JPH02166104A - Production of high-rigidity polypropylene - Google Patents

Abstract

PURPOSE:To produce a high-rigidity PP of excellent transparency by polymerizing propylene with a catalyst prepared by preactivating a TiCl3 composition and an organoaluminum compound by polymerizing a small amount of a specified aromatic monomer thereon and combining the preactivated components with a specified amount of a specified organosilicon compound. CONSTITUTION:Propylene is polymerized with a catalyst comprising a TiCl3 composition (A), an organoaluminum compound (B) and an organosilicon compound (C) having an Si-O-C bond and/or an SH-containing organosilicon compound. Said polymerization reaction is performed by using a catalyst prepared by reacting an organoaluminum compound with TiCl4, optionally polymerizing an alpha-olefin in the presence of the solid product thus obtained, and reacting the product with an electron donor and an electron acceptor as component A, combining it with component B, polymerizing 0.001-100g, per g of component A, of an aromatic monomer of the formula [wherein n is 0, 1 or 2; m is 1 or 2; and R<1> is an (Si-containing) 1-12C hydrocarbon group, H or a halogen atom] on the above obtained combination to form a preactivated catalyst component and optionally combining this component with additional components B and C in a molar ratio (C)/(A) 1.0-10 and a molar ratio (B)/(A) of 0.1-200.

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing highly rigid polypropylene. More specifically, we will discuss a method for producing highly rigid polypropylene with outstanding transparency. [Prior art and its problems] The present inventors used a catalyst made by combining a titanium trichloride composition previously obtained by a specific method, an organoaluminum compound, and a specific silicon compound in a specific usage ratio. A method for producing high-rigidity polypropylene using
No. 3-121523, Japanese Patent Application No. 63-123873, and Japanese Patent Application No. 63-136821 (hereinafter referred to as cholera first invention), according to the method of the earlier invention, no special addition is required. It has now become possible to produce polypropylene that yields molded products with extremely high rigidity even without the use of polypropylene. 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 extensive research into a method for producing highly rigid polypropylene with improved transparency. the result,
A concave titanium trichloride composition similar to that used in the prior invention is combined with an organoaluminum compound, a small amount of a specific aromatic monomer is polymerized to this composition for predictive activation, and a specific organosilicon compound is further activated. Polypropylene obtained by polymerizing propylene using a combination of specific amounts of catalysts not only has significantly superior transparency, but also has greater rigidity than polypropylene obtained by the method of the prior invention. We have found that this can be improved, and have led to 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 object is to provide a highly rigid polypropylene with outstanding transparency.

[Means for solving problems and their effects]

The present invention has the following configuration. (1) [1] Titanium trichloride composition (III), ■ organoaluminum compound (A t ), and [3] S
In a method for producing polypropylene by combining propylene using a catalyst consisting of an organosilicon compound (S) having an i-0-C bond and/or a mercapto group, an organic titanium trichloride composition (■■) is used. Aluminum compound (A) or organic aluminum compound (A2)
A solid product (n) obtained by reacting titanium tetrachloride with the reaction product (1) of and electron donor (B+) is treated with an α-olefin or without polymerization, and Using a titanium trichloride composition (III) obtained by reacting an electron donor (B) with an electron acceptor, combining the titanium trichloride composition (III) and an organoaluminum compound (A-o), (where n is 0, 1, 2, and 1.2; R1 represents a hydrocarbon group having 1 to 12 carbon atoms that may contain silicon, hydrogen, or halogen; When Maro is 2, each R1 may be the same or different.
08 Pre-activated catalyst component obtained by the reaction, additional organoaluminum compound (A,) as required, and further 5
A combination of the organosilicon compound (S) having a l-0-C bond and/or a mercapto group, the organosilicon compound (S) having a 5t-oc bond and/or a mercapto group, and the titanium trichloride composition. (III) (TI
molar ratio (S)/(1■) -t
, aNla. O, and the organoaluminum compound (A,
) and the titanium trichloride composition (Ill) (Al
)/(Ill) A method for producing highly rigid polypropylene, characterized in that propylene is polymerized using a catalyst having a roughness of 0.1 to jloo. (2) The manufacturing method according to item 1 above, in which dialkylaluminum monoparite is used as the organoaluminum compound (A1). (3) As the organoaluminum compound (A1), -the formula is AIR"pR"p+X5-(p*p#l (in the formula, R
*, R3 represents a hydrocarbon group such as an alkyl group, cycloalkyl group, or aryl group or an alkoxy group; The manufacturing method according to item 1 above, using an organoaluminum compound represented by (4) Melt flow rate (MFR) of polypropylene obtained by polymerization and absorbance ratio (IR-τ) determined by infrared absorption spectroscopy. ; Infrared wave number 997cm-' and 9
Absorbance ratio at 73e■-1, ＾＠I? /All? I have a relationship with Ri. At IR- ≧0.02Q3 1og MFR+O,1
50. The production method according to item 1 above. The configuration of the present invention will be explained in detail below. As the titanium trichloride composition (Iil) 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 (81) to obtain the reaction product (1) is carried out in a solvent (D) at a temperature of -20°C to 200°C, preferably -0°C to
(A2), (Bl
), (D) are added in the order of addition, and the ratio of the amounts used is 0.1 to 8 electron donors per mol of organoaluminium.
