JPH0415241A - Production of polypropylene composition - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in rigidity, durability and transparency by mixing a plurality of specified polypropylenes to obtain a mixture containing a crystalline nonlinear olefin polymer. CONSTITUTION:A polypropylene (PP1) having specified properties and obtained by polymerizing propylene, in the presence of a catalyst prepared by combining a TiCl3 composition (i), formed by pretreating a solid product obtained by reacting an organoaluminum compound or a reaction product thereof with an electron donor with TiCl4, with the polymerized product of a nonlinear olefin (e.g. vinylcyclohexane) or a mixture thereof and a linear olefin and further reacting the pretreated product with an electron donor and an electron acceptor, with an organo-aluminum compound (ii) and an aromatic carboxylic acid ester or an organosilicon compound (iii) having an Si-O-C bond and/or an SH group is mixed with a polypropylene (PP2), obtained by polymerizing propylene in the presence of a catalyst prepared by combining a Ti-containing solid catalyst component with an organoaluminum compound and an electron donor as an optional component, to obtain a composition containing 0.1wt. ppm-2wt.% crystalline nonlinear olefin polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing polypropylene compositions. More specifically, the present invention relates to a method for producing a polypropylene composition having excellent transparency, rigidity, and durability.

[Prior art and its challenges] In recent years, the polypropylene manufacturing process has been using high-performance polymerization catalysts, such as Mg compound-supported catalysts, which achieve high polymerization activation while maintaining high stereoregularity of the resulting polypropylene. Therefore, there is a tendency to adopt a gas phase process that omits the catalyst removal step and atactic polymer removal step that are necessary in conventional processes.

By adopting the above-mentioned gas phase process, productivity of polypropylene has improved by a large amount. However, since the atactic polymer removal step is omitted, the atactic polymer produced in a small amount is completely incorporated into the product, so the resulting product is translucent compared to the polypropylene obtained from the conventional process. That's Ll! ! ! !
It had

On the other hand, the present inventors have been conducting research on a method for producing polypropylene with excellent rigidity and transparency, and have already developed a specific titanium trichloride composition containing a non-linear olefin polymer, a specific organoaluminum compound, and a method for producing polypropylene with excellent rigidity and transparency. We have proposed a method for obtaining polypropylene with significantly improved rigidity and transparency using a catalyst that combines a specific third component (Japanese Patent Application No. 1-27043, Japanese Patent Application No. 1-29474, Japanese Patent Application No. No. l-35793, patent application No. 1-42705,
Japanese Patent Application No. 1-49692, Japanese Patent Application No. 1-61460, Japanese Patent Application No. 1-156042, Japanese Patent Application No. 1-160270,
(Japanese Patent Application No. 1-249439, hereinafter referred to as the prior invention).

The polypropylene obtained by the method of the prior invention is a highly homogeneous polypropylene having high rigidity and transparency not found in conventionally known polypropylene. However, since these methods of the prior invention use a titanium trichloride composition as a catalyst component, the problem is that the polymerization activity is lower than that of the single-compound-supported catalyst component described above, and therefore the productivity is low. It had

In view of the current state of the known technology described above, the present inventors have conducted extensive research in order to find a method for efficiently obtaining polypropylene with excellent rigidity and transparency. As a result, molded articles manufactured using a composition obtained by mixing polypropylene obtained by the method of the prior invention and known polypropylene obtained by a known method, for example, the vapor phase process described above, The present invention was completed based on the knowledge that transparency, rigidity, and durability can be improved more than additivity.

As is clear from the above description, an object of the present invention is to provide a method for producing a polypropylene composition that has excellent transparency, rigidity, and durability.

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

(1) (A) [1] Organoaluminum compound (A1) or organoaluminum compound (A1) and electron donor (
A solid product (+1) obtained by reacting titanium tetrachloride with the reaction product (I) with 81) is polymerized with a non-linear olefin, or a linear olefin and a non-linear olefin, Furthermore, a titanium trichloride composition (1) obtained by reacting an electron donor (B2) with an electron acceptor, (1) an organoaluminum compound (A2), and (2) an aromatic carboxylic acid ester (E), or Si-0 A melt fluorate (VFR) obtained by polymerizing propylene using a catalyst combined with an organosilicon compound (S) 5 having a -C bond and/or a mercapto group has a melt fluorate (VFR) of 0.1 to +00 f
g/10 minutes, load 2.16 kgf), isotactic pentad fraction (P) 0.960 to 0.990, ratio of weight average molecular weight to number average molecular weight, weight average molecular weight / number average molecular weight (Q) is 7 to 30 polypropylene (a
) and (8) Propylene is polymerized using a catalyst that combines ■ a titanium-containing solid catalyst component (Tl+, ■ an organoaluminum compound (A1), and, if necessary, ■ an electron donor (8,). A method for producing a polypropylene composition, which comprises mixing the obtained polypropylene (b) with 01jiii!kpPm to 2!% by weight of a crystalline non-KM olefin polymer.

(2) Organoaluminum compound (A1) affected^1) - where the formula is^IR', R', /X5-1p4p/1C, B1. B2 is a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, or an alkoxy group; The manufacturing method according to item 1 above, which uses an organoaluminum compound.

(3) As a non-linear olefin, the following formula, C1h=CH
-R' (1) where R3 represents a saturated cyclic hydrocarbon group with 3 to 18 carbon atoms which may contain silicon and which has a saturated cyclic structure of a hydrocarbon which may contain silicon; The above '! using the saturated ring-containing hydrocarbon R-mer shown below! lS
The manufacturing method according to item 1.

(4) As a non-linear olefin, the following formula, CI42 =
CHR'-R' (wherein, R4 represents a quenched hydrocarbon group having 1 to 3 carbon atoms which may contain silicon, or silicon, and R5
,ua,R? has 1 to 6 carbon atoms and may contain silicon
Bs, Re, R7
The production method according to item 1 above, wherein any one of the branched olefins shown in 1) may be hydrogen.

(5) As a non-linear olefin, the following formula, (1'l').

(In the formula, n is either 0.1.+a is 1.2,
R6 represents a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R9 represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen, or halogen. , when parrot is 2, each 89 may be the same or different.

(6) The manufacturing method according to item 1 above, in which a dialkylaluminum monohalide is used as the organoaluminum compound (A2).

(7) polypropylene (bl) using a Mg compound-supported catalyst component as a titanium-containing catalyst component (TI),
The method for producing polypropylene according to item 1 above, which is polypropylene obtained by gas phase polymerization of propylene.

(8) Instead of the titanium trichloride composition (Ill), a catalyst component preactivated by combining the titanium trichloride composition (Ill) and an organoaluminum compound and reacting with a small amount of solenoid is used. The manufacturing method described in section.

(9) In place of the titanium-containing solid catalyst component (T1), the above item 1 uses a catalyst component that is preactivated by combining a titanium-containing solid catalyst component (TI) and an organoaluminum compound and reacting with a small amount of olefin; Or the manufacturing method described in item 7.

Hereinafter, the configuration of the present invention will be explained in detail.

The polypropylene (a
) is detailed in the specification of the prior invention mentioned above, and the details are as follows.

The titanium trichloride composition (m) used for producing polypropylene (a) is prepared as follows.

First, the organic aluminum compound (A1) or the reaction product (1) of the organic aluminum compound (A1) and the electron donor (B1) is reacted with titanium tetrachloride to obtain a solid product (II).

The reaction between the organoaluminum compound (A1) and the electron donor (B1) to obtain the reaction product (1) is carried out using a solvent (Dl
) in a temperature range of -20°C to 200°C, preferably -1θ°C to 10°C.
It is carried out at 0°C for 30 seconds to 5 hours.

There is no restriction on the order of addition of (A1), (B1), CDI), and the ratio of (2) used is 1 mol to 8 mol, preferably 1 to 4 mol, of the electron donor and 05 to 5 I of the solvent to 1 mol of organoaluminium. , preferably 0.5 to 2 ft.

Preferably, aliphatic hydrocarbons are used as the nuclides, and the reaction product (1) is obtained in this way. ) can be used for the next reaction.

Subsequently, the reaction product (1) is reacted with titanium tetrachloride, or the organoaluminum compound (A1) is reacted with titanium tetrachloride, and the resulting solid product (1) is converted into a non-linear olefin. , or polymerization treatment with linear olefins and non-linear olefins.

