JPH02169606A - Production of high-rigidity polypropylene - Google Patents

Abstract

PURPOSE:To obtain the title polypropylene of improved rigidity by polymerizing propylene in the presence of a catalyst comprising a specified TiCl3 composition, an organoaluminum compound and an aromatic carboxylic ester. CONSTITUTION:A solid product obtained by reacting an organoaluminum compound or a reaction product thereof with an electron donor with TiCl4 is optionally subjected to a treatment of polymerization of an alpha-olefin and reacted with an electron acceptor to obtain a TiCl3 composition (a). 0.001-10g, per g of component (a), of an aromatic monomer of the formula (wherein n is 0-2; m is 1-2; and R<1> is a 1-12C hydrocarbon group which may contain Si, H or a halogen atom, when m is 2, R<1> groups may be the same or different from each other) is polymerized on a mixture of component (a) with an organoaluminum compound (b) to obtain a pre-activated catalyst component, which is mixed with an aromatic carboxylic ester (c) and optionally additional component (b) to obtain a catalyst containing components (a), (b) and (c) in a molar ratio (c)/(a) of 0.1-10.0 and a molar ratio (b)/(a) of 0.1-200. Propylene is polymerized in the presence of this catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing highly rigid polypropylene. More specifically, the present invention relates to a method for producing highly rigid polypropylene with outstanding transparency.

[Prior art and its problems] The present applicant used a catalyst made by combining a titanium trichloride composition previously obtained by a specific method, an organoaluminum compound, and an aromatic carboxylic acid ester in a specific usage ratio. A method for producing high-rigidity polypropylene (Japanese Unexamined Patent Publication No. 511-104907, hereinafter referred to as the prior invention)
), and according to the method of the lead invention, a polypropylene molded article having significantly higher rigidity than polypropylene obtained by conventionally known methods can be obtained without adding any special additives. It became possible to manufacture.

However, although the polypropylene obtained by the method of the prior invention has the above-mentioned high rigidity, it is translucent, which may impair commercial value in the field of application, and improvement in transparency is desirable. It was rare.

The present inventors have conducted intensive research on a method for producing highly rigid polypropylene with improved transparency. As a result, a titanium trichloride composition similar to that used in the prior invention was combined with an organoaluminum compound, a small amount of a specific aromatic monomer was polymerized to this composition for preactivation, and an aromatic carboxylic acid The polypropylene obtained by polymerizing propylene using a catalyst consisting of a combination of specific amounts of esters not only has significantly superior transparency, but also has significantly higher rigidity than the polypropylene obtained by the method of the prior invention. It was also found that the present invention can be further improved.

As is clear from the above description, an object of the present invention is to provide a method for producing highly rigid polypropylene with extremely excellent transparency. Another object is to provide a highly rigid polypropylene with outstanding transparency.

[Means to solve the problem 1 The present invention has the following configuration.

(1) [1] A method for producing polypropylene by polymerizing propylene using a catalyst consisting of a titanium chloride composition (III), an organoaluminum compound (A), and an aromatic carboxylic acid ester (E) In, as the titanium trichloride composition (Ill), an organoaluminum compound (A) or an organoaluminum compound (
The solid product obtained by reacting titanium tetrachloride with the reaction product of electron donor (81) and electron donor (81)
- with or without polymerization treatment with olefin;
Furthermore, using the titanium trichloride composition (III) obtained by reacting the electron donor (B) and the electron acceptor, the titanium trichloride composition (Ill) and the organoaluminum compound (All) were combined. This combination has the following formula, (where n is either 0.1.2, fat is 1.2, and 11 is a hydrocarbon group having from 1 to 12 carbon atoms that may contain silicon, (represents hydrogen or halogen, and when - is 2, each R' may be the same or different) is added to the titanium trichloride composition (III
) per Ig, 0.001g to 100g of the pre-activated catalyst component obtained by polymerization reaction is combined with an additional organoaluminum compound (A) and an aromatic carboxylic acid ester (E) as necessary, and the aromatic Group carboxylic acid ester (E) and the titanium trichloride composition (III) (TI
Molar ratio (E)/(Summer+1)-0 (same as below atomic number standard)
, 1 to 1O10, and the organic aluminum compound (A,
) and the titanium trichloride composition (III) (A+
)/(II) A method for producing highly rigid polypropylene, characterized by polymerizing propylene using a catalyst having a ratio of -0.1 to 200.

(2) The method according to item 1 above, in which a dialkylaluminum monohalide is used as the organoaluminum compound (AI).

(3) As the organoaluminum compound (A2), -the formula is klR2,R', *Xs-+e*e'+ (in the formula, R
2. R$ represents 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' represent any number in the range O<p◆p°≦3. , ) The method according to item 1 above, using an organoaluminum compound represented by:

(4) The relationship between the isotactic pentad fraction (P) of the polypropylene obtained by polymerization and MFH is 1.00≧P≧0.015 log FR+0.
955.

