JPH04202507A - Production of propylene, polypropylene, polypropylene composition and use thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing polypropylene, a polypropylene obtainable by the method, a composition of polypropylene and a nucleating agent obtainable by the method, and uses thereof. .

Technical Background of the Invention Crystalline polyolefins such as crystalline polypropylene are made into olefins by a so-called Ziegler-Natsuta catalyst, which is composed of transition metal compounds of groups ■ to ■ of the periodic table and organometallic compounds of metals of groups ■ to ■. It is well known that polyolefins can be obtained by polymerizing polyolefins, and methods for obtaining polyolefins with high polymerization activity and high stereoregularity have been sought.

Among these, a titanium-containing solid catalyst component containing titanium, magnesium, halogen, and an electron donor is used as one that exhibits extremely high polymerization activity while maintaining high stereoregularity, and this is combined with an organoaluminum compound and an electron donor. In recent years, methods for producing polyolefins by polymerizing olefins using a combination of catalysts have been actively studied (for example, Japanese Patent Application Laid-Open No. 61-209207, Japanese Patent Application Laid-Open No. 62-104810, Japanese Patent Application Laid-open No. 62-104811).
No. 62-104812, JP-A-62-104812, JP-A-62-104812
-104813, JP 1-311106, JP 1-318011, JP 2-1661
Publication No. 04, etc.).

Furthermore, the present applicant has already made numerous proposals in this field (for example, JP-A-50-108385, JP-A-50-126590, JP-A-51-2).
0297, JP 51-28189, JP 51-64586, JP 51-92885, JP 51-136625, JP 52-
No. 87489, JP-A-52-100596,
JP-A-52-147688, JP-A-52-104
No. 593, JP-A No. 53-2580, JP-A-Sho 5
3-40093, JP 53-40094, JP 53-43094, JP 55-135
102, JP 55-135103, JP 55-152710, JP 56-811, JP 56-11908, JP 56-18
606, JP 58-83006, JP 58-138705, JP 58-138706
No. 58-138707, Japanese Patent Application Laid-Open No. 1982-138707
-138708, JP 58-138709, JP 58-138710, JP 58-1
Publication No. 38715, Japanese Unexamined Patent Publication No. 138720/1983,
JP-A-58-138721, JP-A-58-215
408, JP 59-47210, JP 59-117508, JP 59-117509
Publication No. 1987-207904, Japanese Patent Application Laid-Open No. 1987-207904
-206410, JP 59-206408, JP 59-206407, JP 131-
69815, JP 61-69821, JP 61-69822, JP 61-69823
JP-A-63-22806, JP-A-63-22806, JP-A-63-22806
95208, JP 63-199702, JP 63-199703, JP 63-2026
03, JP 63-202604, JP 63-223008, JP 63-223009
No. 63-264609, JP-A-64
-87610, JP 64-156305, JP 2-77407, JP 2-84404
No. 2-229807, JP-A No. 2-2-2
29806, JP-A-2-229805, etc.).

Highly crystalline polypropylene has high rigidity and generally has high heat distortion temperature, melting point, and crystallization temperature, so it exhibits excellent properties such as excellent heat resistance, fast crystallization rate, and high transparency. . Therefore, higher rigidity, heat resistance,
It is suitably used in various applications such as containers and films that require high-speed moldability and transparency. In addition, it also has advantages over conventional applications, such as reducing the density of the product by reducing the amount of filler such as talc added, and making the product thinner.

There are various methods for producing highly crystalline polypropylene, which has many advantages, such as adding a nucleating agent to the polypropylene obtained using the above-mentioned catalyst. The tic pentad value is about 90-97%, and the rigidity
There were limits to the improvement of heat resistance, etc.

In view of the above-mentioned conventional technology, the present inventors conducted intensive studies in order to obtain highly crystalline polypropylene with further excellent rigidity, heat resistance, etc., and found that a special silicon compound was used as an electron donor during propylene polymerization. In addition to using it as
The present invention was completed by discovering that a so-called multi-stage polymerization method using a plurality of polymerization vessels could be adopted.

Purpose of the Invention The present invention provides a method for producing polypropylene that has a high degree of crystallinity, high stereoregularity, excellent rigidity, heat resistance, transparency, etc., and can be molded at high speed, and a polypropylene that can be obtained by the production method. The object of the present invention is to provide polypropylene, a composition of polypropylene and a nucleating agent obtainable by the production method, and uses thereof.

Summary of the invention The method for producing polypropylene according to the present invention comprises [III]
[A] A solid titanium catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components, and [B] an organometallic catalyst component, and at least one reactive monomer selected from the following group a. , 0.1 to 1000 g per 1 g of the solid titanium catalyst component [A], a prepolymerized catalyst formed by prepolymerization, and Group 8: 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl. -1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4.4-dimethyl-1-hexene, 4.4-dimethyl-1-pentene, 4
-ethyl-1-hexene, 3-ethyl-1-hexene,
Allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes [II] Organometallic catalyst component ['B] And, [■ko the following formula (
1) (However, in formula (1), R1 and R2 are each independently a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentajenyl group, or 3
Indicates a class hydrocarbon group. ) In carrying out the polymerization of propylene using two or more polymerization vessels in the presence of an olefin polymerization catalyst consisting of a silicon compound represented by In the reactor, a propylene polymer with an intrinsic viscosity [η] of 5 to 40 dl/g is produced in a proportion of 0.1 to 35% by weight based on the total amount of polymer obtained, and then in the remaining polymerization reactor, Furthermore, the method is characterized in that a propylene polymer is produced to obtain a polypropylene that satisfies the following requirements (a) to (C).

(a) Crystallinity is 60% or more; (b) Melt flow rate at 230°C is 0.
1 to 2000 g/10 minutes, (C) 3000 to 1
Polypropylene made by polymerizing 00000g of propylene.

The polypropylene according to the present invention is characterized by scales obtained from the above production method.

The polypropylene composition according to the present invention is characterized by comprising the above polypropylene and a nucleating agent.

The stretched film according to the present invention is characterized by being made of the above polypropylene or the above polypropylene composition.

Further, the injection molded article according to the present invention is characterized in that it is made of the above-mentioned polypropylene or the above-mentioned polypropylene composition.

DETAILED DESCRIPTION OF THE INVENTION The method for producing polypropylene, polypropylene, polypropylene composition, and uses thereof according to the present invention will be specifically described below.

In the method for producing polypropylene according to the present invention, [III] [A] solid titanium catalyst component, and [B]
A prepolymerized catalyst obtained by prepolymerizing a reactive monomer using an organometallic catalyst component, and an olefin polymerization catalyst consisting of an organometallic catalyst component [B] and a silicon compound. Carry out polymerization of propylene.

FIG. 1 shows an example of a flowchart of the method for preparing the catalyst used in the present invention.

Such [A] solid titanium catalyst component is prepared by contacting a magnesium compound, a titanium compound, and an electron donor as described below.

[A] Specific examples of the titanium compound used for preparing the solid titanium catalyst component include a tetravalent titanium compound represented by the following formula.

Ti(OR)tX4-l R is a hydrocarbon group, X is a halogen atom, 0≦g≦4 Such compounds include, specifically, Tick4, TiBr
4. Titanium tetrahalides such as TiI4, Ti(○CH,)(13, Ti(OC2H5)Cffi3, Ti(On C4H9)CI!!!, Ti(O)
Trihalogenated alkoxytitaniums such as C2H6)Brz, TI(Ol5O-C4H9)Bra, Ti(OCH3)2Clt, Ti(OC2H5)2Ci2, TI(On C4H9)2Cl2, Ti(O
Dihalogenated dialkoxytitanium such as C2H6)28r2, Ti(OCHs)sCI! , Ti(OCtHs>scl.

Monohalogenated trialkoxytitanium such as Tl(On-CiH*) Examples include tetraalkoxytitanium such as -1so-C4H*)4 and Ti(0-2-ethylhexyl)4.