The polymerization treatment method includes: (1) adding a non-linear olefin, or a linear olefin and a non-linear olefin in any process of the reaction of the reaction product (r) or the organoaluminum compound (AI+) with titanium tetrachloride; and then polymerize the solid product (II).
After the reaction between I) and titanium tetrachloride is completed, a non-linear olefin or a linear olefin and a linear olefin are added to polymerize the solid product (II); ) or organoaluminum compound (
After the reaction between A1) and titanium tetrachloride is completed, the liquid portion is separated and removed by filtration or decantation, the obtained solid product (II) is suspended in a solvent, and an organoaluminum compound is further added, There is a method in which a non-linear olefin, or a linear olefin and a non-linear olefin are added and polymerized.

In addition, the above-mentioned polymerization treatment using a non-linear olefin or a 101 olefin and a non-linear olefin may be a polymerization treatment using a non-linear olefin alone. The obtained titanium trichloride composition (II
I) is preferred in terms of polymerization runnability when used, improved rigidity of the obtained polypropylene, and uniformity of JitP1.

Furthermore, in addition to the above-mentioned method in which a linear olefin and a non-linear olefin are used at least once each, the polymerization treatment can be carried out two or more times, for example, after the polymerization treatment of a non-linear olefin, a linear olefin is further added. It is also possible to carry out a polymerization treatment.

Reaction product (1) or organoaluminum compound (A
1) with titanium tetrachloride, with or without the addition of linear and non-linear olefins at any step of the reaction, at temperatures ranging from -10°C to 200°C, preferably from 0°C to 1°C.
It is carried out at 00° C. for 5 minutes to 10 hours.

Although it is preferred not to use a solvent, aliphatic or aromatic hydrocarbons can be used. (I) or the organic aluminum compound (A1), titanium tetrachloride, and the solvent may be mixed in any order, and the linear olefin and non-linear olefin may be added at any stage.

(1) or the organoaluminum compound (A1), titanium tetrachloride, and the entire amount of the solvent are preferably mixed within 5 hours, and the reaction is continued during the mixing. It is preferable to continue the reaction for another 5 hours after mixing the entire amount.

The amount of each used in the reaction is 1 mole of titanium tetrachloride, the solvent is 0 to 3.000+), the reaction product (1>K
Preferably, the organoaluminum compound (A1) is the organic aluminum compound (1)
Alternatively, the ratio (Al/Ti) of the number of A1 atoms in the (AI) to the number of Ti atoms in titanium tetrachloride is 0.05 to 10, preferably 0.06 to 03.

The polymerization treatment with a non-linear olefin, or a linear olefin and a non-linear olefin, is performed in any process of the reaction of the reaction product (1) or the organoaluminum compound (A1) with titanium tetrachloride. When adding a linear olefin and a non-linear olefin, and after the reaction product (1) or organoaluminum compound (A1) and titanium tetrachloride are added, the non-linear olefin or the linear olefin and the non-linear olefin are added. When adding an olefin, the reaction temperature is 0°C to 90°C in both polymerization treatments using linear olefins and n-linear olefins.
℃ for 1 minute to 10 hours, reaction pressure was atmospheric pressure (Okgf/c
m2G) ~10 kgf/cm'G, per 100 g of solid product (II), linear olefin O~1
00kg, and non-linear olefin 0.01g~1
The final titanium trichloride composition (III
) in the case of non-linear olefin homopolymerization treatment, the content of the non-linear olefin polymer is 0.01% to 99% by weight.
% by weight, and when linear olefins and non-linear olefins are used, the content of the linear olefin polymer block is O,I@@% to 49.5% by weight, and non-linear olefins are The content of olefin polymer block is o,
Polymerization is carried out so that the amount of o+i is 495% by weight.

The content of the non-linear olefin polymer block is 0.01
g [% by mass, the resulting titanium trichloride composition (II
The effect of improving the rigidity of polypropylene produced using I) is insufficient, and if the above range is exceeded, the improvement of the effect is not significant, resulting in operational and economical disadvantages.

As mentioned above, it is preferable to use a non-linear olefin in the polymerization treatment, and in this case, the weight ratio of the linear olefin polymer block to the non-linear olefin polymer block is determined to improve driveability, Considering both the effect of improving rigidity and the effect of improving rigidity, it is preferable to set it to 98/2 or less.

After the polymerization treatment using a non-linear olefin or a linear olefin and a non-linear olefin is completed, the liquid portion is separated by filtration or decantation after the reaction of the reaction product (summer) or organoaluminum compound (AI) with titanium tetrachloride. If the solid product (II) is suspended in a solvent after separation and removal of the linear olefin,
In any polymerization process with non-linear olefins, 100 aj of solvent is used for 100 g of solid product (II).
2~s, ooo Maro 1, organoaluminum compound 0.5g
In the presence of ~5,000 g, the reaction temperature was 0°C to 90°C for 1 minute to 10 hours, and the reaction pressure was atmospheric pressure (Okgf/ctx"G
) ~ lOkgf/cm'G.

Solid product (II) 0 linear olefins per IHg
~100kg, and 0.01g of non-linear olefin
~100 g of the titanium trichloride composition (III
) in the case of non-linear olefin homopolymerization treatment, the content of the non-linear olefin polymer is o, ox! i amount%~99g
Also linear olefins and non-linear! 1
) When using search reflexin, the content of the linear olefin polymer block is 0.1% to 49.5% by weight, and the content of the non-linear olefin polymer block is 0.01% to 49.5% by weight. Polymerization is carried out so that the amount of the polymer is 51 L and the weight ratio of the linear olefin polymer block to the non-linear olefin polymer block is 98/2 or less.

In any of the multi-stage polymerization treatments described above, after each stage of polymerization treatment using a linear olefin or non-linear olefin is completed, the reaction mixture can be used as it is in the next stage polymerization treatment. In addition, the coexisting solvent, unreacted linear olefin or non-linear olefin, and organoaluminum compound, etc. are removed by filtration or decantation, and the solvent and organoaluminum compound are added again. It may also be used for polymerization treatment with chain olefins or straight chain olefins.

The solvent used during embedding is preferably an aliphatic hydrocarbon,
Even if the organoaluminum compound is the same one used to obtain the reaction product (1) or the one used directly in the reaction with titanium tetrachloride without reacting with the electron donor (8,), It can be different.

After the reaction is completed, the liquid portion is separated and removed by filtration or decantation, and then washed with a solvent repeatedly.
The obtained solid product subjected to polymerization treatment (hereinafter sometimes referred to as solid product (II-A)) may be used in the next step while suspended in a solvent, or it may be further dried to form a solid product. You may take it out and use it as an object.

The solid product (n-A) is then reacted with an electron donor (B1) and an electron acceptor (F).

Although this reaction can be carried out without using a solvent, preferable results are obtained using an aliphatic hydrocarbon.

The amount used is (Ba) 0.1 g to 1,000 g, preferably 0.58 to 200 g, and (F) 0.1 g to 1,00 g, per 100 g of the solid product (II-A).
0g, preferably 0.28-500g, solvent 0-3.0
00m1, preferably 100-1. ．． 000+aj2
It is.

The reaction methods include: (1) reacting the solid product (o - A ) with an electron donor CB1) and an electron acceptor (F) at the same time, (2) reacting (F) with (II -A ), and then ( B1) Method of reacting ■(II-A) with C
Method of reacting (F) after reacting B1), ■(
There is a method of reacting B2) with (F) and then reacting with (n-A), but any method may be used.

The reaction conditions are 40°C to
It is desirable to react at 200°C, preferably 50°C to 100°C for 30 seconds to 5 hours.
- Reaction of A) and (B1) at 0℃ to 50℃ for 1 minute to 3 minutes.
After reacting for a period of time, it is reacted with (F) under the same conditions as in (1) and (2) above.

In addition, in method (■), (B1) and (F) are heated at 10°C to 1
After reacting at 00°C for 30 minutes to 2 hours, the mixture was cooled to 40°C or lower, and (II-A) was added thereto, followed by reaction under the same conditions as in previous statements (1) and (2).

After the reaction of the solid products (II-A), (821, and (F)), the liquid portion is separated and removed by filtration or decantation, and washing with a solvent is repeated to obtain the titanium trichloride composition used in the present invention. Product (III) is obtained.

The organoaluminum compound (A1) used in the production of the titanium trichloride composition (III) has the general formula A
IR', R'pxs-+p*p> (wherein, R1 and R2 represent a hydrocarbon group or an alkoxy group represented by an alkyl group, cycloalkyl group, or aryl group, X represents a halogen, and P, P' An organoaluminum compound represented by 1), which represents an arbitrary number satisfying o<p+p'≦3, is used.

Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, trimy-butylaluminum, tri-n-hexylaluminum, trimy-hexylaluminum, tri-2-methylpentylaluminium, tri-n-octyl Aluminum, trialkylaluminums such as tri-n-decylaluminum, diethylaluminum monochloride, moro-propylaluminum monochloride, dij-butylaluminum monochloride, diethylaluminum monofluoride, diethylaluminium monobromide, diethylaluminium monoiodide dialkyl aluminum monohalides such as, dialkyl aluminum hydrides such as diethyl aluminum hydride, alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, monoalkyl such as ethyl aluminum dichloride, i-butyl aluminum dichloride, etc. Examples include aluminum cibaride, and alkoxyalkylaluminums such as monoethoxydiethylaluminum and jetoxymonoethylaluminum can also be used.

These organoaluminum compounds can also be used in combination with ZPAs or more.

As the electron donor used to produce the titanium trichloride composition (n+) used in the present invention, various ones are shown below, but (Bl) and (B1) are mainly ethers. It is preferable to use the other electron donor in combination with ethers.

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

Specific examples include diethyl ether, moro-propyl ether, di-n-butyl ether, diisoamyl ether, moro-pentyl ether, moro-hexyl ether,
Diisoamyl ether, Moro-octyl ether, Diisoamyl ether, Moro-dodecyl ether, Diphenyl ether, Ethylene glycol monoethyl ether,
Ethers such as tetrahydrofuran, methanol, ethanol, propatool, butanol, pentanol, hexanol, octatool, phenol, cresol,
Alcohols or phenols such as xylenol, ethylphenol, naphthol, methyl methacrylate,
Ethyl acetate, butyl formate, amyl acetate, vinyl butyrate, vinyl acetate, ethyl benzoate 2-propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, 2-ethylhexyl toluate , esters such as methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate, acetaldehyde, Aldehydes such as benzaldehyde, fatty acids such as formic acid, acetic acid, propionic 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, Nitriles such as acetonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β(N,N-dimethylamino)ethanol, pyridine, quinoline, α-picoline, 2,4.6-
1-limethylpyridine, N,N.

No, No-tetramethylethylenediamine, aniline, dimethylaniline and other amines, dilumamide, hexamethylphosphoric triamide, N, N, NN', N''
-Pentamethyl-N゛~β-dimethylaminomethylphosphoric acid triamide, amine Fs such as octamethylpyrophosphoramide, ureas such as N,N,N',N'-tetramethylurea, phenyl isocyanate, tolylisocyanate incyanates such as, azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-butylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxyto, dimethylphosphite, moro- triethylphosphite, triethylphosphite,
Phosphites such as tri-n-butyl phosphite and triphenyl phosphite; phosphites such as ethyl diethyl phosphinite, ethyl dibutyl phosphinite, and phenyl diphenyl phosphinite; diethyl thioether, diphenyl thioether, methyl phenyl thioether; Other examples include thioethers such as ethylene sulfide and propylene sulfide, and thioalcohols such as ethylthioalcohol, n-propylthioalcohol and thiophenol.

These electron donors can also be used in combination1
The electron donor (B1) to obtain the reaction product (r), the solid product (II) or (B1) to be reacted with (II-A) may be the same or different.

Straight chain olefins used in polymerization include ethylene,
Propylene, butene-1) pentene-1, hexene-1
, octene-1 and the like are used, and ethylene and propylene are particularly preferably used. One or more types of these straight chain olefins are used.

The non-linear olefin used in the polymerization process has the following formula: CH, = CH-R' (wherein R3 has a saturated cyclic structure of a hydrocarbon that may contain silicon, and may contain silicon) A saturated ring-containing hydrocarbon monomer represented by 1) representing a saturated ring-containing hydrocarbon group having 3 to 18 carbon atoms, represented by the following formula, CH,=CH-R'-R' (wherein, R' is silicon R'
, R6 and R7 represent a silane hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, but R5, R6 and R
Any one of 7 may be hydrogen. Branched olefins represented by 1), zero-order formula, (where n is 0.1, m is 1.2, and R
6 represents a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R@ represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen, or a halogen. and when m is 2, each R1) is an aromatic monomer represented by 1), which may be the same or different.

To be more specific, examples of the saturated ring-containing hydrocarbon monomer (1) include vinylcyclopropane, vinylcyclobutane, vinylcyclopentane, 3-methylvinylcyclopentane, vinylcyclohexane, 2-methylvinylcyclohexane, 3- In addition to vinylcycloalkanes such as methylvinylcyclohexane, 4-methylvinylcyclohexane, and vinylcyclohebutane, allylcycloalkanes such as allylcyclopentane and allylcyclohexane, cyclotrimethylenevinylsilane, cyclotrimethylenemethylvinylsilane, and cyclotetramethylene Vinylsilane, cyclotetramethylenemethylvinylsilane, cyclopentamethylenevinylsilane, cyclopentamethylenemethylvinylsilane, cyclopentamethyleneethylvinylsilane, cyclohexamethylenevinylsilane, cyclohexamethylenemethylvinylsilane, cyclohexamethyleneethylvinylsilane, cyclotetramethyleneallylsilane, Single saturated ring hydrocarbons having a silicon atom in the saturated ring structure such as cyclotetramethylenemethylallylsilane, cyclopentamethyleneallylsilane, cyclopentamethylenemethylallylsilane, cyclopentamethyleneethylallylsilane, cyclobutyldimethylvinylsilane, cyclopentyldimethyl Vinylsilane, cyclopentylethylmethylvinylsilane, cyclopentyldiethylvinylsilane, cyclohexylvinylsilane, cyclohexyldimethylvinylsilane, cyclohexylethylmethylvinylsilane, cyclobutyldimethylallylsilane, cyclopentyldimethylallylsilane, cyclohexylmethylallylsilane, cyclohexyldimethylallylsilane, cyclohexylethylmethylallylsilane,
Examples include saturated ring-containing hydrocarbon monomers containing a silicon atom in addition to the saturated ring structure, such as cyclohexyldiethylallylsilane, 4-trimethylsilylvinylcyclohexane, and 4-trimethylsilylallylcyclohexane.

Examples of the branched olefins (3) include 3-methylbutene-1,3-methylpentene-1,3-ethylpentene-
1st class 3-position branched olefin, 4-ethylhexene-1,
4-position technical olefins such as 4,4-dimethylpentene-1,4,4-dimethylhexene-1, vinyltrimethylsilane, vinyltriethylsilane, vinyltri-n-butylsilane, allyltrimethylsilane, allylethyldimethylsilane, allyldiethylmethyl silane, alkenylsilanes such as allyltriethylsilane, allyltri-n-propylsilane, 3-butenyltrimethylsilane, 3-butenyltriethylsilane, dimethyldiallylsilane,
Examples include diallysilanes such as ethylmethyldiallylsilane and diethyldiallylsilane.

In addition, as the aromatic monomer (2), styrene, its rust conductor, alkylstyrenes such as 0-methylstyrene and pt-butylstyrene, 24-dimethylstyrene, 2,5-dimethylstyrene, Dialkylstyrenes such as 3.4-dimethylstyrene and 3.5-dimethylstyrene, 2-methyl-4-fluorostyrene, 2-ethyl-4-chlorostyrene, 0-fluorostyrene, p-
Halogen-substituted styrenes such as fluorostyrene, trialkylsilylstyrenes such as P-trimethylsilylstyrene, ah-triethylsilylstyrene, p-ethyldimethylsilylstyrene, allyltoluenes such as 0-allyltoluene and p-allyltoluene, 2 -Allylxylene such as allyl-p-xylene, 4-allyl-〇-xylene, 5-allyl-xylene, vinyldimethylphenylsilane, vinylethylmethylphenylsilane, vinyldiethylphenylsilane, allyldimethylphenylsilane, allyl ethyl Examples include alkenylphenylsilanes such as methylphenylsilane, 4-(o-)lyl)-butene-1 and 1-vinylnaphthalene, and 1) or more of these non-linear olefins are used.

Electron acceptor (II-A) reacted with solid product (II-A)
F) is typified by halides of elements in Groups ■1 to V1 of the periodic table. Specific examples include anhydrous aluminum chloride,
Silicon tetrachloride, stannous chloride, stannic chloride, titanium tetrachloride, zirconium tetrachloride, phosphorus trichloride, phosphorus pentachloride,
Examples include vanadium tetrachloride and antimony pentachloride.
These can also be used in combination. Most preferred is titanium tetrachloride.