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

As the titanium trichloride composition (dll) used in the present invention, a titanium trichloride composition similar to that used in the prior invention is used. The details of the manufacturing method are detailed in the specification of the prior invention and are as follows.

First, the reaction between the organoaluminum compound (A) and the electron donor (B1) to obtain the reaction product (1) is carried out in a solvent (0) at -20°C to 200°C, preferably at -0°C. ~
Perform at 100°C for 30 seconds to 5 hours, (A2), (B+
There is no restriction on the order of addition of ) and (o), and the ratio of the amounts used is 0.1 to 8 mol, preferably 1 to 4 mol, and 0.5 to 51 mol, preferably 1 to 4 mol, of the electron donor and 0.5 to 51 mol, preferably 1 mol of the organic aluminum. is suitably between 0.5 and 21. Preferably, the solvent is an aliphatic hydrocarbon.In this way, the reaction product (1) is obtained.The reaction product (1) is in a liquid state (which can be referred to as reaction product liquid (1)) as it is after the reaction is completed without separation. ) can be subjected to the next reaction.

Next, the reaction between the reaction product (I) or the organoaluminum compound (A) and titanium tetrachloride (C) is
The reaction is carried out at 200° C., preferably 10 to 0° C. for 5 minutes to 8 hours. It is preferable not to use a solvent, but aliphatic or aromatic hydrocarbons can be used. (A,) or (1
), (C) and the solvent may be mixed in any order, and it is preferable that the mixing of the entire amount be completed within 5 hours.The amount of each used in the reaction is based on 1 mole of titanium tetrachloride.
The solvent is 0 to 3,000 mfl, the organoaluminum compound (A,) or the reaction product (1) is the number of ^1 atoms in said (A,) or said (1), and the TI in titanium tetrachloride.
The ratio of the number of atoms (A1/TI) is O, OS~! 0, preferably 0.06 to 0.2.

After the reaction is completed, the liquid portion is separated and removed by filtration or decantation, and after repeated washing with the solvent, the obtained solid product (II) is suspended in the solvent for 50 minutes.
It may be used in the next step, or it may be further dried and taken out as a solid for use.

Alternatively, the solid product (! summer) obtained by reacting this organoaluminum compound (A2) or reaction product (1) with titanium tetrachloride may be polymerized with an α-olefin and used for the next reaction. is also possible.

In the present invention, the term "polymerization treatment" refers to bringing a small amount of α-olefin into contact with the solid product (11') under polymerizable conditions to polymerize the α-olefin.
Through this polymerization treatment, the solid product (+1) becomes coated with the polymer. As a method for polymerizing with an α-olefin, (1) an α-olefin is added in any process of the reaction between the organoaluminum compound (A) or the reaction product (1) and titanium tetrachloride to form a solid product. (II), (2) After the reaction of the organoaluminum compound (A) or the reaction product (1) with titanium tetrachloride, α-olefin is added to form the solid product (II). A method of polymerization treatment, (3) After the reaction between the organoaluminum compound (A) or the reaction product (1) and titanium tetrachloride, the liquid portion is separated and removed by filtration or decantation, and the obtained solid is obtained. There is a method in which the product (11) is suspended in a solvent, an organoaluminum compound and an α-olefin are further added, and the product is polymerized.

Organoaluminum compound (A2) or reaction product (
When an α-olefin is added in any process of the reaction between 1) and titanium tetrachloride, and when an organoaluminum compound (82
) or the reaction product (if α-olefin is added after the reaction with titanium tetrachloride, the reaction temperature is 30~
Pass α-olefin at atmospheric pressure for 5 minutes to 10 hours at 90℃ or 10kg/crr? Add so that the pressure is below G. The amount of α-olefin added is determined by the amount of α-olefin added to form the solid product (I
I) 100g&: vs. 10-5,000g α-
It is desirable to use olefin and polymerize 0.05g to 1.000g.

After the polymerization treatment with α-olefin is completed with the organoaluminum compound (A2) or the reaction product (titanium tetrachloride), the liquid portion is separated and removed by filtration or decantation, and the obtained solid product is (+r) is suspended in a solvent, the solid product (II
) loog to solvent 1G (1+mi~2, QOOmI
L, add 5g to 500g of organoaluminum compound,
10 to 5,000 g of α-olefin at 0 to 10 kg/crtIIG for 5 minutes to 10 hours at a reaction temperature of 30 to 90°C.
It is desirable to add O,OS to 1.000 gm.

The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound may be the same as that used in (A2) or different. After the reaction, the liquid portion was separated and removed by filtration or decantation. After further repeated washing with a solvent, the resulting 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 may be further dried and taken out as a solid for use.

