JPH02265905A - Production of polypropylene - Google Patents

Abstract

PURPOSE:To obtain stably a polypropylene having a very small content of voids and remarkably excellent transparency by polymerizing propylene by using a catalyst preactivated with a linear olefin and a nonlinear olefin in two stages. CONSTITUTION:Propylene is polymerized or propylene is copolymerized with an olefin other than propylene by using a catalyst prepared by the following process. Namely, a titanium-containing catalyst component is combined with an organoaluminum compound (A1) and optionally an electron donor (B1), this combination is preactivated by (1) polymerizing 0.01-100g of a linear olefin per g of a titanium-containing solid catalyst component, and further preactivated by (2) polymerizing 0.001-100g of a nonlinear olefin per g of the titanium- containing catalyst component, and the preactivated catalyst is shaped. Examples of the linear olefins include ethylene and propylene, and examples of the nonlinear olefins include vinylcyclopropane, 3-methylpentene-1 and styrene.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for producing polypropylene, and more specifically, a method for producing polypropylene with high crystallinity and good transparency using a specific preactivated catalyst. Regarding how to.

[Conventional technology and its issues] Compared to other plastics, polypropylene has excellent lightness, moldability, mechanical strength, chemical stability, etc., and is also economically advantageous, so it has been widely used in films and sheets. It is widely used in the production of various molded products.

However, polypropylene is translucent, which may impair its commercial value in the field of use, and there has been a desire for improved transparency.

For this reason, attempts have been made to improve the transparency of polypropylene. There is a method of adding a nucleating agent to polypropylene, such as those disclosed in Japanese Patent Publications, etc., but when aluminum salts of aromatic carboxylic acids are used, the dispersibility is poor and the effect of improving transparency is insufficient. Furthermore, when a benzylidene sorbitol conductor is used, although a certain improvement is seen in transparency, there are problems such as a strong odor during processing and a bleed phenomenon (embossment) of additives. was.

In order to improve the above-mentioned problem when adding a nucleating agent, we have used a catalyst that has been preactivated by polymerizing a small amount of vinylcyclohexane, pt-butylstyrene, allyltrimethylsilane, 4,4-dimethylpentene-1, etc. A method of polymerizing propylene using
No. 15.804, JP-A No. 63-218,709, etc.), but when the present inventors produced polypropylene according to the proposed method, in both methods, propylene An industrial long-term continuous polymerization method cannot be used because not only the polymerization activity decreases but also operational problems such as the formation of lumpy polymer, scale adhesion to the walls of the polymerization vessel, and poor control of the polymerization reaction occur. It was a method.

Furthermore, when the obtained polypropylene was processed into a film, although a certain improvement in transparency was observed, the film had many voids, which impaired its commercial value.

In addition, as an improved technique for this method, a method is proposed in which propylene is polymerized using a two-stage preactivated catalyst obtained by polymerizing a small amount of vinylcyclohexane or the like and then further polymerizing a small amount of propylene (Japanese Patent Laid-Open No. 63-37.1 .05 Publication) has been proposed, but even with this proposed method, the improvement in operability is insufficient, and continuous operation for a long period of time is not possible, especially in the gas phase polymerization method in which propylene is reacted in the gas phase. Not only that, but it also had the same problem as the one-stage preactivation technique described above, that is, the generation of voids in the film.

The present inventors have conducted extensive research into a method for stably producing polypropylene with fewer voids and improved transparency over a long period of time, which solves the problems faced by the above-mentioned conventional techniques. As a result, when producing polypropylene using a catalyst that has been subjected to two-stage preactivation treatment, which is obtained by polymerizing a small amount of straight-chain olefin and then polymerizing a small amount of non-linear olefin, it is difficult to produce polypropylene using the conventional method described above. The inventors have found a way to solve the technical manufacturing and purchasing problems, and have arrived at the present invention.

As is clear from the above description, an object of the present invention is to provide a method for stably producing polypropylene with very few voids and excellent transparency without causing operational problems. Another object of the present invention is to provide a polypropylene with extremely low void generation and excellent transparency.

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

(1) [1] Combine the titanium-containing solid catalyst component, (1) an organoaluminum compound (A1), and, if necessary, (1) an electron donor (B1), and (1) add the linear olefin to the titanium-containing solid catalyst component. After the reaction of 0.01 g to 1008 m per 1 g of the solid catalyst component, 1.0.0 g of non-linear olefin is added per 1 g of the titanium-containing solid catalyst component. 1. A method for producing polypropylene, which comprises polymerizing propylene, or propylene and an olefin other than propylene, using a preactivated catalyst obtained by a reaction of θO1 g to 100 g1i.

(2) The manufacturing method according to item 1 above, in which a titanium trichloride composition is used as the titanium-containing solid catalyst component.

(3) As the titanium-containing solid catalyst component, the first method uses a titanium-containing supported catalyst component containing titanium, magnesium, halogen, and an electron donor (B1) as essential components.
The manufacturing method described in section.

(4) As an organoaluminum compound (AI), -the formula is AIR', R'', +Xs-+psw・+ (in the formula R
1, R2 is a hydrocarbon group or alkoxy group such as a 7 alkyl group, cycloalkyl group, or aryl group, X represents a halogen, and p and p' represent any number in the range of Q<p◆p゛≦3. . ) The manufacturing method according to item 1 above, using an organoaluminum compound represented by:

(5) As a non-linear olefin, a saturated cyclic hydrocarbon car having 5 to 20 carbon atoms and optionally containing silicon, having a saturated cyclic structure and c=c bond. 2. The manufacturing method according to item 1 above, which uses a polymer.

