JPH02238005A - Production of polypropylene having high rigidity - Google Patents

Abstract

PURPOSE:To produce the subject polymer having high transparency by using a catalyst containing an organic Al compound, an organic Si compound and a TiCl3 composition produced by reacting an organic Al compound with TiCl4, an electron donor, an electron acceptor, etc., and preliminarily polymerizing a branched olefin to the reaction product. CONSTITUTION:The objective polymer is produced by polymerizing propylene using a catalyst produced by polymerizing (A) a titanium trichloride composition produced by reacting titanium tetrachloride to an organic A1 compound or a reaction product of the Al compound and an electron donor and reacting the resultant solid substance with an electron donor and an electron acceptor with (B) 0.001-100g (based on 1g of the component A) of a branched olefin of formula (R<1> is Si, 1-3C hydrocarbon group, etc.; R<2> to R<4> are H, 1-6C hydrocarbon group, etc.) and compounding the obtained preliminarily activated catalyst component with (C) an organic Al compound and (D) an organic Si compound having Si-O-C bond and/or mercapto group at molar ratios (D/A) of 0.1-10.0 and (C/A) of 0.1-200.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial 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 inventors have previously developed a catalyst made by combining a titanium trichloride composition obtained by a specific method with an organoaluminum compound and a specific organosilicon compound in specific proportions. A method for producing highly rigid polypropylene using
No. 1, Japanese Patent Application No. t3-136821, hereinafter referred to as the invention of the earlier application 1), has proposed a method of the invention of the earlier application, which can achieve extremely high rigidity without adding any special additives. It has now become possible to produce polypropylene that can be used to form molded products. 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 being held. 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 specific branched olefins was prepolymerized to this composition, and a specific branched olefin was preactivated. Polypropylene obtained by polymerizing propylene using a combination of specific amounts of catalysts not only has significantly superior transparency but also greater rigidity than polypropylene obtained by the method of the prior invention. We have found that this can be improved, and have come up with the present invention. 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 objective is to provide highly rigid polypropylene with outstanding transparency. [A thousand steps to solve the problem] The present invention has the following configuration. (1) [1] Titanium trichloride composition (II+) and ■
organoaluminum compound (Al), and ■51-0-
In a method for producing polypropylene by polymerizing propylene using a catalyst consisting of an organosilicon compound having a C bond and/or a mercapto group, an organoaluminum compound (A
2) Alternatively, a solid product (1!) obtained by reacting titanium tetrachloride with the reaction product (1) of an organoaluminum compound (A2) and an electron donor (B1) is polymerized with an α-olefin. Using the titanium trichloride composition (II1) obtained by further reacting the electron donor (B2) and the electron acceptor without any treatment or polymerization treatment, the titanium trichloride composition (II+) and Organoaluminum compound (A1
) is combined with the following formula, (wherein R1 represents a hydrocarbon group having 1 to 3 carbon atoms which may contain silicon or silicon, R2, R
3. R4 represents a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and any one of R2, R3, and R4 may be hydrogen in the order of branched olefin shown in 1) per Ig of the titanium trichloride composition (+11), [
l. 001g-100gii combination reaction, an additional organoaluminum compound (Al) if necessary, and an organosilicon compound (S) having a Si-0-f bond and/or a mercapto group. molar ratio (S)/(+II)- of the organosilicon compound (S) having the Si-Q-C bond and/or mercapto group and the titanium trichloride composition (m).
0.1 to 10.0, and the organic aluminum compound (
A1] and the titanium trichloride composition (II+) in a molar ratio (A+)/(n+) of 0.1 to 200.

(2) The production method according to the above item 1, in which the organoaluminum compound (A1) is a dialkylaluminum monohalide, (3) the organoaluminum compound (A2) has the general formula ^l R'pR', +Xi - fp+pri (in the formula, R
5, R6 represents a hydrocarbon group such as an alkyl group, cycloalkyl group, or aryl group, or an alkoxy group; X represents a halogen; and p. 1. The method according to item 1 above, wherein p' represents an arbitrary number in the range 0<p◆p゛≦3.

(4) Melt flow rate (MFR) of polypropylene
The relationship between and the absorbance ratio determined by infrared absorption spectroscopy (absorbance ratio at infrared wave numbers 997c+a-' and 973cm-' in IR-, 811117/A973) is!
The manufacturing method according to item 1 above, which satisfies the formula: R-τ≧0.0203 log MFR+0.950.

The configuration of the present invention will be explained in detail below. As the titanium trichloride composition (II+) 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 (A2) and the electron donor (B1) to obtain the reaction product (!) is carried out in a solvent (D) at -20°C to 200°C, preferably at -10°C to
Perform at 100°C for 30 seconds to 5 hours - (A2), (a
ll. There is no restriction on the order of addition of ([1)], and the ratio of the amount used is 0.1 mol of electron donor to 1 mol of organoaluminium.
~8 mol, preferably 1-4 mol, solvent 0.5-51,
Preferably, 0.5 to 2 ft is appropriate. Aliphatic hydrocarbons are preferred as solvents. Thus the reaction product (1)
is obtained. The reaction product (1) can be subjected to the next reaction in a liquid state (sometimes referred to as a reaction product liquid (1)) without being separated.