Moles, preferably 1 to 4 moles, 0.5 to 5 J2% of solvent, preferably 0.5 to 2 J2 are suitable. Preferably, the solvent is an aliphatic hydrocarbon.In this way, the reaction product (1) is obtained.The reaction product (1) remains in a liquid state after the reaction without separation (which can be referred to as reaction product liquid (1)). )'1s-)v can be subjected to the reaction. Next, the reaction between the reaction product (I) or the organoaluminum compound (A2) and titanium tetrachloride (C) is
The reaction is carried out at 00°C, preferably from 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 snow) or (1)
, (C) and the solvent may be mixed in any order, and it is preferable to complete the mixing of the entire amount within 5 hours.The amount of each used in the reaction is 1 mole of titanium tetrachloride, and the solvent is 0 ~3,000-k, organoaluminum compound (A
2) or the reaction product (1) has a ratio of the number of A1 atoms in (A2) or (1) to the number of TI atoms in titanium tetrachloride (Al/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 decanting, and after repeated washing with a solvent, the obtained solid product (!1) is suspended in a solvent and transferred to the R1 next step. It may be used for this purpose, or it may be further dried and taken out as a solid substance for use. In addition, a solid product (!) obtained by reacting this organic alkenium compound (At) or reaction product (1) with titanium tetrachloride is polymerized with an α-olefin and used for the next reaction. In addition, in the present invention, "g11 polymerization treatment" refers to polymerizing the α-olefin by bringing a small amount of α-olefin into contact with the solid product (II) under polymerizable conditions. ,
Through this polymerization treatment, the solid product (II) becomes coated with the polymer. The method of polymerizing with an α-olefin includes a method of adding an α-olefin in any step of the reaction between the acid (1) and titanium tetrachloride to polymerize a solid product ((2) A method of polymerizing the solid product (II) by adding an α-olefin after the reaction of the organic aluminum compound (A,) or the reaction product (1) with titanium tetrachloride, (3) Organoaluminum After the reaction between the compound (A,) or the reaction product (ri) and titanium tetrachloride, the liquid portion is separated and removed by filtration or decanting, and the obtained solid product (II) is suspended in a solvent. There is a method in which an organoaluminum compound (A) is added, and an organoaluminum compound (A,
When an α-olefin is added in any step of the reaction with titanium tetrachloride and an organoaluminum compound (A,)
Alternatively, if α-olefin is added after the reaction between the reaction product (1) and titanium tetrachloride, the reaction temperature is 30~30°C.
lot: ``I' Is minutes to 10 hours, the α-olefin is passed through at atmospheric pressure or added to a pressure below tokg/cnfa.The amount of α-olefin added is determined per 100 g of solid product (If). On the other hand, 10~S, 000
Using g of α-olefin, O,O5g~t,oc+
og! It is desirable to match E1. After the polymerization treatment with α-olefin is completed, the reaction product (A) or the reaction product (titanium tetrachloride) is separated and removed by filtration or decanting, and the obtained solid is obtained. When the product (II) is suspended in a solvent, the solid product (II)
Loog the solvent 100JL ~ 2, (loosJ!,
Add 5g''~500g of an organoaluminum compound, add 10~S,000g of α-olefin at a reaction temperature of 30~90°C for 5 minutes~10 hours,
O,OS~t,ooog polymerization is desirable. The solvent is preferably an aliphatic hydrocarbon, and the organoaluminum compound may be the same as that used in (A) or different. After the reaction is complete, separate the liquid part by filtration or decantation. After the removal, washing with the solvent was repeated, and the resulting polymerized solid product (hereinafter sometimes referred to as solid product (II-A)) was suspended in the solvent. It can be used in the next step,
It may be further dried and taken out as a solid for use. The solid product (II) or (II-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 (II) or % (II-
^) For 100g, (Bri) 0.1g to 1.0
00g, preferably o,,sg~200g, (F)
0.1g to 1.000g, preferably 0.23 to 500
g, solvent O~3.000@j! , preferably 100~
0 reaction method with 1,000 points is as follows: ■ Solid product (II) or (n - A ) is given an electron donor (al)
A method for simultaneously reacting with and electron acceptor (F), ■(
Purchase 1) or (II - A) is reacted with (''), and then (B,) is reacted, ■(II) or (
A method of reacting (F) after reacting (B) with (n - A), ■ After reacting (B,) and (F), (n
) or (u-A), 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 (n-A) and (8-containing) reaction at 0°C to 5
After reacting at 0°C for 1 minute to 3 hours, (F) is
React under the same conditions as in ■. *In the method (2), (B2) and (F) are reacted at 10°C to 100°C for 30 minutes to 2 hours, and then cooled to 40°C or lower. After adding (X or (u - A), the above
React under similar conditions. After the reaction of the solid products (1-A), (Ih), and (F) is completed, the liquid portion is separated and removed by filtration or decantation, and then washed with a solvent repeatedly. A titanium trichloride composition (m) used in the invention is obtained.Titanium trichloride composition (nt) obtained as above
and an organoaluminum compound (A,), and this product has the following linear formula: represents a hydrocarbon group having 1 to 12 carbon atoms, hydrogen, or halogen, and when there are 2 layers, each R1 may be the same or different. (sometimes abbreviated as aromatic monomer) is added to the titanium trichloride composition (
III) O,001g~toog per Ig! The preactivated catalyst component reacted with the preactivated catalyst component, optionally an additional organoaluminum compound (A2), and an organosilicon compound having a 5l-0-C bond and/* or a mercapto group (
S) (hereinafter sometimes abbreviated as organosilicon compound (S)) to form the catalyst used in the present invention. Preactivation is performed for titanium trichloride composition (m)Ig.