The solid product (11) or (II-A) is then reacted with an electron donor (B2) 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 the solid product (II) or (II-
A) For 1G+Ig, (lh) 0.1g to 1
．． 000g, preferably 0.5g to 200g, (F)
O, 1 g to 1.000 g, preferably 0.2 g to 5 (l
og, solvent 0 to: 1.000 mA, preferably 100
~1,000+1J2 The reaction method is as follows: ■ Solid product (Natsuri or (II-A)
B,) and the electron acceptor (F) are reacted simultaneously, ■ (Natsuri or (n - A ) is reacted with (F) and then (B2) is reacted, ■ (11) or ( I
A method of reacting I-A) with (B,) and then reacting (F), ■ After reacting (B2) with CF), (I
There is a method of reacting (II-A) or (II-A), and either 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.
I) or (II-A) and (B,) reaction at 0℃~
After reacting at 50° C. for 1 minute to 3 hours, the mixture is reacted with (F) under the same conditions as in (1) above. In addition, in method (■), (B,) and (F) are heated at lO℃~10.0℃ for 30 minutes~
After reacting for 2 hours, the mixture is cooled to 40° C. or lower, and (II) or (II-A) is added thereto, followed by reaction under the same conditions as in (1) and (2) above. Solid product (1■) or (I
After the reactions of I-A), (th), and (F) are completed, the liquid portion is separated and removed by filtration or decantation, and then washing is repeated with a solvent to prepare the titanium trichloride composition used in the present invention. ) is obtained.

The titanium trichloride composition (1) obtained as described above was combined with an organoaluminum compound (A+), and this product was combined with the following formula: (where n is 0, 1.2, and 1. 2, and R1 represents a hydrocarbon group having 1 to 12 carbon atoms that may contain silicon, hydrogen, or a halogen, and when the intestine is 2, each R1 may be the same or different.) The aromatic monomer represented by (hereinafter sometimes abbreviated as specific aromatic monomer) is added to the titanium trichloride composition (
III) 0.001g to 100g per Ig of the polymerized preactivated catalyst component, optionally an additional organoaluminum compound (A1), and an aromatic carboxylic acid ester (E) are combined, and according to the present invention, The catalyst used.

Pre-activation is performed by adding 0.05g to 5g of organoaluminum compound (A,) to Ig of titanium trichloride composition (III).
00g, solvent O~50λ, hydrogen 0~1,000mJZ,
and specific aromatic monomer 0.01g~l, 00
Use 0g.

The polymerization reaction temperature is from 0°C to 100°C for 1 minute to 20 hours, and a specific aromatic polymer is reacted to form a titanium trichloride composition (I
II) 0.001g-100g per Ig, preferably 0
．． It is desirable to polymerize 01g to 100g of a specific aromatic caramer.If the polymerization reaction amount is less than 0.001g, the effect of improving transparency and rigidity will be insufficient, and if it exceeds 100g, the effect will be significantly improved. This will result in an economic disadvantage.

Preactivation may be carried out in a hydrocarbon solvent such as n-pentane, n-hexane, n-hebutane, or toluene. It is also possible to add the aromatic carboxylic acid ester (E) in advance.

After the preactivation reaction is completed, the catalyst obtained by adding a predetermined amount of aromatic carboxylic acid ester (E) to the preactivated catalyst component slurry can be used as it is for propylene polymerization, or the coexisting solvent can be used as is. , the unreacted specific aromatic monomer, and the organoaluminum compound (A) are removed by filtration, and a solvent is added to the dried powder or the powder to form a suspension. A method for polymerizing propylene using a combination of an additional organoaluminum compound (A1) and an aromatic carboxylic acid ester (E), a coexisting solvent, and an unreacted specific aromatic monomer. Evaporate by vacuum distillation or inert gas stream, etc., add powder or granules to a suspended state, and add organoaluminum compound (AI) to this as necessary. However, it is also possible to further combine it with an aromatic carboxylic acid ester (E) to form a catalyst and use it for the polymerization of propylene.

During the polymerization of propylene, the above titanium trichloride composition (III), an additional organoaluminum compound (Al
) and the amount of the aromatic carboxylic acid ester (E) used, the molar ratio of the aromatic carboxylic acid ester (E) and the titanium trichloride composition (II+) (E)/(I+Ri is 0.
1 to 10.0, and the organoaluminum compound (Al)
and the titanium trichloride composition (II+) molar ratio (AI)
/ (II+) is used within a range of 0.1 to 200.

If the amount of aromatic carboxylic acid ester (E) is too small, the isotuffity is insufficiently improved and high rigidity cannot be achieved, and if too much is added, the polymerization activity decreases and is not practical. The number of moles of composition (II+) refers to the number of Ti gram atoms substantially contained in (II+).

The organoaluminum compound (A2) used in the production of the titanium trichloride composition (■) used in the present invention has - formulas AIR", R', +X5-ip+p'l (in the formula R2
, ns represents a hydrocarbon group or alkoxy group represented by an alkyl group, cycloalkyl group, or aryl group, × represents a halogen, and p and p' represent any number in the range of O<pep'≦3). The organoaluminum compounds represented are used.

Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-l-butylaluminum, tri-n-hexylaluminum, trinyhexylaluminum, tri-2-methylpentylaluminum, tri-n-octylaluminum. Aluminum, trialkylaluminums such as tri-n-decylaluminum, diethylaluminium monochloride, moro-propylaluminum monochloride, di-l-butylaluminum monochloride, diethylaluminium monofluoride, diethylaluminum monobromide, diethylaluminium sonoiodide, etc. dialkyl aluminum hydrides such as diethyl aluminum hydride; alkyl aluminum sesquihalides such as methyl aluminum sesquichloride and ethyl aluminum sesquichloride; monoalkyl aluminum cybarides such as ethyl aluminum dichloride and l-butyl aluminum dichloride; In addition, alkoxyalkylaluminiums such as monoethoxydiethylaluminum and jetoxymonoethylaluminum can also be used. Two or more types of these organoaluminum compounds can also be used in combination.

As the electron donor used in the present invention, there are various ones shown below, but for (B+) and (lh), ethers are mainly used, and other electron donors are used in combination with ethers. is preferable, and those used as electron donors are organic compounds having any one of oxygen, nitrogen, sulfur, and phosphorus atoms, i.e., ethers, alcohols,
Esters, aldehydes, fatty acids, ketones, nitriles, amines, amides, urea or thioureas, isocyanates, azo compounds, sphines, phosphites, phosphinites, hydrogen sulfide or thioethers, These include thioalcohols.

Specific examples include diethyl ether, moro-propyl ether, moro-butyl ether, diisoamyl ether, moro-pentyl ether, moro-hexyl ether,
Diisoamyl ether, Moro-octyl ether, Diisoamyl ether, Moro-dodecyl ether, Diphenyl ether, Ethylene glycol monoethyl ether,
Ethers such as tetrahydrofuran, methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, phenol, cresol,
Alcohols 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, 2-ethylhexyl naphthoate, and ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, formic acid, acetic acid, and propionic acid. , fatty acids such as butyric acid, oxalic acid, succinic acid, acrylic acid, and maleic acid, aromatic acids such as benzoic acid, ketones such as methyl ethyl ketone, methyl isobutyl ketone, and benzophenone, nitrile acids such as acetonitrile, methylamine, diethylamine, and doli Butylamine, 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.

Amides of N', N', N"-pentamethyl-No-β-dimethylaminomethyl phosphoric acid triamide, octamethyl bilobosphoramide, ureas such as N, N, N'-N'-tetramethyl 2, etc. , isocyanates such as phenyl isocyanate and toluyl isocyanate, azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, and triphenylphosphine oxyto, dimethyl Phosphites such as phosphite, moro-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, triphenyl phosphite, ethyl diethyl phosphinite, ethyl butyl phosphinite, phenyl diphenyl phosphinite, etc. Thioethers such as phosphinites, diethylthioether, diethylthioether, methylphenylthioether, ethylene sulfide and propylene sulfide, and thioalcohols such as ethylthioalcohol, lowpropylthioalcohol and thiophenol are also included.

These electron donors can also be used in combination.
The electron donor (B1) to obtain the reaction product (1), the solid product (II) or (B2) to be reacted with (II-A) may be the same or different.

The electron acceptor (F) used in the present invention is found in periodic table III.
It is represented by halides of elements in group ~■. Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, and antimony pentachloride. , these can also be used in combination. Most preferred is titanium tetrachloride.

The following solvents are used. Examples of aliphatic hydrocarbons include n-pentane, 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, aniline, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, and l-phenylnaphthalene, and halogens such as monochlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, dichlorobenzene, and bromobenzene. Chemical substances, etc. are shown.

The α-olefins used in the polymerization treatment include linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, and 4-methyl-pentene-1,2-methyl- Branched monoolefins such as pentene-1 are used. These α-olefins can also be used in combination of two or more α-olefins.

The specific aromatic monomer used for preactivation has the following formula: It is an aromatic monomer representing a hydrocarbon group, hydrogen, or halogen of numbers 1 to 12, and when the number is 2, each R1 may be the same or different. Specific examples include styrene and its recognized conductors, 0-methylstyrene, p-
Alkylstyrenes such as t-butylstyrene, 2.4-
Dimethylstyrene, 2.5-dimethylstyrene, 3.4
- Dimethylstyrene, dialkylstyrenes such as 3,5-dimethylstyrene, halogen-substituted alkylstyrenes such as 2-methyl-4-fluorostyrene, 2-ethyl-4-chlorostyrene, 0-fluorostyrene, p-fluorostyrene, etc. Halogen-substituted styrenes such as styrene, p-tonmethylsilylstyrene, -trimethylsilylstyrene,
Trialkylsilylstyrenes such as p-triethylsilylstyrene, Otori-triethylsilylstyrene, p-ethyldimethylsilylstyrene, O-allyltoluene, p-
Allyltoluenes such as allyltoluene, 2-allyl-p
-xylene, 4-allyl-0-xylene, 5-allyl-
Allylxylenes such as I-xylene, and 4-(o-
)-lyl)-1-butene, 1-vinylnaphthalene, etc., and these specific aromatic monomers are 1f! The above is used.