Next, the reaction between the reaction product (■) or the organoaluminum compound (A2) and titanium tetrachloride (C) is
00°C, preferably 10 to 90°C for 5 minutes to 8 hours. Although it is preferable not to use a solvent, aliphatic or aromatic hydrocarbons can be used. (A2) or (
1). (C) and the solvent may be mixed in any order,
Preferably, the mixing of the entire amount is completed within 5 hours. The amount of each used in the reaction is 0 to 3,000 mfl of the solvent per 1 mole of titanium tetrachloride, and the organoaluminum compound (A2) or reaction product (1) is Number of A1 atoms and TI in titanium tetrachloride
The ratio of the number of atoms (AI/Ti) is 0.05 to 1O, preferably 0.06 to 0.2.

After the completion of the reaction, the liquid portion is separated and removed by filtration or decantation, and after repeated washing with a solvent, the obtained solid product (I1) is sent to the next step while suspended in the solvent. It may be used, or it may be further dried and taken out as a solid substance for use.

Further, the solid product (II) obtained by reacting this organoaluminum compound (82) or reaction product (1) 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. In this polymerization process, the solid product (!!) becomes coated with the polymer. As a method for polymerizing with an α-olefin, (1) an α-olefin is added in any step of the reaction between the organoaluminum compound (A2) or the reaction product (1) and titanium tetrachloride to form a solid product ( (2) After the reaction between the organoaluminum compound (A2) or the reaction product (!) and titanium tetrachloride, an α-olefin is added and the solid product (I1) is polymerized. (3) After the reaction between the organoaluminum compound (A2) or the reaction product (!) and titanium tetrachloride, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product ( There is a method in which I+) is suspended in a solvent, an organoaluminum compound and an α-olefin are further added, and polymerization is carried out. Organoaluminum compound (A2)
Or when α-olefin is added at any stage of the reaction between the reaction product (1) and titanium tetrachloride, and after the reaction between the organoaluminum compound (A2) or the reaction product (1) and titanium tetrachloride is completed. , when adding an α-olefin, the reaction temperature is 30 to 90°C for 5 minutes to 10 hours, α-
The alpha-olefin is passed under atmospheric pressure or added to a pressure of 10 kg/cm"G or less. The amount of alpha-olefin to be added is 100 g per 100 g of the solid product (II).
~5,005g using α-refin of OOOg
It is desirable to polymerize ~t,ooog. Polymerization treatment with α-olefin is combined with organoaluminum compound (A2
) or after the reaction between the reaction product (1) and titanium tetrachloride is completed, the liquid portion is separated and removed by filtration or decantation, and the obtained solid product (!1) is suspended in a solvent. If carried out, the solid product (I!) 1
00g was added with solvent 100+af~2, QOOsj2, organoaluminum compound 5g~SOOg, and the reaction temperature was 30
α-olefin at ~90 °C for 5 min ~ lO h
llkg/crn”G 10~5, add OOOg,
It is desirable to combine 0.05 to t,ooogl. The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound may be the same as or different from that used in (A2). After the reaction is complete, the liquid portion is separated and removed by filtration or decantation, and the resulting polymerized solid product (
The solid product (hereinafter sometimes referred to as (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 (1!) or (II-A) is
Next, add an electron donor (B2) and an electron acceptor (F) to this.
react with. Although this reaction can be carried out without using a solvent, better results are obtained using an aliphatic hydrocarbon. The amount used is the solid product (II) or
For 100g of (II-A), (82) 0.1g~
1,000 g, preferably 0.5 g to 200 g, (F
) 0.1g to 1,000g, preferably 0.2g to 5
00g, solvent O~3. OOOmJZ. Preferably 1
00 to 1. OOOmu. As for the reaction method,
■Method of simultaneously reacting an electron donor (B2) and an electron acceptor (F) with a solid product (I!) or (n-A), ■Method of reacting (!!) or (II-A) with (II-A)
Method of reacting (B2) after reacting F), ■(
1! ) or (U-A) is reacted with (B2), and then (F) is reacted; ■ (B2) and (FL are reacted, and then (II) or (II-A) is reacted. There are ways to do this, but either method is fine.

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 (!-A) and (B2) at 0℃~
After reacting at 50°C for 1 minute to 3 hours, react with (F) under the same conditions as in (2) above. In addition, in method (■), (B2) and (F) are heated for 30 minutes to 2
After reacting for an hour, cool to 40°C or less, add (■!) or (u-A), and react under the same conditions as in (■) and (■) above. Solid product (II) or (I
After the reaction of I-A), (Bz), and (F) is 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 (II+) used in the present invention. ) is obtained. Titanium trichloride composition obtained as above (II+
) and an organoaluminum compound (AI), and this compound is combined with the following formula: R
3. R4 represents a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and any one of R2, R', and R4 may be hydrogen. Branched olefin represented by 1) (hereinafter sometimes abbreviated as branched olefins 1) per Ig of the titanium trichloride composition (III),
0.001g - A preactivated catalyst component obtained by a long polymerization reaction, and optionally an additional organoaluminum compound (8n, and an organosilicon compound (S) having an Sl-0-C bond and/or a mercapto group). (hereinafter sometimes abbreviated as organosilicon compound (S) 1) to form the catalyst used in the present invention.Pre-activation is carried out by combining organosilicon compound (S) with organosilicon compound (S). Compound (A+) 0.05g to 500g.
'111 medium 0 ~ 50j! , hydrogen 0 ~ 1, OOOm
u, and branch olefins 0. Olg-1.0
0 (using Ig.

