JPH0713108B2 - High stereoregular polypropylene - Google Patents

Description

TECHNICAL FIELD The present invention relates to highly stereoregular polypropylene. More specifically, a molded product having remarkably excellent transparency, rigidity, and durability can be obtained by an ordinary molding method without adding any special additive. The molecular weight distribution is wide and the stereoregularity is extremely high. Regarding polypropylene.

[Conventional technology and its problems] Polypropylene has excellent heat resistance, chemical resistance, and electrical properties, and further has good rigidity, tensile strength, optical characteristics, and processability. Widely used for blow molding.

However, known ordinary polypropylene has limitations in use due to limitations in physical properties and processability. To solve the problem, performance improvement of polypropylene, especially retention of rigidity and strength at high temperature, durability, and large molded product There is a strong demand for improvement in moldability and the like.

Regarding the improvement of the above performances, the stereoregularity of polypropylene is increased to improve the physical properties such as heat resistance, rigidity and strength, and the molecular weight distribution is broadened to increase the strength and durability depending on the high molecular weight part. However, efforts have been made to improve the moldability of extrusion molding and hollow molding.

The applicant of the present invention has already disclosed in JP-A-59-22913 and JP-A-63
Japanese Patent Laid-Open No. 191809 proposes a highly stereoregular polypropylene having a wide molecular weight distribution. By using the polypropylene, a molded product having significantly higher rigidity and durability as compared with the conventionally known polypropylene was obtained, and it became possible to expand the use to certain application fields. Although the heptane-insoluble portion has high stereoregularity, the stereoregularity of the entire polymer is insufficient,
Further, improvement of stereoregularity is desired, and improvement of transparency is also desired.

Further, as another technique for providing polypropylene having relatively high stereoregularity, for example, polypropylene obtained by using a catalyst in which a titanium trichloride composition is combined with an alkoxyaluminum compound and an ester compound (Japanese Patent Publication No. 9325/1989). Gazette), a polypropylene obtained by prepolymerizing a non-linear olefin such as 4-methylpentene-1 using a catalyst composed of a titanium trichloride composition and an organoaluminum compound, and then polymerizing propylene (special (Kaisho 61-155404), polypropylene obtained by using a catalyst in which a titanium trichloride composition is combined with an organoaluminum compound, an organometallic intramolecular coordination compound, and an electron donor (JP-A-62-100505). ) Etc. as a solid catalyst component such as a polypropylene obtained by using a titanium trichloride composition or a magnesium compound. Polypropylene obtained by using a catalyst in which a so-called supported solid catalyst component in which titanium tetrachloride is supported on an object and an organic aluminum compound, and an organic silicon compound are further combined (JP-A-58-83006,
JP-A 64-66217).

However, JP-B-64-9325 and JP-A-62-62
Since the polypropylene described in JP-A-100505 has insufficient stereoregularity as a whole polymer, a molded article obtained by using the polypropylene has insufficient rigidity, heat resistance and the like. In addition, JP-A-58-83006 and JP-A-6-
The polypropylenes described in JP-A-1-155404 and JP-A-64-6621 have a certain degree of stereoregularity, but the molecular weight distribution is narrow, so that the durability was extremely insufficient. Further, the polypropylene described in JP-A-61-155404 shows a certain degree of improvement in transparency, but it is still insufficient, and JP-B-64-9325 and JP-A-58-83.
006, JP 62-100505, JP 64-6621
The polypropylene described in Japanese Patent Laid-Open Publication was extremely insufficient in transparency.

On the other hand, as a technique for providing polypropylene having improved transparency, a method of prepolymerizing a non-linear olefin such as vinylcyclohexane using a catalyst composed of a titanium compound and an organoaluminum compound, and then polymerizing propylene ( JP-A-60-139710). Although the polypropylene obtained by the method shows a certain degree of improvement in transparency, there is a problem such as inhomogeneity of the polymer due to polymerization instability due to poor shape of the catalyst component after prepolymerization, Due to insufficient stereoregularity and narrow molecular weight distribution, it was inferior in rigidity and durability.

In view of the state of the art described above, the inventors of the present invention can obtain a molded article having excellent transparency, rigidity, and durability by an ordinary molding method without adding any special additive. We have conducted intensive studies to find polypropylene with a wide distribution and extremely high stereoregularity. As a result, they have completed the present invention by knowing that a molded product excellent in transparency, rigidity, and durability can be obtained by molding a novel polypropylene satisfying the requirements of the present invention described later.

As is clear from the above description, the object of the present invention is to provide a novel polypropylene capable of producing a molded article having excellent transparency, rigidity and durability. Another purpose is to expand the field of specific applications of polypropylene.

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

(1) a solid product (II) obtained by reacting an organoaluminum compound (A ₁ ) or a reaction product (I) of an organoaluminum compound (A ₁ ) and an ether compound with titanium tetrachloride After multi-stage polymerization treatment with olefin and any one or more non-linear olefins represented by the following formulas a to c, at least once, respectively, further ether compound and Ti
A titanium trichloride composition (III) obtained by reacting X ₄ and / or SiX ₄ and a. A saturated ring hydrocarbon monomer represented by the formula CH ₂ ═CH—R ³ (wherein R ³ Has a saturated hydrocarbon cyclic structure which may contain silicon,
Saturated ring monomer having 3 to 18 carbon atoms which may contain silicon) b. Formula (In the formula, R ⁴ represents a chain hydrocarbon group having 1 to 3 carbon atoms which may contain silicon, or silicon, and R ⁵ , R ⁶ , and R ⁷ represent silicon. Represents a chain hydrocarbon having 1 to 6 carbon atoms which may be contained,
Any one of R ⁵ , R ⁶ and R ⁷ may be hydrogen. ) C. Expression An aromatic monomer represented by (wherein n is 0, 1 or m is 1 or 2, and R ⁸ is a carbon atom which may contain silicon: 1
Represents a chain hydrocarbon group of 1 to 6 and R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen or halogen, and when m is 2, R ⁹ is the same. But it may be different. ) As an organoaluminum compound (A ₂ ) and a third component, an aromatic carboxylic acid ester (E) or Si-O-
Obtained by polymerizing propylene using a catalyst in which an organosilicon compound (S) having a C bond and / or a mercapto group is combined, and a melt flow rate (MFR) of 0.1 to
100 (g / 10 min, 230 ° C, load 2.16 kgf), isotactic pentad fraction (P) 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 10
High stereoregular polypropylene characterized in that it is from 0,000 to 1,000,000.

(2) Instead of the titanium trichloride composition (III), the titanium trichloride composition (III) is combined with an organoaluminum compound, and a pre-activated catalyst component obtained by reacting this with an olefin is used. The polypropylene described in the above item 1.

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

Melt flow rate (MFR) of the polypropylene of the present invention
Is 0.1g / 1 when the load is 2.16kgf under the temperature condition of 230 ℃.
0 minutes to 100 g / 10 minutes, preferably 0.5 g / 10 minutes to 80 g / 10
Minutes. If the MFR is less than 0.1 g / 10 minutes, the fluidity at the time of melting will be insufficient, and if it exceeds 100 g / 10 minutes, the strength of the obtained molded product will be insufficient.

Further, the amount of polypropylene of the present invention is 0.975 to 0.990 as the isotactic pentad fraction (P) which is a measure of stereoregularity which is a characteristic physical property. Here, the isotactic pentad fraction (P) is based on A. Zambelli et al.
It is the isotactic fraction in pentad units in polypropylene molecules measured using the method published in Macromolecules 6 925 (1973), ie ¹³ C-NMR. In other words, the fraction (P) means the fraction of propylene monomer units at the center of a chain in which five propylene monomer units are continuously meso-bonded.

