JPH01292011A - Production of highly rigid polypropylene - Google Patents

Abstract

PURPOSE:To provide the subject polymer having no odor, by polymerizing propylene in the presence of a catalyst comprising an organic Al compound, an organic Si compound and a composition produced by reacting a solid comprising an organic Al compound, TiCl4, etc., with an electron donor and an electron acceptor. CONSTITUTION:The objective high rigid polypropylene is obtained by polymerizing propylene in the presence of a catalyst comprising (A) a titanium trichloride composition, (B) an organic aluminum compound and (C) an organic silicon compound having an alkoxy or phenoxy group in a molar ratio of the component C/the component A of 1.5-10.0. The titanium trichloride composition is prepared by subjecting or not subjecting a solid product to a polymerization treatment using alpha-olefin and further reacting the product with an electron donor and an electron acceptor, the solid product being prepared by reacting an organic aluminium compound or a reaction product thereof with an electron donor with titanium tetrachloride.

Description

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

[Prior art and its problems] The present applicant has previously discovered the existence of a catalyst made by combining a titanium trichloride composition obtained by a specific method with a specific usage ratio of an organoaluminum compound and an aromatic carboxylic acid ester. We have proposed a method of manufacturing highly rigid polypropylene by polymerizing propylene (JP-A-58-104,907, hereinafter sometimes referred to as "prior invention (1) 2)". According to the method of the prior invention (1), polypropylene is produced that allows molded articles to be obtained that have significantly higher rigidity than polypropylene obtained by conventional methods, even without the addition of any special additives. It became possible.

However, when the method of the prior invention (1) is applied to a gas phase polymerization process that does not use a solvent in principle, the aromatic carboxylic acid ester, which is a component of the catalyst, will all be contained in the polypropylene. Since the aromatic carboxylic acid ester generates a strong odor even in the presence of a trace amount, polypropylene produced by a gas phase polymerization process using the aromatic carboxylic acid ester contains the aromatic carboxylic acid ester, and the polypropylene A bad odor is generated during the granulation process or molding process. Therefore, there have been problems of environmental pollution and poor workability during production or processing on an industrial scale in the gas phase polymerization process of polypropylene.

In addition, the present inventors have already developed a catalyst combining a titanium trichloride composition similar to that used in the method of the prior invention (1), an organoaluminum compound, and an organosilicon compound having an alkoxy group or a phenoxy group. A method of polymerizing α-olefins such as propylene in the presence of
No. 2-72,828 and below, 2), which is sometimes referred to as the prior invention (2), has been filed. The molar ratio used is 0.05 to 1.4 mol, and the prior invention (2
) is characterized by improved polymerization activity and high crystallinity as shown by the residual rate of boiling an-hexane extraction. The rigidity was inferior to that of the molded article using polypropylene obtained by the method of the prior invention (1).

The present inventors have conducted extensive research into a manufacturing method that can produce odorless, highly rigid polypropylene even in a gas phase polymerization process. As a result, it was found that odorless and highly rigid polypropylene can be obtained even in a gas phase polymerization process when the catalysts combined according to the method of the prior invention (2) are used and the usage ratio is limited to a specific range. The invention has been completed.

As is clear from the above description, an object of the present invention is to provide a method capable of producing odorless, highly rigid polypropylene even in a gas phase polymerization process. Another object is to provide an odorless, highly rigid polypropylene.

[Means to solve problems and their effects 1 The present invention has the following configuration.

(1) [1] Organoaluminum compound (A1) or organoaluminum compound (^2) and electron donor (Ill
A solid product (!) obtained by reacting titanium tetrachloride with the reaction product (1) with (1) is polymerized with an α-olefin or without polymerization, and is further treated with an electron donor (B2).
titanium trichloride composition (III) obtained by reacting with an electron acceptor; ■ an organoaluminum compound (A2); and ■ an organosilicon compound having an alkoxy group or a phenoxy group (S
), and the molar ratio (S)/(III) of the organosilicon compound (S) and the titanium trichloride composition (1) is 1.
．． A method for producing high-rigidity polypropylene, which comprises polymerizing propylene in a gas phase in the presence of a catalyst having S~10.0.

(2) The manufacturing method according to item 1 above, wherein the organoaluminum compound (A2) is a dialkylaluminum monohalide.

(3) The manufacturing method according to item 1 above, wherein the combination of titanium trichloride composition (III) and organoaluminum compound (^2) is preactivated by reacting with an α-olefin.

(4) The manufacturing method according to item 1 above, in which propylene is vapor-phase polymerized.