The polymerization reaction temperature was 0°C to 100°C for 1 minute to 20 hours to react the branch olefins, and the titanium trichloride composition (+11
)0.001g to 100g per Ig, preferably 0.0
It is desirable to polymerize 1 g to 100 g of branched olefins. ! ! If the reaction amount is less than 0.001 g, the effect of improving transparency and rigidity will be insufficient, and if it exceeds 100 g, the improvement in effect will not be significant and this will be economically disadvantageous. Preactivation can also be carried out in a hydrocarbon solvent such as n-bentane, rhohexane, n-hebutane, toluene, etc. Hydrogen may be present in the preactivation. It is also possible to add an organosilicon compound (S) in advance during preactivation.

After the preactivation reaction is completed, the catalyst obtained by adding a predetermined amount of the organosilicon compound (S) to the preactivated catalyst component slurry can be used as it is for the polymerization of propylene, or the coexisting solvent and unused catalyst can be used as is. Reaction branch olefins,
and the organoaluminum compound (A1) are separately removed, a solvent is added to the dried powder or the powder and the powder is suspended, and an additional organoaluminum compound (A2) and the organosilicon compound ( S) as a catalyst and subjecting it to polymerization of propylene, the coexisting solvent and unreacted olefins are removed by vacuum distillation or an inert gas stream, etc., and powder and granules are prepared. Alternatively, a solvent is added to the powder to form a suspension, and if necessary, an organoaluminum compound (A
It is also possible to add 1) and further combine it with an organosilicon compound (S) to form a catalyst and use it for propylene polymerization. During propylene polymerization, N of the titanium trichloride composition (II+) and the organoaluminum compound (A+) including the additional organoaluminum compound (A2) is
Regarding the amount of A and the amount of organosilicon compound <S> used, the molar ratio (S)/(o summer) of the organosilicon compound (S) and the titanium trichloride composition (II+) is 01 to 10.
, 0, and the solubility ratio (All/( I
I+) is used within a range of 0.1 to 200.

If the addition of the organosilicon compound (S) is too small, the improvement in crystallinity will be insufficient and high rigidity will not be achieved, and if the addition is too large, the polymerization activity will decrease, making it impractical.

The number of moles of the titanium trichloride composition (II+) refers to the number of T1 gram atoms substantially contained in (II+). The organoaluminum compound (A) used in the production of the titanium trichloride composition (II+) used in the present invention has the general formula ^IR'JZ'X3-(pllpll (wherein RII.R6 is an alkyl group, An organoaluminum compound represented by 1) in which a hydrocarbon group such as an alkyl group or an aryl group or an alkoxy group, X represents a halogen, and p.p' represents an arbitrary number of O<p◆p゜≦3 is used. Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, tri-butylaluminum, tri-n-hexylaluminum, tri-hexylaluminum, tri-2-methylbenzene. trialkylaluminum such as tri-n-octylaluminium, tri-n-decylaluminum, diethylaluminum monochlorite, di-n-probylaluminium monochloride, di-i-butylaluminum monochloride, diethylaluminium monofluoride, diethyl Aluminum monobromide, dialkyl aluminum monohalides such as diethyl aluminum sonoiodide, dialkyl aluminum hydrides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, l-butyl Examples include monoalkylaluminum dihalides such as aluminum dichloride, and alkoxyalkylaluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can also be used.Two or more types of these organoaluminum compounds can be used. It is also possible to use a mixture of (at).(B2
), it is preferable to mainly use ethers and share the other electron donors with ethers. Those used as electron donors are organic compounds having any of oxygen, nitrogen, sulfur, and phosphorus atoms, i.e., polymers,
Alcohols, esters, aldehydes, fatty acids,
These include ketones, nitriles, amines, amides, ureas or thioureas, isocyanates, azo compounds, phosphines, phosphites, phosphinites, hydrogen sulfide or thioethers, thioalcohols, etc. Specific examples include diethyl ether, di-n-propyl ether, di-n-butyl ether, diisoamyl ether, di-n-bentyl ether, di-n-hexyl ether, di-I
-hexyl ether, di-n-octyl ether, di-I-
Octyl ether, di-n-dodecyl ether, diphenyl ether, ethylene glycol sonoethyl ether,
Ethers such as tetrahydrofuran, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, phenol, cresol,
Alcohols such as xylenol, ethylphenol, naphthol, or phenol neck, methyl methacrylate, ethyl acetate, butyl formate, amyl acetate, vinyl butyrate,
Vinyl acetate, ethyl benzoate, brobyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, probyl anisate , esters such as ethyl cinnamate, methyl naphthoate, ethyl naphthoate, brobyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, and ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, formic acid, acetic acid, and bropyryl naphthoate. Fatty acids such as citric acid, butyric acid, oxalic acid, succinic acid, acrylic acid, maleic acid, aromatic acids such as benzoic acid, ketones such as methyl ethyl ketone, methyl isobutyl ketone, benzophenone, nitrile acids such as acetonitrile, methylamine, Diethylamine, tributylamine, triethanolamine, β(N,N-dimethylamino)ethanol, pyridine, quinoline, α-vicolin, 2,4.8
-trimethylpyridine, N,N,N',N'-tetramethylethylenediamine, aniline, dimethylaniline and other amines, formamide, hexamethylphosphoric acid triamide, N,NN',N',N"-bentamethyl-N゜- β-dimethylaminomethyl phosphoric acid triamide,
Amides such as octamethyl biphosphoramide, N. N
, ureas such as N'-N'-tetramethylurea, isocyanates such as phenyl isocyanate and tolyl isocyanate, azo compounds such as azobenzene, ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-butylphosphine, Phosphines such as triphenylphosphine and triphenylphosphine oxide; phosphites such as dimethyl phosphite, di-n-octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, and triphenyl phosphite; ethyl jetyl phosphite; Phosphinites such as night, ethyl butyl phosphinite, phenyl diphenyl phosphinite, thioethers such as diethyl thioether, diphenyl thioether, methyl phenyl thioether, ethylene sulfide, propylene sulfide, ethyl thio alcohol, n-propyl thio alcohol and thioalcohols such as thiophenol. These electron donors can also be used in combination. Electron donor (B2) to obtain reaction product (1), solid product (II-A)
(B2) may be the same or different.