The organoaluminum compound (A1) to be combined with the titanium trichloride composition (III) and the organoaluminum compound (A1) used or used as necessary have the following formula:
A dialkylaluminum monohalide represented by IR'R'X is preferred; in the formula, 84 and R5 represent a hydrocarbon group such as an alkyl group, an aryl group, an alkaryl group, or a cycloalkyl group, or an alkoxy group, and X represents a halogen Specific examples thereof include diethylaluminium monochloride, moro-propylaluminum monochloride, dialkyl aluminum monohalide, moro-butyl aluminum monochloride, diethylaluminum monoiodide, diethylaluminium monobromide, and the like.

Specific examples that can be used as the aromatic carboxylic acid ester (E), which is another component constituting the catalyst, include ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate,
Methyl toluate, ethyl toluate, 2-toluate
Ethylhexyl, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate,
Propyl naphthoate, butyl naphthoate, naphthoic acid 2
-ethylhexyl, ethyl phenylacetate, etc.

The catalyst used in the present invention thus obtained is used in the polymerization of propylene. The polymerization format for propylene is propylene (n-hexane, n-hebutane,
It can be carried out by slurry polymerization carried out in a hydrocarbon solvent such as n-octane, benzene or toluene, or by bulk polymerization and gas phase polymerization carried out in liquefied propylene.

Regarding the crystallinity of the polymer that can exhibit the effects of the present invention for polypropylene obtained by the various polymerization methods described above, the isotactic pentad fraction (P) is M
In relation to FR, 1≧P≧0.015 log MFR
+0.955 range.

The higher the MFR, the higher the P tends to be, and the MFR is usually 0.05 to 200, preferably about o, i to 100 for practical purposes. Polymerization temperature is usually 20 to 100°C, preferably 40 to 85 It is ℃. If the temperature is too low, m
If the synthesis activity is too low to be practical, and if the temperature is high, it becomes difficult to increase isotuffity. l
i Normal pressure: Normal pressure ~ 50 kg/cm'G, usually 30 minutes ~ 1
During zero polymerization, which is carried out for about 5 hours, adding an appropriate amount of hydrogen to adjust the molecular weight is the same as in conventional polymerization methods.

Thus, the polypropylene obtained by the method of the present invention is a highly rigid polypropylene having extremely high transparency, and can be used for various molded products by known techniques such as injection molding, vacuum forming, extrusion molding, and blow molding. Ru.

(Function) The highly rigid polypropylene obtained by the method of the present invention contains a specific aromatic polymer with high stereoregularity dispersed therein. By exhibiting a nucleating effect, it promotes the crystallization of polypropylene, thereby increasing the transparency and crystallinity of the polypropylene as a whole.

Further, as described above, the specific aromatic polymer introduced by the method of the present invention is a stereoregular high molecular weight polymer, and therefore does not bleed onto the surface.

〔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) CY: indicates polymerization activity and represents the polymer yield (g) per Ig of titanium trichloride composition (■■),
(Unit: g/g) (2) MFR:
Melt flow index ^5TilD-1238 (
(Unit: g/lo min) (3) Isotactic pentad fraction (P): Macromolecule
es 8687 (1975) Measured based on IZ. This is the isotactic fraction in pentad units in the polypropylene molecular chain using 13C-NMR.

(4) Internal haze: This is the haze inside the film excluding the influence of the surface.
Polypropylene was formed into a film with a thickness of 150 μm under conditions of 00 Kg/c+*2G, and after coating both sides of the film with liquid paraffin, the haze was measured in accordance with JIS K 7105. (Unit: 2%
) (5) Crystallization temperature; lO℃ using differential scanning calorimeter
It was measured at a rate of descent of /min.

(Unit: °C) (6) Rigidity: Polypropylene 100! Tetrakis[methylene-3-(3',5°-di-t-
Butyl-4°-hydroxyphenyl)propionate]
1 liz part of methane and 0.1 part by weight of calcium stearate were mixed, and the mixture was passed through a screw with a diameter of 40 mm.
Granulation was performed using an m+s extrusion granulator. Then, the granules were heated in an injection molding machine at a molten resin temperature of 230°C and a mold temperature of 50°C.
A JIS type test piece was prepared, and the test piece was left in a room with a humidity of 50% and a room temperature of 23° C. for 72 hours, and then measured using the method described below.

(a) Flexural modulus, 1st place according to JIS 7203:
kgf/crn”) (b) Tensile strength: Based on JIS 7113 (unit: kg
f/cm”1 (c) Rockwell hardness (R scale): 72 according to JIS
Compliant with 02 (d) Heat distortion temperature (HDT): JIS K 7207
(Unit: 2°C) Example 1 (1) Preparation of titanium trichloride composition (III') n-hexane 6It, diethylaluminum monochloride (
DEAC) 5.0 mol, diisoamyl ether 12.
0 mol was mixed at 25°C for 1 minute and reacted at the same temperature for 5 minutes to form a reaction product solution (diisoamyl ether/DEAC).
A molar ratio of 2,4) was obtained. 40 mol of titanium tetrachloride was placed in a reactor purged with nitrogen, heated to 35°C, and the entire amount of the reaction product liquid (1) was added dropwise over 30 minutes, kept at the same temperature for 30 minutes, and heated to 75°C. The temperature was raised and the reaction was continued for another 1 hour, cooled to room temperature, the supernatant liquid was removed, and 20IL of n-hexane was added.
The operation of adding and removing the supernatant liquid by decantation was repeated four times to obtain a solid product (I+).