(5) Melt flow rate (VFR) of polypropylene
and the absorbance ratio (IR-γ,
The absorbance ratio at infrared wave numbers 997 cm-' and 973 cm-' (^s++y/A++ts) is IR-τ≧
The manufacturing method according to item 1 above, in which the formula of 0.0O2031o MFR+ 0.950 is added.

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

As the titanium trichloride composition (2) used in the present invention, a titanium trichloride composition similar to that used in the prior inventions (1) and (2) is used. The details are the prior invention (1)
The details of (2) and (2) are as follows.

First, the reaction between the organoaluminum compound (^I) and the electron donor (B+) to obtain the reaction product (I) is carried out in a solvent (0) at a temperature of -20°C to 200°C, preferably - to -200°C.
Perform at too℃ for 30 seconds to 5 hours, (^l), (81
), (D) are added in the order of addition, and the ratio of the amounts used is 0.1 to 8 mol, preferably 1 to 4 mol, of the electron donor and 0.5 to 5 It, preferably the solvent, per 1 mol of organic aluminum. is suitably 0.5 to 2j2. As the solvent, an aliphatic hydrocarbon is preferable.In this way, the reaction product (I) is obtained.The reaction product (I) is in a liquid state as it is after the reaction has been completed without separation (this can be called a reaction product liquid (summer)). be)
can be used for the next reaction.

Next, the reaction between the reaction product (I) or the organoaluminum compound (^1) and titanium tetrachloride (C) is carried out at 0 to 20
Conducted at 0°C, preferably 10 to 90°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)
, (II:) and the solvent may be mixed in any order,
It is preferable that the mixing of the total amount be completed within 5 hours.The amount of each used in the reaction is 0 to 3,000 1 mol of titanium tetrachloride, the organic aluminum compound (^1) or the reaction product. Product (I) has a ratio of the number of AI atoms in (A+) or (1) to the number of Ti atoms in titanium tetrachloride (^l/Tl) of 0.05 to 1O1, 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 a solvent, the obtained solid product (II) is left suspended in the solvent.
It may be used in the next step, or it may be further dried and taken out as a solid for use.

Further, a solid product (!■) obtained by reacting this organoaluminum compound (A+) or reaction product (I 2) with titanium tetrachloride is polymerized with an α-olefin and used for the next reaction. It 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 (II) under polymerizable conditions to polymerize the α-olefin.
Through this polymerization treatment, a solid product (1) becomes coated with the polymer.As a method of polymerization treatment with α-olefin, A method of polymerizing a solid product (!■) by adding an α-olefin in any step of the reaction with titanium chloride, (2) Tetrachloride with an organoaluminum compound (＾鵞) or reaction product (1) After completion of the reaction with titanium, add α-olefin to polymerize the solid product (!■). (3) Combination of organoaluminum compound (^1) or reaction product (summer) with titanium tetrachloride. After the reaction is completed, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product (!■) is suspended in a solvent, and an organoaluminum compound and an α-olefin are further added, followed by polymerization. There is a way.

Organoaluminum compound (^1) 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 (^1
) or when adding an α-olefin after the reaction between the reaction product (1) and titanium tetrachloride, the reaction temperature is 30°C.
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 the solid product (
11) lO~s, 000g α- for 100g
It is desirable to use olefin and polymerize 0.05g to 1.000g.

After the polymerization treatment with α-olefin is completed, the reaction between the organoaluminum compound (I) or the reaction product (I) and titanium tetrachloride is completed, and the liquid portion is separated and removed by filtration or decantation, and the obtained solid is When the product (U) is suspended in a solvent, the solid product (II
) 100g of solvent 1001℃~2.000mf,
Add 5g to 500g of an organoaluminum compound, and heat the α-olefin to zero at a reaction temperature of 30 to 90°C for 5 minutes to 10 hours.
~l Add 10-5,000g at OKg/cnfG,
0.05-1. It is desirable to polymerize QOOg.

The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound may be the same as that used in (^l) or a different one. After the reaction is complete, separate and remove the liquid part by filtration or decantation. After further repeated washing with a solvent, the resulting polymerized solid product (hereinafter sometimes referred to as solid product (11-^)) is
It may be used in a suspended state in a solvent in the next step, or it may be further dried and taken out as a solid for use.

The solid product (II) or (n-A) is then reacted with an electron donor (B2) and an electron acceptor (E). 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 (H) or (II-A) 1
00g, (B2) 0-1g to 1.000g, preferably 0.5g to 200g, (E) 0.1g to 1.0g.
000g, preferably 0.2g to 500g, solvent θ~3
．． 000mj! , preferably 100 to 1,00011
0 reaction methods include: (1) reacting the solid product (11) or (II -A ) with an electron donor (B2) and an electron acceptor (E) at the same time; (2) (n ) or (n -A ) is reacted with (E) and then (B2) is reacted, ■(II) or )(II-A) is reacted with (
Method of reacting (E) after reacting B2), ■(
After reacting B2) and (E), (II) or (n
There is a method of reacting -A), but any method may be used.