However, the method for determining the attribution of the NMR absorption peaks described above is based on Macromo
lecules 8 687 (1975).

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

If P is less than 0.975, the desired high rigidity and high heat resistance cannot be achieved. The upper limit of P is not limited, but P = 0.99 due to the restrictions on the production of the polypropylene according to the present invention.
About 0 can be actually used at the present time of the present invention.

Furthermore, the ratio of the weight average molecular weight to the number average molecular weight, which is another characteristic of the polypropylene of the present invention, which is a measure of the molecular weight distribution, is 7 to 30 (weight average molecular weight / number average molecular weight (Q)). Regarding the molecular weight distribution,
Generally, the ratio of the weight average molecular weight to the number average molecular weight, the weight average molecular weight / number average molecular weight (Q) is used as a scale, and the larger the ratio (Q), the wider the molecular weight distribution. When Q is less than 7, the durability of the resulting molded article is poor, and when it exceeds 30, the workability is poor. The weight average molecular weight at this time is 100,000 to 1,000,000.

The method for producing the highly stereoregular polypropylene of the present invention satisfying the above requirements will be described below.

First, in the production of the highly stereoregular polypropylene of the present invention, a titanium trichloride composition (III), an organoaluminum compound (A ₁ ) and a third component as a specific mole relative to the titanium trichloride composition (III) are used. A catalyst in which a ratio of the aromatic carboxylic acid ester (E) or the organosilicon compound (S) having a Si—O—C bond and / or a mercapto group is combined is used. The basic aspects of these are the same as those of Japanese Patent Application Nos. 1-156042 and 1-160270 of the present applicant, but the molar ratio of (E) or (S) is There are specific differences in that they are selective.

The above-mentioned titanium trichloride composition (III) is produced as follows. First, an organoaluminum compound (A ₁ ) is reacted with an ether compound to obtain a reaction product (I), and the solid product (II) obtained by reacting this (I) with titanium tetrachloride, or an organic compound Solid product (II) obtained by reacting aluminum compound (A ₁ ) with titanium tetrachloride
Of the present invention as a final solid product obtained by polymerizing at least one time with a linear olefin and a non-linear olefin in multiple stages and then further reacting the ether compound with TiX ₄ and / or SiX _4. The titanium trichloride composition (III) used for the production of polypropylene is produced.

In the present invention, the term “polymerization treatment” means that a linear olefin or a linear olefin obtained by contacting the solid product (II) with a specific non-linear olefin according to the present invention is polymerized. It means to polymerize a non-linear olefin. By this polymerization treatment, the solid product (II) is in a state of being coated with the polymer.

The above-mentioned reaction between the organoaluminum compound (A ₁ ) and the ether compound is carried out in the solvent (D ₁ ) at −20 ° C. to 200 ° C., preferably −10 ° C. to 100 ° C. for 30 seconds to 5 hours. (A ₁ ),
There is no limitation on the order of addition of (B ₁ ) and (D ₁ ), and the amount ratio used is 0.1 mol to 8 mol, preferably 1 mol to 4 mol, of ether compound to 1 mol of organoaluminum compound (A ₁ ) and solvent ( D ₁ ) 0.5L to 5L, preferably 0.5L to 2L.

Thus, the reaction product (I) is obtained. The reaction product (I) can be subjected to the next reaction in a liquid state (the reaction product (I) may be referred to as it is) after completion of the reaction without separation.

The reaction product (I) and titanium tetrachloride or the solid product (II) obtained by reacting the organoaluminum compound (A ₁ ) and titanium tetrachloride are used for the linear olefin and the above-mentioned present invention. as a method of polymerization treatment in multiple stages in a particular non-linear olefin, the reaction product (I) or an organoaluminum compound in any course of the reaction of (a ₁₎ with titanium tetrachloride, linear olefins and non-linear A method of polymerizing the solid product (II) in multiple stages by adding olefins in multiple stages, after the reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride, A method for polymerizing a solid product (II) in multiple stages by adding linear olefins in multiple stages. After the reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product (II) is used as a solvent. There is a method in which a linear olefin and a non-linear olefin are added in multiple stages, followed by a polymerization treatment, after the suspension is added to the above, and an organoaluminum compound is added.

Regarding the order of the multi-stage polymerization treatment using a linear olefin and a non-linear olefin, the linear olefin,
Any of the non-linear olefins may be added first, but from the viewpoint of polymerization operability when the final titanium trichloride composition (III) obtained is used and the performance of the obtained polypropylene, first the linear olefin is used. It is preferable that the polymerization treatment is carried out with, followed by the specific non-linear olefin according to the present invention. By this multi-stage polymerization treatment, the linear olefin-specific non-linear olefin block copolymer according to the present invention is formed, and the solid product (II) is covered with the block copolymer.

Furthermore, in the multi-stage polymerization treatment, as described above, the titanium trichloride composition (which achieves the object of the present invention by using the linear olefin and the above-mentioned specific non-linear olefin according to the present invention at least once each) III) is obtained,
It is also possible to perform the polymerization treatment by adding a linear olefin further twice or more, for example, after the polymerization treatment of the specific non-linear olefin according to the present invention.

The reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride is carried out by adding or not adding the linear olefin and the specific non-linear olefin according to the present invention in any process of the reaction. -10 ℃ ~ 200
C., preferably 0 to 100.degree. C. for 5 minutes to 10 hours.

Although it is preferable not to use a solvent, an aliphatic or aromatic hydrocarbon can be used. (I) or the organoaluminum compound (A ₁ ), titanium tetrachloride, and the solvent may be mixed in any order, and the addition of the linear olefin and the above-mentioned specific non-linear olefin according to the present invention may be performed at any stage. You may go in.

Mixing of the reaction product (I) or the organoaluminum compound (A ₁ ), titanium tetrachloride, and the solvent is preferably completed within 5 hours, and the reaction is performed during the mixing. It is preferable to continue the reaction within 5 hours after mixing the whole amount.

The amount of each used in the reaction is 1 to 1 mol of titanium tetrachloride, the solvent is 0 to 3,000 ml, and the reaction product (I) or the organoaluminum compound (A ₁ ) is in the (I) or the (A ₁ ). The ratio (A1 / Ti) of the number of A1 atoms to the number of Ti atoms in titanium tetrachloride is 0.05 to 10, preferably 0.06 to 0.3.

The polymerization treatment with the linear olefin and the above-mentioned specific non-linear olefin according to the present invention is carried out at any stage of the reaction between the reaction product (I) or the organoaluminum compound (A ₁ ) and titanium tetrachloride. And when the above-mentioned specific non-linear olefin according to the present invention is added and after the reaction of the reaction product (I) or the organoaluminum compound (A ₁ ) with titanium tetrachloride, the linear olefin and the above-mentioned book are added. When the specific non-linear olefin according to the invention is added, in any polymerization treatment with the linear olefin or the specific non-linear olefin according to the present invention, the reaction temperature is 0 ° C to 90 ° C for 1 minute to 10 minutes. time, reaction pressure under the conditions of atmospheric pressure ^{(0kgf / cm 2 G) ~10kgf} / cm 2 G, certain of the solid product (II) 100 g per linear olefins 0.1G～100kg, and the foregoing the present invention Non-linear Fin 0.01g~100
kg is used to produce the final solid product (III), namely the titanium trichloride composition (II
The content of the linear olefin polymer block in I) is 0.1% by weight to 49.5% by weight, and the content of the specific non-linear olefin polymer block according to the present invention is 0.01% by weight.
To 49.5% by weight and the weight ratio of the linear olefin polymer block to the specific non-linear olefin polymer block according to the present invention is 2/98 to 98/2 in multiple stages. Polymerize.