Reiki Alkunirim Compound (AI) (1,05g~so
og, solvent 0-5 oul, hydrogen ON 1. OOOmj! ,
and 0.01g to 1.000g of specific aromatic monomer
Use. The specific aromatic monomer is reacted at a polymerization reaction temperature of 0° C. to 10° C. for 1 minute to 20 hours, and the titanium trichloride composition (
II1) It is desirable to polymerize O,001g to 100g, preferably 0,01g to loOg of the specific aromatic monomer per Ig! ! 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-pentane, n-hexane, n-hebutane, toluene, etc. Hydrogen may also be allowed to coexist in the gap during preactivation. It is also possible to add organosilicon compounds (S). 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. The specific aromatic monomer for the reaction and the organoaluminum compound (A1) are removed by filtration, and a solvent is added to the dried powder or the powder to form a suspension, and an additional organic A method in which an aluminum compound (A) and an organosilicon compound (S) are combined as a catalyst and subjected to polymerization of propylene, a coexisting solvent, and an unreacted specific aromatic monomer are distilled under reduced pressure, or Evaporate with an inert gas, add a solvent to the powder or the powder to make it into a suspended state, and add the V-machine aluminum compound (A1) to this as necessary. In addition, it is also possible to use it in combination with an organosilicon compound (S) to form a catalyst for propylene polymerization. When polymerizing propylene, the above titanium trichloride composition (III) and an additional organoaluminum compound (AI
), and the amount of organosilicon compound (S) used, including the organosilicon compound (S) and the titanium trichloride composition (!■)
The molar ratio (S)/(m) is 1.0 to 10.0. Further, the organoaluminum compound (A,) the titanium trichloride composition (
ill) molar ratio (A1)/(!■) is O21~20
Use within the range of 0. 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.If the addition is too large, the polymerization activity will decrease, making it impractical. ) refers to the number of T1 gram atoms substantially contained in (m ). The organoaluminum compound (At) used in the production of the titanium trichloride composition (III) used in the present invention includes:
- The formula is AIR"J'*. In addition, an organic aluminum compound represented by p%p' represents an arbitrary number of o<pop'≦3 is used.Specific examples thereof include trimethylaluminum, triethylaluminum, trilopropylaluminum, tri-1-butyl Aluminum, trialkylaluminums such as trilodecylaluminum, tri-n-hexylaluminum, tri-l-hexylaluminum, tri-2-methylpentylaluminium, tri-n-octylaluminum, trilodecylaluminum, diethylaluminum monochloride, dilopropylaluminum monochrome di-I-butylaluminum monochloride, diethylaluminum monofluoride, diethylaluminum monobromide, diethylaluminum monohalides such as diethylaluminum sonoiodide, dialkylaluminum pallites such as diethylaluminum hydride, methylaluminum sesquichloride, Examples include alkylaluminum sesquihalides such as ethylaluminum sesquichloride, monoalkylaluminum cybarides such as ethylaluminum dichloride, ■-butylaluminum dichloride, and alkoxyalkyl such as monoethoxydiethylaluminum and jetoxymonoethylaluminum. Aluminums can also be used.These organoaluminum compounds can also be used in combination with 21m or more.As the electron donor used in the present invention, the following various ones are shown, but (L) , It is preferable to mainly use ethers as (El2) and share the other electron donors with ethers.The electron donor used is one of oxygen, nitrogen, sulfur, and phosphorus atoms. Organic compounds containing ethers, alcohols, esters, aldehydes, fatty acids, ketones, nitriles/amines/amides, urea or thioureas, isocyanates, azo compounds, phosphines/phosphites , phosphinites, hydrogen sulfide or thioethers,
These include thioalcohols. Specific examples include diethyl ether, moro-propyl ether, di-n-butyl ether, diisoamyl ether, moro-pentyl ether, moro-hexyl ether,
Cytohexyl 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, fi12-ethylhexyl benzoate, methyl toluate, ethyl toluate, fi2-ethylhexyl toluate, methyl anisate, ethyl anisate, propyl anisate, silicon Ethyl naphthoate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate,
Esters such as ethyl phenylacetate, aldehydes such as acetaldehyde and benzaldehyde, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid, acrylic acid,
Fatty acids such as 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-picoline, 2
．． 4.8-Trimethylpyridine, N,N. N°, N°-Amines such as tetramethylethylenediamine, aniline, dimethylaniline, formamide, hexamethylphosphoric triamide, N,N. No・Ni°・No-pentamethyl-No-β-dimethylaminomethylphosphoric acid triamide, octamethylpyrophosphoramide! i%N, N, N'-N'-Ureas such as tetramethylurea, isocyanates such as phenyl isocyanate and toluyl isocyanate, azo compounds such as azobenzene, ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n - phosphines such as octylphosphine, triphenylphosphine, and triphenylphosphine oxyto; phosphites such as dimethylphosphite, monocutylphosphine, triethylphosphite, tri-n-butylphosphite, and triphenylphosphite; Phosphinites such as ethyldiethylphosphinite, ethylbutylphosphinite, phenyldiphenylphosphinite,
Other examples include thioethers such as diethylthioether, diphenylthioether, methylphenylthioether, ethylene sulfide and propylene sulfide, and thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol. These electron donors can also be used in combination.