(6) As a non-linear olefin, the following formula, CI+, -CH
-83-R' (wherein, R3 represents a C1-3 dehydrogenated hydrocarbon group which may contain silicon, or silicon; R4
, R5 and R6 represent a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, but R4, R6, R6
Any one of them may be hydrogen). ) The production method according to item 1 above, using the branch daughter olefins represented by:

(7) As a non-linear olefin, the following formula, (where n is O
ll and m are either 1.2, Loa represents a hydrocarbon group having 1 to 6 carbon atoms that may contain silicon, and R6 represents a hydrocarbon group having 1 to 6 carbon atoms that may contain silicon. Represents up to 12 hydrocarbon groups, hydrogen, or halogen, and when ■ is 2, each Re+ may be the same or different. )
The manufacturing method according to item 1 above, using an aromatic monomer represented by:

As the titanium-containing solid catalyst component used in the present invention, any known titanium-containing solid catalyst component for producing stereoregular polypropylene can be used. A titanium-containing solid catalyst component whose main component is a titanium trichloride composition obtained by the method described in JP-A No. 28,573, JP-A-1988-104, JP-A-62-104-810, etc. Publication, JP-A-62
-104,811 Publication, JP-A-82-104.812
A titanium-containing supported catalyst component, in which titanium tetrachloride is supported on a magnesium compound described in the above publication, is used, which contains titanium, magnesium, halogen, and an electron donor as essential components.

In addition, as an organoaluminum compound (^1), -the formula is AIR'pR'e'X5-1p+*'l (in the formula,
R', R2 represents a hydrocarbon group or alkoxy group represented by a baflkyl group, cycloalkyl group, or aryl group, X represents a halogen, and p and p' represent any number in the range of 0<p÷p°≦3 An organoaluminum compound represented by 1) is used.

Specific examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n
-butylaluminum, tri-l-butylaluminum,
Tri-n-hexylaluminum, trialkylaluminum Method 2-Methylpentylaluminum, tri-n-
octylaluminum,] n-decylaluminum trialkylaluminum, diethylaluminum monochloride, di-n-propylaluminum monochloride, di-i-butylaluminum monochloride,
Dialkyl aluminum monohalides such as diethyl aluminum monofluoride, diethyl aluminum monobromide, and diethyl aluminum monoiodide; dialkyl aluminum hydrides such as diethyl aluminum hydride; alkyl aluminum sesquihalides such as diethyl aluminum sesquichloride and ethyl aluminum sesquichloride; Examples include monoalkylaluminum cibarides such as ethylaluminum dichloride and 1-butylaluminum dichloride, and alkoxyalkylaluminums such as monoethoxydiethylaluminium and jetoxymonoethylaluminum can also be used. These organoaluminum compounds have 2 J! It is also possible to mix and use more than one type.

Furthermore, as the electron donor (B1) used as necessary,
During normal propylene polymerization, a known electron donor is used for the purpose of improving stereoregularity.

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, bosphines, phosphites, phosphinites, Hydrogen sulfide or thioethers, thioalcohols, silanols and S! -0-(: An organosilicon compound having a bond.

Specific examples include dimethyl ether and diethyl ether5. Di-n-propyl ether, di-lobtyl ether, sheet amyl ether, di-lopendel ether, di-hexyl ether, di-hexyl ether, di-n-octyl ether, sheet octyl ether, di-n-dodecyl ether, diphenyl ether,
Ethylene glycol monoethyl ether, jedi; non-glycol dimethyl ether, ethers such as tetrahydrofuran, methanol, ethanol, propatool,
Alcohols such as butanol, pentanol, hexanol, octatool, 2-ethylhexanol, allyl alcohol, benzyl alcohol, ethylene glycol, glycerin, phenols such as phenol, cresol, xylenol, ethylphenol, naphthol,
Methyl methacrylate, methyl formate, methyl acetate, methyl butyrate, ethyl acetate, vinyl acetate, l-propyl acetate, l-propyl acetate, butyl formate, amyl acetate, n-butyl acetate, octyl acetate, phenyl acetate, ethyl propionate, Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-benzoate
Ethylhexyl, methyl toluate, ethyl toluate, methyl anisate, ethyl anisate, propyl anisate, phenyl anisate, ethyl cinnamate, methyl naphthoate, ethyl naphthoate, naphthoate, propyl lactate, butyl naphthoate, Monocarboxylic acid esters such as 2-ethylhexyl naphthoate and ethyl phenylacetate; aliphatic polycarboxylic acid esters such as diethyl succinate, diethyl methylmalonate, diethyl butylmalonate, dibutyl maleate, and diethyl butyl maleate; Monomethyl phthalate, dimethyl phthalate, diethyl phthalate, di-n-propyl phthalate, mono-n-butyl phthalate, di-n-butyl phthalate, sheetbutyl phthalate, di-n-hebutyl phthalate, phthalate di-2-ethylhexyl isophthalate, di-n-octyl phthalate, diethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, di-2-ethylhexyl isophthalate, diethyl terephthalate,
Aromatic polycarboxylic acid esters such as dipropyl terephthalate, dibutyl terephthalate, di-I-butyl naphthalene dicarboxylate, aldehydes such as acetaldehyde, propionaldehyde, benzaldehyde, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, succinic acid. Acid, acrylic acid6. Carboxylic acids such as maleic acid, valeric acid, benzoic acid,
Acid anhydrides such as benzoic anhydride, phthalic anhydride, and detrahydrophthalic anhydride; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and benzophenone;
Nitriles such as acetonitrile and benzonitrile, methylamine, diethylamine, tributylamine, triethanolamine, β(N,N-dimethylamino)ethanol, pyridine, quinoline, α-picoline, 2,4.
5-)-limethylpyridine, 2,2,8.6-ketonemethylbiveridine, 2゜2,5゜5-tetramethylpyrrolidine, N,N,N',N'-tetramethylethylenediamine, aniline, Amines such as dimethylaniline, formamide, hexamethylphosphoric triamide, N, N,
Amides such as N', N', N"-pentamethyl-N'-β-dimethylaminomethylphosphoric acid triamide and octamethyl bilohonuformamide; ureas such as N, N, N', N'-tetramethylurea , isocyanates such as phenyl isocyanate and toluyl isocyanate, azo compounds such as azobenzene, phosphines such as ethylphosphine, triethylphosphine, tri-n-octylphosphine, triphenylphosphine, triphenylphosphine oxyto, dimethylphosphite, di-n - Phosphites such as octyl phosphite, triethyl phosphite, tri-n-butyl phosphite, triphenyl phosphite, phosphinites such as ethyl diethyl phosphinite, ethyl butyl phosphinite, phenyl diphenyl phosphinite, Thioethers such as diethylthioether, diphenylthioether, methylphenylthioether, thioalcohols such as ethylthioalcohol, n-propylthioalcohol, thiophenol, thiophenols, silanols such as trimethylsilanol, triethylsilanol, triphenylsilanol, Trimethylmethoxysilane, dimethyldimethoxysilane
Methylphenyldimethoxysilane, diphenyldimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, trimedyl-oxysilane, dimethyljethoxysilane, diphenyljethoxysilane, methyltriethoxysilane,
Examples include organosilicon compounds having a 5l-0-G bond such as ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, ethyltritobroboxysilane, and vinyltriacetoxysilane.