The reaction conditions are 40°C to
It is desirable to react at 200°C, preferably 50°C to 100°C for 30 seconds to 5 hours.
) or (II-A) and (B2) at θ℃~
After reacting at 50°C for 1 minute to 3 hours, (E) is
, React under the same conditions as in ■. In addition, in method (■), (B2) and (E) are heated at 10℃ to 100℃ for 30 minutes to 2
After reacting for a period of time, the mixture is cooled to 40° C. or below, and (II) or (n −A ) is added, followed by reaction under the same conditions as in (1) and (2) above. Solid product (1■) or (II-
After the reactions of A), (112), and (E) are completed, the liquid portion is separated and removed by filtration or decantation, and then washing is repeated with a solvent to obtain the titanium trichloride composition (III) used in the present invention. can get.

The titanium trichloride composition (Ill
) is a combination of 0.1 mol to 500 mol of an organoaluminum compound (^2) and a predetermined amount of an organosilicon compound (S) having an alkoxy group or phenoxy group, which will be described later, per mol of titanium in (m). or, more preferably, the combination of (at > and (^2) is preactivated by reacting with an α-olefin, and then the organosilicon compound (S) is added to use in the present invention. Use as a catalyst.

The organoaluminum compound (^l) used in the production of the titanium trichloride composition (m) used in the present invention has -maximum ^IR'@R"+a・X5-1+++**・+ (
In the formula, R1 and R2 represent a hydrocarbon group or an alkoxy group represented by an alkyl group, a cycloalkyl group, or an aryl group,
represents a halogen, and @j' represents an arbitrary number in the range 0<m◆■°≦3. An organoaluminum compound represented by 2) is used.

Specific examples include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, tri-butylaluminum, tri-n-hexylaluminum, tri-l-hexylaluminum, tri-2-methylpentylaluminum, tri- Trialkylaluminums such as n-octylaluminum and tri-n-decylaluminum, diethylaluminium monochloride, moro-propylaluminium monochloride, di-i-butylaluminum monochloride, diethylaluminium monofluoride, diethylaluminium monobromide, diethylaluminium Dialkyl aluminum monohalides such as monoiodide, dialkyl aluminum halides such as diethyl aluminum hydride, alkyl aluminum sesquiparites such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, monomers such as ethyl aluminum dichloride, dobutyl aluminum dichloride, etc. Examples include alkylaluminum cybarides, and alkoxyalkylaluminums such as monoethoxydiethylaluminum and jetoxysonoethylaluminum can also be used.

These organic aluminums can also be used in combination of two or more types.

Various electron donors are shown below to be used in producing the titanium trichloride composition (!■) used in the present invention, but (81) and (B2) are mainly ethers. It is preferable to use the other electron donor together with the ether.

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

Specific examples include diethyl ether, di-n-propyl ether, di-n-butyl ether, diisoamyl ether, di-n-pentyl ether, di-n-hexyl ether,
Diisoamyl ether, di-n-octyl ether, cytooctyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol monoethyl ether,
Ethers such as tetrahydrofuran, methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, phenol, cresol,
Alcohols or phenols such as xylenol, ethylphenol, naphthol, methyl methacrylate,
Ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl acetate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, Esters such as methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate, acetaldehyde, benzaldehyde aldehydes such as formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid, fatty acids such as maleic acid, aromatic acids such as benzoic acid, ketones such as methyl ethyl ketone, methyl isobutyl ketone, benzophenone, acetonitrile Nitrilic acid, methylamine, diethylamine, tributylamine, triethanolamine, β(N,N-dimethylamino)ethanol, pyridine, quinoline, α-picoline, 2,4,6-trimethylpyridine, N,N.

N', N'-tetramethylhexaneethylenediamine,
Amines such as aniline and dimethylaniline, formamide, hexamethylphosphoric triamide, N, N, N',
Amides of N',N-pentamethyl-N'-β-dimethylaminomethylphosphoric acid triamide, octamethylpyrophosphoramide, ureas such as N,N,N'-N'-tetramethylurea, phenyl isocyanate, Isocyanates such as toluyl isocyanate, azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxyto, dimethylphosphine, dimethylphosphine, Phosphites such as n-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, triphenyl phosphite, phosphites such as ethyl diethyl phosphinite, ethyl butyl phosphinite, phenyl diphenyl phosphinite, Examples include thioethers such as diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide and propylene sulfide, and thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol.