The electron donor (B1) to obtain the reaction product (1), the solid product (II) or (B2) to be reacted with (If-A) may be the same or different. The electron acceptor (F) used in the present invention is I11 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. As the solvent, a number of solvents are used. Examples of m-aliphatic hydrocarbons include n-pentane, n-hexane, n-heptane, low octane, and 1-octane. , or together therewith, halogenated carbon hydrogens such as carbon tetrachloride, chloroform, dichloroethane, trichloroethylene, and tetrachlorethylene can also be used.As aromatic compounds, aromatic hydrocarbons such as naphthalene,
and its rust conductors mesitylene, delene, ethylbenzene, isopropylbenzene, toethylnaphthalene,
Examples include alkyl substituted products such as 1-phenylnaphthalene, halides such as chlorobenzene, chlorotoluene, chloroxylene, chloroethylbenzene, dichlorobenzene, and brombenzene. The α-olefins used in the polymerization treatment include linear monoolefins such as ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, 4-methyl-pentene-1, and tomethyl-pentene-1. Branched chain sonoolefins such as No. 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 is expressed by the following formula, (wherein is 0, 1, or 2, m is 1.2, and R1 is the number of carbon atoms that may contain silicon. It is an aromatic monomer represented by 1 to 12 hydrocarbon groups, hydrogen, or halogen, and when the number is 2, each R1 may be the same or different. Specific examples include styrene, its 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-trimethylsilylstyrene, l-trimethylsilylstyrene,
Trialkylsilylstyrenes such as +1-triethylsilylstyrene, ■-triethylsilylstyrene, p-ethyldimethylsilylstyrene, o-allyltoluene, p
-Allyltoluenes such as allyltoluene, toarylupe
-xylene, 4-allyl-0-xylene, allylxylenes such as toaryl-xylene, and 4-(o
-tolyl)-1-butene! -vinylnaphthalene, etc., and one or more types of these specific aromatic monomers are used. The organoaluminum compound (A1) to be combined with the titanium trichloride composition (!■) and the organoaluminum compound (A,) used if necessary have the formula - ^IR'
Dialkyl aluminum chloride represented by R'X is preferred; in the formula, R4 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. ,
Specific examples include diethylaluminum monochloride, monopropylaluminum monochloride, di-l-
Examples include butylaluminum monochloride, di-butylaluminum monochloride, diethylmolanimonium monoiodide, diethylaluminum monochloride, and the like. Specific examples that can be used as the organosilicon compound (S) having a 5l-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 , propyltriethoxysilane, allyltrimethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, n-octyltriethoxysilane, n-octadecyltriethoxysilane, 6-driethoxysilyl-2-norbornene, dimethyljethoxysilane , diethyljethoxysilane, diphenyljethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylethoxysilane, allyloxytrimethylsilane, methyltril-propoxysilane, dimethyldil-propoxysilane, trimethyll-propoxysilane, tetra n-butoxy Silane, methyltri-n-butoxysilane, tetra(2-ethylbutoxy)silane, methyltriphenoxysilane, dimethyldiphenoxysilane, trimethylphenoxysilane, trimethoxysilane, triethoxysilane, triethoxychlorosilane, tri-I-propoxychlorosilane, Tri-n-butoxychlorosilane, tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, methyldiacetoxysilane, diacetoxymethylvinylsilane, dimethyldiacetoxysilane, methylphenyldiacetoxysilane, diphenyldiacetoxy Silane, trimethylacetoxysilane, triethylacetoxysilane, phenyldimethylacetoxysilane,
Organosilicon compounds having a 5t-oc bond such as triphenylacetoxysilane, bis(trimethylsilyl)adipate, trimethylsilylbenzoate, triethylsilylbenzoate, mercaptomethyltrimethylsilane, 2-mercaptoethyltrimethylsilane, tomercabutobrobyltrimethylsilane , 4-mercapto-n
-butyltrimethylsilane, mercaptomethyltriethylsilane, tomercaptoethyltriethylsilane, 3-
Having a mercapto group such as mercaptopropyltriethylsilane, l-mercaptoethyltrimethylsilane, 3-mercaptopropyldimethylphenylsilane, 3-mercaptopropylethylmethylphenylsilane, 4-mercaptobutyldiethylphenylsilane, 3-mercaptopropylmethyldiphenylsilane organosilicon compounds,