Among these, halogen-containing titanium compounds, particularly titanium tetrahalide, are preferred, and titanium tetrachloride is more preferred. These titanium compounds may be used alone or in combination of two or more.

Furthermore, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

In the present invention, examples of the magnesium compound used for preparing the solid titanium catalyst component [A] include magnesium compounds having reducibility and magnesium compounds having no reducibility.

Examples of magnesium compounds having reducing properties include magnesium-carbon bonds or magnesium-carbon bonds.
Mention may be made of magnesium compounds having hydrogen bonds. Specific examples of magnesium compounds having such reducing properties include dimethylmagnesium, diethylmagnesium, dipropylmagnesium, dibutylmagnesium, cyamylmagnesium, didecylmagnesium, didecylmagnesium, ethylmagnesium chloride,
Propyl magnesium chloride, butyl magnesium chloride,
hexylmagnesium chloride, amylmagnesium chloride,
Examples include butyl ethoxymagnesium, ethylbutylmagnesium, butylmagnesium nohydride, and the like. These magnesium compounds may be used alone or may form a complex with an organometallic compound described below. Moreover, these magnesium compounds may be liquid or solid.

Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, nidoxymagnesium chloride, isopropoxymagnesium chloride, and butoxymagnesium chloride. Magnesium chloride, alkoxymagnesium halides such as octoxymagnesium chloride, allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxy Examples include alkoxymagnesiums such as magnesium; allyloxymagnesiums such as phenoxymagnesium and dimethylphenoxymagnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate.

These magnesium compounds without reducing properties may be compounds derived from the above-mentioned magnesium compounds having reducing properties or compounds derived during the preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducing magnesium compound, for example, a reducing magnesium compound can be derived from a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an ester, an alcohol, etc. All you have to do is bring it into contact with a compound.

In addition, in the present invention, the magnesium compound includes not only the above-mentioned magnesium compounds having reducing properties and non-reducing properties, but also complex compounds, composite compounds of the above-mentioned magnesium compounds and other metals, or other metal compounds. It may be a mixture of. Furthermore, a mixture of two or more of the above compounds may be used.

In the present invention, among these, magnesium compounds that do not have reducing properties are preferred, and halogen-containing magnesium compounds are particularly preferred, and among these, magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride are preferably used.

[A] The solid titanium catalyst component used in the present invention is formed by bringing the magnesium compound described above into contact with the titanium compound and electron donor described above.

[A] Specific examples of the electron donor used in preparing the solid titanium catalyst component include the following compounds.

Amines such as methylamine, ethylamine, dimethylamine, diethylamine, ethylenediamine, tetramethylenediamine, hexamethylenediamine, tributylamine, tribenzylamine; Pyrroles such as pyrrole, methylpyrrole, dimethylpyrrole: Pyrroline: Pyrrolidine : Indole; Pyridine such as pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, chloride pyridine; Nitrogen-containing such as piperidine, quinoline, isoquinoline, etc. Cyclic compounds; Cyclic oxygen-containing compounds such as tetrahydrofuran, 1.4-cineole, 1.8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalan, tetrahydropyran, pyran, ditedropyran; methanol, Ethanol, propatool, pentanol, hexanol, octatool, 2-ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol,
Alcohols with 1 to 18 carbon atoms such as isopropyl alcohol and isopropylbenzyl alcohol: phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol, etc., which may have a lower alkyl group. Phenols having 6 to 20 carbon atoms; Ketones having 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetylacetone, and benzoquinone; Aldehydes with 2 to 15 carbon atoms; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methacryl methyl acid,
Ethyl crotonate, ethyl cyclohexanecarboxylate,
Methyl benzoate, ethyl benzoate, propyl benzoate,
Butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzyl benzoate, methyl toluate, ethyl toluate, amyl toluate, ethyl ethylbenzoate, methyl anisate, n-maleate
Butyl, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadic acid, diisopropyl tetrahydrophthalate, diethyl phthalate,
Organic acid esters having 2 to 30 carbon atoms, such as diisobutyl phthalate, di-n-butyl phthalate, di-2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, and ethyl carbonate; acetyl chloride, benzoyl chloride acid halides having 2 to 15 carbon atoms, such as toluic acid chloride, and anisyl chloride; Ethers; 2-isopentyl-2-isopropyl-1,3-dimethoxypropane, 2,2-isobutyl-1,3-dimethoxypropane, 2,2-isopropyl-1,3-dimethoxypropane, 2-cyclohexylmethyl-2 -isopropyl-1,3-dimethoxypropane, 2,2-isopentyl-1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1, 3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane,
2.2-dicyclopentyl-1,3-dimethoxypropane, 1.2-bis-methoxymethyl-bicyclo-[2,
2,11-heptane, diphenyldimethoxysilane, isopropyl-t-butyldimethoxysilane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-
Diethers such as isopentyl-2-isopropyl-1,3-dimethoxycyclohexane; Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; Nitriles such as acetonitrile, benzonitrile, tolnitrile; Acetic anhydride, phthalic anhydride , benzoic anhydride and other acid anhydrides are used.

Further, as an electron donor, a [I[] silicon compound represented by the general formula (1) as described below can also be used.

Further, when the titanium compound, magnesium compound, and electron donor as described above are brought into contact with each other, a carrier-supported type [A] solid titanium catalyst component can also be prepared using the following carrier compound.

Such carrier compounds include A1720z, 5i0
2, B2O3, MgO1CaO1T i O2, ZnO
1ZnO, SnO□, BaO1ThO and resins such as styrene-divinylbenzene copolymer and MgCf2
, Mg(OH)2, MgCO2, Mg(OEt
)z, magnesium stearate, etc.

Among these carrier compounds, preferably 5i02, A1
720z, MgO, ZnO1Z n 02 and the like.

[A] The solid titanium catalyst component can be produced by bringing the above-described titanium compound, magnesium compound, and electron donor into contact with each other. [A] In order to produce the solid titanium catalyst component, a known method for preparing a highly active titanium catalyst component from a titanium compound, a magnesium compound, and an electron donor can be employed. In addition,
The above components may be contacted in the presence of other reactants such as silicon, phosphorous, aluminum, etc.

Several examples of the manufacturing method of these [A] solid titanium catalyst components will be briefly described below.

(1) A method of contacting and reacting a magnesium compound, an electron donor, and a titanium compound in any order.

In this reaction, each component may be pretreated with a reaction aid such as an electron donor, an organoaluminum compound, or a halogen-containing silicon compound before and/or during the reaction.

(2) A method in which a non-reducing liquid magnesium compound and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid magnesium-titanium complex.

(3) A method in which the reaction product obtained in (1) or (2) is further reacted with a titanium compound.

(4) A method in which the reaction product obtained in (1) or (2) is further reacted with an electron donor and a titanium compound.

(5) A method including a crushing step in the process of bringing a magnesium compound, an electron donor, and a titanium compound into contact to obtain a solid titanium composite. Incidentally, after the pulverization, it may be pretreated with a reaction aid. Examples of the reaction aid include organoaluminum compounds and halogen-containing silicon compounds.

Further, after the reaction, it can be treated with a halogen, a halogen compound, an aromatic hydrocarbon, or the like.

(6) A method of treating the compound obtained in the above (1) to (4) with a halogen, a halogen compound, an aromatic hydrocarbon, or the like.

(7) A method of contacting a contact reaction product with a metal oxide, an organomagnesium compound, and a halogen-containing compound with an electron donor and a titanium compound.

(8) A method of bringing a magnesium compound such as a magnesium salt of an organic acid, alkoxymagnesium, or aryloxymagnesium into contact with an electron donor, a titanium compound, and, if necessary, a halogen-containing compound.

(9) A method of reacting a hydrocarbon solution containing a small amount of a magnesium compound and alkoxytitanium with a titanium compound, an electron donor, and, if necessary, a halogen-containing silicon compound.