These electron donors can also be used in combination.
To obtain the reaction product (1), the electron donor (B2) is reacted with the solid product (! or (II-^)) (B2
) may be the same or different.

The α-olefins used in the polymerization treatment include straight chain monoolefins such as ethylene, propylene, butene-11pentene-1 and hexene-11heptene-1, and branched chain monoolefins such as 4-methyl-pentene-1. be. As these α-olefins, a mixture of two or more α-olefins can also be used.

The electron acceptor (E) used in the production of the titanium trichloride composition Hn) used in the present invention is typified by halides of elements of groups 1 to 1 of the periodic table. Specific examples include anhydrous aluminum chloride, silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride, vanadium tetrachloride, and antimony pentachloride. , these can also be used in combination.

Most preferred is titanium tetrachloride.

The following solvents are used in the present invention.

Examples of aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, n-octane, i-octane, etc. Carbon tetrachloride, chloroform , dichloroethane, trichlorethylene, tetrachlorethylene, and the like can also be used.

As aromatic compounds, aromatic hydrocarbons such as naphthalene,
and its derivatives such as alkyl 1ifJA bodies such as mesitylene, durene, ethylenebenzene, isopropylbenzene, 2-ethylnaphthalene, l-phenylnaphthalene, monochlorobenzene, chlorotoluene, chloroxylene, chloroethylenebenzene, dichlorobenzene, bromobenzene, etc. halides, etc. are shown.

The titanium trichloride composition (tn) thus obtained is combined with the organoaluminum compound (^2) and the organosilicon compound (S) having an alkoxy group or phenoxy group as a catalyst as described above, and propylene is added in accordance with a conventional method. or, more preferably, preactivated by reacting with an α-olefin. Used as a catalyst.

The organoaluminum compound (B2) has the formula (^IR'
A dialkylaluminum monohalide represented by R' Representing halogens of bromine and iodine, specific examples include diethylaluminum monochloride, di-n-propylaluminum monochloride, di-I-butylaluminum monochloride, diethylaluminum monofluoride, diethylaluminium monobromide, diethylaluminium monoidide. etc. can be mentioned.

The polymerization type of propylene polymerization using the above-mentioned catalyst is not limited, and it can be suitably carried out not only in liquid phase polymerization such as slurry polymerization and bulk polymerization but also in J gas phase polymerization. For slurry or bulk polymerization titanium trichloride compositions ('II+
) and an organoaluminum compound are sufficiently effective, but when used in gas phase polymerization, it is preferable to use a catalyst with higher activity that has been preactivated by roughly reacting with an α-olefin. When performing gas phase polymerization following polymerization or bulk polymerization, even if the catalyst initially used is the former, it must be the same as the latter because the propylene reaction has already taken place during gas phase polymerization. Excellent effects can be obtained.

Preactivation is performed using 0.1 g to 500 g of organic aluminum and 0 to 5 g of solvent to titanium trichloride composition (III) Ig.
0J2, hydrogen O~1,0OOsJZ and α-olefin 0.05g~S,000g preferably 0.05g~3
,0001g was used to react the α-olefin at 0°C to 100°C for 1 minute to 20 hours to produce a solid product (+n)Ig
0.01 to 2.0 QOg, preferably 0.05 to 2
It is desirable to react 00 g of α-olefin.

The reaction of α-olefins for preactivation can be carried out in aliphatic or aromatic hydrocarbon solvents, or in liquefied α-olefins such as liquefied propylene, liquefied butene-1, etc. without using a solvent, ethylene, propylene, etc. It is also possible to react in the gas phase. In addition, the α-olefin used for preactivation can be carried out in the presence of a pre-obtained α-olefin polymer or hydrogen. Examples include α-olefins similar to those used in the polymerization process.Also, as the organoaluminum compound, those similar to those mentioned in (^1) above can be used, but those used in (^2) are preferably used. A dialkyl aluminum monohalide is used.

After the preactivation, the solvent, organoaluminum compound, and unreacted α-olefin are removed by distillation under reduced pressure, and the dried powder can be used for polymerization, or the solid product (I
II) It can also be used in a suspended state in a solvent that does not exceed 8oJ2 per Ig, and the solvent, unreacted α-olefin, and organoaluminum compounds can be removed by filtration or decantation, or dried to form a powder. It can also be used as granules.

It is also possible to add an organoaluminum compound before polymerization.

