting in poor transparency. It is presumed to be excellent.

[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 7210
According to condition 14 in Table 1. (Unit: g/lo min) (2
) Isotactic pentad fraction (P): Measured using JEOL GX-270, manufactured by JEOL, based on the method described above.

(31Ii weight average molecular weight and weight average molecule!/number average molecular weight (Q): Measured and determined by GPC-150c gel permeation chromatography manufactured by Waters.

(4) Melting point: -2
The temperature was lowered to -60°C at a rate of 0°C/min, held at the same temperature for 10 minutes, and then measured under the condition of a temperature increase of 20°C/min.
(Unit: °C) (5) Rigidity, strength, heat resistance: Tetrakis [methylene-3
-(3°,5'-di-t-butyl-4°-hydroxyphenyl)propionate cometa (20.1 parts by weight) and calcium stearate (0.1 parts by weight) were mixed, and the mixture was extruded into a screw having a diameter of 40+sm. It was granulated using a granulator. Then, the granulated material was heated to a melt resin temperature of 23°C using an injection molding machine.
A JIS type test piece was prepared at 0° C. and a mold temperature of 50° C., and the test piece was left in a room with a humidity of 50% and a room temperature of 23° C. for 96 hours, and then measured by the following method.

■Bending elastic modulus: The elastic modulus was measured at 23° C. in accordance with JIS 7203. (Unit: kgf/crn”
) ■Tensile strength: 23 according to JIS K 7113
Tensile strength was measured at °C. (Unit: kgf/c
m') ■ Heat distortion temperature: The heat distortion temperature was measured in accordance with JIS 7202. (Unit: °C) (6
) Durability: A test piece was prepared in the same manner as in (5), and JiS
Tensile creep test (load fi 24) in accordance with 7115
gf/cm'') to measure the creep rupture time. (2 hours) After applying liquid paraffin to both sides of the film, JI
Internal haze was measured in accordance with SK7105.

(Unit: %) Example 1 (1) Preparation of titanium trichloride composition (m) n-hexane 6
1. Diethyl aluminum monochloride (DEAC)
5.0 mol, diisoamyl ether 12゜0 mol 2
The mixture was mixed at 5° C. for 1 minute and reacted at the same temperature for 5 minutes to obtain a reaction product liquid (■) (molar ratio of diisoamyl ether/DEAC 2.4).

Put 40 moles of titanium tetrachloride into a reactor purged with nitrogen,
Heated to 35°C, and added the entire amount of the reaction product H) to it.
After dropping for 10 minutes, keep at the same temperature for 80 minutes and raise to 80℃.
The temperature was raised to 100°C and the reaction was allowed to proceed for an additional 1 hour, cooled to room temperature, the supernatant liquid was removed, n-hexane 20j2 was added, and the supernatant liquid was removed by decantation.The operation was repeated 4 times to obtain a solid product (!■ ) was obtained.

The entire amount of this (!) was suspended in n-hexane 30J2, 400g of diethylaluminum monochloride was added, 1.5kg of propylene was added at 30°C, and 1.5kg was added at the same temperature.
After 0 reaction time of the time polymerization treatment, the supernatant liquid was removed by decantation, and the solid was washed twice with 30 Jil of n-hexane. Subsequently, n-hexane 30
After adding IL and 400 g of diethylaluminium monochloride, the temperature was raised to 40°C, and vinylcyclohexane 1
．． 9 kg was added, and polymerization treatment was performed at 40°C for 2 hours.

After the reaction is complete, remove the supernatant! The operation of adding tn-hexane 301 and removing the supernatant liquid by decantation was repeated four times to obtain a solid product (II-A) subjected to multistage polymerization treatment with propylene-vinylcyclohexane.

The total amount of this solid product was mixed with n-hexane9j! At room temperature, 3.5 kg of titanium tetrachloride was suspended in a
After adding 1.8 kg of diisoamyl ether for 30 minutes at 80°C and reacting for 1 hour at 80°C, the operation of removing the supernatant liquid was repeated 5 times. , dried under reduced pressure, titanium trichloride composition (nl
) was obtained.