(10) A method in which a non-reducing liquid magnesium compound and an organoaluminum compound are reacted to precipitate a solid magnesium-aluminum complex, and then an electron donor and a titanium compound are reacted.

(11) A method in which the reaction products obtained in (5) to (10) are further reacted with a titanium compound.

(12) A method in which the reaction products obtained in (5) to (10) are further reacted with a titanium compound and an electron donor.

[A] The amount of each of the above-mentioned components used in preparing the solid titanium catalyst component varies depending on the preparation method and cannot be unconditionally defined. mole, preferably 0.1
used in an amount of ~1 mol, and the titanium compound is used in an amount of 0.01-1
000 mol, preferably from 0.1 to 200 mol.

The solid titanium catalyst component [A] thus obtained contains magnesium, titanium, halogen, and an electron donor as essential components.

In this [A] solid titanium catalyst component, halogen/
Titanium (atomic ratio) is about 2 to 200, preferably about 4 to 1
00, and the electron donor/titanium (molar ratio) is approximately 0.
．． 01 to 100, preferably about 0.2 to IO, and the magnesium/titanium (atomic ratio) is preferably about 1 to 100, preferably about 2 to 50.

In the method for producing polypropylene according to the present invention, prior to propylene polymerization, reactive monomers are prepolymerized using the above [A] solid titanium catalyst component and the following [B] organometallic catalyst component, [ A] Produce a solid titanium catalyst component.

[B] As the organometallic catalyst component, organometallic compounds of metals from Groups 1 to 1 of the periodic table are used, and specifically, the following compounds are used.

(1) R', Al1 (OR2), H, X.

(In the formula, R1 and R2 usually have 1 to 15 carbon atoms,
Preferably, it contains 1 to 4 hydrocarbon groups, which may be the same or different from each other. X represents a halogen atom, 0<m≦3, n is 0≦n<3, p is 0≦p<3, q
is a number such that 0≦q<3, and m+n+p+q=3
An organoaluminum compound represented by

(2) M’A I! R’.

(In the formula, Ml is Li, =Na, and R1 is the same as above) A complex alkylated product of a Group 1 metal and aluminum.

(3) R'R2M2 (wherein, R1 and R2 are the same as above. M2 is M
A dialkyl compound of Group 1 or Group 2 represented by Zn, Zn or Cd.

As the organoaluminum compound belonging to the above (1), the following compounds can be exemplified.

-Formula R'mA I! (OR2) g-(wherein, R1
and R2 are the same as above. m is preferably 1.5≦m≦
3), - Formula R',, A f X 2-m (In the formula, R1 is the same as above. R',, A j' Ha- (wherein R1 is the same as above. m is preferably 2≦m<3
), general formula R', AI! (OR2)ゎX@(In the formula, R1 and R2 are the same as above. X is) 10 gen, O<m≦3.
0≦n<3, O≦q<3, and m+n+q=3.

More specifically, aluminum compounds belonging to (1) include trialkylaluminum such as triethylaluminum and tributylaluminium; trialkenylaluminum such as triisoprenylaluminum; dialkylaluminum such as diethylaluminum ethoxide and dibutylaluminum butoxide. Alkoxides: Alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, R'2. sAI! (OR”) Partially alkoxylated alkylaluminum with an average composition expressed as o, s, etc.; dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide; ethylaluminum sesquichloride, butylaluminum Alkylaluminum sesquihalides such as sesquichloride, ethylaluminum sesquipromide; Partially halogenated alkylaluminums such as alkylaluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; diethylaluminum hydride, dibutyl Dialkyl aluminum hydrides such as aluminum hydride; Other partially hydrogenated alkylaluminums such as alkyl aluminum dihydrides such as ethyl aluminum dihydride, probylaluminum dihydride; ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy Mention may be made of partially alkoxylated and halogenated alkyl aluminums such as bromides.

Compounds similar to (1) include organoaluminum compounds in which two or more aluminum atoms are bonded via oxygen atoms or nitrogen atoms. Examples of such compounds include (C2H6) 2AfOAA (
C2H6)2, (C4H#)2AIOAI! (C4H
j) 2, (C2H6) 2AI! NAf (C2H6)
In addition to 2C2Hs, aluminoxanes such as methylaluminoxane can be mentioned.

Examples of compounds belonging to the above (2) include LiAl (C2H6)4 and LiAA (C7HI5)4.

Among these, organoaluminum compounds are preferably used, and halogen-containing alkylaluminum compounds are particularly preferably used.

[III] Reactive monomers used in the production of the prepolymerized catalyst include 3-methyl-1-butene, 3-methyl-1-butene,
1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-
Dimethyl-I-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluene monomers such as allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, and allyltrialkylsilanes, preferably 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl- Examples include 1-hexene, vinylcyclohexane, allyltrimethylsilane, dimethylstyrene, and particularly preferred are 3-methyl-1-butene, vinylcyclohexane, and allyltrimethylsilane.

In the prepolymerization, a considerably higher concentration of catalyst can be used than in the main polymerization of propylene.

The concentration of the solid titanium catalyst component [A] in the prepolymerization is usually in the range of about 0.01 to 200 mmol, preferably about 0.05 to 100 mmol, in terms of titanium atoms, per liter of the inert hydrocarbon medium described below. It is desirable to do so.

[B] The amount of the organometallic catalyst component is 1 to 500 g of O per 1 g of the solid titanium catalyst component [A], preferably 0.3 to 500 g.
The amount may be such that 300 g of polymer is produced; [
A] per mole of titanium atoms in the solid titanium catalyst component,
Usually about 0.1 to 100 mmol, preferably about 0.5 to 100 mmol
A range of 50 mmol is desirable.

Further, when performing preliminary polymerization, in addition to [A] the solid titanium catalyst component and [B] the organometallic catalyst component, [C] an electron donor may be used. Specifically, as this [C] electron donor, in addition to the electron donor previously used in producing the [A] solid titanium catalyst component, the following general formula [I a
] It is also possible to use an organosilicon compound represented by the following.

R, s i (OR') a-,... [I a [wherein R and R' are hydrocarbon groups, 0<n<4
] Specifically, the organosilicon compound represented by the above general formula [I a] includes trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diisopropyldimethoxysilane, t- Butylmethyldimethoxysilane, t-
Butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bis0-tolyldimethoxysilane, bis m-tolyldimethoxysilane, bis p-)lyldimethoxysilane, Bis p4 lyldiethoxysilane, bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, Ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxysilane, n-butyltriethoxysilane, 1so-butyltriethoxysilane,
Phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane,
Cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethinosilicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxy(at ly 10XY) silane, vinyltris(β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, etc. are used.

Furthermore, as the electron donor (a), the following general formula [
It is also possible to use an organosilicon compound represented by I[a].

SiR'R2, (OR')s-, -[IIa] [wherein,
R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, R2 is a group selected from the group consisting of an alkyl group, a cyclopentyl group, and a cyclopentyl group having an alkyl group, R3 is a hydrocarbon group, and m is 0≦ m≦2. In the above formula [I[a], R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R
Examples of 1 include cyclopentyl groups having alkyl groups such as 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, and 2,3-dimethylcyclopentyl group in addition to cyclopentyl group.

Further, in formula [I[a], R2 is an alkyl group, a cyclopentyl group, or a cyclopentyl group having an alkyl group, and examples of R2 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. , an alkyl group such as a hexyl group, or a cyclopentyl group having an alkyl group and a cyclopentyl group exemplified as R1.

Further, in formula [IIa], R3 is a hydrocarbon group, and examples of R3 include hydrocarbon groups such as an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

Examples of such organosilicon compounds include trialkoxysilanes such as cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, 2,3-dimethylcyclopentyltrimethoxysilane, and cyclopentyltriethoxysilane; Dialkoxysilanes such as silane, bis(2-methylcyclopentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane; tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethyl Examples include monoalkoxysilanes such as methoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, and cyclopentyldimethylethoxysilane.