The preactivated catalyst thus obtained can be used in slurry polymerization of propylene in a hydrocarbon solvent such as n-hexane, n-heptane, n-octane, benzene, or toluene, or in bulk polymerization in a liquefied polymer. It can be carried out by polymerization or gas phase polymerization, but in order to increase the crystallinity of the obtained polypropylene, an organosilicon compound (S) having an alkoxy group or a phenoxy group is added to a titanium trichloride composition (Ill) ( S)/(m)-1,5~1
It is necessary to add 0.0 (molar ratio). If too little (S) is added, the improvement of crystallinity is insufficient, and if too much (S) is added, the catalytic activity decreases, making it impractical.

Specific examples of the organosilicon compound (S) having an alkoxy group or phenoxy group include tetramethoxysilane,
Methyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, triphenylmethoxysilane, tetraethoxysilane, methyltriethoxy Silane, ethyltriethoxysilane, vinyltriethoxysilane, propyltriethoxysilane, allyltriethoxysilane,
Pentyltriethoxysilane, phenyltriethoxysilane, n-octyltriethoxysilane, n-octadecyltriethoxysilane, 6-driethoxysilane 2-
Norbornene, dimethyljethoxysilane, diethyljethoxysilane, diphenyljethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylethoxysilane, allyloxytrimethylsilane, tetra-n-butoxysilane, methyltriisopropoxysilane, dimethyldiiso Propoxysilane, trimethylisopropoxysilane, tetra-n-butoxysilane, methyltri-n-butoxysilane, tetra(2-ethylbutoxy)silane, methyltriphenoxysilane, dimethyldiphenoxysilane, trimethylphenoxysilane, trimethoxysilane, triethoxy Silane, triethoxychlorosilane, triisopropoxychlorosilane,
Examples include tri-n-butoxychlorosilane.

The usage ratio of the organoaluminum compound (^2) and the titanium trichloride composition (In) is (At)/(In) -0,
1 to 500 (!Ratio), preferably 1 to 100.

Incidentally, the number of moles of the titanium trichloride composition (1) essentially refers to the number of atoms in 71 g in the (■).

Polymer crystallinity that can exhibit the effects of the present invention includes the melt flow rate (VFR) of polypropylene and the absorbance ratio (IR-τ, the wave number of infrared rays! 197c*-' and 973C The absorbance ratio, Book A77/^・AS) is IR-τ≧0.020
It is characterized by satisfying the formula 3O2031o◆o, sso.

VFR is usually 0.05-200, preferably 0.1-200
The practical polymerization temperature is about 100. The polymerization temperature is usually 20 to 10
0°C, preferably 40-85°C. If the temperature is too low, the catalyst activity will be low, making it impractical; if the temperature is too high, it will be difficult to increase the isotuffity. During zero polymerization, which is carried out for about 30 minutes to 15 hours, adding an appropriate amount of hydrogen to adjust the molecular weight is the same as in conventional polymerization methods.

The highly rigid polypropylene of the present invention thus obtained can be used for various molded products by known techniques such as injection molding, vacuum forming, extrusion molding, and blow molding.

[Effects of the Invention] An effect of the present invention is that odorless, highly rigid polypropylene can be produced. As is clear from the examples shown below, the polypropylene obtained by the method of the present invention was
Compared to the high-rigidity polypropylene (Comparative Example 2) obtained by the method of the prior invention (1), the odor is significantly reduced. The rigidity has also been improved, with a bending modulus of approximately 700 kgf/cn? It's improving.

Furthermore, even if a catalyst similar to the method of the present invention is used, the prior invention (
When the molar ratio of the specific organosilicon compound to the titanium trichloride composition is less than 1.5 as in method 2) (Comparative Example 3.5), the stiffness of the polypropylene obtained using the method of the present invention is significantly inferior to.

[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) IR-τ The sample was formed into a film in a pressure molding machine at 200°C by preheating for 1 minute and applying pressure for 1 minute, then immediately cooled with water to 20°C, and then
A 0μ film was obtained. Then, the film was put into an annealing tube, and after being vacuumed, it was annealed in an oil bath at 135°C for one hour.
Cut out several small films and use each of these small films as a measurement sample at 997cm-' and 973cm-'.
-1 and the absorbance ratio (f097811.) is measured, and the average value is taken as the I to τ value. The IR measurement was carried out using a Perkin Elmer model 783 infrared spectrophotometer.

(2) MFRCf1fiy door 0-L/-t):
Compliant with JISK 6758.