The content of the linear olefin polymer block is 0.1% by weight.
When the amount is less than the above, the runnability when using the obtained titanium trichloride composition and the homogeneity of the obtained polypropylene are insufficient, resulting in poor appearance and insufficient improvement in strength or rigidity when formed into a molded product. Further, even if it exceeds 49.5% by weight, the effect becomes insignificant, which is disadvantageous in terms of operation and economy.

Further, if the content of the specific non-linear olefin polymer block according to the present invention is less than 0.01% by weight, the stereoregularity of the obtained polypropylene and the effect of improving transparency when formed into a molded article are insufficient. However, if it exceeds 49.5% by weight, the improvement of the effect is not remarkable, which is disadvantageous in terms of operation and economy.

The weight ratio of the linear olefin polymer block to the specific non-linear olefin polymer block according to the present invention is 2/98 to 98 from the balance of the above-mentioned various improving effects.
It is preferably set to / 2.

A multi-stage polymerization treatment with a linear olefin and the above-mentioned specific non-linear olefin according to the present invention is conducted to obtain a reaction product (I).
Alternatively, after the reaction between the organoaluminum compound (A ₁ ) and titanium tetrachloride is completed, the liquid portion is separated and removed by filtration or decantation, and then the obtained solid product (II) is suspended in a solvent. In some cases, linear olefins,
In any polymerization treatment with the above-mentioned specific non-linear olefin according to the present invention, based on 100 g of the solid product (II),
Solvent 100 ml ~ 5,000 ml, organoaluminum compound 0.5 g ~ 5,
The presence of 000 g, 1 minute to 10 hours at a reaction temperature of 0 ° C. to 90 ° C., the reaction pressure under conditions of atmospheric pressure ^{(0kgf / cm 2 G) ~10kgf} / cm 2 G, the solid product (II) 100 g per , Linear olefin 0.1g ~
Using 100 kg and 0.01 g to 100 kg of the specific non-linear olefin of the present invention described above, the final solid product (II
I), that is, the content of the linear olefin polymer block in the titanium trichloride composition (III) used for the production of the polypropylene of the present invention is 0.1% by weight to 49.5% by weight, and the above-mentioned specific non- The content of the linear olefin polymer block is 0.01 wt% ~ 49.5 wt%, and the weight ratio of the linear olefin polymer block and the specific non-linear olefin polymer block according to the present invention described above. 2 /
Polymerize in multiple stages to obtain 98-98 / 2.

In any of the multi-stage polymerization treatments described above, after the completion of the polymerization treatment in each stage with the linear olefin or the specific non-linear olefin according to the present invention, the reaction mixture is used as it is in the next stage polymerization treatment. be able to.
Further, the coexisting solvent, unreacted linear olefin or the specific non-linear olefin according to the present invention, the organoaluminum compound and the like are removed by filtration or decantation, and the solvent and the organoaluminum compound are added again. Then, it may be used in the next stage of the polymerization treatment with the specific non-linear olefin or linear olefin according to the present invention.

The solvent used during the polymerization treatment is preferably an aliphatic hydrocarbon,
The organoaluminum compound may be the same as that used in obtaining the reaction product (I) or the one used in the reaction with titanium tetrachloride directly without reacting with the electron donor (B ₁ ), It can be different.

After completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and after further washing with a solvent,
The obtained solid product subjected to the polymerization treatment (hereinafter sometimes referred to as solid product (II-A)) may be used in the next step as it is in a suspended state in a solvent, and further dried to obtain a solid product. You may take it out and use it.

The solid product (II-A) is then reacted with ethers (B ₂ ) and TiX ₄ and / or SiX ₄ (F). This reaction can be carried out without using a solvent, but using an aliphatic hydrocarbon gives preferable results.

The amount used is 100 g of solid product (II-A),
(B ₂ ) 0.1 g to 1,000 g, preferably 0.5 g to 200 g, (F) 0.
1g-1,000g, preferably 0.2g-500g, solvent 0-3,000m
l, preferably 100-1,000 ml.

As the reaction method, preferably, the solid product (II-A) is reacted with ethers (B ₂ ) and TiX ₄ and / or SiX ₄ (F) at the same time, and (II-A) is reacted with (F). And then reacting with (B ₂ ), reacting (II-A) with (B ₂ ) and then reacting with (F),
There is a method of reacting (B ₂ ) with (F) and then reacting with (II-A), but any method may be used.

The reaction conditions are 40 ° C. to 20 ° C. in the above method.
It is desirable to carry out the reaction at 0 ° C., preferably 50 ° C. to 100 ° C. for 30 seconds to 5 hours, and in the method of (II-A) and (B ₂ ) the reaction is performed at 0 ° C. to 50 ° C. for 1 minute to 3 hours. After the reaction, (F) is reacted under the same conditions as described above.

In the other method, (B ₂ ) and (F) are heated at 10 ℃ to 100 ℃.
After reacting for 30 minutes to 2 hours, cool to 40 ° C or lower (II
After the addition of -A), the reaction is carried out under the same conditions as above.

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

The organoaluminum compound (A ₁ ) used for producing the titanium trichloride composition (III) has a general formula of A 1AR ¹ pR ² _{p ′.}
X _{3- (p + p ')} (wherein R ¹ and R ² represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group or an alkoxy group, X represents a halogen, and p and p ′ are 0 < p
+ P'≤3. ) Is used.

Specific examples thereof include trimethyl aluminum, triethyl aluminum, tri n-propyl aluminum, tri n-butyl aluminum, tri i-butyl aluminum, tri n-hexyl aluminum, tri i-hexyl aluminum, tri 2-methylpentyl aluminum,
Trialkylaluminums such as tri-n-octylaluminum and tri-n-decylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, di-butylaluminium monochloride, diethylaluminum monofluoride, diethylaluminum monobromide, Dialkyl aluminum monohalides such as diethyl aluminum monoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, i-butyl aluminum dichloride, etc. Monoalkyl aluminum dihalides of Monoethoxy diethylaluminum, alkoxyalkyl aluminum such as diethoxy monoethyl aluminum can also be used to. Two or more kinds of these organoaluminum compounds may be mixed and used.

Various electron donors other than ethers used for the production of titanium (III) trichloride are shown below, but ethers are mainly used as (B ₁ ) and (B ₂ ),
Other electron donors are preferably shared with ethers.

What is used as an electron donor is an organic compound having any atom of oxygen, nitrogen, sulfur and phosphorus, that is, ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles, amines. And amides, urea or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, hydrogen sulfide or thioethers, and thioalcohols.

Specific examples include diethyl ether, di-n-propyl ether, di-n-butyl ether, diisoamyl ether, di-n-pentyl ether, di-n-hexyl ether, di-hexyl ether, di-n-octyl ether, di-i-. Ethers such as octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol,
Alcohols such as cresol, xylenol, ethylphenol, naphthol, or phenols, methyl methacrylate, ethyl acetate, butyl formate, amyl acetate,
Vinyl butyrate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, Propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, esters such as ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, formic acid, acetic acid , Propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid and other aliphatic acids, benzoic acid and other aromatic acids, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as benzophenone, nitriles such as acetonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β (N, N-dimethylamino) ethanol, pyridine, quinoline, α-picoline, 2,4,6-trimethyl Amines such as pyridine, N, N, N ′, N′-tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N ′, N ′, N ″ -pentamethyl-N ′ -Β
Amides such as dimethylaminomethylphosphoric triamide, octamethylpyrophosphoramide, ureas such as N, N, N ′, N′-tetramethylurea, phenyl isocyanate,
Isocyanates such as toluyl isocyanate, azo compounds such as azobenzene, ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-
Phosphines such as octylphosphine, triphenylphosphine and triphenylphosphine oxide, dimethylphosphite, di-n-octylphosphite, triethylphosphite, tri-n-butylphosphite, triphenylphosphite and other phosphites, ethyldiethyl Phosphinites such as phosphinite, ethyldibutylphosphinite, and phenyldiphenylphosphinite, thioethers such as diethyl thioether, diphenylthioether, methylphenylthioether, ethylene sulfide, and propylene sulfide,
Ethyl thio alcohol, n-propyl thio alcohol,
Thioalcohols such as thiophenol can also be mentioned.