The above-mentioned ∎ titanium-containing solid catalyst component, ∎ organoaluminum compound (^1), and if necessary ∎ electron donor (B1) are combined, and then ∎ linear olefin is added to the titanium-containing solid catalyst. 0.01g per 1g of ingredient
After ~100g polymerization reaction, 1g of non-linear olefin was added per 18g of the titanium-containing solid catalyst component at 0.θO1g.
~ +0081i reaction is carried out and preactivated in two stages to obtain a preactivated catalyst used in the present invention.

In the first stage preactivation using a straight olefin, an organoaluminum compound (
^1) 0.0058~SOQg, electron donor (B+)
O~500g, solvent o~5oλ, hydrogen 0~1,000m
0.01 g to 5,000 g of u and straight 3n olefins are used.

The first stage preactivation with straight-quenching olefin is performed at 0°C to io
At a temperature of 0℃, under a pressure of atmospheric pressure ~ 50kg/c■2G,
0.01 g to 100 g of straight olefin is polymerized per 1 g of the titanium-containing solid catalyst component over a period of 1 minute to 10 hours. The amount of polymerization reaction per gram of titanium-containing solid catalyst component is 0.
．． If it is less than 100 g, the effect of improving driveability and suppressing voids will be insufficient, and if it exceeds 100 g, the improvement in the effect will not be significant, resulting in a disadvantage in operation.

After the first stage preactivation reaction is completed, the reaction mixture can be used as it is for the next second stage preactivation reaction. In addition, the coexisting solvent, unreacted direct olefin, organoaluminum compound (^1), etc. are filtered or decanted, and then a solvent is added to the granular material or the granular material to suspend it. An additional organoaluminum compound (^1) and, if necessary, an electron donor (B1) may be added to this product for use in the second stage of preactivation with a non-linear olefin.

In the second stage preactivation with a non-linear olefin, under the same reaction conditions as the first stage preactivation, 0.0.
0.01g to 1.0g per 1g of titanium-containing solid catalyst component using a non-linear olefin of 0.01g to 1.0g, aoag. OO
g, preferably 0.01 g to 100 g. If the polymerization reaction amount is less than 0.001 g, the effect of improving transparency will be insufficient, and if it exceeds 100 g, the improvement in effect will not be significant, and it will be economically disadvantageous. It will be disadvantageous.

The above first and second stage preactivation treatments are carried out in accordance with the above method.
It is an essential condition to perform embedding and then preactivation treatment with a non-linear olefin, and if the order of the preactivation treatment is reversed, the effects of the present invention cannot be obtained.

In addition, after the completion of the second-stage preactivation treatment, it is also possible to additionally perform a third-stage preactivation treatment using a linear olefin in a reaction amount of 100 g or less per 1 g of the titanium-containing solid catalyst component.

Preactivation can also be performed in a hydrocarbon solvent such as n-pentane, n-hexane, rhoheptane, toluene, etc., and hydrogen may be present in the preactivation.

After the preactivation reaction is completed, the preactivated catalyst can be used as it is for the polymerization of propylene, or propylene and an olefin other than propylene, or
The coexisting solvent, unreacted non-linear olefin, bridged aluminum compound (^1), etc. are removed by filtration or decantation, and the powder or granules are suspended by adding a solvent. , an additional bridged aluminum compound (A1), and if necessary an electron donor (
B2) is used as a catalyst to polymerize propylene, or propylene and an olefin other than propylene. After removing the granules, add a solvent to the powder or granules to make a suspension, add the aluminum compound (^1) as necessary, and further add electrons as necessary. It is also possible to use the compound (B1) in combination as a catalyst for the polymerization of propylene, or propylene and olefins other than propylene.

As the straight chain olefin used in the first step activation of the present invention, straight chain olefins such as ethylene, propylene, butene-I, pentene-1, hexene-1, etc. are used, and ethylene and propylene are particularly preferably used. These straight olefins are 1f! The above is used.

The non-linear olefin used in the second stage activation of the present invention has (1) a saturated cyclic structure of a hydrocarbon which may contain silicon and a c=c bond, and has a carbon number of 5 or more which may contain silicon; a saturated ring-containing hydrocarbon monomer of up to 20, ■ the following formula, CL"ll: H-R'-R' (wherein R3 is a dehydrated carbon having 1 to 3 carbon atoms which may contain silicon) Represents a hydrogen group or silicon R4
, all, R11 represents a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, but R4, R6
, any one of R6 may be hydrogen, and branched olefins represented by 1), zero-order formula, (where n is 0.1 and ■ is either 1 or 2, R
7 represents a hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, R6 represents a hydrocarbon group having 1 to 12 carbon atoms which may contain silicon, hydrogen, or halogen; , ■ is 2, each R11 is an aromatic monomer represented by 1), which may be the same or different.