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

<2) Preparation of pre-activated catalyst component After purging a stainless steel reactor with a stirrer and equipped with inclined blades with an internal volume of 1,501 liters with nitrogen gas, 90 ml of n-hexane was added.
JZ, diethyl aluminum monochloride 1.71K
g, titanium trichloride composition (III') obtained in (1)
1.8 kg was added at room temperature, followed by 1.1 kg of propylene.
(0.5 g of propylene per Ig of titanium trichloride composition (III), and reacted at 30°C for 2 hours.
After the reaction, unreacted ethylene was removed to obtain a preactivated catalyst component in the form of a slurry.

(3) Production of polypropylene The preactivated catalyst component slurry obtained in (2) above (note: contains diethylaluminium monochloride) is placed in a polymerization reactor equipped with a stirrer and a two-stage turbine blade with an internal volume of 150 IL that is purged with nitrogen. n-hechitin was added as a catalyst from the same pipe and from a separate pipe at a rate of 11.5 milligram atoms/hr in terms of titanium atoms, and methyl 11-toluate at a molar ratio of 1.8 to titanium atoms. 13Kg/
It was fed continuously at hr. Furthermore, hydrogen was added so that the concentration in the gas phase of the polymerization vessel was maintained at 11% by volume, and the total pressure was 1'OK.
The slurry polymerization of propylene was carried out at 60°C by supplying each propylene so as to maintain g/cm”G.
This was done continuously for 20 hours.

During the polymerization, the polymer slurry was continuously drawn out from the polymerization vessel into a flash tank having an internal volume of 50 IL so that the retention level of the polymer slurry in the vessel was 75% by volume. The pressure drops in the flash tank and unreacted hydrogen,
While removing propylene, methanol is added to IKg/hr.
The contact treatment was carried out at 70°C. Subsequently, after neutralizing the polymer slurry with an aqueous sodium hydroxide solution, the polymer is washed with water, separated, and dried.
Obtained at 0Kg/hr.

When the polypropylene was analyzed, the MFR was 4.0.
(g/10 min), isotactic pentad fraction (P
) is Q, 985, weight average molecular weight/number average molecular weight (Q
) is 13.5, weight average molecular weight is 340,000, melting point is 168
．． It was 0°C.

Comparative Example 1 (1) In (1) of Example 1, the solid product (I+
A titanium trichloride composition was obtained in the same manner except that the solid product (!!-8) was obtained without carrying out the multi-stage polymerization treatment with propylene and vinylcyclohexane.

(2) In (2) of Example 1, the preactivated catalyst component was prepared in the same manner except that 0.9 kg of the titanium trichloride composition obtained in (1) above was used instead of the titanium trichloride composition (In). I got it.

(3) In (3) of Example 1, the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component, and each catalyst component was added to the polymerization vessel at a total pressure of 10 glC in an amount of 2G.
Polypropylene was obtained by polymerizing propylene in the same manner except that it was supplied to the polymerization vessel so as to maintain the following.

Comparative Example 2 (1) In a stainless steel reactor equipped with a stirrer, 31 g of decane, 480 g of anhydrous magnesium chloride, 1.7 g of n-butyl orthotitanate, and 1.95 g of 2-ethyl-1-hexanol were mixed. , 130℃ while stirring
The mixture was heated for 1 hour to dissolve and form a uniform solution. The homogeneous solution was heated to 70°C, and 1 diisobutyl phthalate was added while stirring.
Add 110g and after 1 hour 5.2Kg of silicon tetrachloride
was added dropwise over 2.5 hours to precipitate a solid, and then further heated at 70°C.
The mixture was heated for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product (m).

The entire amount of the solid product (III) was mixed with 15 liters of titanium tetrachloride dissolved in 151 liters of 1,2-dichloroethane, and then 360 g of diisobutyl phthalate was added, and the mixture was reacted at 100°C for 2 hours with stirring, and then heated at the same temperature. Remove the liquid phase by decantation, add 15g of 1,2-dichloroethane and 15IL of titanium tetrachloride again,
The mixture was stirred at 100° C. for 2 hours, washed with hexane, and dried to obtain a titanium-containing supported catalyst component.

(2) After replacing a stainless steel reactor with inclined blades with an internal volume of 30 liters with nitrogen gas, 2041 n-hexane, 1.5 kg of triethylaluminum, 480 g of diphenyldimethoxysilane, and the titanium-containing supported catalyst component obtained in (i) were added. 100g was added at room temperature. Subsequently, 115 g of vinylcyclohexane was added and reacted at 40° C. for 2 hours (0.5 g of vinylcyclohexane reacted per 1 g of the titanium-containing supported catalyst component) to obtain a preactivated catalyst in the form of a slurry.