These electron donors can also be used as a mixture.
The electron donor (B ₁ ) for obtaining the reaction product (I) and the solid product (II-A) reacted (B ₂ ) may be the same or different.

TiX ₄ and / or used for the production of titanium trichloride composition (III)
Alternatively, the electron acceptor (F) other than SiX ₄ is represented by a halide of an element of Group III to VI of the periodic table. As a specific example,
Anhydrous aluminum chloride, stannous chloride, stannic chloride,
Examples thereof include zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, antimony pentachloride and the like, and these may be used in combination.

The following are used as the solvent, and as the aliphatic hydrocarbon, n-pentane, n-hexane, n-heptane, n-octane, i-octane and the like are shown, and instead of the aliphatic hydrocarbon, Alternatively, it is also possible to use halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloroethane, trichloroethylene, and tetrachloroethylene.As aromatic compounds, aromatic hydrocarbons such as benzene and naphthalene, and mesitylene which is a derivative thereof. , Alkylated compounds such as durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, and 1-phenylnaphthalene, and halides such as monochlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, dichlorobenzene, and bromobenzene are shown. .

As the linear olefin used for the polymerization treatment, ethylene,
Propylene, butene-1, pentene-1, hexene-1
And other linear olefins are used, and ethylene and propylene are particularly preferably used. One or more kinds of these linear olefins are used.

The aforementioned specific non-linear olefin according to the present invention used for the polymerization treatment has the following formula: CH ₂ ═CH—R ³ (wherein R ³ represents a saturated cyclic structure of a hydrocarbon which may contain silicon). Represents a saturated ring hydrocarbon group having 3 to 18 carbon atoms and optionally containing silicon), a saturated ring hydrocarbon monomer represented by the following formula: (In the formula, R ⁴ has 1 to 3 carbon atoms which may contain silicon.
Represents a chain hydrocarbon group up to, or silicon, R ⁵ ,
R ⁶ and R ⁷ represent a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and any one of R ⁵ , R ⁶ and R ⁷
The individual may be hydrogen. ) Branched-chain olefins represented by (In the formula, n is 0, 1 or m is 1, 2 and R ⁸
Represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen or halogen. , M is 2, each R ⁹ may be the same or different. ) Is an aromatic monomer.

Hereinafter, when simply referred to as a non-linear olefin, any one or more of these or all of them are shown.

Specifically, examples of the saturated ring hydrocarbon monomer include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, 3-methylvinylcyclopentane, vinylcyclohexane, 2-methylvinylcyclohexane, 3-methyl. In addition to vinylcycloalkanes such as vinylcyclohexane, 4-methylvinylcyclohexane and vinylcycloheptane, allylcycloalkanes such as allylcyclopentane and allylcyclohexane,
Cyclotrimethylenevinylsilane, cyclotrimethylenemethylvinylsilane, cyclotetramethylenevinylsilane, cyclotetramethylenemethylvinylsilane, cyclopentamethylenevinylsilane, cyclopentamethylenemethylvinylsilane, cyclopentamethyleneethylvinylsilane, cyclohexamethylenevinylsilane, cyclohexamethylenemethylvinylsilane, Saturated ring-containing hydrocarbons having a silicon atom in the saturated ring structure, such as cyclohexamethyleneethylvinylsilane, cyclotetramethyleneallylsilane, cyclotetramethylenemethylallylsilane, cyclopentamethylenemethylallylsilane, cyclopentamethylenemethylallylsilane, and cyclopentamethyleneethylallylsilane. Polymer, cyclobutyldimethylvinylsilane, cyclopen Didimethylvinylsilane, cyclopentylethylmethylvinylsilane, cyclopentyldiethylvinylsilane, cyclohexylvinylsilane, cyclohexyldimethylvinylsilane, cyclohexylethylmethylvinylsilane, cyclobutyldimethylallylsilane, cyclopentyldimethylallylsilane, cyclohexylmethylallylsilane, cyclohexyldimethylallylsilane, cyclohexylethylallylsilane, cyclohexyldiethylallylsilane , 4-trimethylsilylvinylcyclohexane, 4-trimethylsilylallylcyclohexane, and the like, and saturated ring-containing hydrocarbon monomers containing a silicon atom in addition to the saturated cyclic structure.

Examples of the branched chain olefins include 3-methylbutene-1,3-methylpentene-1,3-ethylpentene-
3-position branched olefin such as 1, 4-ethylhexene 1,4,
4-dimethylpentene-1,4,4-dimethylhexene-1
4-position branched chain olefins such as vinyltrimethylsilane, vinyltriethylsilane, vinyltri-n-butylsilane,
Alkenylsilanes such as allyltrimethylsilane, allylethyldimethylsilane, allyldiethylmethylsilane, allyltriethylsilane, allyltrin-propylsilane, 3-butenyltrimethylsilane and 3-butenyltriethylsilane, dimethyldiallylsilane, ethylmethyl. Examples thereof include diallylsilanes such as diallylsilane and diethyldiallylsilane.

As the aromatic monomer, styrene, and alkylstyrenes such as o-methylstyrene and pt-butylstyrene, which are derivatives thereof, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-Dimethylstyrene, 3,5-dimethylstyrene dialkylstyrenes, 2-methyl-4-fluorostyrene, 2-ethyl-
Halogen-substituted styrenes such as 4-chlorostyrene, o-fluorostyrene, p-fluorostyrene, p-trimethylsilylstyrene, m-triethylsilylstyrene,
Trialkylsilylstyrenes such as p-ethyldimethylsilylstyrene, o-allyltoluene, allyltoluenes such as p-allyltoluene, 2-allyl-p-xylene, 4-allyl-o-xylene, 5-allyl-m. -Allylxylenes such as xylene, vinyldimethylphenylsilane, vinylethylmethylphenylsilane, vinyldiethylphenylsilane, allyldimethylphenylsilane,
Alkenylphenylsilanes such as allylethylmethylphenylsilane, and 4- (o-tolyl) -butene-1
And 1-vinylnaphthalene, etc., and one or more kinds of these non-linear olefins are used.

Titanium trichloride composition (III) obtained as described above
And an organoaluminum compound (A ₂ ), and an aromatic carboxylic acid ester (E) or an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group in a predetermined amount described below, Or a catalyst used for the production of polypropylene, more preferably,
It is used as a catalyst pre-activated by reacting an olefin.

Pre-activation is based on 1 g of titanium trichloride composition (III),
Organoaluminum compound 0.005 g to 500 g, solvent 0 to 50,
Using 0 to 1,000 ml of hydrogen and 0.01 g to 5,000 g of olefin, preferably 0.05 g to 3,000 g, the olefin is reacted at 0 ° C. to 100 ° C. for 1 minute to 20 hours to prepare a titanium trichloride composition (II
I) It is desirable to polymerize 0.01 g to 2,000 g, preferably 0.05 g to 200 g of olefin per 1 g.

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

In the preliminary activation, it is also possible to add an aromatic carboxylic acid ester (E) or an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group in advance.

Examples of the olefin used for preactivating include linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, 4-methyl-pentene-1. , Branched-chain monoolefins such as 2-methyl-pentene-1 and the like,
One or more olefins are used. Further, as the organoaluminum compound, the same ones as the above-mentioned (A ₁ ) can be used, but a dialkylaluminum monohalide similar to the below-mentioned (A ₂ ) is preferably used.