Also, mercaptomethyltrimethoxysilane, mercaptomethyldimethylmethoxymethylsilane, mercaptomethyldimethoxymethylsilane, mercaptomethyltriethoxysilane, mercaptomethyljethoxymethylsilane, mercaptomethyldimethylethoxysilane, tomercabutethyltrimethoxysilane, 3-mercapto Propyltrimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, 3-mercaptopropyltriethoxysilane, jetoxy-3-mercaptopropylmethylsilane, mercaptomethyldimethyl-2-phenylethoxysilane, 2-mercaptoethoxytrimethylsilane, 3- Organosilicon compounds having an S'1-0-C bond and a mercapto group such as mercaptopropoxytrimethylsilane, 3-aminopropyltrimethoxysilane,
3-7 Minopropyltriethoxysilane, 3-aminopropyljethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 2-aminoethylaminomethyltrimethoxysilane , 3-(2-aminoethylaminopropyl)dimethoxymethylsilane, 2-aminoethylaminomethylbenzyloxydimethylsilane, 3-(2-(2-aminoethylaminoethylamino)propyl)trimethoxysilane, etc. Examples include organosilicon compounds having an 0-C bond and an amino group. The catalyst used in the present invention thus obtained is used in the polymerization of propylene. The polymerization method for propylene is to convert propylene into n-hexane, n-hebutane,
Slurry polymerization carried out in a hydrocarbon solvent such as n-octane, benzene or toluene, or bulk polymerization and gas phase polymerization carried out in liquefied propylene can be carried out. Regarding polypropylene obtained by the above-mentioned various polymerization methods, the crystallinity of the polymer that can exhibit the effects of the present invention is determined by the melt flow rate (MF) of the polypropylene.
Absorbance ratio (I) and infrared absorption spectroscopy
R-τ; infrared wave number 197cm-' and 1l3cm-'
The relationship between the absorbance ratio and A *sy/A et2) is IR-t≧0.0203 log MFR+O,! 15
Characterized by titrating the formula 0. MFR is usually 0.05 to 200, preferably 0. lN
A value of about 100 is practical. Polymerization temperature is usually 20-100℃, preferably 40-8s
It is ℃. If the temperature is too low, the polymerization activity will be low, making it impractical; if the temperature is too high, it will be difficult to increase crystallinity. I! Combined pressure normal pressure -50kg/cm
'G' usually takes about 30 minutes to 15 hours. During the 11th polymerization, 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 with 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. be done. C effect) The highly rigid polypropylene obtained by the method of the present invention contains a specific aromatic polymer with high stereoregularity dispersed therein, so that the specific aromatic polymer does not dissolve during melt molding. exhibits a nucleating effect, promoting the crystallization of polypropylene, thereby increasing the transparency and crystallinity of the polypropylene as a whole. In addition, 1. Since the specific aromatic polymer introduced by the method of the present invention is a stereoregular high molecular weight polymer as described above, it 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 the 211 synthesis activity and represents the polymer yield (g) per Ig of titanium trichloride composition (III),
(Unit: g/g) (2) MF
R: Melt flow index ^STMD-1238 (
L) @758 According to e. (Unit: g/lo min) (3
) IR-τ: The sample was formed into a film using a pressure molding machine at 200° 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 40 μm. The film was then put into an annealing tube, vacuumed, and annealed for one hour in an oil bath at 135°C. Three small films were cut out from the annealed film, and each of these small films was As a measurement sample, 997c amount-1
Absorbance ratio of and 973C Otori-1, (A・1A89γ$)
are measured, and the average value is taken as the IR-τ value. This IR-
The measurements were carried out using a PerkinElmer 783 infrared spectrophotometer. (4) Internal haze: This is the haze inside the film excluding the influence of the surface.