(3) CY, showing polymerization activity, 1 g of titanium trichloride composition
Represents the polymer yield (g) per unit (g/g) (
4) Stiffness: 0.1% by weight each of tetrakis[methylene-3-(3°65°-di-t-butyl-4°-hydroxyphenyl)propionate comethane and calcium stearate were mixed into polypropylene powder, and The mixture was granulated using an extrusion granulator with 401 screw diameters. Next, a JIS type test piece was made from the granules using an injection molding machine at a molten resin temperature of 230°C and a mold temperature of 50°C, and the test piece was conditioned for 72 hours in a room with a humidity of 50% and a room temperature of 23°C. , was measured by the following method.

b) Flexural modulus: Based on JIS K 7023.

(Unit: kgf/cgo) Mouth) Tensile strength: Based on JIS K 7113.

(Unit: kgf/err?) C) Rockwell hardness (R scale): 720 according to JIS
Compliant with 2.

2) Heat distortion temperature (HDT): Compliant with JIS 7207.

(Unit: kgf/cnf) (5) Polymer odor After the obtained polymer was left to stand at 70° C. for 3 hours in a nitrogen atmosphere, it was evaluated by an odor sensory test.

The odor sensory test was classified by 10 experimenters into four levels from O to X, indicating the presence or absence of odor. If all 10 people judged that there was no odor (0), if 1 to 4 out of 10 judged that there was an odor (0), if 5 to 9 out of 10 judged that there was an odor (Δ), and when all 10 people judged that there was an odor (X).

Example 1 (1) Preparation of titanium trichloride composition (m) n-hexane 6
j! , diethylaluminum monochloride (DHAC)
5.0 solu, 12 moles of diisoaluminum ether at 25℃
Mix for 1 minute at
．． 4) was obtained. Titanium tetrachloride 4 was added to a reactor purged with nitrogen.
0 mol, heated to 35°C, added the entire amount of the reaction product liquid (1) dropwise over 30 minutes, kept at the same temperature for 30 minutes, raised the temperature to 75°C, and reacted for an additional hour. Cool to room temperature, remove the supernatant, and add 20j of n-hexane! Add and remove the supernatant by decantation 4 times,
1.9 kg of solid product (II) was obtained.

The entire amount of (II) was suspended in 30 liters of n-hexane, 200 g of diethylaluminum monochloride was added, and 1.0 g of propylene was added at 30°C. okg was added and reacted for 1 hour to obtain a polymerized solid product (n-A) (
After the reaction, remove the supernatant, add 30 It of n-hexane, remove by decantation, and repeat the procedure twice to obtain a solid product (II-A) that has been subjected to the above polymerization treatment. 2.5 kg to n-hexane 6
1, and added 3.5 kg of titanium tetrachloride at room temperature for about 1 minute. After reacting at 80°C for 30 minutes, further added 1.6 kg of diisoaluminum ether, and at 80°C. After the reaction was completed for 1 hour, the supernatant was removed by decantation, 40J2 of n-hexane was added, and 1
The mixture was stirred for 0 minutes, left to stand, and the supernatant liquid was removed, which was repeated five times, and then dried under reduced pressure to obtain a titanium trichloride composition (m). The titanium content in 1 g of titanium trichloride composition (m) is 1
It was 921g.

(2) Pre-activated catalyst volume: 80J! After replacing the stainless steel reactor with inclined blades with nitrogen gas, 4o1 of n-hexane, 43g1 of diethylaluminium monochloride, and 450g of the titanium trichloride composition (m) obtained in (1) were added at room temperature.
Ethylene was supplied at 0.9 Nm' over 2 hours at 0°C and reacted (2.9 Nm' of ethylene was supplied per 1 g of titanium trichloride composition).
After 0g reaction), unreacted ethylene was removed to obtain a preactivated catalyst.

(3) Internal volume after replacing propylene with polymerized nitrogen +10j! Ll with a stirrer
After charging 20 kg of MFR1, 5 polypropylene powder into a horizontal polymerization reactor of O.3, the amount of the preactivated catalyst was 1.118 g/hr in terms of titanium trichloride composition (m), and 6.4 g/hr of diethylaluminium monochloride. , and phenyltriethoxysilane 3.6. g/hr was continuously fed as catalyst. In addition, hydrogen was supplied so that the concentration in the gas phase was maintained at 1.9% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg/cs"G, and the gas phase polymerization of propylene was continuously carried out at 70°C for 120 hours. So I went.

During the polymerization period, the polymer retention level in the polymerization vessel is 50%.
Continuously add the polymer from the polymerization vessel to 10% by volume.
It was extracted at kg g7 hr. The extracted polymer was then contacted with nitrogen gas containing 0.2% by volume of propylene oxide at 95°C for 30 minutes.
The product was obtained as a powder.