After the preliminary activation reaction is completed, a predetermined amount of the aromatic carboxylic acid ester (E) or the organosilicon compound (S) having a Si—O—C bond and / or a mercapto group (S) is added to the preliminary activation catalyst component slurry. The added catalyst can be used as it is for the polymerization of propylene, and the coexisting solvent, the unreacted olefin and the organoaluminum compound are removed by filtration or decantation, and the dried powder or a solvent for the powder or granules is used. To give a suspension, which is combined with an organoaluminum compound (A ₂ ) and (E) or (S) to form a catalyst, which is used for the polymerization of propylene, a coexisting solvent, and an unreacted olefin. Is removed by evaporation under reduced pressure, or by an inert gas flow, and the powder or granules or a state in which a solvent is added to the powder or granules is suspended. , Add the organoaluminum compound (A ₂₎ as required to the ones, and further (E) or (S) by combining a catalyst, it is also possible to use in the polymerization of propylene.

During the polymerization of propylene, the above-mentioned titanium trichloride composition (III), organoaluminum compound (A ₂ ), aromatic carboxylic acid ester (E) or organic compound having a Si—O—C bond and / or a mercapto group is used. Regarding the amount of the silicon compound (S) used, when an aromatic carboxylic acid ester (E) is used as the third component of the catalyst, the molar ratio (E) between the (E) and the titanium trichloride composition (III) is used. / (III)
Is 0.2 to 10.0, and when an organosilicon compound (S) having a Si—O—C bond and / or a mercapto group is used, the molar ratio of (S) to (III) (S) / (III) 1.
5 to 10.0, and in any case, the molar ratio (A ₂ ) / (III) of the organoaluminum compound (A ₂ ) and the titanium trichloride composition (III) is 0.2 to 200, preferably Is used in the range of 0.2 to 100.

It should be noted that the high stereoregularity polypropylene of the present invention is not always obtained if it is carried out within the above-mentioned molar ratio range of each catalyst component, and the individual polymerization conditions (particularly the polymerization temperature and the use (E) or ( It is necessary to confirm the specific type of S) and the molar ratio to (III).

Further, the number of moles of the titanium trichloride composition (III) refers to the number of Ti gram atoms substantially contained in (III).

As the organoaluminum compound (A ₂ ) to be combined with the titanium trichloride composition (III) during the polymerization of propylene, a dialkylaluminum monohalide represented by the general formula of AlR ¹⁰ R ¹¹ X is preferable.

In the formula, R ¹⁰ and R ¹¹ 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 halogen.

As specific examples, diethylaluminum monochloride, di-n-propylaluminum monochloride, dii
-Butyl aluminum monochloride, di-n-butyl aluminum monochloride, diethyl aluminum monoiodide, diethyl aluminum monobromide and the like can be mentioned.

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.

Specific examples of the Si-O-C component and / or the mercapto group-containing organosilicon compound (S) that can be used as the third component of the catalyst instead of the aromatic carboxylic acid ester (E) include methyltrimethoxysilane. , Vinyltrimethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane,
Trimethylmethoxysilane, triphenylmethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, propyltriethoxysilane, allyltriethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, n- Octyltriethoxysilane, n
-Octadecyltriethoxysilane, 6-triethoxysilane-2-norbornene, dimethyldiethoxysilane, diethyldiethoxysilane, diphenyldiethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylethoxysilane, allyloxytrimethylsilane, methyltri i-propoxysilane,
Dimethyldi-propoxysilane, trimethyli-propoxysilane, tetra-n-butoxysilane, methyltri-n-butoxysilane, tetra (2-ethylbutoxy) silane, methyltriphenoxysilane, dimethyldiphenoxysilane, trimethylphenoxysilane, trimethoxysilane , Triethoxysilane, triethoxychlorosilane, tri i-propoxychlorosilane, tri n-butoxychlorosilane, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, methyldiacetoxysilane, diacetoxymethylvinylsilane, Dimethyldiacetoxysilane, methylphenyldiacetoxysilane, diphenyldiacetoxysilane, trimethylacetoxysilane, triethylacetate Tokishishiran, phenyl dimethylacetoxysilane, triphenyl acetoxy silane, bis (trimethylsilyl) adipate, trimethylsilyl benzoate, such as triethylsilyl benzoate Si-
An organosilicon compound having an O—C bond, mercaptomethyltrimethylsilane, 2-mercaptoethyltrimethylsilane, 3-mercaptopropyltrimethylsilane,
4-mercapto-n-butyltrimethylsilane, mercaptomethyltriethylsilane, 2-mercaptoethyltriethylsilane, 3-mercaptopropyltriethylsilane, 1-mercaptoethyltrimethylsilane, 3-mercaptopropyldimethylphenylsilane, 3-mercaptopropylethylmethyl Organosilicon compounds having a mercapto group such as phenylsilane, 4-mercaptobutyldiethylphenylsilane and 3-mercaptopropylmethyldiphenylsilane, and also mercaptomethyltrimethoxysilane, mercaptomethyldimethylmethoxymethylsilane, mercaptomethyldimethoxymethylsilane, mercapto Methyltriethoxysilane, mercaptomethyldiethoxymethylsilane, mercaptomethyldimethylethoxysilane, 2 Mercaptoethyl trimethoxysilane, 3-mercaptopropyl trimethoxy silane, dimethoxy-3-mercaptopropyl methyl silane, dimethoxy-3-mercaptopropyl methyl silane, 3-mercaptopropyl triethoxysilane, diethoxy-3
An organosilicon compound having a Si—O—C bond and a mercapto group such as mercaptopropylmethylsilane, mercaptomethyldimethyl-2-phenylethoxysilane, 2-mercaptoethoxytrimethylsilane, and 3-mercaptopropoxytrimethylsilane, and 3-aminopropyltrisilane. Methoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-
Aminopropyldimethylethoxysilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 2-aminoethylaminomethyltrimethoxysilane, 3- (2-aminoethylaminopropyl) dimethoxymethylsilane, 2-aminoethylaminomethyl Benzyloxydimethylsilane, 3- [2-
An organosilicon compound having a Si—O—C bond and an amino group, such as (2-aminoethylaminoethylamino) propyl] trimethoxysilane, can be mentioned.

Polymerization of propylene is carried out with the catalyst thus combined or with the preactivated catalyst. Polymerization modes for polymerizing propylene include n-hexane, n
-Slurry polymerization carried out in a hydrocarbon solvent such as heptane, n-octane, benzene or toluene, or bulk polymerization carried out in liquefied propylene, or gas phase polymerization carried out in a gas phase, most preferably a slurry polymerization method. Is.

The polymerization temperature is usually 20 to 75 ° C., preferably 40 to 65 ° C., and particularly preferably 40 ° C. to 60 ° C., which is a relatively low temperature. If the polymerization temperature is too high, it becomes difficult to increase the stereoregularity of the obtained polypropylene, and if the polymerization temperature is too low, the polymerization rate of propylene becomes slow, which is not practical. Polymerization pressure is normal pressure (0 kgf / cm ² G) to 50 kgf / cm ² G, usually 3
The polymerization time is about 0 minutes to 15 hours. During polymerization,
The addition of an appropriate amount of hydrogen for controlling the molecular weight is the same as the conventional propylene polymerization method.

The polymerization can be carried out by either batch polymerization or continuous polymerization. After completion of the 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 in detail 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 antioxidant. Agents, ultraviolet absorbers, anti-blocking agents, stabilizers and additives such as colorants, further nucleating agents, inorganic fillers, various synthetic resins and the like are blended, and after being pelletized if necessary, It is used for various molded articles by known techniques such as injection molding, extrusion molding and blow molding.