The following solvents (Ol) are used.

Examples of aliphatic hydrocarbons include n-pentane, n-hexane, n-hebutane, n-octane, i-octane, etc. In addition, instead of or together with aliphatic hydrocarbons, carbon tetrachloride, Halogenated hydrocarbons such as chloroform, dichloroethane, trichloroethylene, and tetrachloroethylene can also be used. Aromatic compounds include aromatic hydrocarbons such as benzene and naphthalene, and their derivatives such as mesitylene, durene, ethylbenzene, isopropylbenzene, 2-ethylnaphthalene, and alkyl substituted products such as 1-phenylnaphthalene, monochlorobenzene, and chlorine. Examples include halides such as toluene, chloroxylene, chloroethylbenzene, dichlorobenzene, and brombenzene.

The titanium trichloride composition obtained from the above cherry blossoms (III
), an organoaluminum compound (A1), and an aromatic carboxylic acid ester (E) or an organosilicon compound having a 5i-0-C bond and/or a mercapto group (S
) in a predetermined amount as described below to form a catalyst used in the production of polypropylene (a), or more preferably, to use it as a preactivated catalyst by reacting an olefin.

Pre-activation is performed using titanium trichloride (1 g of titanium trichloride, 0.005 g of organoaluminum compound - 0.00 g of organic aluminum compound, 0 soybean solvent)
~50IL, hydrogen 0-1. o00sj), and olefin 0.01g to 5,000g, preferably 0.05g
~3.000g of titanium trichloride composition (II
I) It is desirable to polymerize 0.0 to 2.000 g, preferably 0.05 to 2 QOg of olefin per Ig.

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

In the preactivation C, it is also possible to add in advance an aromatic carboxylic acid ester (E) or an organosilicon compound (S) having an S+-0-C bond and/or a mercapto group.

Examples of olefins used for preactivation include ethylene, propylene, butene-15pentene-1, hexene-1) heptene-1, octene-1, etc.
ij! Monoolefins, 4-methyl-pentene-1,
Examples include branched monoolefins such as 2-methyl-pentene-1, and one or more types of olefins are used. In addition, as the organoaluminum compound, those similar to the above-mentioned (A1) can be used, but preferably the below-mentioned (A
The same dialkyl aluminum monohalide as in 2) is used.

After the preactivation reaction is completed, a predetermined amount of aromatic carboxylic acid ester (E) or organosilicon compound (S) having a 5i-0-C bond and/or mercapto group is added to the preactivated catalyst component slurry. The added catalyst can also be used as it is for propylene polymerization.

In addition, coexisting solvents, unreacted olefins, and organoaluminum compounds are removed by filtration or decantilization, and a solvent is added to the dried powder or granules to form a suspension. Aluminum compound (A
1) and (E) or (S) are combined as a catalyst and subjected to polymerization of propylene, and the coexisting solvent and unreacted olefin are removed by distillation under reduced pressure or by evaporating with an inert gas stream, etc. , add a solvent to the granular material or the granular material to form a suspended state, add organoaluminum compound (A1) as necessary to this, and further combine with (E) or (S) to prepare the catalyst. It can also be used in the polymerization of propylene.

The above titanium trichloride composition (Ill), organoaluminum compound (A2), during propylene polymerization,
Furthermore, aromatic carboxylic acid ester (E) or 5i-0
Regarding the usage amount of the organosilicon compound (S) having a -C bond and/or a mercapto group, when an aromatic carboxylic acid ester (E) is used as the third component of the catalyst, the amount of the organosilicon compound (S) to be used is The molar ratio of the composition (Ill) (
E)/(Ill) is 0.1 to 1O10, and 5t-0-
When using an organosilicon compound (S) having a C bond and/or a mercapto group, the (S) and the (Ill
) molar ratio (S)/(+1))1.0 to ]0.0, and in both cases, the organoaluminum compound (A2) and the titanium trichloride composition (Il
molar ratio (A1)/(Ill) of 0.1 to 20
0, preferably 0.2 to +00.

Titanium trichloride composition (Ill) during polymerization of propylene
The organoaluminum compound (A1) to be combined with is preferably a dialkylaluminum monohalide having the general formula ^IRIORIIX.

In the formula, RIO and H1+ represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, an alkaryl group, or an alkoxy group, and X represents a halogen.

Specific examples include diethylaluminum monochloride, di-n-propylaluminum monochloride, dialkylaluminum monohalide, moro-butylaluminum monochloride, diethylaluminum monoiodide, diethylaluminium monobromide, and the like.

Specific examples of the aromatic carboxylic acid ester (E) that can be used as the third component constituting the catalyst include ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, and toluic acid. Methyl, ethyl toluate, 2-ethylhexyl toluate, methyl anisate, ethyl anisate, propyl anisate, ethyl cinnamate, methyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, ethyl phenylacetate can be given.

A specific example of an organosilicon compound (S) having a 5i-0-C bond and/or a mercapto group that can be used as the third component of the catalyst in place of the aromatic carboxylic acid ester (E) is methyltrimethoxysilane. , vinyltrimethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, triphenylmethoxysilane, tetraethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane Ethoxysilane, vinyltriethoxysilane, propyltriethoxysilane, allyltriethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, n-octyltriethoxysilane, n
-Octadecyltriethoxysilane, 6-driethoxysilyl-2-norbornene, dimethyljethoxysilane, diethyljethoxysilane, diphenyljethoxysilane, trimethylethoxysilane, triethylethoxysilane, triphenylethoxysilane, allyloxytrimethylsilane, methyltriethoxysilane n-butoxysilane, dimethylcytopropoxysilane, trimethylmipropoxysilane, tetra-n-butoxysilane, methyltri-n-butoxysilane, tetra(2-ethylbutoxy)silane,
Methyltriphenoxysilane, dimethyldiphenoxysilane, trimethylphenoxysilane, trimethoxysilane, triethoxysilane, triethoxychlorosilane,
Tri-propoxychlorosilane, tri-n-butoxydichlorosilanetetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, methyldiacetoxysilane, diacetoxymethylvinylsilane, dimethyldiacetoxysilane, methylphenyldiacetoxy 5j-0-C such as silane, diphenyldiacetoxysilane, trimethylacetoxysilane, triethylacetoxysilane, phenyldimethylacetoxysilane, triphenylacetoxysilane, bis(trimethylsilyl)adipate, trimethylsilylbenzoate, triethylsilylbenzoate, etc.
Organosilicate metals having a bond, mercaptomethyltrimethylsilane, 2-mercaptoethyltrimethylsilane, 3-mercaptopropyltrimethylsilane, 4-mercapto-〇-butyltrimethylsilane, mercaptomethyltriethylsilane, 2-mercaptoethyltriethylsilane, 3-mercaptopropyltriethylsilane,
Organosilicon compounds having a mercapto group such as l-mercaptoethyltrimethylsilane, 3-mercaptopropyldimethylphenylsilane, 3-mercaptopropylethylmethylphenylsilane, 4-mercaptobutyldiethylphenylsilane, and 3-mercaptopropylmethyldiphenylsilane; , mercaptomethyltrimethoxysilane, mercaptomethyldimethylmethoxymethylsilane, mercaptomethyldimethoxymethylsilane, mercaptomethyltriethoxysilane, mercaptomethyljethoxymethylsilane, mercaptomethyldimethylethoxysilane, 2-mercaptoethyltrimethoxysilane, 3
-Mercaptopropyltrimethoxysilane, dimethoxy-3-mercaptopropylmethylsilane, dimethoxy-
5i such as 3-mercaptopropylmethylsilane, 3-mercaptopropyltriethoxysilane, jetoxy-3-mercaptopropylmethylsilane, mercaptomethyldimethyl-2-phenylethoxysilane, 2-mercaptoethoxytrimethylsilane, 3-mercaptopropoxytrimethylsilane, etc. -Organosilicon compounds having a -0-C bond and a mercapto group, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane,
3-aminopropyljethoxymethylsilane, 3-aminopropyldimethylethoxysilane, 3-aminophenoxydimethylvinylsilane, 4-aminophenoxydimethylvinylsilane, 2-aminoethylaminomethyltrimethoxysilane, 3-(2-amineethylaminopropyl) ) dimethoxymethylsilane, 2-aminoethylaminomethylbenzyloxydimethylsilane, 3-[2-(2-
Examples include organosilicon compounds having an S+-0-C bond and an amino group, such as aminoethylaminoethylamino)propylcotrimethoxysilane.