Specifically, the saturated ring-containing hydrocarbon of ■! # Examples of polymers include vinylcyclopropane, vinylcyclobutane,
Vinylcycloalkanes such as vinylcyclopentane, 3-methylvinylcyclopentane, vinylcyclohexane, 2-methylvinylcyclohexane, 3-methylvinylcyclohexane, 4-methylvinylcyclohexane, vinylcyclohebutane, allylcyclopentane, allylcyclohexane, etc. In addition to allylcycloalkanes,
Cyclotrimethylenevinylsilane, cyclotrimethylenemethylvinylsilane, cyclotetramethyleneallylsilane, cyclotetramethylenemethylvinylsilane, cyclopentamethylenevinylsilane, cyclopentamethylenemethylvinylsilane, cyclopentamethyleneethyl and nylsilane, cyclohexamethylene and nylsilane, cyclohexamethylene Having a silicon atom in a saturated cyclic structure such as methylvinylsilane, cyclohexamethyleneethylvinylsilane, cyclotetramethyleneallylsilane, cyfrothyramethylenemethylallylsilane, cyclopentamethyleneallylsilane, cyclopentamethylenemethylallylsilane, cyclopentamethyleneethylallylsilane, etc. Saturated ring-containing hydrocarbon monomers, cyclobutyldimethylvinylsilane, cyclopentyldiethylvinylsilane, cyclopentylethylmethylvinylsilane, cyclopentyldiethylvinylsilane, cyclohexylvinylsilane, cyclohexyldimethylvinylsilane, cyclohexylethylmethylvinylsilane, cyclobutyldimethylallylsilane, cyclopentyl A saturated ring containing a silicon atom in addition to the saturated ring structure such as dimethylallylsilane, cyclohexylmethylallylsilane, cyclohexyldimethylallylsilane, cyclohexylethylmethylallylsilane, cyclohexyldiethylallylsilane, 4-trimethylsilylvinylcyclohexane, 4-trimethylsilylallylcyclohexane, etc. Examples include hydrocarbon 4i-mer.

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 n8M olefin such as 4,4-dimethylbenten-1,4,4-dimethylhexene-1, vinyltrimethylsilane, vinyltriethylsilane, vinyltri-n-butylsilane, allyltrimethylsilane, allylethyldimethylsilane, allyldiethylmethylsilane , allyltriethylsilane, allyltri-n-propylsilane, 3-butenyltrimethylsilane, 3-butenyltriethylsilane, and other alkenylsilanes, and dimethyldiallylsilane, ethylmethyldiallylsilane, diethyldiallylsilane, and other diallysilanes. can give.

Examples of the aromatic monomer (2) include styrene and alkylstyrenes such as 0-methylstyrene and pt-butylstyrene, which are derivatives thereof.

Dialkylstyrenes such as 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 2-methyl-4-fluorostyrene, 2-ethyl-4-chloro Styrene, halogen-substituted styrenes such as 0-fluorostyrene and p-fluorostyrene, trialkylsilylstyrenes such as p-trimethylsilylstyrene, Peng-triethylsilylstyrene, and p-ethyldimethylsilylstyrene, 0-allyltoluene, p - allyltoluenes such as allyltoluene,
2-allyl-p-xylene, 4-allyl-0-xy I/
allylxylenes such as 5-allyl-xylene,
Alkenylphenylsilanes such as vinyldimethylphenylsilane, vinylethylmethylphenylsilane, vinyldiethylphenylsilane, allyldimethylphenylsilane, allylethylmethylphenylsilane, and 4
Examples include -(o4lyl)-butene-1 and l-vinylnaphthalene, and these non-linear olefins are 1f! The above are used.

In addition, during the polymerization or copolymerization of propylene, the organoaluminum compounds (^1) and (^1) and electron donors (B2) and (B1), which are used as necessary, are used for the preactivation reaction, respectively. Examples include those similar to the organoaluminum compound (A+) and electron donor (L) used in this case, and those of the same or different type are 1 f! Used in Class II and above. The amount used is also within the same range as in the preactivation reaction. The pre-activated catalyst thus obtained is used for homopolymerization of propylene or copolymerization of propylene and an olefin other than propylene, but it can also be used for polymerization in the form of a slurry by adding a solvent.

In the method of the present invention, the polymerization method for polymerizing propylene, or propylene and solenoid other than propylene is: (1) Bulk polymerization carried out in liquefied propylene; (2) Gas phase polymerization in which propylene is polymerized in the gas phase; In either case, the polymerization temperature was room temperature (2
0°C) to 200°C5 Polymerization pressure is atmospheric pressure (Okg/cm”
G) - 50 kg/ci'G, and is usually carried out for about 5 minutes - 20 hours.

During polymerization, steps such as adding an appropriate amount of hydrogen to control the molecular weight are the same as in conventional polymerization methods.

In the method of the present invention, the olefins subjected to polymerization together with propylene include ethylene, butene-1, hexene-1
Straight chain monoolefins such as 1-octene-1, branched monoolefins such as 4-methylpentene-1,2-methyl-pentene-1,3-methyl-butene-1, butadiene, isoprene, chlorobrene, etc. In the method of the present invention, propylene and other olefins are not only homopolymerized, but also propylene is combined with other olefins, such as propylene and ethylene, propylene and butene, etc.
Propylene, ethylene, butene-
] Copolymerization can be carried out by combining three components, or block copolymerization can be carried out in which another resin is polymerized in the first or second stage of propylene polymerization in multi-stage polymerization.

(Function) In the conventional method of preactivating with only a nonlinear olefin, or preactivating a nonlinear olefin with propylene, the titanium-containing solid catalyst component is During the polymerization reaction of chain olefins, the titanium-containing solid catalyst component becomes ultrafine or swollen, and even if it is subsequently preactivated with propylene, the deteriorated shape of the titanium-containing solid catalyst component cannot be recovered. When a catalyst component is dried before being used for propylene polymerization, it may solidify into lumps during drying, resulting in the production of lumpy polypropylene, or the preactivated catalyst component may remain in a slurry state. When used in the polymerization of propylene, it causes operational problems such as runaway polymerization reaction and scale adhesion to the reactor wall. In some cases, this may be the cause of numerous voids.

In contrast to the above conventional techniques, the two-stage preactivation treatment according to the present invention produces a solid titanium-containing solid that has a good shape and is less likely to be crushed by the first-stage preactivation treatment using a directly-quenched olefin. By forming the catalyst component, it maintains its good shape even during the second stage preactivation treatment with non-linear olefin. Therefore, when the preactivated catalyst is used for the polymerization of propylene, or propylene and an olefin other than propylene, M
Continuous polymerization operation becomes possible.