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

The characteristic physical properties of the polypropylene of the present invention, which acts on the excellent performance of the molded article obtained by using the polypropylene of the present invention, are as described above, but the present invention supports the characteristic physical properties. Although the details of the manufacturing effect are not clear, it is estimated as follows.

The titanium trichloride composition (III) according to the production of the polypropylene of the present invention is a polypropylene having a high isotactic pentad fraction as compared with conventionally known titanium trichloride compositions, as will be apparent from the examples described later. It has a production performance, but this is a linear olefin-non-linear olefin block copolymer produced by a multi-stage polymerization treatment during the production of the titanium trichloride composition (III), particularly the non-linear olefin polymer block. Is considered to have imparted a high degree of stereospecificity to the polymerization active point.

The aromatic carboxylic acid ester (E) or Si is used as the third component of the catalyst for producing polypropylene of the present invention.
The organosilicon compound (S) having a —O—C bond and / or a mercapto group imparts a broad molecular weight distribution and high stereoregularity to the polypropylene of the present invention.

Furthermore, in the polypropylene of the present invention, the above-mentioned linear olefin-non-linear olefin block copolymer derived from the titanium trichloride composition (III) of the present invention is dispersed. As the linear olefin polymer block of the polymer is compatible with polypropylene, the dispersibility of the non-linear olefin polymer block in polypropylene is highly improved. Therefore, since the nucleating action of the non-linear olefin polymer block is remarkably exhibited, the molded article produced by using the obtained polypropylene has a high degree of crystallinity and a fine spherulite morphology, so that the transparency is high. Presumed to be excellent.

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

(1) MFR: Melt flow rate According to JIS K 7210, condition 14 in Table 1. (Unit: g / 10 min) (2) Isotactic pentad fraction (P): Measured using JEOL GX-270 manufactured by JEOL Ltd. based on the method described above.

(3) Weight average molecular weight and weight average molecular weight / number average molecular weight (Q): determined by gel permeation chromatography of GPC-150C type manufactured by Waters.

(4) Melting point: A sample was kept at 230 ° C for 10 minutes using a 1090 type differential scanning calorimeter manufactured by DuPont, then cooled to -60 ° C at -20 ° C / min and kept at the same temperature for 10 minutes. And then at 20 ℃
It was measured under a temperature rising condition of / min.

(Unit: ° C) (5) Rigidity, strength, heat resistance: Tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] based on 100 parts by weight of polypropylene Methane (0.1 parts by weight) and calcium stearate (0.1 parts by weight) were mixed, and the mixture was granulated using an extruder having a screw diameter of 40 mm. Then, using the granule injection molding machine, a molten resin temperature of 230 ℃, to create a JIS type test piece at a mold temperature of 50 ℃, humidity of the test piece 50%, after leaving for 96 hours at room temperature of 23 ℃, It was measured by the following method.

Flexural modulus: 23 ℃ and 80 ℃ according to JIS K 7203
The elastic modulus was measured by. (Unit: kgf / cm ² ) Tensile Strength: Tensile strength was measured at 23 ° C. according to JIS K 7113. (Unit: kgf / cm ² ) Heat distortion temperature: The heat distortion temperature was measured according to JIS K 7202. (Unit: ° C) (6) Durability: Prepare test pieces in the same manner as (5), and
Tensile creep test (load 248kgf /
cm ² ), and the creep rupture time was measured. (unit:
Time) (7) Transparency: temperature 200 ℃, pressure 200 kg using a press
A polypropylene film having a thickness of 150 μ was formed under the condition of f / cm ² , and after coating both surfaces of the film with liquid paraffin, JI
The internal haze was measured according to SK 7105. (Unit:%) Example 1 (1) Preparation of titanium trichloride composition (III) n-hexane 6, diethylaluminum 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 (I) (diisoamyl ether / DEAC molar ratio 2.
4) got.

Put 40 mol of titanium tetrachloride in a reactor purged with nitrogen and
It is heated to ℃, and the total amount of the above reaction product liquid (I) is added to 180
After dripping in minutes, keep at the same temperature for 60 minutes, raise to 80 ° C and react for 1 hour, cool to room temperature, remove the supernatant liquid, add n-hexane 20 and decant it. The operation except for was repeated 4 times to obtain a solid product (II).

The whole amount of this (II) was suspended in n-hexane 30, 400 g of diethylaluminum monochloride was added, 1.5 kg of propylene was added at 30 ° C., and a polymerization treatment was carried out at the same temperature for 1 hour. After the reaction time had elapsed, the supernatant was removed by decantation, and the solid was washed twice with 30 n-hexane.
Subsequently, n-hexane 30 and 400 g of diethylaluminum monochloride were added, the temperature was raised to 40 ° C., 1.9 kg of vinylcyclohexane was added, and polymerization was carried out at 40 ° C. for 2 hours.

After the reaction was completed, the supernatant was removed, n-hexane 30 was added, and the operation of removing the supernatant by decantation was repeated 4 times.
A solid product (II-A) which was subjected to a multi-stage polymerization treatment with propylene-vinylcyclohexane was obtained.

With the total amount of this solid product suspended in n-hexane 9, 3.5 kg of titanium tetrachloride was added at room temperature for about 10 minutes and reacted at 80 ° C for 30 minutes, and then diisoamyl ether was added. 1.6 kg was added and reacted at 80 ° C. for 1 hour. After the reaction was completed, the operation of removing the supernatant was repeated 5 times and then dried under reduced pressure to obtain a titanium trichloride composition (III).

In the obtained titanium trichloride composition (III), the propylene polymer block content was 25.0% by weight, the vinylcyclohexane polymer block content was 25.0% by weight, and the titanium content was 12.6% by weight.

(2) Preparation of pre-activated catalyst component After replacing the stainless reactor equipped with a stirrer with an inclined blade with an internal volume of 150 with nitrogen gas, n-hexane 90,
After 1.71 kg of diethyl aluminum monochloride and 1.8 kg of the titanium trichloride composition (III) obtained in (1) were added at room temperature, 1 kg of propylene was subsequently added and reacted at 30 ° C. for 2 hours (3 After 1 g of titanium chloride composition (III) was reacted with 0.5 g of propylene), unreacted propylene was removed to obtain a preactivated catalyst component in a slurry state.

(3) Production of polypropylene A pre-activated catalyst component slurry obtained in the above (2) was added to a polymerization vessel equipped with a stirrer and equipped with a two-stage turbine blade with an internal volume of 150, which had been purged with nitrogen. ) Is 11.5 mg atom / h in terms of titanium atom
r, and methyl p-triylate with respect to the titanium atom,
N-Hexane was continuously fed at 13 kg / hr as a catalyst from the same pipe or from another pipe so that the molar ratio was 1.8. Furthermore, hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 11% by volume, and propylene was supplied so that the total pressure was maintained at 10 kg / cm ² G, to carry out slurry polymerization of propylene at 60%.
It was carried out continuously at 120 ° C. for 120 hours.

During the polymerization, the retention level of the polymer slurry in the polymerization vessel is
The polymer slurry was continuously withdrawn from the polymerization vessel so as to be 75% by volume into a flash tank having an internal volume of 50. While depressurizing in a flash tank to remove unreacted hydrogen and propylene, methanol was supplied at 1 kg / hr and contact treatment was performed at 70 ° C. Subsequently, the polymer slurry was neutralized with an aqueous sodium hydroxide solution, and the polymer was washed with water, separated, and dried to obtain polypropylene at 10 kg / hr.