(3) In (3) of Example 1, the above (
1) The preactivated catalyst slurry obtained in step 1 (containing triethylaluminum and diphenyldimethoxysilane in addition to the preactivated titanium-containing supported catalyst component) was continuously fed at a rate of 0.27 milligram atoms/hr in terms of titanium atoms. In addition, the hydrogen concentration in the gas phase of the polymerization reactor should be
．． When propylene was polymerized in the same manner except that the concentration was kept at 5% by volume, the resulting bulk polymer blocked the pipe for extracting the polymer slurry from the polymerization vessel.
The propylene polymerization had to be stopped 6 hours after the polymerization started.

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 the titanium trichloride composition obtained in the same manner as above and 120 g of diethylaluminum monochloride as catalysts, 100 g of n-hexane! After polymerizing 1.3 kg of vinyl cyclohexane at 60° C. for 2 hours, washing with methanol and drying, 950 g of the resulting vinyl cyclohexane polymer was pulverized for 5 hours at room temperature in a moving mill with a capacity of 10 It. Thereafter, a titanium trichloride composition containing 33.311% by weight of vinylcyclohexane polymer was obtained in the same manner except that it was suspended in the titanium tetrachloride.

(2) Instead of the titanium trichloride composition (111), the above (
A preactivated catalyst component was obtained in the same manner as in Example 1 (2) except that 1.35 g of the titanium trichloride composition obtained in 1) was used.

(3) In (3) of Example 1, the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component,
In addition, each catalyst component was adjusted to a total pressure of 10 g/cm' in the polymerization vessel.
Polypropylene was obtained by polymerizing propylene in the same manner except that it was supplied to the polymerization vessel so as to maintain G.

Comparative Example 4 4IL of n-hexane and 10 moles of titanium tetrachloride were placed in a reactor purged with nitrogen and kept at 0°C. After dropwise adding n-hexane solution 41 containing 8 moles of diethylaluminium monochloride, the temperature was raised to 40°C. The temperature was raised and the reaction was further continued for 1 hour. Next, 1.5 g of propylene was added and polymerization was carried out at the same temperature for 2 hours. After IA filling, after removing the supernatant
-Wash the solid twice with 101 hexane and 88 ml of n-hexane.
It was suspended in J2. Subsequently, 300 g of diethylaluminum monochloride was added, 1.9 g of vinylcyclohexane was added, and polymerization was performed at 40°C for 2 hours. After the supernatant was removed, n- hexane 5f
The operation of adding t and removing by decantation was repeated three times, and the solid product subjected to multistage polymerization was added to n-hexane 9f.
It was suspended in t. Subsequently, 3.5 kg of titanium tetrachloride
was added at room temperature and reacted at 90° C. for 1 hour. After completion of the reaction, the mixture was washed with n-hexane to obtain a titanium trichloride composition. Comparative Example 1 except for using the titanium trichloride composition
Polypropylene was obtained in the same manner.

Comparative Example 5 In (3) of Example 1, p which is the third component of the catalyst
- Supplying the preactivated catalyst component slurry without supplying methyl toluate so that the total pressure in the polymerization vessel is maintained at 1axgIc12G, and the hydrogen concentration in the gas phase in the polymerization vessel is 5.2% by volume. Propylene was polymerized in the same manner except that polypropylene was obtained.

Comparative Example 6 Propylene was polymerized in the same manner as in Example 5, except that the preactivated catalyst component slurry obtained in the same manner as (2) of Comparative Example 1 was used as the preactivated catalyst component slurry, Polypropylene was obtained.

Example 2.3 In (3) of Example 1, the hydrogen concentration in the polymerization vessel was set to 3
．． 2% by volume (Example 2) and 18% by volume (Example 3), except that each catalyst component was supplied to the polymerization vessel so that the total pressure in the polymerization vessel was kept at 1O and g/C 2G. Propylene was polymerized in the same manner to obtain polypropylene.