In addition, as a result of stable polymerization operation, the quality of the polypropylene obtained is stable, and the straight olefin-non-linear olefin block copolymer produced by the two-stage preactivation treatment is a non-linear olefin homopolymer. Since the direct olefin block portion is more compatible with polypropylene than in the case of coalescence, the film produced from the obtained polypropylene has extremely few voids.

In addition, due to the high degree of dispersibility of the block copolymer, the non-linear olefin block exhibits a remarkable internal nucleation effect, resulting in excellent transparency and crystallinity.

[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.

VFR: ,I Lutoflow Index ASTM D
-1238 (L), (11th place:
g/io min) Internal haze: This is the haze inside the film excluding the influence of the surface.
Polypropylene was formed into a film with a thickness of 150 μm under conditions of a pressure of zookg/c × 2G, and after coating both sides of the film with liquid paraffin, the haze was measured in accordance with JIS 7105.

(Unit: 2%) Crystallization temperature: Measured using a differential scanning calorimeter at a temperature decreasing rate of Rot: 7 minutes. (Unit: 2°C) Flexural modulus: Tetrakis[methylene-3-(3°-05゛-di-t-butyl-4) relative to 100 parts by weight of polypropylene
-Hydroxyphenyl)propionate comethane 0.1
Part by weight, and 0.1 [strain part] of calcium stearisoate were mixed, and the mixture was granulated using an extrusion granulator with a screw diameter of 40 mm. Next, a JIS type test piece was made from the granules using an injection molding machine at a molten resin temperature of 230°C and a mold temperature of 50°C, and the test piece was heated at a humidity of 50%.
, after being left indoors at a room temperature of 23°C for 72 hours, JIS K
The flexural modulus was measured in accordance with 7203.
(Unit: kgf/cm") Void: Polyolefin is granulated in the same manner as in the previous section, and the resulting granules are
-Using a die forming @ machine, extrude the molten resin at a temperature of 250°C, and create a sheet with a thickness of Imm with a cooling roll at 20°C.
Ta. The sheet was heated with hot air at 150° C. for 70 seconds, and then stretched 7 times in both length and width directions using a biaxial stretching machine to obtain a biaxially stretched film with a thickness of 20 μm. The film was observed with an optical microscope, and the number of voids with a diameter of 10 μ or more was measured, and less than 30 voids per cII2 were marked with ○, and 30 or more voids were marked with X.

Example 1 (1) Production of titanium-containing solid catalyst component n-hexane 61. Diethylaluminum monochloride (DEAC) 5.0 mol, diisoamyl ether 1
2.0 mol was mixed at 25°C for 1 minute and reacted at the same temperature for 5 minutes to form reaction product solution (I) (diisoamyl ether/D
A molar ratio of EAC of 2,4) was obtained. 40 mol of titanium tetrachloride was placed in a reactor purged with nitrogen, heated to 35°C, and the entire amount of the reaction product solution (I) was added dropwise over 30 minutes, kept at the same temperature for 30 minutes, and heated to 75°C. The temperature was raised and the reaction was further carried out for 1 hour, cooled to room temperature, the supernatant liquid was removed, and n-hexane 2
Add 01 and remove the supernatant by decantation.
Repeated times, a solid product (II) was obtained.

Suspend the entire amount of this (11) in n-hexane 3i,
Add 200g of diethylaluminum monochloride,
Propylene 1. at 30°C. Add Okg and react for 1 hour.
A polymerized solid product (II-A') was obtained (propylene reaction amount eoog). After the reaction, the supernatant was removed, and n-hexane 3GOmj2 was added and removed by decantation twice. Repeatedly, 2.5 kg of the solid product (II-A) subjected to the above polymerization treatment was suspended in n-hexane 6J2 to obtain 3.5 kg of titanium tetrachloride.
was added at room temperature for about 10 minutes, reacted at 80°C for 30 minutes, further added 1.6 kg of diisoamyl ether, and reacted at 80°C for 1 hour. After the completion of the reaction, the supernatant was decanted. 40 J2 of n-hexane was added, the mixture was stirred for 10 minutes, allowed to stand, and the supernatant liquid was removed. The procedure was repeated five times, followed by drying under reduced pressure to obtain a titanium trichloride composition.

(2) Preparation of preactivated catalyst component After purging a stainless steel reactor with inclined blades with a volume of 80 Il with nitrogen gas, 40 g of n-hexane, 200 g of diethylaluminium monochloride, and titanium-containing solid catalyst component (1) 450g of titanium trichloride composition obtained in
was added at room temperature, the temperature inside the reactor was raised to 40°C, 600g of propylene was added, and the first preactivation treatment was carried out at 40°C for 1 hour (1 g of titanium trichloride composition, 1 oz of propylene). .Og reaction).

After the reaction time had elapsed, the supernatant was removed by decantation, and the solid was washed twice with 40J2 of n-hexane. Subsequently, after adding 401 g of n-hexane and 200 g of diethylaluminium monochloride, the temperature inside the reactor was lowered to 40 g.
Bring to 0°C, add 0.7 g of vinylcyclohexane, and add 4
A second preactivation treatment was carried out at 0°C for 2 hours (vinylcyclohexane 1.0% per 1g of titanium trichloride composition).
g reaction) After the completion of the reaction, wash with n-hexane, and then
A preactivated catalyst component was obtained by filtration and drying.

(3) Propylene polymerization L/D equipped with a stirrer with an internal volume of 1,501 liters replaced with nitrogen
After putting 30g of polypropylene powder with an MFR of 2.0 into a single-stage polymerization vessel with a horizontal cabinet of 4.0 g, n-hexane was added to the preactivated catalyst component obtained in (2) above, and 4.0% by weight of n-hexane was added to the preactivated catalyst component obtained in (2) above. - After making a hexane suspension, the suspension is converted into a titanium atom at a rate of 5.0 milligram atoms/hr, and a 30% by weight hexane solution of diethylaluminum monochlorite is converted into a hexane suspension at a rate of 4-2 g/hr as a diethylaluminum monochloride.
was supplied continuously.