Polymerization of propylene is carried out using the catalyst thus combined or the preactivated catalyst. The polymerization format for propylene is n-hexane, n-hexane,
Examples include slurry polymerization carried out in a hydrocarbon solvent such as -hebutane, low octane, benzene or toluene, bulk polymerization carried out in liquefied propylene, and gas phase polymerization carried out in the gas phase.

Polymerization temperature is 20°C to 85°C, preferably 20°C to 85°C.
Relatively low temperatures of 80°C, particularly preferably 40°C to 75°C, are suitable. If the polymerization temperature is too high, it will be difficult to increase the stereoregularity of the resulting polypropylene, and if the polymerization temperature is too low, the polymerization rate of propylene will be slow, and the impractical 0 polymerization pressure will be lower than normal pressure. (OKHf/ca
+2G) to 50 gf/lIn'G'r' usually for 30 minutes to +5 hours, usually for about 3 hours, and adding hydrogen in order to adjust the molecular weight is the same as in the conventional propylene polymerization method.

It should be noted that polypropylene (1) used in the present invention may not necessarily be obtained as long as the molar ratio of each catalyst component and the above polymerization conditions are within the ranges described, and depending on the individual polymerization conditions (in particular, the polymerization conditions) It is necessary to confirm the temperature, the specific type of (E) or (S) to be used, and the molar ratio to (In), and select it so as to satisfy the physical property requirements necessary for polypropylene (a), which will be described later.

The propylene polymerization described above can be carried out by either batch polymerization or continuous 1)). After completion of the polymerization, known post-treatment processes such as catalyst deactivation process and catalyst residue removal process are carried out as necessary. After blushing, the polypropylene (a
) is obtained.

The polypropylene (8) thus obtained must have the following physical properties. That is, the melt flow rate (MF
R) has a load of 2.16gf under the temperature condition of 230℃.
In the case of 0.1g 710 minutes to 100g 710 minutes,
Preferably it is 0.5g/710 minutes to 80g/10 minutes.

If the MFR is less than O, 1 g/10 minutes, the fluidity during melting will be insufficient, and if it exceeds 100 g/710 minutes, the strength of the molded product obtained will be insufficient.

Further, the isotactic pentad fraction (P), which is a measure of stereoregularity, which is the most characteristic physical property of polypropylene (a), is 0.960 to 0.990. Here, isotactic pentad minutes! I(P) means ^, Za
Macro-molecules by mbelN et al.
6925 (1973), namely,
It is the isotactic fraction in pentad units in a polypropylene molecule measured using 13C-NMR.

In other words, Terugo I! (P) means the fraction of the propylene monomer unit at the center of a chain of five consecutive meso-bonded propylene base units.

However, the above-mentioned method for determining the attribution of the NIIR absorption peak is
acromolecules 881) 7 (1975)
Based on. Note that the value of the isotactic pentad fraction (P) in the present invention is the value of the stereoregular polypropylene as it is, and is not the value of the polypropylene after extraction, fractionation, etc.

If P is less than 0960, the desired high rigidity and high heat resistance will not be achieved.There is no upper limit for P, but due to constraints in the production of polypropylene according to the present invention, P -0
, 990 or so can actually be used at the present time of the present invention.

Furthermore, the number of weight average molecular weight, which is a measure of molecular weight distribution, which is another characteristic physical property of polypropylene (a), is determined by the ratio to average molecular weight, weight average molecular weight/number average molecular weight (
Q) is 7-30. Regarding the molecular weight distribution,
Generally, the ratio of weight average molecular weight to number average molecular weight, weight average molecular weight/number average molecular weight (Q), is used as a measure, and the larger the ratio (Q), the broader the molecular weight distribution. If Q is less than 7, the durability of the obtained molded product will be poor, and if it exceeds 30, the processability will be poor.

As mentioned above, the polypropylene (b) used in the production of the composition of the present invention uses a Mg compound-supported catalyst component as the titanium-containing solid catalyst component (T+), and an organoaluminum compound (A1) or Polypropylene obtained by gas phase polymerization of propylene or propylene and an olefin other than propylene using a catalyst in combination with an electron donor (B1) if necessary is preferably used for the purpose of the invention. However, it is not limited to this.

That is, a so-called Ziegler-Natsuta catalyst is used, which is a combination of a known titanium-containing solid catalyst component (T1), an organoaluminum compound catalyst component (A3), and an electron donor (B1) as necessary. By polymerizing propylene by slurry polymerization carried out in a solvent, bulk polymerization using propylene itself as a solvent, or gas phase polymerization carried out in a gas phase mainly composed of propylene gas, or by copolymerizing propylene and an olefin other than propylene. Any polypropylene available can be used.

More specifically, one or more of the known monopoles of propylene alone, propylene-olefin random copolymers, and propylene-olefin block copolymers can be mentioned.

Those used as the titanium-containing solid catalyst component (T1) are disclosed in JP-A-52-104810 and JP-A-62.
-10481), JP-A-62-104812, etc., the so-called Mg compound-supported catalyst component in which titanium tetrachloride is supported on an Mg compound, and JP-B-10481).
Examples include titanium trichloride compositions described in JP-A-28573, JP-A-58-17104, and the like.

The organoaluminum compound (A1) used in combination with the titanium-containing solid catalyst component is the same as the organoaluminum compound (A1) used in preparing the titanium trichloride composition (m) described above. Available for use.

In addition to the electron donors (B1) mentioned above, examples of the electron donor (B1) used as necessary include aromatic carboxylic acid esters used in producing polypropylene (a). (E) and organosilicon compounds (S
) can be used.

By mixing the thus obtained polypropylene (a) and polypropylene (b), the desired polypropylene composition is obtained.

Note that the polypropylene (a) contains a crystalline non-linear olefin polymer derived from the polymerization process using a non-linear olefin during the preparation of the titanium trichloride composition (Ill) described above. When mixing polypropylene (a) and polypropylene (b), the mixing ratio should be such that the crystalline non-linear olefin polymer is contained in the composition in an amount of 0.1 pps to 2% by weight. is necessary.

Specific proportions include 0.5% by weight of polypropylene (a) to 901i% by weight, with the total amount being 100% by weight;
Polypropylene (b) 99.5% to 101% by weight
That's about it.

Content of crystalline non-linear olefin polymer is 0.1 weight p
If it is less than pm, the transparency of the molded article manufactured using the obtained composition will be insufficient, and if it exceeds 2% by weight, the improvement in transparency will not be significant and it will be uneconomical.

In the method for producing the composition of the present invention, predetermined amounts of the polypropylene (a) and polypropylene (b) may be mixed and then sufficiently kneaded.

As a mixing device, a high-speed stirring device such as a Hensel mixer (trade name) or a super mixer may be used, and as a kneading device, a Pan Bali mixer, roll, co-kneader, axle-shaft or twin-shaft extruder, etc. may be used. ,W
The conditions for the first reaction are not limited, but are from room temperature to 100°C, preferably from room temperature to 60°C, for 1 minute to 1 hour, preferably 3 minutes to 30 minutes. Also, the crosstalk conditions are not limited, but
The residence time in the extruder is 10 seconds to 15 minutes, preferably 2 seconds to 10 minutes. Mixed M temperature is 180-30
The temperature is 0°C, preferably 200-280°C.

After kneading, it is desirable to cool and cut the mixture and use it as a pellet-like composition.

The composition of the present invention may optionally contain various additives that are normally added to polypropylene compositions, such as antioxidants, antistatic agents, ultraviolet absorbers, copper inhibitors, flame retardants, pigments, etc. can do. Furthermore, the composition of the present invention includes:
Polymers such as polyethylene, polybutene, ethylene-propylene rubber, and any filler may be contained within a range that does not significantly impair the object of the present invention. Examples of fillers include glass fiber, talc, mica, wood powder,
Examples include inorganic or organic materials such as synthetic Ill fibers.

The resulting polypropylene composition can be processed by injection molding,
Vacuum forming, extrusion molding, blow molding, stretched film,
Used for molded products such as sheets.

[Examples] 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.

(IIMFR: Melt flow rate JIS K 72
30 According to condition 14 in Table 1. (Unit: g/io min) (
2) Isotactic pentad fraction (P).

Based on the method described above, JEOL GX-2 manufactured by JEOL Ltd.
70 was used to add Wei I.