Practical Example 2.3 In (3) of Example 1, the hydrogen concentration in the gas phase was set to 3', 5% by volume (Example 2), and 6.8% by volume (Example 3), and the total pressure Polypropylene was obtained in the same manner as in Example 1, except that the amount of titanium trichloride composition (m) supplied was adjusted so as to maintain the amount of titanium trichloride at 23 kg/c*'G.

Comparative Example 1 Example 1 (3) except that phenyltriethoxysilane was not supplied and the amount of titanium trichloride composition was adjusted so that the total pressure was maintained at 2G o'hg/c. Polypropylene was obtained in the same manner as in Example 1.

Comparative Example 2 The same procedure as in Example 2 was carried out except that methyl p-toluate was used instead of phenyltriethoxysilane and the molar ratio with the titanium trichloride composition (In) was 2.0. Polymerization of propylene was carried out in the same manner as in Example 2.

Comparative Example 3.4 and Example 4 In Example 2, the amount of phenyltriethoxysilane supplied was adjusted to a molar ratio of 0.5 (Comparative Example 3>, 3.o (Execution) to the titanium trichloride composition (at), respectively. Example 4)
, ts, o (Comparative Example 4) Polypropylene was obtained in the same manner as in Example 2 except for changing it so that it became .

Example 5 (1) Preparation of titanium trichloride composition 81 n-heptane, 16 moles of moro-butylaluminum monochloride, and 10 moles of moro-butyl ether were heated at 30°C.
Mix for 10 minutes and react for 20 minutes to prepare the reaction product liquid (
1) was obtained. The total amount of this reaction product liquid (r) was added to toluene 5j! maintained at 45°C. was added dropwise over 60 minutes to a solution consisting of 64 mol of titanium tetrachloride, heated to 85°C and reacted for an additional 2 hours, cooled to room temperature, the supernatant liquid was removed, and n-
A solid product (II) was obtained by adding hebutane at 30°C and removing the supernatant with decantation twice.
) 4.9 kg was obtained. The entire amount of (II) was suspended in 301 ml of n-heptane and 2.0 ml of di-n-butyl ether.
0 kg and 15 kg of titanium tetrachloride were added at room temperature for about 20 minutes, reacted at 90°C for 2 hours, and after cooling, the mixture was decanted, washed with n-hebutane, and dried to obtain a titanium trichloride composition (Ill). Ta. Titanium trichloride composition (III
) The content of titanium atoms in 1 g was 255 g.

(2) Preparation of preactivated catalyst In (2) of Example 1, the titanium trichloride composition (m)
As, the titanium trichloride composition (In) obtained in the above (1)
Pre-activation was performed in the same manner except that .

(3) Polymerization of propylene In (3) of Example 1, the total pressure was 23 kg/cm'
In order to maintain G, the preactivated catalyst obtained in (2) above was used, and allyltriethoxysilane was used instead of phenyltriethoxysilane at a ratio of 1.8 to the titanium trichloride composition (III). Polypropylene was obtained in the same manner except that it was supplied as follows.

Comparative Example 5 Polypropylene was obtained in the same manner as in Example 5, except that in (3) of Example 5, the molar ratio of allyltriethoxysilane and titanium trichloride composition (1) was set to 0.4. .

Comparative Example 6 Polypropylene was obtained by polymerizing propylene in the same manner as in Example 5 (3) except that allyltriethoxysilane was not supplied.

Example 6 n-hexane 12j! 27.0 mol of titanium tetrachloride was added to the mixture, and after cooling to 1°C, 12.51 mol of n-hexane containing 27.0 mol of diethylaluminum monochloride was added.
was added dropwise over 4 hours at 1°C. After the completion of the dropwise addition, the temperature was kept at the same temperature for 15 minutes to react, then 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 operation of removing the supernatant, adding n-hexane, and removing by decantation was repeated 5 times to obtain a solid product (11).
Of the 5.7 kg, 1.8 kg was suspended in n-hexane 4J2, and 1.6 IL of diisoaluminum ether was added thereto. This suspension was stirred at 35° C. for 1 hour and then washed 5 times with 31 portions of n-hexane to obtain a treated solid. The obtained treated solid was added to 6 Jl of a 40% by volume titanium tetrachloride solution in n-hexane.
suspended in it.

This suspension was heated to 65°C and reacted at the same temperature for 2 hours. After 6 reactions, 201 n-hexane was used at once,
After washing the obtained solid three times, it was dried under reduced pressure to obtain a titanium trichloride composition (!■).

(2) In Example 1 (2), the titanium trichloride composition (■) obtained in the above (1) was preactivated in the same manner except that the titanium trichloride composition (■) was used.