In addition, hydrogen was supplied so that the concentration in the gas phase of the polymerization reactor was maintained at 1.0% by volume, and propylene was supplied so that the total pressure was maintained at 23 kg/crn''G, and the gas phase polymerization of propylene was carried out at 70°C. The test was carried out continuously for 160 hours.

During the polymerization, the polymer was continuously extracted at a rate of 13.5 g/hr so that the polymer retention level in the polymerization vessel was 45% by volume. The extracted polymer was then contacted with nitrogen gas containing 0.2% by volume of propylene oxide at 95° C. for 30 minutes to obtain polypropylene.

Comparative Example 1 In (2) of Example 1, the first and second stage preactivation treatments were performed in the reverse order, and propylene was reacted after the reaction of vinylcyclohexane to obtain a preactivated catalyst component. Polymerization of propylene was carried out in the same manner as in Example 1 (3) except for using the preactivated catalyst component.
The polymerization of propylene had to be stopped 6 hours after the start of polymerization because the produced bulk polymer blocked the extraction pipe.

Comparative Example 2 In (2) of Example 1, the first stage preactivation treatment with propylene is omitted, only vinylcyclohexane is reacted to obtain a preactivated catalyst component, and the preactivated catalyst component is used. When propylene was polymerized in the same manner as in Example 1 (3), the bulk polymer produced in the same manner as in Comparative Example 1 was extracted and blocked the piping, so 4 hours after the start of polymerization. The polymerization of propylene had to be stopped at

Comparative Example 3 In (2) of Example 1, the second-stage preactivated catalyst treatment with vinylcyclohexane was omitted, only propylene was reacted to obtain a preactivated catalyst component, and the preactivated catalyst component was Polymerization of propylene was carried out in the same manner as in Example 1 (3) except for using the following.

Comparative Example 4 Propylene polymerization was carried out in the same manner as in Example 1 (3) except that the titanium trichloride composition obtained in Example 1 (1) was used instead of the preactivated catalyst component. Ta.

Comparative Example 5 and Example 2.3 In (2) of Comparative Example 1, the amounts of propylene and vinylcyclohexane used for preactivation were changed to produce titanium trichloride compositions with reaction amounts as shown in the table. Obtained. Thereafter, polypropylene was obtained in the same manner as in Example 1 (3).

Example 4 (1) Preparation of titanium-containing solid catalyst component In a stainless steel reactor equipped with a stirrer, decane 3I
1. , 480 g of anhydrous magnesium chloride, 1.7 kg of n-butyl 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 heated to 70°C, and diisobutyl phthalate 18 was added while stirring.
0g was added and after 1 hour, 5.2kg of silicon tetrachloride was added.
．． It was added dropwise over 5 hours to precipitate the solid, and then heated to 70°C for 1 hour.
heated for an hour. The solid was separated from the solution and washed with hexane to give a solid product (Iil).

The entire amount of the solid product (III) was mixed with 15λ of titanium tetrachloride dissolved in 1,2-dichloroethane + 51 L, and then 380 g of diisobutyl phthalate was added, and the mixture was reacted at 100°C for 2 hours with stirring, and then heated at the same temperature. The liquid phase was removed by decantation, 15 liters of 1,2-dichloroethane and 15 liters of titanium tetrachloride were added again, stirred at 100°C for 2 hours, washed with hexane and dried to obtain a titanium-containing supported catalyst component. Ta.

(2) Preparation details of preactivated catalyst component fA, after purging a 30N stainless steel reactor with inclined blades with nitrogen gas, 201. , 400 g of diethylaluminum monochloride, and 55 g of diphenyldimethoxysilane were added, and then 280 g of propylene was added.
g was supplied, and the first stage preactivation treatment was carried out at 30°C for 2 hours (1.8 g of propylene was reacted per 1 g of titanium-containing supported catalyst component).Then, the reaction mixture was washed with n-hebutane, and then filtered. A solid was obtained.

Subsequently, 2 fl of n-heptane, 400 g of diethylaluminum monochloride, 120 g of diphenyldimethoxysilane, and 0.5 kg of allyltrimethylsilane were added, and a second preactivation treatment was performed at 45°C for 2 hours (
2. allyltrimethylsilane per gram of titanium-containing supported catalyst component. (Og reaction), a preactivated catalyst component was obtained in a slurry state.

(3) Propylene polymerization L/D equipped with a stirrer with internal volume aOX and nitrogen substitution =
After charging 20 kg of 1iFR2.0 polypropylene powder into the polymerization reactor in step 3, add the preactivated catalyst component slurry obtained in step (2) above at 0.302 milligram atom/hr in terms of titanium atoms, and further add 2.7 g of triethylaluminum. /
hr, and diphenyldimethoxysilane at 0.50
They were continuously supplied from separate supply ports at a rate of g/hr.

In addition, hydrogen was supplied so that the concentration in the gas phase of the polymerization reactor was maintained at 0.15% by volume, and propylene was supplied at a total pressure of 23 kg/crn'G to control the gas phase polymerization of propylene for 70%. The test was carried out continuously for 120 hours at ℃. During the polymerization, the polymer retention level in the polymerization vessel was 60% by volume.
10.0 kg of the polymer was continuously extracted in a batch of 10.0 kg so that
A contact treatment was carried out for 0 minutes to obtain polypropylene.

Comparative Example 6 (1) A titanium-containing supported catalyst component was obtained in the same manner as in Example 4 (1).

(2) Preactivation was performed in the same manner as in (2) of Example 4, except that the order of the first and second preactivation treatments was reversed and propylene was reacted after the reaction of allyltrimethylsilane. A catalyst component was obtained.

(3) In Example 4 (3), propylene polymerization was carried out in the same manner as in Example 4 (3) except that the preactivated catalyst component obtained in (2) above was used as the preactivated catalyst component. When this process was carried out, the produced bulk polymer blocked the extraction pipe, so the propylene polymerization had to be stopped 15 hours after the polymerization started.