The entire amount of (I+) was suspended in 301 g of 0-hexane, 200 g of diethylaluminium monochloride was added, and 1.1 g of propylene was added at 30°C. After the reaction, the supernatant was removed, and 300aIL of n-hexane was added and the mixture was decanted with decane. 2.5 kg of the solid product (II-A) subjected to the above polymerization treatment was suspended in n-hexane 6F, and 3.5 kg of titanium tetrachloride was dissolved at room temperature. After adding for 10 minutes and reacting for 30 minutes at 80°C, 1.8 kg of diisoamyl ether was added and reacted for 1 hour at 80°C. After the reaction was completed, the supernatant was removed by decantation. , 401 n-hexane was added, stirred for 10 minutes, left to stand, and the supernatant liquid removed.
After repeating this process several times, it was dried under reduced pressure to obtain a titanium trichloride composition (Ill). Titanium trichloride composition (III) 1
The titanium content in g was 192 mg.

(2) Preparation details of preactivated catalyst component f After purging a JI80IL stainless steel reactor with inclined blades with nitrogen gas, 40 Il of n-hexane, 200 g of diethylaluminium monochloride, and the titanium trichloride composition obtained in (1). (Titanium trichloride composition (III ) per Ig, 2.4-
Dimethylstyrene 1. og reaction).

After the reaction was completed, unreacted 2,4-dimethylstyrene and the solvent were removed by filtration, washed with n-hexane, and dried to obtain a preactivated catalyst component in the form of powder.

(3) Polymerization of propylene After purging a stainless steel reactor equipped with a stirrer with an internal volume of 5,000 liters of nitrogen gas, it was heated to 200 ml of n-hexane at room temperature. ,
70g of diethylaluminum monochloride, (2)
A titanium trichloride composition (Il
20g as l), 12g of methyl 9-toluate
g, and hydrogen 20011j! added. Subsequently, propylene was polymerized for 3 hours at a polymerization temperature of 70°C and a propylene partial pressure of 10 kg/crn'G. After the completion of the reaction, 1 Oj2 of methanol was supplied, and after treatment at 70°C for 30 minutes, unreacted propylene and unreacted propylene were removed. The reaction hydrogen was discharged. 20 more
Add 100g of sodium hydroxide aqueous solution of 2% by weight.
It was treated at 70°C for 0 minutes. After sewing, 100j of pure water
After adding 2 and stirring for 10 minutes, the aqueous layer was extracted twice, and the polymer slurry was extracted, filtered, and dried to obtain a polymer. Since the resulting one coalescence contained lumps, the entire polymer was pulverized by a pulverizer to obtain 59.2 kg of polypropylene with an MFR of 1.5.

Comparative Example 1 In (3) of Example 1, the titanium trichloride composition (I) obtained in (1) of Example 1 was used instead of the preactivated catalyst component.
Polypropylene was obtained in the same manner except that 10 g of iodine diethylaluminum monochloride and methyl p-toluate were each used in an amount of 1/2.

Implementation (H2, 3) Polypropylene was obtained in the same manner as in Example 1 except that in (3) of Example 1, the amount of hydrogen charged was changed to 3001 (Example 2) and aooIL (Example 3).

Comparative Example 2.3 In (3) of Actual IM Example 1, the amount of hydrogen charged was 270j
Polypropylene was obtained in the same manner as in Comparative Example 1 except that the amounts were changed to 2 (Comparative Example 2) and 54 OJl (Comparative Example 3).

Comparative Example 4 A preactivated catalyst component was obtained in the same manner as in (2) of Example 1, except that propylene 5 [iQg was used instead of 2,4-dimethylstyrene, and the rest was the same as in Example 1.
Propylene was polymerized in the same manner as in (3) above to obtain polypropylene.

Comparative Example 5 In (3) of Comparative Example 1, polypropylene was obtained in the same manner as in Comparative Example 1 except that methyl pt-ruylate as a catalyst component was not used.

Comparative Example 6 and Example 4.5 In (2) of Example 1, 4-allyl-0-xylene was used instead of 2,4-dimethylstyrene, and the amounts used were 1 g and 400 g% 12 kg, respectively. Polypropylene was obtained in the same manner as in Example 1, except that the preactivation reaction was carried out with different conditions.