(3) In (3) of Example 1, the total pressure was 23 kg/
The molar ratio of the preactivated catalyst obtained in (2) above and the titanium trichloride composition (■■) of vinyltriethoxysilane instead of phenyltriethoxysilane was adjusted to maintain cm''G. Polypropylene was obtained in the same manner except that the amount of water was 0.

Comparative Example 7 Polypropylene was obtained in the same manner as in Example 6 except that vinyltriethoxysilane was not supplied in (3) of Example 6.

Example 7 (1) A reaction solution obtained by reacting 41 moles of n-heptane, 5.0 moles of diethylaluminium monochloride, 9.0 moles of diisoaluminum ether, and 5.0 moles of moro-butyl ether at 18°C for 30 minutes was prepared. It was added dropwise to 27.5 mol of titanium tetrachloride at 40°C for 300 minutes, and then heated to the same temperature for 1.5 mol.
After reacting for 5 hours, the temperature was raised to 65°C, reacted for 1 hour, the supernatant liquid was removed, n-hexane 201 was added and removed by decantation, and the operation was repeated 6 times to obtain a solid product (II). 1.8 kg of diethylaluminum monochloride 2θOg was suspended in n-hexane 5OIt.
of propylene at 80°C. A solid product (II-A) was obtained by adding Okg and reacting for 1 hour, followed by polymerization treatment.
After the reaction, after removing the supernatant liquid, adding 30j2 of n-hexane and removing by decantation was repeated twice to obtain a solid product (propylene reaction amount: 0.5 kg). II-A) (2,3 kg) to n-
1.8 kg of titanium tetrachloride suspended in hexane 4J2
Add 1.8 kg of 1n-butyl ether and heat at 60°C for 30 minutes.
After 0 hours of reaction, the supernatant was removed by decantation, 201 n-hexane was added, stirred for 5 minutes, left to stand, and the supernatant removed. After repeating this process three times, the pressure was reduced. was dried to obtain a titanium trichloride composition (m). The content of titanium atoms in 1 g of titanium trichloride composition (III) was 200 g.

(2) In (2) of Example 1, a preactivated catalyst was prepared in the same manner except that the titanium trichloride composition (1■) obtained in (1) above was used as the titanium trichloride composition (1■). Prepared.

(3) In (3) of Example 1, the concentration in the gas phase is 3
．． Hydrogen was added so that the concentration was 8% by volume, and the total pressure was 23kg/cm2.
In order to maintain G, the preactivated catalyst obtained in (2) above was also replaced with phenyltriethoxysilane, and the molar ratio of triethoxychlorosilane to the titanium trichloride composition (Ill) was 2.2. Similarly, propylene was further polymerized in the same manner except that di-n-propylaluminum monochloride was fed to the polymerization vessel at a rate of 1.1 g/hr in addition to diethylaluminium monochloride to obtain polypropylene.

Comparative Example 8 Polypropylene was obtained in the same manner as in Example 5 except that triethoxychlorosilane was not supplied in (3) of Example 7.

[Brief explanation of the drawing]

FIG. 1 is a flow sheet showing the manufacturing process of the method of the present invention. that's all

Claims (5)

[Claims] (1) [1] Organoaluminum compound (A_1) or organoaluminum compound (A_1) and electron donor (B
The solid product (II) obtained by reacting the reaction product (I) with titanium tetrachloride with _1) is treated with an α-olefin or without polymerization, and is further treated with an electron donor (
Titanium trichloride composition (III) obtained by reacting B_2) with an electron acceptor, [2] organoaluminum compound (A_2) and [3]
An organosilicon compound (S) having an alkoxy group or a phenoxy group is combined, and the molar ratio (S)/(III) of the organosilicon compound (S) and the titanium trichloride composition (III) is 1.5.
1. A method for producing highly rigid polypropylene, which comprises polymerizing propylene in the presence of a catalyst having a molecular weight of 10.0 to 10.0. (2) The manufacturing method according to claim 1, wherein the organoaluminum compound (A_2) is a dialkyl aluminum monohalide. (3) Claim 1: The combination of titanium trichloride composition (III) and organoaluminum compound (A_2) is preactivated by reacting with an α-olefin.
The manufacturing method described in section. (4) The manufacturing method according to claim 1, in which propylene is subjected to gas phase polymerization. (5) Melt flow rate (MFR) of polypropylene
and the absorbance ratio (IR-γ,
Infrared wave numbers 997cm^-^1 and 973cm^-^1
absorbance ratio, A_9_9_7/A_9_7_3)
and IR-τ≧0.0203logMFR+0.950
The manufacturing method according to claim 1, which satisfies the following formula.