Further, this [C] electron donor is 0.1 to 50 mol, preferably 0.5 to 30 mol, more preferably 1 to 10 mol, per 1 mol of titanium atom in the solid titanium catalyst component [A].
Used in molar amounts.

Prepolymerization is preferably carried out under mild conditions by adding the above-mentioned reactive monomer and the above-mentioned catalyst component to an inert hydrocarbon medium.

Examples of the inert hydrocarbon medium used in this case include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, and methylcyclopentane. Examples include alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and contact substances thereof. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons.

The reaction temperature for prepolymerization may be any temperature such that the prepolymer to be produced is not substantially dissolved in the inert hydrocarbon medium, and is usually about -20 to +100°C, preferably about -2°C.
It is desirable that the temperature be in the range of 0 to +80°C, more preferably 0 to +40°C.

Incidentally, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. Such a molecular weight modifier is 1
The intrinsic viscosity [η] of the polymer obtained by prepolymerization measured in decalin at 35 ° C, or about 0.2 dl/g or more,
Preferably, it is used in an amount of about 0.5 to 10 dl/g.

The prepolymerization is carried out in an amount of about 0.1 to 1000 g, preferably about 0.3 to 1000 g, per 1 g of the solid titanium catalyst component [A] as described above.
It is desirable to carry out the process so that 500 g of polymer is produced. If the amount of prepolymerization is too large, the production efficiency of polypropylene in the main polymerization may decrease, and when a film is formed from the obtained polypropylene,
Fish eyes may occur more easily.

Prepolymerization can be carried out batchwise or continuously.

When propylene is polymerized using such a [III] prepolymerization catalyst, highly crystalline polypropylene can be obtained.

In the method for producing polypropylene according to the present invention, propylene polymerization is carried out in the presence of an olefin polymerization catalyst comprising the above-mentioned [III] prepolymerized catalyst, [II] an organometallic catalyst component, and [III] a silicon compound. Let's do it. [I[] As the organometallic catalyst component, the above-mentioned [III]
The same organometallic catalyst component [B] used in the preparation of the prepolymerized catalyst can be used.

The [III] silicon compound used in the method for producing polypropylene according to the present invention is represented by the following formula (1).

However, in formula (1), R' and R2 each independently represent a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentagenyl group, a substituted cyclopentagenyl group, or 3
Indicates a class hydrocarbon group.

Examples of substituted cyclopentyl groups include cyclopentyl groups having an alrylic group, specifically 2-methylcyclopentyl groups, 3-methylcyclopentyl groups, 2-methylcyclopentyl groups, and 2-methylcyclopentyl groups.
-ethylcyclopentyl group, 2,3-dimethylcyclopentyl group, specifically 2-methylcyclopentyl group, 3
-Methylcyclopentyl group, 2-ethylcyclopentyl group, 2-n-butylcyclopentyl group, 2,3-dimethylcyclopentyl group, 2,4-dimethylcyclopentyl group, 2,5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3.4-) dimethylcyclopentyl group, 2,3. trimethylcyclopentyl group,
2.3.4- Triethylcyclohentyl group, tetramethylcyclopentyl group, tetraethylcyclopentyl group, etc. can be exemplified.

Examples of substituted cyclopentenyl groups include cyclopentenyl groups having an alkyl group, specifically 2-
Methylcyclopentenyl group, 3-methylcyclopentenyl group, 2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2.4-dimethylcyclopentenyl group, 2.5-
Dimethylcyclopentenyl group, 2,3.4-trimethylcyclopentenyl group, 2.3.5-trimethylcyclopentenyl group, 2.3.4-triethylcyclopentenyl group, tetramethylcyclopentenyl group, tetraethylcyclopentenyl group, etc. I can give an example.

Examples of the substituted cyclopentadienyl group include cyclopentadienyl groups having an alkyl group, specifically 2-methylcyclopentadienyl group, 3-methylcyclopentadienyl group, and 2-ethylcyclopentadienyl group. Jenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentadienyl group, 2,4-dimethylcyclopentadienyl group, 2.5-dimethylcyclopentadienyl group, 2.3- diethylcyclopentadienyl group,
2.3.4-trimethylcyclopentadienyl group, 2
．． 3.5-trimethylcyclopentadienyl group, 2.
3.4- triethylcyclopentadienyl group, 2.3
．． 4.5-tetramethylcyclopentadienyl group, 2.
3.4.5-tetraethylcyclopentadienyl group, l
, 2.3.4.5-pentamethylcyclopentagenyl group, 1.2.3.4.5-pentaethylcyclopentagenyl group, and the like.

Examples of the tertiary hydrocarbon group include t-butyl group, t-amyl group, α, α°-dimethylbenzyl group, and atmantyl group.

More specific examples of such silicon compounds represented by formula (1) include dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-t-butyldimethoxysilane, and dicyclopentyldimethoxysilane. (2-Methylcyclopentyl)dimethoxysilane, di(3-methylcyclopentyl)dimethoxysilane, di(2-ethylcyclopentyl)dimethoxysilane, di(2,3-ditycyclopentyl)dimethoxysilane, di(2,4-dimethylcyclopentyl) Dimethoxysilane, di(2,5-dimethylcyclopentyl)dimethoxysilane, di(2,3-diethylcyclopentyl)dimethoxysilane, di(2,3,4-trimethylcyclopentyl)dimethoxysilane, di(2,3,5-) dimethylcyclopentyl)dimethoxysilane, di(2,3
,4-)diethylcyclopentyl)dimethoxysilane,
di(tetramethylcyclopentyl)dimethoxysilane,
di(tetraethylcyclopentyl)dimethoxysilane,
di(2-methylcyclopentenyl)dimethoxysilane,
di(3-methylcyclopentenyl)dimethoxysilane,
di(2-ethylcyclopentenyl)dimethoxysilane,
Di(2-n-butylcyclopentenyl)dimethoxysilane, di(2,3-dimethylcyclopentenyl)dimethoxysilane, di(2,4-dimethylcyclopentenyl)dimethoxysilane, di(2,5-dimethylcyclopentenyl)dimethoxy Silane, di(2,3,4-trimethylcyclopentenyl)dimethoxysilane, di(2,3,5-
trimethylcyclopentenyl) dimethoxysilane, di(
2,3,4-triethylcyclopentenyl)dimethoxysilane, di(tetramethylcyclopentenyl)dimethoxysilane, di(tetraethylcyclopentenyl)dimethoxysilane, di(2-methylcyclopentajenyl)dimethoxysilane, di(3-methyl cyclopentadienyl)dimethoxysilane, di(2-ethylcyclopentajenyl)dimethoxysilane, di(2-n-butylcyclopentenyl)dimethoxysilane, di(2,3-dimethylcyclopentajenyl)dimethoxysilane, di(2-n-butylcyclopentenyl)dimethoxysilane, (2,4-
dimethylcyclopentagenyl)dimethoxysilane, di(2,5-dimethylcyclopentagenyl)dimethoxysilane, di(2,3-diethylcyclopentagenyl)
Dimethoxysilane, di(2,3,4-)dimethylcyclopentadienyl)dimethoxysilane, di(2,3,5-
) dimethylcyclopentadienyl) dimethoxysilane,
Di(2,3,4-triethylcyclopentadienyl)dimethoxysilane, Di(2,3,4,5-tetramethylcyclopentajenyl)dimethoxysilane, Di(2,3,
4,5-tetraethylcyclopentagenyl)dimethoxysilane, di(1,2i 3.4.5-pentamethylcyclopentagenyl)dimethoxysilane, di(1,2,
3,4,5-pentaethylcyclopentadienyl)dimethoxysilane, di-t-amyl-dimethoxysilane, di(
α,α゛-dimethylbenzyl)dimethoxysilane, di(
atmantyl)dimethoxysilane, atmantyl-t-
Mention may be made of butyldimethoxysilane and cyclopentyl-t-butyldimethoxysilane.