Comparative Examples 7 to 9 and Example 6.7 In (2) of Example 1, instead of 2,4-dimethylstyrene,! 1-trimethylsilylstyrene 1.5k
g, and in (3), the molar ratio of methyl p-toluate to titanium trichloride composition (III) was changed as shown in the table below.
Polypropylene was obtained in the same manner as in Example 1. However, in Comparative Examples 7 and 8 and Example 6, the preactivated catalyst component was replaced with the titanium trichloride composition (
10 g of In ) and 35 g of diethylaluminum monochloride were used.

Example 8 (1) Preparation of titanium trichloride composition (III) Rhohebutane 8J2. 16 moles of di-n-butylaluminum monochloride and 10 moles of moro-butyl ether were mixed at 30°C.
Mix for 0 minutes and react for 20 minutes to obtain reaction product liquid (I)
I got it. The entire amount of reaction product liquid (I) was added dropwise over 60 minutes to a solution consisting of 51 moles of toluene and 64 moles of titanium tetrachloride kept at 45°C, and then the temperature was raised to 85°C and the reaction was further carried out for 2 hours. , Cool to room temperature, remove the supernatant, add n-heptane 3 (Ii, and remove the supernatant by decantation, and repeat the procedure twice to obtain a solid product (Ii) 4
．． I got 9 kg. This (I) total amount of n-hebutane 30
1, and added 2.0 kg of moro-butyl ether and 15 kg of titanium tetrachloride at room temperature for about 20 minutes.
The reaction was carried out at 0°C for 2 hours, and after cooling, decantation n-
After washing and drying with hebutane, titanium trichloride composition (m
) was obtained. The content of titanium atoms in 1 g of titanium trichloride composition (III) was 2551 mg.

(2) Preparation of preactivated catalyst component In (2) of Example 1, titanium trichloride composition (I
II), the titanium trichloride composition obtained in (1) above (
III) Using 450 g, 2-methyl-4-fluorostyrene 8 was used instead of 2,4-dimethylstyrene.
．． A preactivated catalyst component was obtained in the same manner as in Example 1 (2) except that 5 kg was used.

(3) Polymerization of propylene In (3) of Example 1, 38 g (20 g as titanium trichloride composition (III)) of the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component, and Polypropylene was obtained in the same manner as in Example 1 (3) except that the amount of methyl p-toluate added was 16 g.

Comparative Example 10 In (3) of Example 8, the titanium trichloride composition (1) obtained in (1) of Example 8 was used instead of the preactivated catalyst component.
Polypropylene was obtained in the same manner except that 20 g of (2) was used.

Example 9 (1) Preparation of titanium trichloride composition (III) 27.0 mol of titanium tetrachloride was added to n-hexane 12J2 and heated at 1°C.
After cooling, n-hexane 12,i containing 27.0 mol of diethylaluminum monochloride was added dropwise at 1°C over 4 hours. After the completion of the dropwise addition, the mixture was kept at the same temperature for 15 minutes and reacted. The temperature was raised to 65°C over 1 hour, and the reaction was further carried out at the same temperature for 1 hour.The supernatant liquid was removed and n-
The operation of adding hexane 101 and removing by decantation was repeated 5 times, resulting in a solid product (11) 5.7k
Of these, 1.8 kg was suspended in 1141 g of n-hexane, and 1.61 g of diisoamyl ether was added thereto.

After stirring this suspension at 35°C for 1 hour, n-hexane 3I
A treated solid was obtained by washing with 5 times of water. The obtained treated solid was suspended in an n-hexane solution 61 containing 40% by volume of titanium tetrachloride.

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

(2) Preparation of preactivated catalyst component In (2) of Example 1, titanium trichloride composition (I
The titanium trichloride composition obtained in (1) above as (ll)
III) A preactivated catalyst component was obtained in the same manner as in Example 1 (2) except that 450 g of styrene was used and 1.5 kg of styrene was used instead of 2,4-dimethylstyrene.

(3) Polymerization of propylene In (3) of Example 1, 80 g (20 g as titanium trichloride composition (Ill)) of the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component, and p
Polypropylene was obtained in the same manner as in Example 1 (3) except that the amount of methyl toluate added was 17 g.

Comparative Example 11 In (3) of Example 9, the titanium trichloride composition (I) obtained in (1) of Example 9 was used instead of the preactivated catalyst component.
Polypropylene was obtained in the same manner except that 20 g of ll) was used.

Example 1O (1) Preparation of titanium trichloride composition (■1) n-heptane 4fL, diethylaluminium monochloride 5.0
The reaction solution obtained by reacting 960 mol of diisoamyl ether, 5.0 mol of di-0-butyl ether at 18°C for 30 minutes was dissolved in 27.5 mol of titanium tetrachloride at 40°C.
After stirring and dropping for 00 minutes, keep at the same temperature for i, s hours to react, then raise the temperature to 65°C, react for 1 hour, remove the supernatant, add 20 Il of n-hexane and remove by decantation. The operation was repeated 6 times to obtain a solid product (11
) 1.8kg 1kN-Hexane was suspended in 50IL, 200g of diethylaluminium monochloride was added, and propylene 1.8kg was suspended at 60°C. A solid product (II-A) subjected to polymerization treatment was obtained by adding Okg and reacting for 1 hour (propylene reaction amount: 0.5 kg).