The electron acceptor (F) used in the present invention is Il1 of the periodic table.
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-bentane, n-hexane, rhohebutane, n-octane, i-octane, etc. In addition, instead of or together with aliphatic hydrocarbons, carbon tetrachloride,
Chloroform, dichloroethane, trichlorethylene,
Hydrogen halides such as tetrachloroethylene can also be used.

As aromatic compounds, aromatic hydrocarbons such as naphthalene,
and its bending conductors such as mesitylene, durene, ethylbenzene, isobrobylbenzene, 2-ethylnaphthalene, l-phenylnaphthalene and other alkyl substituted products, monochlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, dichlorobenzene, bromobenzene, etc. halides, etc. are shown.

The α-olefins used in the polymerization process include ethylene, propylene, straight monoolefins such as butene-11pentene-11hexene-1, hebutene-1, 4-methyl-bentene-1, 2-methyl-bentene-1, etc. Branched monoolefins, etc. are used. These α-olefins can also be used in combination of two or more α-olefins. The branched olefins used for preactivation have the following formula: (wherein R' represents a hydrocarbon group having 1 to 3 carbon atoms which may contain silicon, or
2, R3, and R4 represent a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and any one of R2, R3, and B4 may be hydrogen. They are olefins. Specific examples include 3-position branched olefins such as 3-methylbutene-1, 3-methylbentene-1 and 3-ethylbentene-1, 4-ethylhexene-1, 4.4-dimethylbentene-1, 4. 4-position branched olefin such as 4-dimethylhexene-1, vinyltrimethylsilane, vinyltriethylsilane, vinyltri-n-butylsilane, vinyldimethylcyclohexylsilane, vinyldimethylphenylsilane, allyltrimethylsilane, allyldimethylcyclohexylsilane, Allyltriethylsilane, allyltri-n-pro and lucilane, 3
Examples include alkenylsilanes such as -butenyltrimethylsilane and 3-butenyltriethylsilane, and diallysilanes such as dimethyldiallylsilane, ethylmethyldiallylsilane and diethyldiallylsilane. One or more of these branch olefins are used. The organoaluminum compound (A1) combined with the titanium trichloride composition (II!) and the organoaluminum compound (A1) used as necessary have the general formula ^
Dialkyl aluminum monohalides represented by IR'R'X are preferred. In the formula, R7, na represents a hydrocarbon group such as an alkyl group, an aryl group, an alkaryl group, a cycloalkyl group, or an alkoxy group, and X represents a halogen, and specific examples include diethylaluminum monochloride, Di-n-propylaluminum monochloride, di-i-butylaluminum monochloride, di-n-
Examples include butylaluminum monochloride, diethylaluminum monoiodide, diethylaluminum monobromide, etc. Specific examples that can be used as the organosilicon compound (S) having a St-0-C bond and/or mercapto group, which is another component constituting the catalyst, include methyltrimethoxysilane, vinyltrimethoxysilane, allyl trimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, triphenylmethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, Probyltriethoxysilane, allyltriethoxysilane, benzyltriethoxysilane, phenyltriethoxysilane, n-octyltriethoxysilane, n-octadecyltriethoxysilane, 6-triethoxysilyl-2-norbornene, dimethyldiethoxysilane , diethyljethoxysilane, diphenyldiethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylethoxysilane, allyloxytrimethylsilane, methyltri-proboxysilane, dimethyldi-1-propoxysilane, trimethyltobroboxysilane, tetra-n-butoxy Silane, methyltri-n-butoxysilane, tetra(2-ethylbutoxy)silane, methyltosophenoxysilane, dimethyldiphenoxysilane, trimethylphenoxysilane, trimethoxysilane, triethoxysilane, triethoxychlorosilane, tril-propoxysilane , tri-n-butoxysilane,
Tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, methyldiacetoxysilane, diacetoxymethylvinylsilane, dimethyldiacetoxysilane, methylphenyldiacetoxysilane, diphenyldiacetoxysilane, trimethylacetoxysilane, triethyl Organosilicon compounds having St-0-C bonds such as acetoxysilane, phenyldimethylacetoxysilane, triphenylacetoxysilane, bis(trimethylsilyl)adipate, trimethylsilylbenzoate, triethylsilylbenzoate, mercaptomethyltrimethylsilane, 2-mercaptoethyl Trimethylsilane, 3-mercaptobutyltrimethylsilane, 4-mercapto101butyltrimethylsilane, mercaptomethyltriethylsilane, 2-mercaptoethyltriethylsilane, 3
-Mercaptobutyltriethylsilane, 1-mercaptoethyltrimethylsilane, 3-mercaptopyrudimethylphenylsilane, 3-mercaptobutylmethylphenylsilane, 4-mercaptobutyldiethylphenylsilane, 3-mercaptobutyldimethyldiphenylsilane Organosilicon compounds having a mercapto group such as mercaptomethyltrimethoxysilane, mercaptomethyldimethylmethoxymethylsilane, mercaptomethyldimethoxymethylsilane, mercaptomethyltriethoxysilane, mercaptomethyldiethoxymethylsilane, mercaptomethyldimethylethoxysilane, 2-
Mercaptoethyltrimethoxysilane, 3-mercaptobutyltrimethoxysilane, dimethoxy-3-mercaptobutylmethylsilane, 3-mercaptobutyltriethoxysilane, diethoxy-3-mercaptobutylmethylsilane, mercaptomethyldimethyl-2- Organosilicon compounds having an SI-0-C bond and a mercapto group such as phenylethoxysilane, 2-mercaptoethoxytrimethylsilane, 3-mercaptobropoxytrimethylsilane, 3-aminobrobyltrimethoxysilane, 3-aminobrobyltrimethylsilane, etc. Ethoxysilane, 3-aminobropyldiethoxymethylsilane, 3-aminobropyldimethylethoxysilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 2-aminoethylaminomethyltrimethoxysilane, 3-(2- Si-0-C bonds and amino Examples include organosilicon compounds having groups.