[3] Weight average molecular weight and weight average molecular weight/number average molecular weight (Q): Measured and determined by GCP-15QC gel vermiace chromatography manufactured by Waters.

(4) Rigidity: Melt the polypropylene composition in an injection molding machine #(1)! Temperature: 230°C, mold temperature: 50r: A test piece of type JI5 was prepared. After leaving the test piece in a room with a humidity of 50% and a room temperature of 23°C for 96 hours, it was rated 2 in accordance with JIS K 72 (13).
Flexural modulus was measured at 3℃ (
Unit: kgf/cs2) (5) Durability: A test piece was prepared in the same manner as in (4), and JIS 71)5
Tensile creep test (load 248 kgf/c1)
) and the creep rupture time was measured.
(Unit: 2 hours) (6) Using a transparent nibless machine at a temperature of 20℃ and a pressure of 200kgf/cs.
A polypropylene composition was formed into a film with a thickness of 150 μm under the conditions of 1. After coating both sides of the film with liquid paraffin, the internal haze was measured in accordance with JIS K7105.

(Unit: %) Example 1 (1) Production of polypropylene (a) ■ Preparation of titanium trichloride composition (m) 61 n-hexane, 5.0 mol of diethylaluminium monochloride (DEAC), 12 mol of diisoamyl ether
．． 0 mol was mixed at 25°C for 1 minute and reacted at the same temperature for 5 minutes to form reaction product liquid (I) (diisoamyl ether/
A DEAC molar ratio of 2.4) was obtained.

Put 40 moles of titanium tetrachloride into a reactor purged with nitrogen,
It was heated to 35°C, and the entire amount of the reaction product liquid (1) was added dropwise thereto over 180 minutes, and then kept at the same temperature for 60 minutes, and heated to 80°C.
The temperature was raised to ℃ and reacted for another 1 hour, cooled to room temperature, the supernatant liquid was removed, 20K of n-hexane was added, and the supernatant liquid was removed using a decanter. This operation was repeated 4 times to obtain a solid product ( II) was obtained.

This reaction (total amount of (1) was suspended in n-hexane 30J2, 400 g of diethylaluminium monochloride was added, 1.5 kg of propylene was added at 30°C, and polymerization was carried out at the same temperature for 1 hour). After a period of time, the supernatant was removed by decantation, and then diluted with 301 n-hexane.
The solid was washed twice.

Subsequently, after adding 301 g of n-hexane and 400 g of diethylaluminium monochloride, the temperature was raised to 40°C, and 5.7) tg of vinylcyclohexane was added, and the temperature was raised to 40°C.
After the completion of the polymerization treatment for 2 hours, the supernatant liquid was removed.
! The operation of adding n-hexane 30J2 and removing the supernatant liquid by decanting was repeated four times to obtain a solid product (n-A) subjected to multi-stage polymerization treatment with propylene-vinylcyclohexane.

While the entire amount of this solid product (II-A) was suspended in n-hexane 91, 3.5 kg of titanium tetrachloride was added at room temperature over about 10 minutes, and the mixture was reacted at 80°C for 30 minutes. After that, add 1.6 kg of diisoamyl ether,
After the reaction was completed for 1 hour at 80° C., the supernatant was removed five times, followed by drying under reduced pressure to obtain a titanium trichloride composition (III).

The content of the propylene polymer block in the obtained titanium trichloride composition (■1) was 16.7% by weight, the content of the vinylcyclohexane polymer block was SO, O, and the titanium content was 8.4% by weight. % by weight.

■Preparation of preactivated catalyst component A stainless steel reactor with an internal volume of 1,501 mm equipped with a stirrer with inclined blades was replaced with nitrogen gas, and 100 j of n-hexane was used.
, diethylaluminum monochloride 1.14kg
, and titanium trichloride composition (III) 1 obtained in the above
．． 8 was added at room temperature. Next, the temperature inside the reactor was increased to 3
The temperature was set to 0°C. Subsequently, 1 kg of propylene was added and reacted at the same temperature for 2 hours (titanium trichloride composition (III)
After the reaction (0.5 g of propylene per Ig), unreacted propylene was removed to obtain a preactivated catalyst component in the form of a slurry.

■Polymerization of propyleneInto a nitrogen-substituted polymerization vessel equipped with a stirrer and a two-stage turbine blade with an internal volume of 15,041 mm, the preactivated catalyst component slurry (note, including diethylaluminium monocrite) obtained in step (■) above was added to a polymerization vessel equipped with a stirrer and nitrogen-substituted with titanium atoms. Converted to 1). 5 milligram atoms/
hr, and p-methyl toluate was used as a catalyst at a molar ratio of 1.8 to titanium atoms from the same pipe, and n-hexane was continuously fed from a separate pipe at a rate of 13 kg/hr. Furthermore, hydrogen was supplied so that the concentration in the gas phase of the polymerization vessel was 1) volume %, and propylene was supplied so that the total pressure was maintained at 10 kg/cs'G, and slurry polymerization of propylene was carried out at 60°C. The test was carried out continuously for 120 hours.

During the polymerization, the polymer slurry was continuously drawn out from the polymerization vessel into a flash tank having an internal volume of 501 so that the retention level of the polymer slurry in the polymerization vessel was 75% by volume.

The pressure is reduced in the flash tank to remove unreacted hydrogen and propylene, while methanol is pumped at 1 kg/hr.
The contact treatment was carried out at 70°C. Subsequently, after neutralizing the polymer slurry with an aqueous sodium hydroxide solution, the polymer is washed with water, separated, and dried to form polypropylene (a
) was obtained at 10 kg/hr.

The polypropylene (1)) contains 328 pps by weight of crystalline vinylcyclohexane polymer block and has an MFR of
was 4°0 (g/10 min), the isotactic pentad fraction (p) was 0.985, and the weight average molecular weight/number average molecular weight (Q) was 13.5.

(2) Production of polypropylene (b)■ In a stainless steel reactor equipped with a stirrer, decane 3
1. 480 g of anhydrous magnesium chloride, 1.7 kg of loubutyl orthotitanate, and 1.95 kg of 2-ethyl-1-hexanol were mixed and heated to 130° C. for 1 hour with stirring to dissolve and form a uniform solution. The homogeneous solution was
180 g of di-n-butyl phthalate at 0°C with stirring.
After 1 hour, silicon tetrachloride! ! 5.2kg to 2.5
The mixture was added dropwise over a period of time to precipitate a solid, and the mixture was further heated to 70° C. for 1 hour. The solid was separated from the solution and washed with hexane to give a solid product (rV).

The total amount of the solid product (rV) was 15% of 1,2-dichloroethane.
1 and mixed with titanium tetrachloride 15J2 dissolved in
Add 360 g of di-n-butyl phthalate and add 1.
After reacting at 00°C for 2 hours, the liquid phase was removed by decantation at the same temperature, and 15J2 of 1,2-dichlorothane and 15Il of titanium tetrachloride were added again.
The mixture was stirred at 0° C. for 2 hours, washed with hexane, and dried to obtain a Mg compound-supported catalyst component.

■ After purging a stainless steel reactor with an internal volume of 31 with inclined blades with nitrogen gas, use n-hexane 20I1).
150 g of triethylaluminum and Mg obtained in ①
100 g of compound-supported catalyst component was added at room temperature. Subsequently, 60 g of propylene was added and the reaction was carried out at 40°C for 2 hours (propylene 0
．． 5g reaction).

After the reaction was completed, unreacted propylene and the liquid phase were removed, and the solid was washed with n-hexane and further dried to obtain a preactivated catalyst component.

■ L/D equipped with a nitrogen-substituted agitator with an internal volume of aO1.
After pouring 20 kg of polypropylene powder with an MFR of 4.0 into the horizontal polymerization vessel in step 3, n-hexane was added to the preactivated catalyst component obtained in step (3) above to form a 4.0% by weight n-hexane suspension. After that, the suspension has a concentration of 0.0% in terms of titanium atoms.
Further, triethylaluminum at 6.8 g/hr and diphenyldimethoxysilane at 2.1 g/hr were continuously fed from separate feed ports.

In addition, hydrogen was supplied so that the concentration in the gas phase of the polymerization reactor was maintained at 0.3% by volume, and propylene was supplied so that the total pressure was maintained at 23Kg/c@2G, and the gas phase polymerization of propylene was carried out for 70%.
The test was carried out continuously for 120 hours at ℃. During the polymerization, the polymer was continuously drawn out at a rate of fo, OKg/hr so that the polymer retention level in the polymerization vessel was 60% by volume.

The extracted polymer is then treated with 0 propylene oxide.
．． Polypropylene <b> was obtained after being buried in contact with nitrogen gas containing 2% by volume at 95° C. for 15 minutes.

The MFR of the polypropylene (b) is 4.0 (g/10
minute), isotactic pentad fraction (P) is 0.9
54, weight average molecular weight/number average molecular weight (Q) is 4.4
Met.

(3) Production of polypropylene composition (+
3 g of polypropylene (a) obtained in >, 17 g of polypropylene (b) obtained in (2), tetrakis[methylene-3-(3°, 5°-dyl t-butyl-4-hydroxyphenyl) ) Propionate] 10 kg of methane and 10 g of calcium stearate were added and mixed with stirring for 5 minutes. Subsequently, the mixture was melt-kneaded and extruded at 230° C. using a single-screw extruder with an inner diameter of 40 aha, cooled with water, and then cut to obtain a pellet-shaped polypropylene composition containing 491 HLpp+a of crystalline vinylcyclohexane polymer blocks. Ta.

Comparative Example 1.2 and Example 2.3 In (3) of Example 1, the mixing ratio of polypropylene (a) and polypropylene (b) was changed to adjust the content of the crystalline vinylcyclohexane polymer block as described below. A polypropylene composition was obtained in the same manner except for the changes shown in the table.

Comparative Example 3 (1) In (1) of Example 1, the solid product (
II) solid product without multi-stage polymerization treatment with propylene and vinylcyclohexane)
A titanium trichloride composition was obtained in the same manner except that the solid product (II-A) was used.

■ In (1) (■) of Example 1, titanium trichloride composition 1 obtained in the above (■) was used in place of the titanium trichloride composition (Hl).
．． [A preactivated catalyst component slurry was obtained in the same manner except that g was used for l and the amount of diethylaluminium monochloride used was 2.81 kg.

(2) Polypropylene was obtained in the same manner as in Example 1 (1) (2) except that the preactivated catalyst component slurry obtained in (1) above was used as the preactivated catalyst component slurry. The MFR of the polypropylene is 4.0 (g/10 minutes)
, the isotactic bentad fraction (P) is 0.973
The weight average molecular weight/number average molecular weight (Q) was 10.7.

(2) In (3) of Example 1, polypropylene (a
A polypropylene composition was obtained in the same manner except that 3 kg of the polypropylene obtained in (1) above was used instead of (1).

Comparative Example 4 (1) In (1) (■) of Example 1, the preactivated catalyst slurry was prepared at 7.0 milligram atoms per titanium atom, without supplying the third component of the catalyst, methyl ρ-toluate.
Polypropylene was obtained by polymerizing propylene in the same manner, except that the hydrogen concentration in the gas phase in the polymerization vessel was 5.2% by volume. The polypropylene contains 200 ppm by weight of crystalline vinylcyclohexane polymer block, and has an MFR of 4.0 (g
/10 minutes), isotactic cubentad $(P)
was 0.967, and the weight average molecular weight/number average molecular weight (Q) was a, O.

(2) In (3) of Example 1, polypropylene (a
) A polypropylene composition containing 50 pp by weight of a crystalline vinylcyclohexane polymer block except that 5 kg of the polypropylene obtained in the above (1) was used in place of (1), and 5 kg of polypropylene (b) was used for 15. I got it.

Example 4 (1+■ Preparation of titanium trichloride composition (III)) rhohebutane 4j2, diethylaluminium monochloride 5
．． 0 mol, diisoamyl ether 9.0 mol, di-n-
The reaction solution obtained by reacting 5.0 mol of butyl ether at 18°C for 30 minutes was added dropwise to 27.5 mol of titanium tetrachloride at 40°C for 300 minutes, and then kept at the same temperature for 1.5 hours to react. After that, the temperature was raised to 65°C, the reaction was carried out for 1 hour, the supernatant liquid was removed, 20 u of n-hexane was added, and the operation of removing with decanethisilane was repeated 6 times to obtain the solid product (II
) 1.8 kg was suspended in 40 Il of n-hexane, 500 g of diethylaluminum monochloride was added, and 0.9 kg of propylene was added at 30°C and reacted for 1 hour to perform the first stage polymerization treatment.

After the reaction time had passed, the supernatant was removed, and 20% of n-hexane was added.
The operation of adding Il and removing it by decantation was repeated twice. After adding n-hexane 40j2 and 500 g of diethylaluminum monochloride at 1 M, add allyltrimethylsilane to 7.6 g, and add 2 g of allyltrimethylsilane at 40°C.
After reacting for a period of time, a second stage polymerization treatment is carried out, and propylene-
A solid product (II-A) was obtained after a multistage polymerization treatment using allyltrimethylsilane.

After the reaction, after removing the supernatant liquid, adding 20J2 of n-hexane and removing with a decantation process was repeated 2rgJM to convert the solid product (TI-^) subjected to the above polymerization treatment into n-hexane.
Suspended in hexane 71 g% titanium tetrachloride 1,8
Add 1.8 g of n-butyl ether and react at 80°C for 3 hours. After the reaction, remove the supernatant with a decantation, add 201 n-hexane, stir for 5 minutes, and let stand. After repeating the operation of removing the supernatant liquid three times, the mixture was dried under reduced pressure to obtain a titanium trichloride composition (!■).

■ Preparation of preactivated catalyst component In Example 1 (2) ■, titanium trichloride composition (
The titanium trichloride composition (I) obtained above as III)
A preactivated catalyst component slurry was obtained in the same manner except that the amount of diethylaluminum monochloride used was changed to 1.4 g.

■ Polymerization of propylene In (2) (2) of Example 1, the preactivated catalyst component slurry obtained in (1) above was supplied to the polymerization vessel at a rate of 12.0 milligram atoms/hr in terms of titanium atoms. Slurry polymerization of propylene was carried out at 60°C in the same manner except that the concentration of hydrogen in the gas phase in the polymerization vessel was 3.2% by volume. a) to lO in g/hr
I got it.

The polypropylene (a) contains 2251 tpp of crystalline allyltrimethylsilane dish block and has an MFR of
is 0.5 (5710 minutes), isotactic pentad fraction (P) is (1,98+), weight average molecular weight/number average molecular weight (Q) is 1). It was 8.

(2) In (2) of Example 1, except that the hydrogen concentration in the gas phase was set to 0.03% by volume, (2)
Polypropylene (b) was obtained in the same manner as in ).

(3) In (3) of implementation g4+, polypropylene (
Crystalline allyltrimethylsilane was prepared in the same manner except that as a), the polypropylene (a) obtained in step (+1) above (+1) was used in 5 g5, and as polypropylene (b), the polypropylene (b) obtained in step (2) above was used in 15 g. A polypropylene composition containing a polymer block of 56 ppm by weight was obtained.

Comparative Example 5 In (3) of Example 4, polypropylene (a) was not used as the polypropylene, but polypropylene (
b) A polypropylene composition was obtained in the same manner except that 20 kg was used.

Example 5 +1) ■ Preparation of titanium trichloride composition (Ill) 27.0 mol of titanium tetrachloride was added to n-hexane 12J2, and 1
After cooling to 1°C, 12.51 mol of n-hexane containing 27.0 mol of diethylaluminium monochloride was added at 1°C.
After the completion of the 0-drop addition, which took 4 hours, the temperature was kept at the same temperature for 15 minutes to react, and then the temperature was raised to 65 ° C.
The reaction was further continued at the same temperature for 1 hour.

Next, the supernatant liquid was removed, n-hexane Ii was added, and the operation of removing by decantation was repeated 5 times, and 1.8) fg of the obtained solid product (II) was added to 5.7 g of n-hexane II. -suspended in hexane 501), added diethylaluminum monochloride 3508, and then added 3-methylbutene-1
3.8 kg of was added, and polymerization treatment was performed at 40° C. for 2 hours.

After the polymerization treatment, after removing the supernatant liquid, add 30 Jl of n-hexane.
After repeating the operation of adding and removing by decantation twice, the resulting polymerized solid product (II-A
) was suspended in n-hexane IIJ2 and added with 1.2 J! of diisoamyl ether. and ethyl benzoate Q,4 It were added. This suspension was heated at 35°C for 1
After stirring for an hour, the mixture was washed 5 times with 31 portions of n-hexane to obtain a treated solid. The resulting treated solid was suspended in n-hexane solution 61 containing 40% by volume titanium tetrachloride and 10% by volume silicon tetrachloride.