Among the above silicon compounds, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di(2-methylcyclopentyl)dimethoxysilane,
It is desirable to use di(3-methylcyclopentyl)dimethoxysilane, di-t-amyldimethoxysilane, and particularly preferably dicyclopentyldimethoxysilane and di-t-butyldimethoxysilane.

The above-mentioned [III] silicon compound and the above-mentioned [I]
By carrying out the main polymerization of propylene using an olefin polymerization catalyst consisting of a prepolymerized catalyst (II) and an organometallic catalyst component (II), a high degree of crystallinity, which could not be obtained with conventional catalyst systems, can be achieved. Polypropylene having the following properties is obtained.

Incidentally, when carrying out the main polymerization of propylene, in addition to propylene, a small amount of other α-olefin or diene compound other than propylene can also be allowed to coexist in the polymerization system.

Other α-olefins other than propylene include ethylene, ■-butene, I-pentene, l-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, l-octene, 3- Examples include olefins having 3 to 8 carbon atoms such as methyl-1-butene.

As diene compounds, 1,3-butadiene, 1,3-
Pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, methyl-1.
4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1
, 6-octadiene, 6-broby-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6 -nonadiene, 7-ethyl-
1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,
6-undecadiene, 1.7-octadiene, 1.9-
Mention may be made of diene compounds having 4 to 20 carbon atoms such as decadiene, isoprene, butadiene, ethylidenenorbornene, vinylnorbornene and dicyclopentadiene.

The main polymerization of propylene is carried out in two or more vessels, preferably in 2 to 10 vessels.
It is carried out in a gas or liquid phase using a polymerization vessel.

When the polymerization takes the form of slurry polymerization or solution polymerization, the above-mentioned inert hydrocarbons can be used as the reaction solvent.

In the method for producing polypropylene according to the present invention, propylene is polymerized in at least one polymerization vessel among the two or more polymerization vessels. ), the intrinsic viscosity [η] is 5 to 40 dl/g, preferably 7 to
30 dl/g of polymer is produced, particularly preferably 8 to 25 dl/g.

The isotactic pentad value determined by NMR measurement of the polymer in the present invention is 97% or more, preferably 98% or more, particularly preferably 98.5% or more.

Further, the isotactic index (II) of the polymer as a boiling butane extraction residue is 90% or more, preferably 95% or more, particularly preferably 98% or more.
% or more.

The polymer obtained by such A polymerization has an O content of 1 to 35%, preferably 2%, in the finally obtained polypropylene.
-32%, particularly preferably 5-30%.

In the method for producing polypropylene according to the present invention, propylene is polymerized in the remaining polymerization vessel among the two or more polymerization vessels (hereinafter sometimes referred to as B polymerization), and as a final product, melt flow Rate is 0.1~2000
g/l 0 min, preferably 0.2-1500 g71
0 min, particularly preferably from 0.5 to 1000 g/10 min.

In the polymerization system of the A polymerization and B polymerization, the above [I
II] The prepolymerization catalyst has a polymerization volume lI! Hit [III]
In terms of titanium atoms in the prepolymerized catalyst, it is usually about 0.
0.001 to 50 mmol, preferably about 0.01 to 10 mmol. In addition, the [I[] organometallic catalyst component is [II] per mole of titanium atom in the polymerization system.
The metal atoms contained in the organometallic catalyst component are usually about 1 to 2.
000 mol, preferably from about 2 to 500 mol. Furthermore, [III] the silicon compound is [
II] per mole of metal atom in the organometallic catalyst component [II
I] Usually about 0.0 in terms of silicon atom in silicon compound
0.01 to 10 moles, preferably about 0.01 to 5 moles.

In addition, if necessary, [II
I) a solid titanium catalyst component, [II] an organometallic catalyst component, or [III] a silicon compound may be supplied.

Furthermore, in both the A polymerization and B polymerization, the molecular weight of the resulting polymer can be easily adjusted by supplying or excluding hydrogen.

In this case, in the present invention, the crystallinity or stereoregularity index of the obtained polypropylene does not decrease, and the catalytic activity does not decrease. The amount of hydrogen supplied varies depending on various conditions, or the melt flow rate of the final polymer is 0.1 to 2000 g/10
It's fine as long as it's in an amount that fits within minutes.

The polymerization temperature of propylene in the A polymerization and B polymerization is usually about -50 to 200°C, preferably 20°C.
The temperature is ~100°C, and the pressure (usually normal pressure ~100kg)
/cI11 is preferably set at 2 to 50 kg/cfIrl. Polymerization can be carried out in any of the batch, semi-continuous and continuous methods.

The polypropylene obtained by the production method according to the present invention has (a) a crystallinity of 60% or more, preferably 65% or more, and further (=preferably 70%).
or more, particularly preferably 72% or more.

The degree of crystallinity was determined by molding the polymer into a 1 mm thick rectangular plate using a pressure molding machine at 180°C and then immediately cooling it with water.The obtained press sheet was then measured using a rotorflex RtJ300 measuring device manufactured by Rigaku Denki ■. (output 50KV, 250mA). At this time, a transmission method is used as the measurement method, and the measurement is performed without rotating the sample.

In addition, the polypropylene obtained by the method for producing polypropylene according to the present invention has a melt flow rate of (b) 0 at 230°C.
．． 1-2000g/10 minutes, preferably 0.2-2000g/10 minutes
1500g/10 minutes, particularly preferably 0°5-1
000g/10 minutes, and (c) the above [III
] 3.000 to 1,000°000 g, preferably 2
,000-200,000g, particularly preferably s,oo
It is polypropylene obtained by polymerizing 0 to 50.000 g of propylene.

In the present invention, since the yield of stereoregular polypropylene per unit amount of the solid catalyst component is high, it is possible to relatively reduce the catalyst residue, especially the halogen content, in the polypropylene. Therefore, the operation of removing the catalyst in the polypropylene can be omitted, and when molding a molded article using the obtained polypropylene, rusting of the mold can be effectively prevented.

Furthermore, according to the present invention, the polypropylene obtained has very little amorphous components, and thus contains little hydrocarbon-soluble components, and the film formed from this polypropylene has low surface tack.

The polypropylene according to the present invention is characterized by scales obtained by the above production method.

The polypropylene according to the present invention satisfies the above requirements.

The intrinsic viscosity [η] of the polypropylene according to the present invention measured in decalin at 135°C is 30 to 0.001 dll.
g, preferably 10 to 0.01 dllg,
Particularly preferably 5 to 0.05 dllg.

The isotactic index (II) shown by the boiling hebutane extraction residue of polypropylene according to the present invention is 9.
It is 0% or more, preferably 92% or more.

The isotactic pentad value determined by NMR measurement of the polypropylene according to the present invention is 97% or more, preferably 98% or more, particularly preferably 98%.
．． It is 5% or more.

Furthermore, the molecular weight distribution of the polypropylene according to the present invention is GP
The value of Mw/Mn by C measurement is 5 or more,
Preferably it is 6 or more, more preferably 7 or more.

The polypropylene composition according to the present invention comprises the above polypropylene and a nucleating agent. By adding a nucleating agent, crystal grains can be made finer, the crystallization rate can be improved, and high-speed molding can be performed.

As the above-mentioned nucleating agent, various conventionally known nucleating agents can be used without particular limitation.

Among these, preferable nucleating agents include the nucleating agents listed below.