The thus obtained catalyst used in the present invention is used for the polymerization of brohylene. The polymerization method for propylene is to convert propylene into 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 melt flow rate fMF of polypropylene is
R) and the absorbance ratio (I
In R-; infrared wave number 997c+n-' and 973cm
The relationship between the absorbance ratio at −' and A OQ7/A 973) is ≧0.0203 log MFR+0.950 at IR1
It is characterized by satisfying the formula.

VFR is usually 0.05-200, preferably Ol-10
A value of about 0 is practical. Polymerization temperature is usually 20-100°C, preferably 40-85°C.
It is ℃. If the temperature is too low, the polymerization activity will be low and it is not practical, and if the temperature is high, it will be difficult to increase crystallinity.The polymerization pressure is normal pressure ~ 50kg/c+s
It is usually carried out for about 30 minutes to 15 hours on 2G. During polymerization, steps such as adding an appropriate amount of hydrogen to adjust the molecular weight are 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. [For use] The highly rigid polypropylene obtained by the method of the present invention promotes the crystallization of polypropylene by exhibiting a nucleation effect of the highly stereoregular branched olefin am coalescence.
In addition to improving the transparency and crystallinity of the entire polypropylene, the branched olefin polymer introduced by the method of the present invention is a stereoregular high molecular weight polymer, and as a result, it has a high molecular weight on the surface. It does not bleed. [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. (+) CY: Indicates the II synthesis activity and represents the polymer yield (g) per Ig of titanium trichloride composition (III).
(-jIL position: g/gl(2)
MFR: Melt flow index ASTMD
-1238 According to (L). (Unit: g/lo
minute) (311R-τ; The sample was molded into a film using a pressure molding machine at Zoo°C by preheating for 1 minute and applying pressure for 1 minute, and then immediately cooled with water to 20°C to obtain a film of about 40μ. The film is placed in an annealing tube, and after being vacuumed, annealing is performed in an oil bath at 135°C for one hour. Three small films are cut out from the annealed film, and each of these small films is used as a measurement sample. ,997
cm-' and 973cl', (A997
/A973) and take the average value as the IR-τ value. This IR measurement was performed using a PerkinElmer 783 model infrared spectrophotometer. (4) Internal haze: This is the haze inside the film excluding the influence of the surface.
Polypropylene was made into a 150μ thick film under the conditions of 00κg/CII12G, and after coating both sides of the film with liquid paraffin, the haze was measured in accordance with JIS K 7105 (JIL level 2%) (5) Crystallization Temperature: 1 using a differential scanning calorimeter
The temperature was measured at a falling rate of 0°C/min. CJIL rank: °C) (6) Rigidity: Tetrakis[methylene-3-(3゜.5゜-G-t-
Butyl-4゜hydroxyphenyl)propionate]
0.11 parts by weight of methane and 0.1 parts by weight of calcium stearate were mixed, and the mixture was
It was granulated using a 0 mm 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 bead 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 following method. (A) Flexural modulus: Based on JIS K7203 CJE rank: kgf/crn'') (Ex) Tensile strength: Based on JIS K 7113 (JI
L position: kgf/am') (c) Rockwell hardness (R scale): JIS κ72
Compliant with 02 (2) Heat distortion temperature (HDT): JIS K 7207
Example 1 (+) Preparation of titanium trichloride composition (III) n-hexane 6L1 diethylaluminum monochloride (D
5.0 mol of EAC1 and 12 mol of diisoamyl ether were mixed at 25°C for 1 minute and reacted at the same temperature for 5 minutes to obtain reaction product liquid (I) (molar ratio of diisoamyl ether/DEAC 2.4). ．． 40 moles of titanium tetrachloride was placed in a reactor flooded with nitrogen, heated to 35°C, and the entire amount of the reaction product liquid (!) was added dropwise over 30 minutes, kept at the same temperature for 30 minutes, and heated to 35°C. The temperature was raised to ℃ and allowed to react for another 1 hour, cooled to room temperature, the supernatant liquid was removed, and n-hexane 20J2
The operation of adding and removing the supernatant liquid by decantation was repeated four times to obtain 1.9 kg of solid product (II). The entire amount of (I+) was suspended in 3OfL of n-hexane, and 20G of diethylaluminum monochloride was added.
g of propylene at 30°C. Add 0kg and 1
A solid product (n-
A) was obtained (propylene reaction amount: 0.8 kg). After the reaction, the supernatant liquid was removed, and the operation of adding n-hexane 3i and removing by decantation was repeated twice to produce a solid product subjected to the above polymerization treatment. Item (II-A) 2.5k
titanium tetrachloride by suspending g in n-hexane 61
．． After adding 5 kg at room temperature for about 1 minute and reacting at 80°C for 30 minutes, 1.6 kg of diisoamyl ether was added.
was added and reacted at 80°C for 1 hour. After the reaction, the supernatant was removed with decantation, 4i of n-hexane was added, stirred for 10 minutes, allowed to stand, and the supernatant removed five times, then dried under reduced pressure and trichlorinated. A titanium composition (II+) was obtained. Titanium trichloride composition (III)
The titanium content in Ig was 192 mg.