Thickness of polypropylene under the condition of 00Kg/cm''G
The haze was measured according to Jll K 7105 after making a 150μ film and applying combed paraffin on both sides of the film. (J11 2%) (5) Crystallization temperature: using a differential scanning calorimeter,
The rate of fall was measured at °C/min. (Unit: 2℃) (6) Rigidity: Polypropylene 100! ! Tetrakis[methylene-3-(3°, 5°-di-t-
Butyl-4°-hydroxyphenyl)propionate]
methane o, t parts by weight, and calcium stearate 0
．． 1! +! 4 parts of the mixture, and the mixture was
Granulation was performed using a 0 m5 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 t3°C for 72 hours, and then measured using the following method. (a) Flexural modulus: Based on JIS 7203 (unit:
kgf/c&) (b) Tensile strength: Based on JIS 7113 (unit: k
gf/1m') (8) Rockwell hardness (R scale): Compliant with JIS X F202 (d) Heat distortion temperature (IIDT): JIS It 72
Example 1 (1) Titanium trichloride composition (II1) [1] Preparation of rhohexane 6J1. Diethyl aluminum monoloride CD
EAC) 5.0 mol and diisoamyl ether 12 mol were mixed at 25 t for 1 minute and reacted for S minutes at the same temperature to obtain reaction product liquid (1) (molar ratio of diisoamyl ether/DEAC 2.4). . 40 moles of titanium tetrachloride was placed in a reactor purged with nitrogen, heated to 35°C, and the entire amount of the reaction product solution (1) [1] was added dropwise over 30 minutes, and then kept at the same temperature for 311 minutes. , the temperature was raised to 75°C and the reaction was continued for an additional hour, cooled to room temperature, the supernatant liquid was removed, 20 jL of n-hexane was added, and the supernatant liquid was removed by decantation. This operation was repeated four times to obtain a solid product ( II) 1. ! Ikg
I got it. The entire amount of this (Ig) was suspended in n-hexane 3i, 200 g of diethylaluminium monochloride was added, and propylene 1.0 g was added at 3 Qt. After the reaction, the supernatant was removed, and 301 ml of n-hexane was added. Decanter l
Repeat this operation twice and add 2°Skg of the above polymerized solid product (II-A) to 61 kg of n-hexane.
3.5 kg of titanium tetrachloride was added at room temperature for about X minutes, and after reacting at 80°C for 30 minutes, 1.1 kg of diisoamyl ether was added. 1 kg at 80°C.
After one hour of reaction, the supernatant was decanted.
After removing with water, add 40J2 of n-hexane and add 10J2 of n-hexane.
After repeating the procedure of stirring for 5 minutes, standing still, and removing the supernatant liquid 5 times, the titanium trichloride composition (Ill) was dried under reduced pressure.
I got it. The titanium content in 1 g of titanium trichloride composition (III) was 1921 g. (2) Preparation details of preactivated catalyst component 11 a OJ! After a stainless steel reactor with inclined blades was replaced with nitrogen gas, n~hexane 40J2,
Diethylaluminium monochloride 20Gg, (1
) After adding 450 g of the titanium trichloride composition (Ill) obtained in 2.4 at room temperature, the temperature inside the reactor was raised to 40°C.
- Add 4.5 g of dimethylstyrene and react at 40°C for 2 hours. Titanium trichloride composition (III) per Ig of 2
．． 4-dimethylste 121.08 reaction). After the reaction was completed, unreacted 2,4-dimethylstyrene, 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 purging a stainless steel reactor with a stirrer with an internal volume of propylene polymerization of 5 OOJ2 with nitrogen gas, add n-hexane to the reactor at room temperature.
i, 50g of diethylaluminum monochloride, (
The preactivated catalyst component obtained in 2) was mixed with a titanium trichloride composition (
15 g of Ill), 33 g of 3-aminopropyltriethoxysilane, and 15,011 l of hydrogen were added. Subsequently, the polymerization temperature was 70°C, and the propylene partial pressure was 10 kg/c.
After completing one reaction in which propylene was polymerized with m'G for 3 hours, 10 jl of methanol was supplied, and after treatment at 70°C for 30 minutes, unreacted propylene and unreacted hydrogen were discharged. Furthermore, H1fi amount% sodium hydroxide aqueous solution 10
0g was added and treated at 70°C for 20 minutes. After adding pure water toon to the suspension and stirring for 10 minutes, the aqueous layer was extracted twice, and then the polymer slurry was extracted, filtered, and dried to obtain a polymer. The obtained polymer contained lumps, so the entire polymer was pulverized by a pulverizer, and 50k polypropylene with a VFR of 1.8 was produced.
I got g. Comparative Example 1 In (3) of Example 1, the titanium trichloride composition (1) obtained in (1) of Example 1 was used instead of the preactivated catalyst component.
Polypropylene was obtained in the same manner except that 15 g of II1) was used. Examples 2 and 3 In (3) of Example 1, the amount of hydrogen charged was changed to 230 Jt (
Polypropylene was obtained in the same manner as in Example 1, except for using a modified sacell with 430 Jl (Example 3). Comparative Example 2.3 In (3) of Example 1, the amount of hydrogen charged was increased to 2201 (
Comparative example 2), 390J! (Comparative Example 3) Polypropylene was obtained in the same manner as in Comparative Example 1 except for the following changes. Comparative Example 4 A preactivated catalyst component was obtained in the same manner as in (2) of Example 1 except that propylene Smog was used instead of 2,4-dimethylstyrene, and the rest was carried out using Example 1 (3). ) Propylene was polymerized in the same manner as in (1) to obtain polypropylene. Comparative Example 5 In (3) of Comparative Example 1, the catalyst component 3-aminopropyltriethoxysilane was not used, and the amount of titanium trichloride composition (III) used was 10 g. The amount of diethylaluminium monochloride used was 33.