(However, in the above formula, R1 is oxygen, sulfur, or a hydrocarbon group having 1 to 10 carbon atoms, R2 and R3 are hydrogen or a hydrocarbon group having 1 to IO carbon atoms, and R2,
R3 may be of the same type or different types, and R2 and R2,
R3 may be combined with each other or R2 and R3 to form a ring, M is a monovalent to trivalent metal atom, and n is 1 to 3.
is an integer. ) Specifically, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis(4,6-di-t-butylphenyl) phosphate,
Lithium-2,2'-methylene-bis-(4,6-di-t-butylphenyl)phosphate, lithium-2,
2'-ethylidene-bis(4,6-di-t-butylphenyl) phosphate, sodium-2,2°-ethylidene-bis(4-1-propyl-6-t-butylphenyl) phosphate, lithium-2 , 2-methylene-bis(4-methyl-6-t-butylphenyl) phosphate, lithium-2,2-methylene-bis(4-ethyl-6-t-butylphenyl) phosphate, calcium-bis-[ 2,2'-thiobis(4-methyl-6-t
-butylphenyl)phosphate J, calcium-bis-[2,2'-thiobis(4-ethyl-6-t-butylphenyl)phosphate], calcium-bis-[
2,2-thiobis-(4,6-di-t-butylphenyl)phosphate], magnesium-bis-[2,2'
-thiobis(4,6-di-t-butylphenyl)phosphnito, magnesium-bis[2,2-thiobis-
(4-t-octylphenyl)phosphate], sodium-2,2゛-butylidene-bis(4,6-di-methylphenyl)phosphate, sodium-2゜2゜
-butylidene-bis(4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t-ctylmethylene-bis(4,6-di-methylphenyl) phosphate, sodium-2,2' - ctylmethylene-bis(4,6-di-t-butylphenyl) phosphate, calcium-bis-(2,2-methylene-bis(4,6-di-t-butylphenyl) phosphate), magnesium- Bis[2,2-methylene-bis-(
4,6-di-t-butylphenyl) phosphate 1,
Barium-bis-[2,2'-methylene-bis(4,6
-di-t-butylphenyl) phosphate], sodium-2,2-methylene-bis(4-methyl-6-t-
butylphenyl) phosphate, sodium-2,2
'-methylene-bis(4-ethyl-6-t-butylphenyl) phosphate, sodium (4,4'-dimethyl-5,6'-di-t-butyl-2,2°-biphenyl) phosphate, Calcium-bis-[(4,4'-
dimethyl-6,6-di-t-butyl-2,2°-biphenyl) phosphate], sodium-2,2'-ethylidene-bis(4-m-butyl-6-t-butylphenyl) phosphate, sodium -2,2'-methylene-bis(4,6-di-methylphenyl)phosphate, sodium-2,2'-methylene-bis(4,6-cy-nitylphenyl)funasphate, potassium-2,2
'-ethylidene-bis(4,6-di-t-butylphenyl)phosphate, calcium-bis-[2,2'-
ethylidene-bis(4,6-di-t-butylphenyl)
phosphate], magnesium-bis-[2,2°-
ethylidene-bis(4,6-di-t-butylphenyl)
Phosphny H, barium-bis[2,2'-ethylidene-bis(4゜6-di-t-butylphenyl) phosphate], aluminumtris-[2,2-methylene-bis(4゜6-di-t- Examples include aluminum tris-[2,2'-ethylidene-bis(4,6-t-]titylphenyl) phosphate 1 and mixtures of two or more thereof. Particularly preferred is sodium-2,2'-methylene-bis(4,6-di-t-butylphenyl) phosphate.

(However, in the above formula, R4 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, M is a monovalent to trivalent metal atom, and n is an integer of 1 to 3.) Specifics Specifically, sodium-bis-(4-t-butylphenyl)phosphate, sodium-bis-(4-methylphenyl)phosphate, sodium-bis=(4-ethylphenyl)phosphate, sodium-bis-( 4-i-propylphenyl) phosphate, sodium bis-
(4-t~octylphenyl phate, potassium-bis-(4-t-butylphenyl) phosphate, calcium-bis-(4-t-butylphenyl) phosphate, magnesium-bis-(4-t-butylphenyl) )
phosphate, lithium-bis-(4-t-butylphenyl) phosphate, aluminum-bis-(4-
t-butylphenyl) phosphate and these two
A mixture of more than one species can be exemplified. Particularly preferred is sodium bis-(4-t-butylphenyl) phosphate.

H (However, in the above formula, RS is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.) Specifically, l, 3
, 2. 4-dibenzylidene sorbitol, 1,3-
Benzylidene-2. 4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2. 4-p-ethylbenzylidene sorbitol, 1. 3-p-methylbenzylidene-2.4-benzylidene sorbitol, 1,
3-p-ethylbenzylidene-2,4-benzylidene sorbitol, ], ]3-p-methylbenzylidene-2 4-p-ethylbenzylidene sorbitol, 1.
3-p-ethylbenzylidene-2. 4-p-methylbenzylidene sorbitol, 1, 3, 2. 4-ji (
p-methylbenzylidene) sorbitol, 1, 3,
2. 4-di(p-ethylbenzylidene) sorbitol, 1, 3. 2. 4-di(p-n-propylbenzylidene) sorbitol, 1, 3, 2. 4-di(p
-i-propylbenzylidene) sorbitol, 1, 3
, 2. 4-di(p-n-butylbenzylidene) sorbitol, 1, 3, 2. 4-di(p-s-butylbenzylidene) sorbitol, 1,3,2,4-di(p
-t-butylbenzylidene) sorbitol, 1, 3,
2. 4-di(2',4-dimethylbenzylidene)sorbitol, 1, 3, 2. 4-di(p-methoxybenzylidene)sorbitol, 1. 3, 2.
4-di(p-ethoxybenzylidene)sorbitol, 1
．． 3-benzylidene-2-4-p-chlorobenzylidene sorbitol, 1.3-p-chlorobenzylidene-2.
4-benzylidene sorbitol, 1.3-p-chlorobenzylidene-2. 4-p-methylbenzylidene sorbitol, 1. 3-p-chlorobenzylidene-2, 4
-p-ethylbenzylidene sorbitol, 1. 3-p
-Methylbenzylidene-2. 4-p-chlorobenzylidene sorbitol, 1. 3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1, 3, 2. 4-di(p-chlorobenzylidene)
Examples include sorbitol and mixtures of two or more thereof, particularly 1. 3. 2. 4-dibenzylidene sorbitol, 1, 3. 2. 4-di(p-methylbenzylidene) sorbitol, 1, 3. 2. 4-di(p
-ethylbenzylidene) sorbitol, r,3-p-chlorobenzylidene-2. 4-p-methylbenzylidene sorbitol, 1, 3, 2. 4-di(p-chlorobenzylidene) sorbitol and mixtures of two or more thereof are preferred.

Examples of other nucleating agents include metal salts of aromatic carboxylic acids and aliphatic carboxylic acids.Specifically, aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, thiophenecal Examples include sodium ponate and sodium pyrrolecarboxylate.

Further, inorganic compounds such as talc, which will be described later, can also be exemplified.

In the polypropylene composition according to the present invention, the nucleating agent is 0.00 parts by weight based on 100 parts by weight of the polypropylene.
It is desirable to add it in a proportion of 1 to 10 parts by weight, preferably 0.01 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight.

By adding the nucleating agent in the above amount to the polypropylene of the present invention, a polypropylene composition with fine crystal grains and improved crystallinity can be obtained without impairing the excellent properties originally possessed by the polypropylene of the present invention. can get.

In addition to the above-mentioned polypropylene and nucleating agent, the polypropylene composition of the present invention may also contain a rubber component for improving impact strength, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an anti-blocking agent, etc. agent, antifogging agent,
Lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. can be blended, and the blending ratios are appropriate. For example, specific stabilizers that may be added as optional ingredients include tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate 1methane, β-(3,5-di- t-Butyl-4-hydroxyphenyl) propionic acid alkyl ester, 2,2'-oxamitohis[ethyl-3(3, tert-butyl-4-
Phenolic antioxidants such as (hydroxyphenyl) 1 propionate, fatty acid metal salts such as zinc stearate, calcium stearate, calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, pentaerythritol mono Examples include fatty acid esters of polyhydric alcohols such as stearate, pentaerythritol distearate, and pentaerythritol tristearate.