(2) Preparation of preactivated catalyst components After purging a stainless steel reactor with inclined blades having an internal volume aOft with nitrogen gas, 401 g of n-hexane, 20 Gg of diethyl aluminum monochloride. After adding 450 g of the titanium trichloride composition (II+) obtained in (t) at room temperature, the temperature inside the reactor was raised to 40°C, 1.3 κg of allyltrimethylsilane was added, and the reaction was carried out at 40°C for 2 hours (
Allyltrimethylsilane I.g per Ig of titanium trichloride composition (III). Og reaction). After the reaction was completed, unreacted allyltrimethylsilane, solvent, etc. were removed by filtration, washed with n-hexane, and dried to obtain a preactivated catalyst component in the form of powder.

(3) After replacing the stainless steel reactor with a stirrer with an internal volume of 5,001 liters of propylene polymerized with nitrogen gas, the mixture was heated with 200 J of n-hexane at room temperature.
2, 50g of diethylaluminum monochloride, (
The preactivated catalyst component obtained in 2) was mixed with a titanium trichloride composition (
t5g as Il1), 33g of 3-aminobrobyltriethoxysilane, and 150Nj2 of hydrogen.
added. Subsequently, the polymerization temperature was 70°C, and the propylene partial pressure was 10k.
Polymerization of propylene was carried out at g/cm'G for 3 hours. After the reaction was completed, methanol 1OJ2 was supplied and the mixture was heated at 70°C for 3
After treatment for 0 minutes, unreacted propylene and unreacted hydrogen were discharged. Furthermore, 100 g of a 20% by weight aqueous sodium hydroxide solution was added, and the mixture was treated at 70°C for 20 minutes. Subsequently, 100 ft of pure water was added, stirred for 10 minutes, and the aqueous layer was extracted twice. The polymer slurry was extracted, filtered, and dried to obtain a polymer. The obtained polymer contained lumps, so it was crushed by a pulverizer.
The entire amount of the polymer was powdered to obtain 55.5 J of polypropylene with an MF8 of 1.8. Comparative Example 1 In (3) of Example 1, the titanium trichloride composition obtained in (+) of Example 1 was used instead of the Yuwei activation catalyst component (
Polypropylene was obtained in the same manner except that ISg was used for m). Example 2.3 Polypropylene was obtained in the same manner as in Example 1 except that in (3) of Example 1, the hydrogen charge was changed to 230°C (Example 2) and 430J2 (Example 3). Comparative Examples 2 and 3 Polypropylene was obtained in the same manner as in Comparative Example 1 except that in (3) of Example 1, the amount of hydrogen charged was changed to 220° C. (Comparative Example 2) and 39 oz (Comparative Example 3).