This suspension was heated to 65°C and reacted at the same temperature for 2 hours. After one reaction, the resulting solid was washed three times using n-hexane 20j2 once, and then dried under reduced pressure. A titanium trichloride composition (II!) was thus obtained.

■Preparation example of preactivated catalyst component! (1) ■, titanium trichloride composition (
The titanium trichloride composition (III) obtained above as m)
) and a mixture of 1.0 kg of diethylaluminium monochloride and 0.8 g of diethylaluminium monoiodide as the organoaluminum compound, but prepared the preactivated catalyst components in a slurry state. Obtained.

■ Polymerization of propylene In (1) (1) of Example 1, the preactivated catalyst component slurry (note, containing diethylaluminium monochloride and diethylaluminium sonoiodide) obtained in the above (1) was used as the preactivated catalyst component slurry. Polymerization was carried out at a rate of 23 milligram atoms/hr in terms of titanium atoms, and in place of methyl p-toluate as the third component of the catalyst, 3-7minoprobyltriethoxysilane was used at a molar ratio of 2.8 to titanium atoms. Polypropylene (a) was obtained by polymerizing propylene in the same manner except that the hydrogen concentration in the gas phase in the polymerization vessel was 30% by volume.

The polypropylene (a) is crystalline 3-methylbutene-
Contains 418 pp by weight of 1 polymer and has a VFR of 30.0.
(g/10 min), isotactic pentad fraction (P
) is 0.91)0, weight average molecular weight/number average molecular weight (
Q) was 13.0.

(2) In (2) of Example 1, except that the hydrogen concentration in the gas phase is 2.6% by volume in (2) of Example 1.
Polypropylene (b) was obtained in the same manner as above.

(3) In (3) of Example 1, polypropylene (a
), the polypropylene (!l) obtained in (1) above is 3
621 kg of crystalline 3-methylbutene-1 polymer in the same manner except that 171 tg of the polypropylene (b) obtained in (2) above was used as the polypropylene (b).
) A polypropylene composition containing an amount of pp@ was obtained.

Comparative Example 6 In (3) of Example 5, polypropylene (a) was not used as the polypropylene, but polypropylene (
b) A polypropylene composition was obtained in the same manner except that 20 kg was used.

Example 6 (1) In Example 1 (2) (2), the solid product (
+1) After performing the first polymerization process using ethylene 4001 instead of propylene, decanted algae and n
- Titanium trichloride composition was prepared in the same manner, except that without washing with hexane, a second polymerization treatment was performed using p-)limethylsilylstyrene 8,6 in place of vinylcyclohexane. Product (m) was obtained.

■ In Example 1 (r) ■, the titanium trichloride composition (■1) obtained in the above (■) was used as the titanium trichloride composition (1)).
) and ethylene 90ON instead of propylene.
After the completion of one reaction in which the preactivation treatment was performed in the same manner except for using f, the supernatant liquid was removed with a decantation cylinder, washed with n-hexane, filtered, and dried to remove the preactivated catalyst component. Obtained.

(2) In (1) (2) of Example 1, n-hexane was added to the preactivated catalyst component obtained in (1) above as a preactivated catalyst component to form a 4.0% by weight n-hexane slurry, and then The slurry was prepared at a concentration of 10.5 milligram atoms/hr in terms of titanium atoms, and in place of methyl p-toluate, dimethoxy-3-mercaptopropylmethylsilane and diethylaluminium monochloride were used at a molar ratio of 2.5 milligrams per hour per titanium atom. Polypropylene was polymerized at 60°C in the same manner except that it was supplied as a catalyst to the polymerization vessel so that the concentration of polypropylene (a) was 5 and 3.0 g/hr. I got it.

The polypropylene (a) contains 338 pp by weight of crystalline p-trimethylsilylstyrene polymer blocks, and V
FR is 3.8 (g/10 min), isotactic pentad content* (P) is 0.978, weight average molecular weight/number average molecular weight (Q) is 1). It was 0.

(3) In (3) of Example 1, polypropylene (a
) A polypropylene composition containing 51 pp by weight of a crystalline +1-trimethylsilylstyrene polymer block was obtained in the same manner except that the polypropylene (a) obtained in the above (1) was used.

The physical properties of the bo-4 ribropylene constituting the compositions of the above Examples and Comparative Examples and the evaluation results of the compositions are shown in the table.

[Effects of the Invention] As is clear from the Examples described above, by employing the production method of the present invention, it is possible to obtain a polypropylene composition extremely efficiently and having extremely high rigidity, durability, and transparency. It is possible.

Therefore, it becomes possible to rapidly supply large quantities of polypropylene compositions having the above-mentioned properties to various molding fields that require them.

that's all

Claims (1)

[Claims] (1) (A) [1] Organoaluminium compound (A_1)
Alternatively, the solid product (II) obtained by reacting the reaction product (I) of the organoaluminum compound (A_1) and the electron donor (B_1) with titanium tetrachloride is converted into a non-linear olefin or a linear olefin. and a titanium trichloride composition (III) obtained by polymerizing with a non-linear olefin and further reacting an electron donor (B_2) with an electron acceptor, [2] an organoaluminum compound (A_2), and [3]
Aromatic carboxylic acid ester (E) or Si-O-
Melt fluorate (MFR) obtained by polymerizing propylene using a catalyst combining an organosilicon compound (S) having a C bond and/or a mercapto group is 0.
．． 1 to 100 (g/10 minutes, load 2.16 kgf), isotactic pentad fraction (P) 0.960 to 0
．． 990, ratio of weight average molecular weight to number average molecular weight;
Polypropylene (a) having a weight average molecular weight/number average molecular weight (Q) of 7 to 30, (B) [1] Titanium-containing solid catalyst component (T_1), and [
2] Polypropylene (b) obtained by polymerizing propylene using a catalyst in combination with an organoaluminum compound (A_3) and, if necessary, [3] an electron donor (B_3).
), A method for producing a polypropylene composition, characterized in that the composition contains 0.1 ppm to 2% by weight of a crystalline non-linear olefin polymer. (2) Organoaluminium compounds (A_1), (A_3)
, the general formula is AlR^1_PR^2_P_'X_3
＿−＿(＿P＿＋＿P＿′＿)(In the formula, R^1, R^2
represents a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, or an alkoxy group; X represents a halogen;
Further, P and P' represent arbitrary numbers in the range 0<P+P'≦3. ) The manufacturing method according to claim 1, using an organoaluminum compound represented by: (3) The non-linear olefin has the following formula, CH_2=CH-R^3 (wherein, R^3 has a saturated cyclic structure of a hydrocarbon that may contain silicon, and may contain silicon. The manufacturing method according to claim 1, which uses a saturated ring-containing hydrocarbon monomer represented by (representing a saturated ring-containing hydrocarbon group having 3 to 18 carbon atoms). (4) Non-linear olefins include the following formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^4 is a chain hydrocarbon group with 1 to 3 carbon atoms that may contain silicon, or represents silicon, R
^5, R^6, R^7 have a carbon number of 1 and may contain silicon
represents a chain hydrocarbon group from to 6, R^5, R^
Any one of 6 and R^7 may be hydrogen. ) Claim 1 using branched olefins represented by
The manufacturing method described in section. (5) As a non-linear olefin,
The following formula, ▲Mathematical formula, chemical formula, table, etc.▼ (In the formula, n is either 0 or 1, m is either 1 or 2, and R
^8 represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R^9 represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen, or It represents halogen, and when m is 2, each R^9 may be the same or different. ) The manufacturing method according to claim 1, using an aromatic monomer represented by: (6) The manufacturing method according to claim 1, in which a dialkylaluminum monohalide is used as the organoaluminum compound (A_2). (7) Polypropylene (b) is a titanium-containing catalyst component (
As T_1), using a Mg compound supported catalyst component,
The manufacturing method according to claim 1, which is polypropylene obtained by gas phase polymerization of propylene. (8) Instead of the titanium trichloride composition (III), the claim uses a catalyst component that is preactivated by combining the titanium trichloride composition (III) and an organoaluminum compound and reacting with a small amount of olefin. The manufacturing method according to item 1. (9) Instead of the titanium-containing solid catalyst component (T_1), a catalyst component that is preactivated by combining the titanium-containing solid catalyst component (T_1) and an organoaluminum compound and reacting with a small amount of olefin is claimed. The manufacturing method according to item 1 or item 7.