These may be blended alone or in combination; for example, tetrakis[methylene-3(3,
Examples include a combination of 5-di-t-butyl-4-hydroxyphenyl)propionate 1methane, calcium stearate, and glycerin monostearate.

In the present invention, it is particularly preferable to use a phenolic antioxidant and a fatty acid ester of a polyhydric alcohol in combination. Preferably, it is a polyhydric alcohol fatty acid ester.

Such fatty acid esters of polyhydric alcohols include:
Specifically, glycerin fatty acid esters such as glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate, and glycerin dilaurate;
Fatty acid esters of pentaerythritol such as pentaerythritol monostearate, pentaerythritol monolaurate, pentaerythritol dilaurate, pentaerythritol distearate, and pentaerythritol tristearate are used. Such a phenolic antioxidant is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight, and more preferably 0 to 2 parts by weight, based on 100 parts by weight of the polypropylene composition. Fatty acid ester is polypropylene composition 10
It is used in an amount of 0 to 10 parts by weight, preferably 0 to 5 parts by weight.

In addition, in the present invention, silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic Magnesium carbonate, dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass peas, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide , poron fiber, silicon carbide fiber,
Fillers such as polyethylene fibers, polypropylene fibers, polyester fibers, and polyamide fibers may also be blended.

The polypropylene and polypropylene composition according to the present invention as described above have a high degree of crystallinity. Such highly crystalline polypropylene or polypropylene compositions have high stiffness and generally high heat distortion temperatures, melting points,
Because it has a crystallization temperature, it exhibits excellent heat resistance, a fast crystallization rate, and high transparency. Therefore, it is suitably used in various applications such as containers and films that require higher rigidity, heat resistance, high-speed moldability, and transparency. In addition, it also has advantages over conventional applications, such as reducing the density of the product by reducing the amount of filler such as talc added, and making the product thinner.

The highly crystalline polypropylene or composition thereof of the present invention can be used without any particular restriction in fields in which polypropylene has conventionally been used, but is particularly suitable for use as injection molded articles or stretched films.

The injection molded article obtained using the highly crystalline polypropylene or its composition of the present invention has good surface hardness, abrasion resistance, surface gloss, and stability at high temperatures, and is used for automobile parts, housing containers for home appliances, etc. Widely used.

Furthermore, the film obtained using the highly crystalline polypropylene or its composition of the present invention has transparency, mechanical strength,
It has excellent heat resistance, barrier properties, chemical resistance, abrasion resistance, etc., and has characteristics such as being strong and easy to machine bag making.

Depending on the processing method, it is classified into blown film, T-die film, stretched film, etc.

Effects of the Invention As explained above, according to the present invention, it is possible to provide polypropylene having high crystallinity and high stereoregularity. By providing such polypropylene or a composition of polypropylene and a nucleating agent, it becomes possible to manufacture products of excellent quality.

[Examples] The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 (Preparation of solid titanium catalyst component [A]) 95.2 g of anhydrous magnesium chloride, 44 g of decane. After 390°6 g of r+1 and 2-ethylhexyl alcohol was heated at 130°C for 2 hours to form a homogeneous solution, 21.3g of phthalic anhydride was added to this solution, and further heated at 130°C for 1 hour. Stirring and mixing were performed to dissolve phthalic anhydride into this homogeneous solution. After the homogeneous solution thus obtained was cooled to room temperature, the entire amount of 75 ml of this homogeneous solution was dropped over 1 hour into 200 ml of titanium tetrachloride maintained at -20°C. After charging, the temperature of this mixed liquid was raised to 110°C over 4 hours, and when it reached 110°C, 5.22 g of diisobutyl phthalate (DI BP) was added.
was added, and the mixture was kept at the same temperature for 2 hours with stirring.

After the completion of the 2-hour reaction, the solid portion was collected by hot filtration, and after resuspending this solid portion in 275 ml of titanium tetrachloride, the heating reaction was performed again at 110° C. for 2 hours. After the reaction was completed, the solid portion was collected again by hot filtration and thoroughly washed with decane and hexane at 110°C until no free titanium compound was detected in the washing liquid. The solid titanium catalyst component [A] prepared by the above operations was stored as a decane slurry, and a portion of this was dried for the purpose of investigating the catalyst composition. The composition of the solid titanium catalyst component [A] thus obtained was 2.4% by weight of titanium and 60% of chlorine.
wt%, magnesium 20wt% and DrBP13.
It was 0% by weight.

(Preparation of prepolymerized catalyst [III]) Purified hexane 11, 100 mmol of triethylaluminum, 100 mmol of methyltrimethoxysilane (TMMS) and the above solid titanium catalyst component [A] were placed in a 2j7 pressure autoclave at 20°C under a nitrogen atmosphere. After adding 10 mmol of titanium atoms and stirring and mixing, 115 g of 3-methyl-1-butene (3MB-1) was added and heated at 20°C.
A prepolymerization reaction was carried out under stirring for 2 hours while maintaining the temperature.

After the reaction was completed, the supernatant was removed and washed twice with purified hexane, then resuspended in purified decane, and the entire amount was transferred to a catalyst bottle to obtain a prepolymerized catalyst [III]. Poly(3MB-1) in this prepolymerized catalyst [III] was produced at a ratio of 5.5 g to 31 g of the solid titanium catalyst component [A].

(Polymerization) 17I! 4 kg of propylene was injected into the autoclave at room temperature under a propylene atmosphere, and after raising the temperature to 50 °C,
5 mmol of triethylaluminum, 5 mmol of dicyclopentyldimethoxysilane (DCPMS), [III
] A prepolymerization catalyst was added in an amount of 5 mmol in terms of Ti atoms, and a polymerization reaction was carried out at this temperature for 90 minutes. Thereafter, hydrogen was added so that the hydrogen partial pressure at 50°C was 16 kg/cffl, the temperature was raised to 70°C, and polymerization was carried out for 45 minutes. Immediately after the reaction was completed, a small amount of ethanol was added to the system to decompose the catalyst, and unreacted propylene and hydrogen were purged to obtain a white powdery polymer. The yield of white powdered polymer after drying was 1966 g, so the activity was 39°30.
0 g/mmol Ti and the residual rate of boiling hebutane extraction (11
) was 96.3%, MFR was 26.5 g/10 min, and apparent bulk specific gravity was 0.48 g/ml. Crystallinity is 72
．． 1%, the melting point measured by DSC was 162.4°C, and the crystallization temperature was 1'27.0°C.

(Granulation, injection molding of test pieces and evaluation of physical properties) Tetrakis (methylene (3,5-
0.05 part by weight of di-t-butyl-4-hydroxy)hydrocinnamate) methane, 0.05 part by weight of tris (mixed mono & dinonylphenyl phosphite), 0.1 part by weight of calcium stearate and sodium as a nucleating agent. (Bis-4-t-butylphenyl)phosphate (NA-10) 0. 2 parts by weight, 1.3.2.4-di(p-methylhenzylidene) turpinol (MD) 0.
3 parts by weight were mixed, and the mixture was granulated at 250°C using an extrusion granulator manufactured by Thermoplastics with a screw diameter of 20 mm. Next, the granules were heated to 200°C using a Toshiba injection molding machine to prepare various JIS type test pieces, and the bending strength, bending modulus, tensile strength, Young's modulus, and heat distortion temperature were measured. Ta.

The results are shown in Table 1.

Example 2 (Granulation, injection molding of test pieces, and physical property evaluation) Using the highly crystalline polypropylene synthesized in Example 1, sodium-2,2'-methylene-bis-(4,6
-di-t-butylphenyl) phosphate (NA-1
The same procedure as in Example 1 was conducted except that 0.2 parts by weight of 1) was added.

The results are shown in Table 1.