Polypropylene was obtained in the same manner except that the amount was 3 g. Comparative Example 6 and Example 4.5 In Example 1 (2), 4-allyl-O-xylene was used instead of 2,4-dimethylstyrene, and the amount used was changed to 1g% 400g and 12Kg, respectively. Polypropylene was obtained in the same manner as in Example 1, except that phenyltriethoxysilane 291K was used instead of 3-aminopropyltriethoxysilane in (3). Comparative Examples 7 to 9 and Example 6.7 In (!) of Example 1, p-trimethylsilylstyrene 1.5K was used instead of 2,4-dimethylstyrene.
g, and using dimethoxy-3-mercaptopropylmethylsilane instead of 3-aminopropyltriethoxysilane in (3),
Polypropylene was obtained in the same manner as in Example 1, except that the molar ratio of 3-mercaptopropylmethylsilane to titanium trichloride composition (III') was changed as shown in the table below. Example 8 (1) Preparation of titanium trichloride composition (III) n-hebutane 8j! , di-n-butylaluminum monochloride! 6 mol, 10 mol of moro-butyl ether at 30°C.
The reaction product solution (1) was mixed for 0 minutes and reacted for 20 minutes to obtain a reaction product solution (1). After adding dropwise to the solution for 60 minutes, the temperature was raised to 85°C and reacted for an additional 2 hours, then cooled to room temperature and the supernatant liquid was removed. 30 J! of n-heptane was added and the supernatant liquid was removed by decantation. Solid product (II) obtained by repeating the operation twice
4.9 kg was obtained. The entire amount of this (①) was suspended in 30j of n-heptane, and 2.0kg of di-n-butyl ether and 15g of titanium tetrachloride were added.
kg was added over about 20 minutes at room temperature, reacted at 90°C for 2 hours, and after cooling, decantation, washing with n-hebutane, and drying were performed to obtain a titanium trichloride composition (III). The content of titanium atoms in 1 g of titanium trichloride composition (III) was 255 vg. (2) Preparation of preactivated catalyst component In (2) of Example 1, titanium trichloride composition (II
The titanium trichloride composition (I) obtained in (1) above was used as
II) Using 450 g, and 8.5 g of 2-methyl-4-fluorostyrene instead of 2,(-dimethylstyrene)
A preactivated catalyst component was obtained in the same manner as in Example 1 (2) except that Kg was used. (3) Polymerization of propylene In example type (3), 27 g (
Propylene was prepared in the same manner as in Example 1 (3) except that ISg) was used as the titanium trichloride composition (III) and 29 g of allyltriethoxysilane was used instead of 3-aminopropyltriethoxysilane. Polymerization was performed to obtain polypropylene. Comparative Example 1O In (3) of Example 8, the titanium trichloride composition obtained in (1) of Example 8 (!■
) Polypropylene was obtained in the same manner except that 15 g of the compound was used. Example 9 (Preparation of titanium trichloride composition (Ill) 27.0 mol of titanium tetrachloride was added to 119 n-hexane, cooled to 1°C, and further diluted with diethylaluminum monochloride 2.
12°5j of n-hexane containing 7.0 moles! 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 supernatant was removed, 10J2 of n-hexane was added, and the operation of removing by decanting was repeated 5 times to obtain a solid product (II) 5.7
Of the kg, 1.8 kg is n-hexane 11j! 1.8j of diisoamyl ether! was added. This suspension was stirred at 35° C. for 1 hour and then washed 5 times with n-hexane 31 to obtain a treated solid. The resulting treated solid was suspended in a 40% by volume titanium tetrachloride solution aJl in n-hexane. This suspension was heated to 65°C and reacted at the same temperature for 2 hours. After the completion of the reaction, 2o1 of n-hexane was used at a time,
After washing the obtained solid three times, it was dried under reduced pressure to obtain a titanium trichloride composition (Ill). (2) Preparation of preactivated catalyst component In (2) of Example 1, titanium trichloride composition (!■
) as the titanium trichloride composition obtained in (1) above (
A preactivated catalyst component was obtained in the same manner as in (2) of Example 1, except that 450 g of m) was used and 1.6 g of styrene was used instead of 2,4-dimethylstyrene. (3) Polymerization of propylene In (3) of Example 1, 45 g (lsg as titanium trichloride composition (III)) of the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component. Polypropylene was obtained in the same manner as in Example 1 (3) except that 37 g of dimethyldiacetoxysilane was used instead of 3-aminopropyltriethoxysilane. Comparative Example 11 In (3) of Example 9, the titanium trichloride composition (II) 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 0) Preparation of titanium trichloride composition (!■) n-heptane 4
JL, a reaction solution obtained by reacting 5.0 mol of diethylaluminum rhamnosochloride, 9.0 mol of diisoamyl ether, and 5.0 mol of moro-butyl ether at 18°C for 30 minutes in 27.5 mol of titanium tetrachloride. After dropping the mixture at 40°C for 300 minutes or more, the mixture was kept at the same temperature for t and S hours to react, then the temperature was raised to 65°C, reacted for 1 hour, and the supernatant liquid was removed.