When the polypropylene was analyzed, the MFR was 4.0 (g / 10
Min), isotactic pentad fraction (P) is 0.98
5, the weight average molecular weight / number average molecular weight (Q) was 13.5, the weight average molecular weight was 340,000, and the melting point was 168.0 ° C.

Comparative Example 1 (1) In the same manner as in (1) of Example 1, except that the solid product (II) was used as the solid product (II-A) equivalent without being subjected to multi-stage polymerization treatment with propylene and vinylcyclohexane. Similarly, a titanium trichloride composition was obtained.

(2) The titanium trichloride composition obtained in (1) above in place of the titanium trichloride composition (III) in (2) of Example 1.
A preactivated catalyst component was obtained in the same manner except that 0.9 kg was used.

(3) In (3) of Example 1, the pre-activated catalyst component obtained in (2) above is used as the pre-activated catalyst component,
Further, propylene was polymerized in the same manner except that each catalyst component was supplied to the polymerization vessel so that the total pressure in the polymerization vessel was kept at 10 kg / cm ² G to obtain polypropylene.

Comparative Example 2 (1) In a stainless steel reactor equipped with a stirrer, decane 3, anhydrous magnesium chloride 480 g, orthotitanic acid n
-Butyl 1.7 kg, and 2-ethyl-1-hexanol
1.95 kg were mixed and heated to 130 ° C. for 1 hour with stirring to dissolve the mixture into a uniform solution. The temperature of the homogeneous solution is 70 ° C.,
With stirring, 180 g of diisobutyl phthalate was added, and after 1 hour, 5.2 kg of silicon tetrachloride was added dropwise over 2.5 hours to precipitate a solid, and the mixture was further heated to 70 ° C. for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product (III).

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

(2) After replacing the tilted stainless reactor having an inner volume of 30 with nitrogen gas, n-hexane 20, 1.5 g of triethylaluminum, 480 g of diphenyldimethoxysilane and 100 g of the titanium-containing supported catalyst component obtained in (1) were added. Added at room temperature. Next, add 85 g of vinylcyclohexane, and add 40
The reaction was carried out at 0 ° C. for 2 hours (0.5 g of vinylcyclohexane per 1 g of titanium-containing supported catalyst component) to obtain a pre-activated catalyst in a slurry state.

(3) In (3) of Example 1, as a catalyst, the preactivated catalyst slurry obtained in the above (1) (triethylaluminum and diphenyldimethoxysilane are contained in addition to the preactivated titanium-containing supported catalyst component). Was continuously supplied at 0.27 mg atom / hr in terms of titanium atom, and propylene was polymerized in the same manner except that the hydrogen concentration in the gas phase of the polymerization vessel was maintained at 1.5% by volume. Since the produced bulk polymer blocked the polymer slurry withdrawal pipe from the polymerization vessel, it was necessary to stop the polymerization of propylene within 6 hours after the initiation of the polymerization.

Comparative Example 3 (1) A titanium trichloride composition separately obtained in the same manner as in (1) of Comparative Example 1 when the reaction product (I) was reacted with titanium tetrachloride in (1) of Comparative Example 1. Vinylcyclohexane was added to 1.3-kg of n-hexane 100 at 60 ° C for 2 hours and then washed with methanol and dried. United 95
A titanium trichloride composition containing 33.3% by weight of a vinylcyclohexane polymer in the same manner except that 0 g was ground in a vibrating mill having a capacity of 10 at room temperature for 5 hours and then suspended in the titanium tetrachloride. Got

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

(3) In (3) of Example 1, the pre-activated catalyst component obtained in (2) above is used as the pre-activated catalyst component,
Further, propylene was polymerized in the same manner except that each catalyst component was supplied to the polymerization vessel so that the total pressure in the polymerization vessel was kept at 10 kg / cm ² G to obtain polypropylene.

Comparative Example 4 n-Hexane 4 and titanium tetrachloride (10 mol) were placed in a reactor purged with nitrogen and kept at 0 ° C., after which an n-hexane solution 4 containing 8 mol of diethylaluminum monochloride was dropped and then 40 ° C. The temperature was raised to 1, and the reaction was further performed for 1 hour. Then, after 1.5 kg of propylene was added, polymerization was carried out at the same temperature for 2 hours. After the treatment, the supernatant liquid was removed and the solid was washed twice with n-hexane 10 and suspended in n-hexane 8. Then, diethyl aluminum monochloride 30
After adding 0 g, add 1.9 kg of vinylcyclohexane, and add 4
Polymerization was performed at 0 ° C. for 2 hours. After the polymerization treatment, the operation of removing the supernatant liquid, adding n-hexane 5 and removing by decantation was repeated 3 times, and the solid product subjected to the multistage polymerization treatment was suspended in n-hexane 9. 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, it was washed with n-hexane to obtain a titanium trichloride composition. Polypropylene was obtained in the same manner as in Comparative Example 1 except that the titanium trichloride composition was used.

Comparative Example 5 In (3) of Example 1, p- which is the third component of the catalyst was used.
The pre-activated catalyst component slurry was supplied without supplying methyl toluate so that the total pressure in the polymerization vessel was maintained at 10 kg / cm ² G, and the hydrogen concentration in the gas phase part in the polymerization vessel was adjusted to 5.2 volume. Polymerization of propylene was carried out in the same manner except that the content was set to 0.1% to obtain polypropylene.

Comparative Example 6 Polymerization of propylene was carried out in the same manner as in Example 5, except that the pre-activated catalyst component slurry obtained in the same manner as in (2) of Comparative Example 1 was used as the pre-activated catalyst component slurry, Obtained polypropylene.

Examples 2 and 3 In (3) of Example 1, the hydrogen concentration in the polymerization vessel was set to 3.2.
Volume% (Example 2) and 18% by volume (Example 3), respectively, except that each catalyst component was supplied to the polymerization vessel so that the total pressure in the polymerization vessel was maintained at 10 kg / cm ² G. Polymerization of propylene was performed to obtain polypropylene.

Example 4 (1) Preparation of titanium trichloride composition (III) Obtained by reacting n-heptane 4, 5.0 mol of diethylaluminum monochloride, 9.0 mol of diisoamyl ether and 5.0 mol of di-n-butyl ether at 18 ° C. for 30 minutes. The reaction solution was added dropwise to 27.5 mol of titanium tetrachloride at 40 ° C for 300 minutes or once, and then the reaction mixture was kept at the same temperature for 1.5 hours and reacted at 65 ° C.
The mixture is heated to 1, reacted for 1 hour, the supernatant is removed, and n-hexane is added.
The operation of adding 20 and removing by decantation was repeated 6 times, and 1.8 kg of the obtained solid product (II) was added to n-hexane 40
Suspended in diethyl aluminum monochloride
After adding 500 g, 1.5 kg of propylene was added at 30 ° C. and the reaction was carried out for 1 hour to carry out the first stage polymerization treatment.

After the lapse of reaction time, the supernatant was removed and n-hexane 20 was added.
Was added and the operation of removing by decantation was repeated twice. Subsequently, after adding n-hexane 40 and 500 g of diethylaluminum monochloride, 3.0 kg of allyltrimethylsilane was added, and the reaction was carried out at 40 ° C. for 2 hours to carry out a second-stage polymerization treatment, followed by multistage propylene-allyltrimethylsilane. Polymerized solid product (II-A)
Got

After the reaction, the supernatant liquid was removed, and then the operation of adding n-hexane 20 and removing by decantation was repeated twice, and the solid product (II-A) subjected to the above-mentioned polymerization treatment was added to n-hexane 7
The mixture was suspended in the mixture, 1.8 kg of titanium tetrachloride and 1.8 kg of n-butyl ether were added, and the mixture was reacted at 60 ° C for 3 hours. After completion of the reaction, the supernatant was removed by decantation, and then 20 n-
Hexane was added, and the mixture was stirred for 5 minutes and allowed to stand, and the procedure of removing the supernatant was repeated 3 times, and then dried under reduced pressure to obtain a titanium trichloride composition (III).