Example 4 (1) Preparation of titanium trichloride composition (III) n-hebutane 411 diethylaluminum monochloride 5.0
The reaction solution obtained by reacting 8.0 mol of diisoamyl ether and 5.0 mol of di-n-butyl ether at 18°C for 30 minutes was added to 27.5 mol of titanium tetrachloride at 40°C.
After adding dropwise over a period of minutes, the temperature was kept at the same temperature for 1.5 hours to react, then the temperature was raised to 65°C, reacted for 1 hour, the supernatant liquid was removed, n-hexane 21]Q was added, and the mixture was removed by decantation. The operation was repeated 6 times and the obtained solid product (II
) Suspend 1.8 kg in 40 fL of n-hexane,
Add 500g of diethylaluminum monochloride,
1.5 kg of propylene was added at 30° C. and reacted for 1 hour to perform the first stage polymerization treatment.

After the reaction time had elapsed, remove the supernatant and add 20% n-hexane.
The operation of adding 1 and removing by decantation was repeated twice. Subsequently, after adding 40 IL of n-hexane and 500 g of diethylaluminum monochloride, 3. A solid product (II-A) was obtained by adding Okg and reacting at 40° C. for 2 hours to perform a second stage polymerization treatment, and to obtain a solid product (II-A) subjected to a multistage polymerization treatment using propylene-allyltrimethylsilane.

After the reaction, the supernatant was removed, and the operation of adding 20 ft of n-hexane and removing by decantation was repeated twice, and the solid product (II-A) subjected to the above polymerization treatment was suspended in 7 It of n-hexane. Make it cloudy, titanium tetrachloride 1.8 kgn,
1.8 kg of n-butyl ether was added and reacted at 60°C for 3 hours. After the reaction was completed, the supernatant was removed by decantation, 20 Jl of n-hexane was added, and the mixture was stirred for 5 minutes and allowed to stand still. After repeating the operation of removing the clear liquid three times, it was dried under reduced pressure to obtain a titanium trichloride composition (Ill).

(2) Preparation of preactivated catalyst component In (2) of Example 1, titanium trichloride composition ('
A preactivated catalyst component slurry was obtained in the same manner except that the titanium trichloride composition obtained in (1) above was used as the second step.

(3) Production of polypropylene In (3) of Example 1, the preactivated catalyst component slurry obtained in (2) above was used as the preactivated catalyst component slurry, and each catalyst component was heated to the total pressure in the polymerization vessel. lokg/
Polypropylene was obtained by polymerizing propylene in the same manner except that it was supplied to the polymerization vessel so as to maintain cm'G and the hydrogen concentration in the gas phase in the polymerization vessel was 7% by volume. The MFR of the bripropylene is 2.0 (g/10 min), the isotactic pentad fraction is 0.981, Ii
Bean weight average molecular weight Number average molecular weight (Q)! 2.0, the weight average molecular weight was 410,000, and the melting point was 11i7.5°C.

Example 5 (1) Preparation of titanium trichloride composition (Ill) 27.0 mol of titanium tetrachloride was added to n-hexane 21, and after cooling to 1°C, n-hexane containing 27.0 mol of diethylaluminum monochloride was added. - Hexane 12.51 was added dropwise at 1°C over 4 hours. After the completion of 0 dropwise addition, the temperature was kept at the same temperature for 15 minutes to react, and then the temperature was raised to 65°C over 1 hour.
The reaction was further continued at the same temperature for 1 hour.

Next, the supernatant liquid was removed, n-hexane 10J2 was added, and the operation of removing by decantation was repeated 5 times. Of the 5.7 kg of the obtained solid product (■), 1.8 kg was suspended in n-hexane 50J2. The mixture was made cloudy, 350 g of diethylaluminium monochloride was added thereto, and 0.0 g of propylene was added at 30°C.
After further adding 6 kg, polymerization treatment was carried out at the same temperature for 1 hour.

Subsequently, after removing the supernatant by decantation, n
-Wash the solid with 50 It of hexane.

After washing, 50 L of n-hexane and 350 g of diethylaluminum monochloride were added, and further 1.9 kg of 3-methylbutene-1 was added, followed by polymerization at 40° C. for 2 hours.

After the polymerization treatment, after removing the supernatant liquid, adding n-hexane 301 and removing it by decantation was repeated twice, and the resulting multistage polymerization solid product (u-A
) was suspended in 111 L of n-hexane, and to this was added 1.21 L of diisoaluminum ether and 0.0 L of ethyl benzoate.
141 was added. This suspension was stirred at 35° C. for 1 hour and then washed 5 times with 31 portions of n-hexane to obtain a treated solid. The resulting treated solid was suspended in 6 L of a solution of 40% by volume titanium tetrachloride and 10% by volume silicon tetrachloride in n-hexane.