Example 3 (Polymerization) 17I! 4 kg of propylene was poured into a crepe at room temperature under a propylene atmosphere, 100 ml of H2 was added, and the temperature was raised to 50°C.
MS) 5 mmol and [III] 0.05 mmol of prepolymerization catalyst in terms of Ti atoms were added, and the polymerization reaction was carried out at this temperature for 90 minutes. After this, hydrogen was added so that the hydrogen partial pressure at 50°C was 6 kg/cJ, and the temperature was raised to 7°C and polymerization was carried out for 30 minutes. Immediately after the completion of the polymerization, a small amount of ethanol was added into the system. was added to decompose the catalyst, and unreacted propylene and hydrogen were purged to obtain a white powdery polymer.The yield of the white powdery polymer after drying was 1953g, and therefore the activity was 39,100g/mmol. It is Ti, the boiling heptane extraction residual rate (II) is 97.2%, and the MFR is 17.
0 g/10 minutes, and the apparent bulk specific gravity was 0.48 g/ml. The crystallinity was 72.1%, the melting point measured by DSC was 162.2°C, and the crystallization temperature was 127.2°C.

(Granulation, injection molding of test pieces, and evaluation of physical properties) The same procedures as in Examples were performed except that no nucleating agent was added.

The results are shown in Table 1.

Examples 4 to 7 NA-10, NA-1]MD, respectively as nucleating agents
The same procedure as in Example 1 was conducted except that 0.3 parts by weight of pt-butylbenzoic acid aluminum salt (LA) was used.

The results are shown in Table 1.

Example 8 (Granulation, injection of test pieces, molding and physical property evaluation) Example 3
Example 3 was carried out in the same manner as in Example 3, except that the insoluble portion (residual rate: 99.1%) obtained by extracting the polypropylene obtained in Example 3 with boiling hexane was used.

The results are shown in Table 1.

Examples 9 to 12 As nucleating agents, NA-10, NA-11°MD, and
Tri(p-t-butylbenzoic acid aluminum salt (LA)
The same procedure as in Example 1 was carried out except that 0.3 parts by weight of was used.

The results are shown in Table 1.

Comparative Example 1 (Polymerization) Polymerization was carried out in the same manner as in Example 1, except that 0.5 mmol of cyclohexylmethyldimethoxysilane (CMMS) was used in place of DCPMS, and the polymerization was carried out at 70°C for 30 minutes.

The yield of polypropylene obtained was 1713 g, thus the activity was 34,300 g/mmol Ti, IT was 93.0%, and the apparent bulk density was 0°46 g/ml M
The FR was 29.5 g/10 min, the crystallinity was 67.8%, the melting point was 160.7°C, and the crystallization temperature was 126.1°C.

(Granulation, injection molding of test piece, and measurement of physical properties) The same procedure as in Example 3 was carried out except that the above-mentioned polypropylene was used.

The results are shown in Table 1.

Comparative Example 2 The same procedure as in Example 1 was conducted except that 0.2 parts by weight of NA-11 was used as the nucleating agent.

The results are shown in Table 1.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing an example of a catalyst preparation method in the polypropylene manufacturing method according to the present invention. Patent applicant Mitsui Petrochemical Industries Co., Ltd. Agent
Patent Attorney Shunbetsu Meki

Claims (5)

[Claims] (1) [I] [A] Using a solid titanium catalyst component containing magnesium, titanium, halogen and an electron donor as essential components, and [B] an organometallic catalyst component, at least one selected from the following group a. A prepolymerized catalyst obtained by prepolymerizing 0.1 to 1000 g of reactive monomers per 1 g of the solid titanium catalyst component [A]; Group a: 3-methyl-1-butene, 3-methyl-1; -Pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4
-ethyl-1-hexene, 3-ethyl-1-hexene,
Allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes [II] Organometallic catalyst component [B] , [III] The following formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) (However, in formula (1), R^1 and R^2 each independently represent a cyclopentyl group, substituted cyclopentyl group,
It represents a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or a tertiary hydrocarbon group. ) In carrying out the polymerization of propylene using two or more polymerization vessels in the presence of an olefin polymerization catalyst consisting of a silicon compound represented by A propylene polymer having an intrinsic viscosity [η] of 5 to 40 dl/g is produced in a proportion of 0.1 to 35% by weight based on the total amount of polymer obtained, and then, in the remaining polymerization vessel, A method for producing polypropylene that further produces a propylene polymer to obtain a polypropylene that satisfies the following requirements (a) to (c); (a) crystallinity is 60% or more; (b) melt flow at 230°C Rate is 0.1~
2,000 g/10 minutes, and (c) 3,000 to 1 g of the [I] prepolymerized catalyst.
Polypropylene is made by polymerizing 100,000g of propylene. (2) [I] [A] A solid titanium catalyst component containing magnesium, titanium, halogen, and an electron donor as essential components, which is formed by contacting a magnesium compound, a titanium compound, and an electron donor, and [B ] A prepolymerized catalyst obtained by prepolymerizing at least one reactive monomer selected from the following group a using an organometallic catalyst component in an amount of 0.1 to 1000 g per 1 g of the solid titanium catalyst component [A]. , Group a: 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl- 1-hexene, 4,4-dimethyl-1-pentene, 4
-ethyl-1-hexene, 3-ethyl-1-hexene,
Allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes [II] Organometallic catalyst component [B] , [III] The following formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) (However, in formula (1), R^1 and R^2 each independently represent a cyclopentyl group, substituted cyclopentyl group,
It represents a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or a tertiary hydrocarbon group. ) In carrying out the polymerization of propylene using two or more polymerization vessels in the presence of an olefin polymerization catalyst consisting of a silicon compound represented by In the reactor, a propylene polymer with an intrinsic viscosity [η] of 5 to 40 dl/g is produced in a proportion of 0.1 to 35% by weight based on the total amount of polymer obtained, and then in the remaining polymerization reactor, Further, a propylene polymer can be obtained by producing a polymer that (a) has a crystallinity of 60% or more, and (b) has a melt flow rate of 0.1 to 230°C.
2,000 g/10 minutes, (c) 3,000 to 1 g of the [I] prepolymerized catalyst
Propylene is made by polymerizing 100,000g of propylene. (3) [I] [A] A solid titanium catalyst component containing as essential components magnesium, titanium, halogen, and an electron donor formed by contacting a magnesium compound, a titanium compound, and an electron donor, and [B ] A prepolymerized catalyst obtained by prepolymerizing at least one reactive monomer selected from the following group a using an organometallic catalyst component in an amount of 0.1 to 1000 g per 1 g of the solid titanium catalyst component [A]. , Group a: 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl- 1-hexene, 4,4-dimethyl-1-pentene, 4
-ethyl-1-hexene, 3-ethyl-1-hexene,
Allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes [II] Organometallic catalyst component [B] , [III] The following formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) (However, in formula (1), R^1 and R^2 each independently represent a cyclopentyl group, substituted cyclopentyl group,
It represents a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or a tertiary hydrocarbon group. ) In carrying out the polymerization of propylene using two or more polymerization vessels in the presence of an olefin polymerization catalyst consisting of a silicon compound represented by In the reactor, a propylene polymer with an intrinsic viscosity [η] of 5 to 40 dl/g is produced in a proportion of 0.1 to 35% by weight based on the total amount of polymer obtained, and then in the remaining polymerization reactor, Further, a polymer that can be obtained by producing a propylene polymer (a) has a crystallinity of 60% or more, and (b) has a melt flow rate of 0.1 to 230°C.
2,000 g/10 minutes, and (c) 3,000 to 1 g of the [I] prepolymerized catalyst.
Propylene obtained by polymerizing 100,000 g of propylene, and 0.001 to 100 parts by weight of the polypropylene.
A polypropylene composition comprising 10 parts by weight of a nucleating agent. (4) A stretched film comprising the polypropylene according to claim 2 or the polypropylene composition according to claim 3. (5) An injection molded article comprising the polypropylene according to claim 2 or the polypropylene composition according to claim 3.