After the reaction, the supernatant was removed, and the operation of adding 30 Il of n-hexane and removing by decantation was repeated twice to obtain the solid product (, II-A) (2,
3 kg) was suspended in n-hexane 42, 1.8 kg of titanium tetrachloride and 1.11 kg of n-butyl ether were added, and the mixture was reacted at 60°C for 3 hours. 6 After the reaction, the supernatant liquid was removed by decantation. After that, n-hexane 201 was added, stirred for 5 minutes, left to stand, and the supernatant liquid removed. After repeating the operation three times, the titanium trichloride composition (I) was dried under reduced pressure.
ll) was obtained. The content of titanium atoms in 1 g of titanium trichloride composition (III) was 200 mg.

(2) Preparation of preactivated catalyst component In (2) of Example 1, titanium trichloride composition (Il
The titanium trichloride composition (I) obtained in (1) above was used as
ll) 450 g, and 1.3 kg of pt-butylstyrene instead of 2,4-dimethylstyrene.
A pre-activated catalyst component was obtained in the same manner as in Example 1 (2) except that .

(3) Polymerization of propylene In (3) of Example 1, 50 g of the preactivated catalyst component obtained in (2) above (20 g as titanium trichloride composition (III)), aromatic 158 Ethyl p-anisate as carboxylic ester
Polypropylene was obtained in the same manner except that a catalyst consisting of 53 g of diethylaluminium monoiodide and 37 g of moro-propylaluminum monochloride was used as the organoaluminum compound.

Comparative Example 12 Example! Polypropylene was obtained in the same manner as in (3) of Example 10, except that 20 g of the titanium trichloride composition (■I) obtained in (1) of Example 10 was used instead of the preactivated catalyst component.

The main polymerization conditions and polymerization results for each of the above-mentioned implementations and comparisons and the evaluation results of the obtained polypropylene are shown in the table below.

[Effects of the Invention] The main effect of the present invention is that polypropylene with extremely high transparency and rigidity can be obtained.

As is clear from the above-mentioned examples, the internal haze of the film produced using the polypropylene obtained by the method of the present invention is 215 to 215% compared to the case without preactivation with a specific aromatic monomer. 315, and has extremely high transparency.

Further, the crystallization temperature is 2°C to 4°C higher than that of the polypropylene obtained by the method of the prior invention, and as a result of the significantly improved crystallinity, the flexural modulus is also further improved.

[Brief Description of the Drawings] Figure 1 is a manufacturing process diagram (
flowchart).

Claims (1)

[Scope of Claims] (1) Using a catalyst consisting of [1] titanium chloride composition (III), [2] organoaluminum compound (A_1), and [3] aromatic carboxylic acid ester (E), propylene In the method for producing polypropylene by polymerizing titanium trichloride composition (III), an organoaluminum compound (A_2) or an organoaluminum compound (A
Reaction product (I) between _2) and electron donor (B_1)
Solid product (II) obtained by reacting titanium tetrachloride with
using a titanium trichloride composition (III) obtained by polymerizing with an α-olefin or without polymerizing and further reacting an electron donor (B_2) with an electron acceptor. Titanium composition (III) and organic aluminum compound (A_1) are combined, and this product has the following formula, ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, n is 0, 1, 2, m is 1, 2, and R^1 is a carbon number of 1 to 12 that may contain silicon.
represents a hydrocarbon group, hydrogen, or halogen up to m
When is 2, each R^1 may be the same or different. )
The aromatic monomer represented by is added to the titanium trichloride composition (I
II) 0.0018 to 100g per 1g of the preactivated catalyst component obtained by polymerization reaction, and optionally additional organic aluminum compound (A_1) and aromatic carboxylic acid ester (E) are combined, and the aromatic Molar ratio (E)/(III) of the group carboxylic acid ester (E) and the titanium trichloride composition (III) (same based on the number of Ti atoms) = 0.1
~10.0, and the organoaluminum compound (A_1)
and the titanium trichloride composition (III) molar ratio (A_1)/
(III) A method for producing highly rigid polypropylene, which comprises polymerizing propylene using a catalyst having a ratio of 0.1 to 200. (2) The method according to claim 1, in which a dialkyl aluminum monohalide is used as the organoaluminum compound (A_1). (3) As the organic aluminum compound (A_2), the general formula is AlR^2_pR^3_p_'X_3_-_(_p
___+_p__') (wherein, R^2 and R^3 are alkyl groups,
A hydrocarbon group such as a cycloalkyl group or an aryl group or an alkoxy group, X represents a halogen, and p and p' represent any number satisfying 0<p+p'≦3. ) The method according to claim 1, using an organoaluminum compound represented by: (4) The relationship between the isotactic pentad fraction (P) and MFR of the polypropylene obtained by polymerization is within the range of 1.00≧P≧0.015logMFR+0.955, Claim 1 The method described in.