This suspension was heated to 65°C and reacted at the same temperature for 2 hours. After the reaction, the resulting solid was washed three times using n-hexane 20jZ once, and then dried under reduced pressure. A titanium trichloride composition (Ill) was obtained.

(2) Preparation of preactivated catalyst component In (2) of Example 1, titanium trichloride composition (I
The same procedure was followed except that the titanium trichloride composition obtained in the above (1) was used as ll), and a mixture of 1.2 kg of diethylaluminum monochloride and 0.9 kg of diethylaluminium monoiodide was used as the organic aluminum compound. A preactivated catalyst component was obtained in a slurry state.

(3) Production of polypropylene In (3) of Example 1, the preactivated catalyst component slurry obtained in (2) above was used as the preactivated catalyst component (note, including diethylaluminium monochloride and diethylaluminium monoiodide). 22.2 milligram atoms/hr in terms of titanium atoms, and as the third component of the catalyst, 3-aminopropyltriethoxysilane was used in place of methyl p-toluate at a molar ratio of 2 to titanium atoms.
．． Polypropylene was obtained by polymerizing propylene in the same manner except that the hydrogen concentration in the gas phase in the polymerization vessel was maintained at 28% by volume. The MFR of the polypropylene is 30.0 (g/10
minute), isotactic pentad fraction (P) is 0.9
8G, weight average molecular weight/number average molecular weight (Q) is 13.
0, the weight average molecular weight was 190,000, and the melting point was 166.8°C.

Comparative Example 7 (1) In (1) of Example S, the solid product (!■)
A titanium trichloride composition was obtained in the same manner except that the solid product (II-A) was obtained without polymerizing with propylene and 3-methylbutene-1.

(2) A preactivated catalyst component slurry was obtained in the same manner as in (2) of Example 1, except that 1.1 kg of the titanium trichloride composition was used.

(3) In (3) of Example 1, the preactivated catalyst component slurry obtained in the above (2) was used as the preactivated catalyst component slurry, and each catalyst component was (2) Propylene was polymerized in the same manner except that the polymerization vessel was supplied so as to maintain 2G, and polypropylene was obtained.

Regarding the above Examples and Comparative Examples, the catalyst conditions, physical properties of polypropylene, and evaluation results are summarized in the table.

[Effects of the Invention] As is clear from the above-mentioned examples, the polypropylene of the present invention has high stereoregularity, wide molecular weight distribution, and fine spherulite morphology, which are not found in conventional polypropylene. When made into a product, it has significantly higher rigidity, strength, heat resistance, durability, and transparency than conventional molded products made from polypropylene.

Therefore, molded articles produced by various molding methods using the boropropylene of the present invention can be expected to expand into fields of application that have not been used with conventional polypropylene molded articles.

[Brief explanation of drawings]

FIG. 1 is a manufacturing process diagram (flow sheet) for explaining the method for manufacturing polypropylene of the present invention. that's all

Claims (1)

[Claims] (1) (1) Organoaluminum compound (A_1) or organoaluminum compound (A_1) and electron donor (B
The solid product (II) obtained by reacting the reaction product (I) with _1) with titanium tetrachloride is polymerized in multiple stages at least once each with a linear olefin and a non-linear olefin, and then Furthermore, a titanium trichloride composition (III) obtained by reacting an electron donor (B_2) with an electron acceptor, (2) an organoaluminum compound (A_2), and as a third component, (3) an aromatic carboxylic acid ester. (E) or Si
-O-C bond and/or mercapto group-containing organosilicon compound (S), obtained by polymerizing propylene using a catalyst in combination, with a melt flow rate (MFR) of
．． 1 to 100 (g/10 minutes, 230℃, load 2.16k
gf), isotactic pentad fraction (P) is 0.
975 to 0.990, ratio of weight average molecular weight to number average molecular weight, weight average molecular weight/number average molecular weight (Q) is 7 to
30, and the weight average molecular weight is 100,000 to 1
,000,000. Highly stereoregular polypropylene. (2) Instead of the titanium trichloride composition (III), a preactivated catalyst component obtained by combining the titanium trichloride composition (III) and an organoaluminum compound and reacting this with an olefin is used. Polypropylene according to claim 1.