The operation of adding n-hexane 201 and removing with decantation B was repeated 6 times to obtain a solid product (II) 1.8
kg in 11-hexane, 200 g of diethylaluminium monochloride was added, and 1.1 kg of propylene was added at 80°C. Add Okg and let it react for 1 hour! ! A polymerized solid product (II-A) was obtained (propylene reaction amount: 0.5 kg). After the reaction, after removing the supernatant liquid, add 30j of n-hexane! The operation of adding and removing with decantation soda was repeated twice to obtain the solid product (II-A) (2.3k) subjected to the above polymerization treatment.
g) was suspended in n-hexane 41 and titanium tetrachloride 1
．． Add 8 kg of n-butyl, 1.8 kg of n-butyl, and react at 60°C for 3 hours. After the reaction, remove the supernatant with decantation, add 20 jt of n-hexane, stir for 5 minutes, and let stand. After repeating the operation three times to remove the supernatant liquid, the titanium trichloride composition (II) was dried under reduced pressure.
I) was obtained. The content of titanium atoms in the titanium trichloride composition (IIt) tg was 200@II. (2) ml of preactivated catalyst component In (2) of Example 1, the titanium trichloride composition (i
) The titanium trichloride composition obtained in (1) above (m
) 45Og and 1.3g of pt-butylstyrene instead of 2,4-dimethylstyrene, the preactivated catalyst component was prepared in the same manner as in (2) of Example 1. I got it. (3) Polymerization of propylene In (c) of Example 1, 37.5 g of the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component.
(ISg as titanium trichloride composition (III)) A catalyst consisting of 20 g of mercaptomethyltrimethylsilane as the organosilicon compound (S) and 40 g of diethylaluminum monoiodide and 28 g of moro-propyl aluminum monochloride was used as the organoaluminum compound. Polypropylene was obtained in the same manner except for the following. Comparative example! 2 Polypropylene was obtained in the same manner as in Example 10 (3) except that 15 g of the titanium trichloride composition (III) obtained in Example 1G (1) was used instead of the preactivated catalyst component. The main polymerization conditions, polymerization results, and evaluation results of the obtained polypropylene for each of the above implementations and comparisons 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 examples described above (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.In addition, 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 has also been further improved.

[Brief explanation of the drawing]

Figure 1 is a manufacturing process diagram for explaining the present invention in detail (
flowchart). that's all

Claims (4)

[Claims] (1) [1] Titanium trichloride composition (III), [2] organoaluminum compound (A_1), and [3] Si-
In a method for producing polypropylene by polymerizing propylene using a catalyst consisting of an organosilicon compound (S) having an O-C bond and/or a mercapto group, an organoaluminum compound (A_2) is used as the titanium trichloride composition (III). ) or organoaluminum compound (A_2)
The solid product (II) obtained by reacting titanium tetrachloride with the reaction product (I) of
- with or without polymerization treatment with olefin;
Furthermore, using the titanium trichloride composition (III) obtained by reacting the electron donor (B_2) and the electron acceptor, the titanium trichloride composition (III) and the organoaluminum compound (A_
1), and this has the following formula, ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, n is 0, 1, 2, m is either 1 or 2, and R^1 is silicon 1 to 12 carbon atoms, which may contain
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) 0.001g to 100g per gram of a preactivated catalyst component obtained by polymerization reaction, optionally an additional organic aluminum compound (A_1), and an organic compound having a Si-O-C bond and/or a mercapto group. Silicon compounds (
molar ratio (S) of the organosilicon compound (S) having the Si-O-C bond and/or mercapto group and the titanium trichloride composition (III) (same as based on the number of Ti atoms) /(III) = 1.0 to 10.0, and the molar ratio of the organoaluminum compound (A_1) to the titanium trichloride composition (III) (A_1)/(III) = 0.1 to 20.
1. A method for producing highly rigid polypropylene, which comprises polymerizing propylene using a catalyst with a concentration of 0. (2) The production method according to claim 1, in which a dialkylaluminum 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 represent a hydrocarbon group such as an alkyl group, cycloalkyl group, or aryl group or an alkoxy group, X represents a halogen, and p and p' are 0
<p+p'≦3. ) The manufacturing method according to claim 1, using an organoaluminum compound represented by: (4) Melt flow rate (MFR) of polypropylene obtained by polymerization and absorbance ratio determined by infrared absorption spectroscopy (IR-τ: absorbance ratio at infrared wave numbers 997 cm^-^1 and 973 cm^-^1, A_9_9_7
/A_9_7_3) satisfies the following formula: IR-τ≧0.0203logMFR+0.950.