Comparative Example 7 In (2) of Example 4, the first stage preactivation treatment with propylene was omitted, only allyltrimethylsilane was reacted to obtain a preactivated catalyst component, and the preactivated catalyst component was When propylene was polymerized in the same manner as in Example 4 (3) except for the use of the polymer, the bulk polymer produced in the same manner as in Comparative Example 6 was extracted and blocked the piping, so after the start of polymerization %12 Polymerization of propylene had to be stopped in time.

Comparative Example 8 In (2) of Example 4, the second-stage preactivation treatment with allyltrimethylsilane was omitted, only propylene was reacted to obtain a preactivated catalyst component, and the preactivated catalyst component was Polymerization of propylene was carried out in the same manner as in Example 4 (3) except for using the following.

Comparative Example 9 Polymerization of propylene was carried out in the same manner as in Example 4 (3), except that the titanium-containing supported catalyst component obtained in Example 4 (1) was used instead of the preactivated catalyst component. went.

Example 5 (1> Preparation of titanium-containing solid catalyst component. Obtained by reacting 41 moles of n-heptane, 540 moles of diethylaluminum monochloride, 9.0 moles of diisoamyl ether, and 5.0 moles of dibutyl ether at 18°C for 30 minutes. The reaction solution was dissolved in 27.5 mol of titanium tetrachloride.
After dropping at 0°C for 300 minutes, the temperature was increased to 1.
After the reaction was allowed to stand for 5 hours, the temperature was raised to 65°C, the reaction was allowed to proceed for 1 hour, the supernatant liquid was removed from the rice, and 20JZ of n-hexane was added and removed by decantation, which was repeated 6 times to obtain a solid product. (II) 1.8 kg of n-hexane 7I! ,
1.8 kg of titanium tetrachloride and 1.8 kg of n-butyl ether were added and reacted at 60°C for 3 hours. After the reaction, the supernatant was removed by decantation, and the n- Hexane was added, stirred for 5 minutes, allowed to stand, and the supernatant liquid removed, which was repeated three times, and then dried under reduced pressure to obtain a titanium trichloride composition.

(2) Preparation of preactivated catalyst component In (2) of Example 1, the titanium trichloride composition obtained in (1) above was used as the titanium-containing solid catalyst component at 450%
g, the amount of propylene used was 300 g, and in place of vinylcyclohexane, 4,4-dimethylpentene]
A preactivated catalyst component was obtained in the same manner except that 1.5 kg of .

(3) Polymerization of propylene In (3) of Example 1, the preactivated catalyst component obtained in the above (2) was used as the preactivated catalyst component,
Gas phase polymerization of propylene was carried out in the same manner except that the catalyst components were supplied to the polymerization vessel so that the total pressure was maintained at 23 kg/cm''G.

Example 6 (Preparation of 1,1 titanium-containing solid catalyst component) 4.0 g of aluminum trichloride (anhydrous) and 1.2 g of magnesium hydroxide were reacted while being ground in a vibration mill at 250°C for 3 hours. At this point, a reaction occurred with the generation of hydrogen chloride gas. After the heating was completed, the mixture was cooled in a nitrogen stream to obtain a magnesium-containing solid.

In a stainless steel reactor equipped with a stirrer, purified decane 6J2. 3.4 J of g1 loubutyl orthotitanate and 3.9 kg of 2-ethyl-1-hexanol were mixed with 1.0 g of the magnesium-containing solid, and the mixture was heated to 130° C. for 2 hours with stirring to melt and form a homogeneous solution. The i8 was heated to 70℃ overnight, 0.2Kg of ethyl 9-toluate was added and reacted for 1 hour, and then 0.4K of diisobutyl phthalate was added.
After reacting for another 1 hour, silicon tetrachloride 1 (1,4MH) was added dropwise over 2 hours without stirring to precipitate a solid, and the mixture was further stirred at 70°C for 1 hour.The solid was separated from the solution. and washed with purified hexane to give a solid product (I[I)
I got it.

To the total amount of the solid product (m), 101 g of 1,2-dichloroethane and 10 J2 of titanium tetrachloride were added to 0.4 g of diisobutyl phthalate, and heated at 100°C with stirring.
After reacting for 2 hours, the liquid phase was removed by decantation at the same temperature, and 10I of 1,2-dichloroethane was added again.
L, titanium tetrachloride lOn, diisobutyl phthalate 0,4
After reacting at 100°C for 2 hours with stirring, the solid part was collected by hot filtration, washed with purified hexane, and dried under reduced pressure at 25°C for 1 hour to obtain the titanium-containing supported catalyst component. I got it.

(2) Preparation of preactivated catalyst In the reactor used in Example 4 (2), add 2
0J2, 1.5 kg of triethylaluminum, 2708 diisobutyldimethoxysilane, and the titanium-containing supported catalyst component obtained in (1) above were added at room temperature.The temperature in the 0 reactor was brought to 35°C, and at the same temperature, 1 18ONj2 of ethylene was supplied over time to perform the first stage preactivation treatment (per 1g of titanium-containing supported catalyst component,
Ethi I Non 1. Og reaction).

Next, unreacted ethylene was removed, and 450 g of 3-methylbutene-1 was added without washing the reaction mixture.
A second preactivation treatment was performed at 5° C. for 2 hours (145 g of 3-methylbutene-1 was reacted per 1 g of the titanium-containing supported catalyst component) to obtain a preactivated catalyst.

(3) Polymerization of propylene In (3) of Example 4, the preactivated catalyst slurry obtained in (2) above was used instead of the catalyst consisting of the preactivated catalyst component, triethylaluminum, and diphenyldimethoxysilane. and the total pressure is 23kg/c+l
Gas-phase polymerization of propylene was carried out in the same manner except that the catalyst slurry was fed to the polymerization vessel so as to maintain G.