(2) Preparation of pre-activated catalyst component In (2) of Example 1, the titanium trichloride composition (II
A preactivated catalyst component slurry was obtained in the same manner except that the titanium trichloride composition obtained in (1) above was used as I).

(3) Manufacture of polypropylene In (3) of Example 1, using the pre-activated catalyst component slurry obtained in (2) above as the pre-activated catalyst component slurry, each catalyst component was adjusted to a total pressure in the polymerization vessel. 10kg / cm ² G
Was supplied to the polymerization vessel while maintaining the above condition, and propylene was polymerized in the same manner except that the hydrogen concentration in the gas phase in the polymerization vessel was set to 7% by volume to obtain polypropylene. The polypropylene has an MFR of 2.0 (g / 10 minutes), an isotactic pentad fraction of 0.981, a weight average molecular weight / number average molecular weight (Q) of 12.0, a weight average molecular weight of 410,000, and a melting point of 167.5 ° C.
Met.

Example 5 (1) Preparation of titanium trichloride composition (III) 27.0 mol of titanium tetrachloride was added to n-hexane 12 and 1 ° C.
After cooling to 1, the n-hexane 12.5 containing 27.0 mol of diethylaluminum monochloride was further added dropwise at 1 ° C. over 4 hours. After completion of the dropping, the reaction was carried out at the same temperature for 15 minutes, then the temperature was raised to 65 ° C. over 1 hour, and the reaction was further performed at the same temperature for 1 hour.

Next, the procedure of removing the supernatant liquid, adding n-hexane 10 and removing by decantation was repeated 5 times, and 1.8 kg of 5.7 kg of the obtained solid product (II) was suspended in n-hexane 50. , 350g of diethylaluminum chloride,
After further adding 0.6 kg of propylene at 0 ° C., a polymerization treatment was carried out at the same temperature for 1 hour.

Subsequently, after removing the supernatant liquid by decantation, n
-Washed solids with hexane 50, after washing, n-
Hexane 50, diethylaluminum monochloride 35
0 g was added, and 1.9 kg of 3-methylbutene-1 was further added,
Polymerization was performed at 0 ° C. for 2 hours.

After the polymerization treatment, the supernatant was removed, n-hexane 30 was added, and the operation of removing by decantation was repeated twice.
The whole amount of the obtained solid product (II-A) subjected to the multi-stage polymerization treatment was suspended in n-hexane 11, to which diisoaluminum ether 1.2 and ethyl benzoate 0.4 were added. This suspension was stirred at 35 ° C. for 1 hour, and n-hexane 3 was added.
It was washed 5 times with to obtain a treated solid. The treated solid obtained was treated with 40% by volume of titanium tetrachloride and 10% by volume of silicon tetrachloride in n-
Suspended in hexane solution 6.

This suspension was heated to 65 ° C. and reacted at the same temperature for 2 hours. After the reaction was completed, n-hexane 20 was used once and 3
The solid thus obtained was washed and then dried under reduced pressure to obtain a titanium trichloride composition (III).

(2) Preparation of pre-activated catalyst component In (2) of Example 1, the titanium trichloride composition (II
Preliminarily prepared in the same manner, except that the titanium trichloride composition obtained in (1) above is used as I) and that a mixture of diethyl aluminum monochloride 1.2 kg and diethyl aluminum monoiodide 0.9 kg is used as the organoaluminum compound. The activated catalyst component was obtained in a slurry state.

(3) Manufacture of Polypropylene In (3) of Example 1, as the pre-activating catalyst component, the pre-activating catalyst component slurry obtained in the above (2) (Note: contains diethyl aluminum monochloride and diethyl aluminum monoiodide). 2 in terms of titanium atoms
2.2 mg atom / hr and p as the third component of the catalyst
-Supply 3-aminopropyltriethoxysilane in place of methyl toluate to the polymerization vessel so that the molar ratio to titanium atom is 2.8, and further, the hydrogen concentration in the gas phase in the polymerization vessel is 28% by volume. Polymerization of propylene was carried out in the same manner except that the temperature was kept at 1. to obtain polypropylene. The polypropylene has an MFR of 30.0 (g / 10 minutes), an isotactic pentad fraction (P) of 0.980, a weight average molecular weight / number average molecular weight (Q) of 13.0, a weight average molecular weight of 190,000, and a melting point of 166.
It was 8 ° C.

Comparative Example 7 (1) Except that the solid product (II) in Example 1 (1) was used as a solid product (II-A) equivalent without being polymerized with propylene and 3-methylbutene-1. Similarly, a titanium trichloride composition was obtained.

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

(3) In (3) of Example 1, the pre-activated catalyst component slurry obtained in (2) above was used as the pre-activated catalyst component slurry, and each catalyst component had a total pressure of 10 in the polymerization vessel.
Polymerization of propylene was carried out in the same manner except that the polymerization vessel was supplied so as to maintain kg / cm ² G, to obtain polypropylene.

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

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

Therefore, the molded product produced by the various molding methods using the polypropylene of the present invention can be expected to be expanded to the field of use which has not been used in the conventional polypropylene molded product.

[Brief description of drawings]

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

Continuation of front page (56) Reference JP-A-59-149907 (JP, A) JP-A-54-85289 (JP, A) JP-A-60-139710 (JP, A) JP-A-60-139731 (JP , A) JP 61-127716 (JP, A) JP 58-201816 (JP, A) JP 58-17104 (JP, A) JP 58-23806 (JP, A)

Claims (2)

[Claims] 1. A solid product (II) obtained by reacting titanium tetrachloride with an organoaluminum compound (A ₁ ) or a reaction product (I) of an organoaluminum compound (A ₁ ) and an ether compound, Linear olefin and the following formulas ac
Titanium trichloride composition (III) obtained by multi-stage polymerization treatment with one or more non-linear olefins each represented by 1 or more, and then further reacting the ether compound with TiX ₄ and / or SiX ₄ And a. A saturated ring hydrocarbon monomer represented by the formula CH ₂ ═CH—R ³ (wherein R ³ has a saturated ring structure of a hydrocarbon which may contain silicon,
Saturated ring monomer having 3 to 18 carbon atoms which may contain silicon) b. Formula (In the formula, R ⁴ represents a chain hydrocarbon group having 1 to 3 carbon atoms which may contain silicon, or silicon, and R ⁵ , R ⁶ , and R ⁷ represent silicon. Represents a chain hydrocarbon having 1 to 6 carbon atoms which may be contained,
Any one of R ⁵ , R ⁶ and R ⁷ may be hydrogen. ) C. Expression An aromatic monomer represented by (wherein n is 0, 1 or m is 1 or 2, and R ⁸ is a carbon atom which may contain silicon: 1
Represents a chain hydrocarbon group of 1 to 6 and R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen or halogen, and when m is 2, R ⁹ is the same. But it may be different. ) As an organoaluminum compound (A ₂ ) and a third component, an aromatic carboxylic acid ester (E) or Si-O-
Obtained by polymerizing propylene using a catalyst in which an organosilicon compound (S) having a C bond and / or a mercapto group is combined, and a melt flow rate (MFR) of 0.1 to
100 (g / 10 min, 230 ° C, load 2.16 kgf), isotactic pentad fraction (P) 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 10
High stereoregular polypropylene characterized in that it is from 0,000 to 1,000,000. 2. A pre-activated catalyst component obtained by combining the titanium trichloride composition (III) with the titanium trichloride composition (III) and an organoaluminum compound, and reacting this with an olefin. Claim 1 using
Polypropylene according to the item.