Comparative Example 4 A preactivated catalyst component was obtained in the same manner as in (2) of Example 1 except that 560 g of 5-propylene was used instead of allyltrimethylsilane, and then the same procedure as in (2) of Example 1 was carried out.
Propylene was polymerized in the same manner as in 3) to obtain polypropylene. Comparative Example 6 and Example 4.5 In (2) of Example 1, dimethyldiallylsilane was used instead of allyltrimethylsilane, and the amounts used were changed to 0.4 g, 160 g, and 4.8 Kg, respectively. Example 1 except that the activation reaction was carried out and 29 g of phenyltriethoxysilane was used instead of 3-aminobrobyltriethoxysilane in (3).
Polypropylene was obtained in the same manner. Comparative Example 5 In (3) of Comparative Example 1, the catalyst component 3-aminobutyl triethoxysilane was not used, the amount of titanium trichloride composition (II+) was log, and the amount of diethylaluminum monochloride was 33.3g
Polypropylene was obtained in the same manner except for the following.

Comparative Examples 7 to 9 and Example 6.7 In (2) of Example 1, 0.7 kg of 3-methylbutene-1 was used instead of allyltrimethylsilane, and in (3), 3-aminobrobyl trimethylsilane was used instead of allyltrimethylsilane. Titanium trichloride composition of dimethoxy-3-mercaptobutylmethylsilane (II
Polypropylene was obtained in the same manner as in Example 1, except that the molar ratio to (+) was changed as shown in the table. However, in Comparative Example 7.8, 10 g of the preactivated catalyst component as a titanium trichloride catalyst component and 33.3 g of diethylaluminium monochloride were used during propylene polymerization in (3). Example 8 (1) Preparation of titanium trichloride composition (II1) 8 ft of rhobutane, 16 mol of di-n-butylaluminum monochloride, and 10 mol of di-n-butyl ether were mixed at 30°C for 10 minutes, and reacted for 20 minutes. The reaction product solution (1
) was obtained. The entire amount of this reaction product liquid (!) was added dropwise over 60 minutes to a solution consisting of 5β toluene and 64 moles of titanium tetrachloride kept at 45°C, then the temperature was raised to 85°C and the reaction was continued for an additional 2 hours. A solid product (I+) was obtained by cooling to room temperature, removing the supernatant, adding n-hebutane 301, and removing the supernatant by decantation.
I got 4.9kg. The entire amount of this (I1) was suspended in 301 n-hebutane, and 2.0 kg of dibutyl ether was added.
and 15 kg of titanium tetrachloride were added at room temperature for about 20 minutes.
React at 90°C for 2 hours, and after cooling, decantation
- After hebutane washing and drying, the titanium trichloride composition (
II1) was obtained. Titanium trichloride composition (■■) Ig
The content of titanium atoms therein was 255 mg.

(2) Preparation of preactivated catalyst component In (2) of Example 1, titanium trichloride composition (I
I1) was the titanium trichloride composition obtained in (1) above (
A preactivated catalyst component was obtained in the same manner as in Example 1 (2) except that 4SOg (II+) was used and 0.6 kg of 3-methylbentene-1 was used in place of allyltrimethylsilane.

(3) Polymerization of propylene In (3) of Example 1, 27 g (15 g as titanium trichloride composition (II+)) of the pre-activated catalyst component obtained in (2) above was used as the pre-activated catalyst component,
In addition, propylene was polymerized in the same manner as in Example 1 (3) except that 29 g of allyltriethoxysilane was used instead of 3-aminobutyltriethoxysilane to obtain polypropylene. Comparative Example IO In Example 8 (3), the titanium trichloride composition obtained in Example 8 (1) was used instead of the preactivated catalyst component (
Polypropylene was obtained in the same manner except that 15 g of II+) was used. Example 9 (1) Preparation of titanium trichloride composition (II+) 27.0 mol of titanium tetrachloride was added to 171 n-hexane, and the mixture was heated at 1°C.
After cooling to 27. 12.5 molar portions of n-hexane containing θ moles were added dropwise at 1° C. over 4 hours. After the dropwise addition was completed, the temperature was kept at the same temperature for 1 s to react, the temperature was raised to 65°C over 1 hour, and the reaction was continued at the same temperature for another 1 hour. Next, remove the supernatant, and
The operation of adding 10 ft of hexane and removing by decantation was repeated 5 times to obtain a solid product (II) 5
．． Of the 7 kg, 1.8 kg was suspended in 1 liter of 1-hexane, and 1.61 kg of diisoamyl ether was added thereto. This suspension was stirred at 35° C. for 1 hour and then washed five times with 3 liters of n-hexane to obtain a treated solid. The obtained treated solid was suspended in 6 L of a solution of 40% by volume of titanium tetrachloride in n-hexane. This suspension was heated to 65°C and reacted at the same temperature for 2 hours. After the reaction is complete, add 20J of n-hexane at a time.
After washing the obtained solid three times using No. 2 and drying it under reduced pressure, a titanium trichloride composition (II+) was obtained. (
2) Preparation of preactivated catalyst component In (2) of Example 1, titanium trichloride composition (I
The procedure was carried out except that 450 g of the titanium trichloride composition (II+) obtained in the above (1) was used as I1), and 6.0 κg of 4,4-dimethylhexene-1 was used instead of allyltrimethylsilane. A preactivated catalyst component was obtained in the same manner as in Example 1 (2).

(3) Polymerization of propylene In (3) of Example 1, 45 g (15 g as titanium trichloride composition (m)) of the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component, and 3-
Polypropylene was obtained in the same manner as in Example 1 (3) except that 37 g of dimethyldiacetoxysilane was used instead of aminopropylene triethoxysilane.

Comparative Example I1 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 15 g of I+) was used. Example 10 (1) Preparation of titanium trichloride composition (II+) n-hebutane 41, diethylaluminum monochloride 5.
A reaction solution obtained by reacting 0 mol of diisoamyl ether, 9.0 mol of diisoamyl ether, and 5.0 mol of di-n-butyl ether at 18°C for 30 minutes was added to 27.5 mol of titanium tetrachloride at 40°C for 30 minutes.
After dropping for fl minutes, keep at the same temperature for 1.5 hours to react, then raise the temperature to 65°C and react for 1 hour, remove the supernatant, add 20 fl of n-hexane, and remove by decantation. The operation was repeated 6 times and the obtained solid product (I
I > 1.8 kg was suspended in n-hexane 50j2, 20 θg of diethylaluminium monochloride was added, 1 kg of propylene was added at 60°C, and the mixture was reacted for 1 hour.
A solid product (■-A) was obtained after the synthesis treatment (propylene reaction amount: 0.5 kg). After the reaction, the supernatant liquid was removed,
The operation of adding n-hexane 301 and removing by decantation was repeated twice to obtain the solid product (
o - A) (2.3 kg) to n-hexane AJl
1.1 1 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 the reaction was completed, the supernatant liquid was removed by decantation, and then n-hexane (21) was added, stirred for 5 minutes, left to stand, and the supernatant liquid removed three times, and then dried under reduced pressure and trichlorinated. A titanium composition (Il+) was obtained. The content of titanium atoms in 1 g of titanium trichloride composition (III) is 20
It was 0B. (2) Preparation of preactivated catalyst component In (2) of Example 1, titanium trichloride composition (II
450 g of the titanium trichloride composition (II1) obtained in (1) above was used as the titanium trichloride composition (II1), and 2.4-dimethylbentene-1 was used instead of allyltrimethylsilane.
A preactivated catalyst component was obtained in the same manner as in Example 1 (2) except that 3 kg was used. (3) Polymerization of propylene In Example 1 (3), the above ( 37.5g of the preactivated catalyst component obtained in 2)
(15g as titanium trichloride composition (II+))
Polypropylene was prepared in the same manner except that 21 g of mercaptomethyltrimethylsilane was used as the organosilicon compound (S), and a catalyst consisting of 40 g of diethylaluminum monoiodide and 2 Bg of di-0-brobyl aluminum monochloride was used as the organoaluminum compound. Obtained.

The preactivation conditions, polymerization conditions, polymerization results, and evaluation results for each of the above examples and comparative examples are shown in the table on the next page. Comparative Example 12 Polypropylene was obtained in the same manner as in Example IO (3) except that 15 g of the titanium trichloride composition (, II+) obtained in Example IO (11) was used instead of the preactivated catalyst component. Ta.

[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 1/1 that of the case without preactivation with branched olefins.
It has a rating of 4 to 2/5, and has extremely high transparency.
Furthermore, the crystallization temperature is 3°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 explanation of drawings]

FIG. 1 is a manufacturing process diagram (
flowchart). Below

Claims (4)

[Claims] (1) [1] Titanium trichloride composition (III), [2] organoaluminum compound (A_1), and [3] Si-
Polymerizing propylene using a catalyst consisting of an organosilicon compound having an O-C bond and/or a mercapto group,
In the method for producing polypropylene, as the 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. The titanium composition (III) and the organic aluminum compound (A_1) are combined, and this product has the following formula, ▲mathematical formula, chemical formula, table, etc.▼ (wherein, R^1 is carbon that may contain silicon) Represents a hydrocarbon group of numbers 1 to 3 or silicon, R^2
, R^3, R^4 have a carbon number of 1 and may contain silicon
represents a hydrocarbon group from to 6, R^2, R^3,
Any one of R^4 may be hydrogen. ) to the titanium trichloride composition (III).
0.001g to 100g per 1g of preactivated catalyst component obtained by polymerization reaction, optionally additional organoaluminum compound (A_1), and organosilicon compound having Si-O-C bond and/or mercapto group. (S)
and the molar ratio (S)/(III) of the organosilicon compound (S) having a Si-O-C bond and/or mercapto group and the titanium trichloride composition (III) = 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 manufacturing method according to claim 1, in which a dialkyl aluminum monohalide is used as the organoaluminum compound (A_1). (3) As the organoaluminum compound (A_2), the general formula is AlR^5_pR^6_p_'X_3_-_(_p
___+_p_') (wherein, R^5 and R^6 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 manufacturing method according to claim 1, using an organoaluminum compound represented by: (4) Melt flow rate (MFR) of polypropylene
and the absorbance ratio (IR-τ;
Infrared wave numbers 997cm^-^1 and 973cm^-^1
absorbance ratio, A_9_9_7/A_9_7_3)
The relationship is IR-τ≧0.0203logMFR+0
．． 950. The manufacturing method according to claim 1, which satisfies the formula of No. 950.