Example 7 +1) Preparation of titanium trichloride composition 27.0 mol of titanium tetrachloride was added to 12λ of n-hexane, and after cooling to 1°C, 12 mol of n-hexane further containing 27.0 mol of diethylaluminium monochloride was added. ,51
was added dropwise at 1°C over 4 hours. 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 liquid was removed, n-hexane 101 was added, and the operation of removing by decantation was repeated 5 times to obtain a solid product (H) 5
．． 7kg (7) Of which, 1.8kg on-hexane
li, suspended in diisoamyl ether 1.2
j2 and 0.4 IL of ethyl benzoate were added. After stirring this suspension at 35°C for 1 hour, 31% of n-hexane was added to
A treated solid was obtained by washing twice. The resulting treated solid was suspended in an n-hexane solution aiL of 40 vol. % titanium tetrachloride and 10 vol. % silicon tetrachloride.

This suspension was heated to 65°C and reacted at the same temperature for 2 hours. After the reaction is complete, use 201 ml of n-hexane at once,
After washing the obtained solid three times, it was dried under reduced pressure to obtain a titanium trichloride composition.

(2) Preparation of preactivated catalyst component In (2) of Example 1, the titanium dichloride composition obtained in (1) above was used as the titanium-containing solid catalyst component.
A preactivated catalyst component was obtained in the same manner except that the amount of propylene used was 370 g, and 10 kg of p-trimethylsilylstyrene was used instead of vinylcyclohexane.

(3) Polymerization of propylene In (3) of Example 1, the preactivated catalyst component obtained in the above (2) was used as the preactivated catalyst component,
Gas phase polymerization of propylene was carried out in the same manner except that the preactivated catalyst component was supplied to the polymerization vessel so that the total pressure was maintained at 23 kg/cm''G.

Example 8 In (2) of Example 5, the amount of propylene used was increased to 15
0 g, and in place of 4,4-dimethylpentene-1, 2
A preactivated catalyst component was obtained in the same manner except that 2.7 g of -methyl-4-fluorostyrene was used. Subsequently, Example 5 was repeated except that the preactivated catalyst component was used.
Polymerization of propylene was carried out in the same manner as in (3).

Example 9 A preactivated catalyst component was obtained in the same manner as in Example .

Subsequently, Example 1 was carried out except that the preactivated catalyst component was used and ethylene was further supplied so that the concentration in the gas phase of the polymerization vessel was maintained at 0.2% by volume during gas phase polymerization of propylene.
Propylene-ethylene copolymerization was carried out in the same manner as in (3).

Example 10 In Example 9, during the propylene-ethylene copolymerization of (3) without the pre-(i & activation reaction of (2)), (1)
Propylene-ethylene copolymerization was carried out in the same manner except that the titanium trichloride composition obtained in 1 was used instead of the preactivated catalyst component.

The preactivation conditions and results of the above Examples and Comparative Examples are shown in the table.

[Effects of the Invention] The main effects of the present invention are that polypropylene, which has extremely excellent transparency and crystallinity and has few voids even when made into a film, can be stably obtained without any problems in production. It is something that can be done.

As is clear from the examples described above, the method of the present invention does not cause any manufacturing problems and allows stable production over a long period of time. The internal baise of films produced using the obtained polypropylene is also 1.8% to 4.2%, which is about 9% of that of films produced using ordinary polypropylene that is not preactivated with non-linear olefins. ~12%. The crystallization temperature also increased by about 11°C, and as a result of the remarkable improvement in crystallinity, the flexural modulus also improved. (Examples 1 to 9,
(See Comparative Example 3.4.8.9, IO) On the other hand, according to the prior art method, even if the non-linear olefin is preactivated, the two-stage preactivation treatment according to the sequence of the present invention is not carried out. , operation problems occur and long-term continuous operation is impossible. Furthermore, when the obtained polypropylene is made into a film, many voids occur, and improvements in transparency and crystallinity are insufficient because of poor dispersibility. (Comparative Examples 1, 2, 6.
7 reference 1)

[Brief explanation of drawings]

FIG. 1 is a manufacturing process diagram (
flow sheet). that's all

Claims (7)

[Claims] (1) [1] A titanium-containing solid catalyst component, [2] an organoaluminum compound (A_1), and if necessary, [3] an electron donor (B_1) are combined, and this is combined with [4] directly. Add chain olefin to 1 g of the titanium-containing solid catalyst component.
After the polymerization reaction of 0.01g to 100g per unit, [5] non-linear olefin is added to the titanium-containing solid catalyst component 1.
A method for producing polypropylene, which comprises polymerizing propylene, or propylene and an olefin other than propylene, using a preactivated catalyst obtained by polymerization reaction of 0.001 g to 100 g/g. (2) The manufacturing method according to claim 1, in which a titanium trichloride composition is used as the titanium-containing solid catalyst component. (3) The manufacturing method according to claim 1, in which the titanium-containing solid catalyst component is a titanium-containing supported catalyst component containing titanium, magnesium, halogen, and an electron donor (B_2) as essential components. (4) As the organoaluminum compound (A_1), the general formula is AlR^1_pR^2_p'X_3_-_(_p_
+_p'_) (in the formula, R^1 and R^2 represent a hydrocarbon group such as an alkyl group, a cycloalkyl group, an aryl group, or an alkoxy group, X represents a halogen, and p and p' are 0<
Represents an arbitrary number of p+p'≦3. ) The manufacturing method according to claim 1, using an organoaluminum compound represented by: (5) As a non-linear olefin, a saturated cyclic hydrocarbon monomer having 5 to 20 carbon atoms and optionally containing silicon, having a saturated cyclic structure and a c=c bond. 2. The manufacturing method according to claim 1, which uses a polymer. (6) Non-linear olefins include the following formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^3 is a chain hydrocarbon group with 1 to 3 carbon atoms that may contain silicon, or represents silicon, R
^4, R^5, and R^6 represent a chain hydrocarbon group having 1 to 6 carbon atoms that may contain silicon, but R^4,
Either one of R^5 and R^6 may be hydrogen. ) The manufacturing method according to claim 1, using the branched olefins represented by: (7) Non-linear olefins include the following formulas, ▲mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n is either 0 or 1, m is either 1 or 2, and R
^7 represents a chain hydrocarbon group having 1 to 6 carbon atoms which may contain silicon, and R^8 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^8 may be the same or different. ) The manufacturing method according to claim 1, using an aromatic monomer represented by: