JPH04202506A - Production of propylene-based copolymer, propylene-based copolymer, propylene-based copolymer composition and use thereof - Google Patents

Abstract

PURPOSE:To obtain the title polymer having excellent rigidity, heat resistance and impact resistance by polymerizing propylene, etc., by stages by using a catalyst prepared by preliminarily polymerizing a specific monomer in the presence of a specific solid Ti component and an organometallic component, an organometallic catalyst and an Si compound. CONSTITUTION:At a first stage, propylene is homopolymerized or copolymerized with ethylene and/or 4-10C alpha-olefin and at a second stage ethylene is copolymerized with a monomer such as 3-20C alpha-olefin in the presence of an olefin polymerizing catalyst consisting of (A) a preliminarily polymerized catalyst obtained by previously polymerizing 0.1-1,000g based on 1g solid Ti catalytic component of a reactive monomer such as 3-methyl-1-butene, styrene or vinylcyclohexane by using the solid Ti catalytic component containing Mg, Ti, halogen and an electron donor as essential components and an organometallic catalytic component, (B) an organometallic catalytic component and (C) an Si compound shown by the formula (R<1> and R<2> are cyclopentyl) to give the objective polymer having >=60% crystallinity.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a method for producing a propylene copolymer, a propylene copolymer obtainable by the method, and a propylene copolymer obtainable by the method. Compositions with nucleating agents and their uses.

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 ①~■ of the periodic table and organometallic compounds of metals of groups I~■ of the periodic table. 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.).

In addition, 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-53-2580, JP-A-Sho. 5
3-40093 Kohan, 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 59-2Q64Q7, JP 61-6
9815, JP 61-69821, JP 61-69822, JP 61-69823, JP 63-22806, JP 63-9
5208, JP 63-199702, JP 63-199703, JP 63-20260
Publication No. 3, JP-A-63-202604, JP-A-6
3-223008, JP 63-223009, JP 63-264609, JP 64-
No. 87610, JP-A-64-156305,
JP-A-2-77407, JP-A-2-84404, JP-A-2-229807, JP-A-2-22
9806, 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 that require high-speed moldability and transparency, such as containers and films. 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, 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 was a limit 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. It has been found that it is sufficient to use a catalyst containing as follows. Then, such a catalyst system can be used not only for the homopolymerization of propylene, but also for the polymerization of propylene.
We discovered that by copolymerizing with other α-olefins, we can obtain propylene-based copolymers that have properties such as excellent rigidity, heat resistance, and impact resistance that were previously unobtainable. As a result, the present invention was completed.

Purpose of the Invention The present invention provides a method for producing a propylene copolymer, which has the characteristics of having both excellent rigidity, heat resistance, and impact resistance.
The object of the present invention is to provide a propylene copolymer obtainable by the production method, a composition of the propylene copolymer obtainable by the production method and a nucleating agent, and uses thereof.

Summary of the Invention The method for producing a propylene copolymer according to the present invention comprises [I
] [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. and a prepolymerized catalyst obtained by prepolymerizing 0.1 to 1000 g per Ig of the solid titanium catalyst component [A], 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, linorbornane, styrene, dimethylstyrenes, vinylnaphthalenes, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes [II] Organometallic catalyst component [B ] and [■Co the following formula (1) (However, in formula (1), R1 and R2 each independently represent a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group) , substituted cyclopentadienyl group or 3
Indicates a class hydrocarbon group. ) In the first polymerization step, propylene is homopolymerized in the presence of an olefin polymerization catalyst consisting of a silicon compound represented by In the second polymerization step, two or more monomers selected from ethylene and α-olefins having 3 to 20 carbon atoms are copolymerized to produce a crystalline polymer. It is characterized in that a propylene copolymer is produced by producing a crystalline or non-crystalline copolymer.

The propylene copolymer according to the present invention is produced by the above production method and is characterized by scales.

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

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

Moreover, the injection molded article according to the present invention is characterized in that it is made of the above-mentioned propylene-based copolymer or the above-mentioned propylene-based copolymer composition.

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

In the method for producing a propylene copolymer according to the present invention, prepolymerization is performed by prepolymerizing reactive monomers using [I] [A] solid titanium catalyst component and [B]] organometallic catalyst component. Propylene is polymerized using an olefin polymerization catalyst consisting of a catalyst, [III] an organometallic catalyst component [B], and a silicon compound.

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] As the titanium compound used for preparing the solid titanium catalyst component, for example, a tetravalent titanium compound represented by the following formula can be mentioned.

T i (OR) tX 4-g R is a hydrocarbon group, X is a halogen atom, 0≦g≦4 As such a compound, specifically, T1Cl! 4.TiB
r4, titanium tetrahalides such as Ti1a, Tl(OCHs)Czs, Ti(OCzH,)C1,, Ti(On-C4Hs)Cls, Ti(OC2Hs) Brs, Ti(0-iso-CaHs) Trihalogenated alkoxytitanium such as Brs, dihalogenated dialkoxytitanium such as Ti(OCHs)zc122, Ti(OC2HI)2Cf2, Ti(On-C4H9)2C12, Ti(OC2H6)2B T2, Ti( ○CHz: hcI!, T I (OC2H5)2 CI!, T 1 (On-
C4H9) Ic I! , Ti(OCzHs)3Br
Monohalogenated trialkoxytitanium, such as Ti(OCHs)4, Ti(OC2HS)4, Ti(On C4H9)4, Ti(O1so-C4H*)4, Ti(0-2-ethylhexyl)4 Examples include tetraalkoxytitanium such as.

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, the magnesium compound used in the preparation of the solid titanium catalyst component [A] includes magnesium compounds with reducing properties and magnesium compounds without reducing properties.

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, ethyl butylmagnesium, butylmagnesium hydride, and the like. These magnesium compounds may be used alone or may form a complex compound with an organometallic compound described below. Further, these magnesium compounds may be in the form of a liquid or a solid.

Specific examples of non-reducing magnesium compounds include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, and butoxymagnesium chloride. Alkoxymagnesium halides such as magnesium chloride, 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; and carbon ugly salts of magnesium such as magnesium laurate and magnesium stearate.

These non-reducing magnesium compounds may be compounds derived from the above-mentioned reducing magnesium compounds 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 halogen, a polysiloxane compound, a halogen-containing silane compound,
Halogen-containing aluminum compounds, esters, ketones,
It may be brought into contact with a compound such as aldehyde or alcohol.

In addition, in the present invention, the magnesium compound includes not only the above-mentioned reducing magnesium compounds and non-reducing magnesium compounds, but also complex compounds, composite compounds, or other metal compounds of the above-mentioned magnesium compounds and other metals. 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 without 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, methylvirol, dimethylpyrrole; pyrroline; pyrrolidine; indole: pyridine; Pyridines such as methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine, and chloride pyridine: Nitrogen-containing cyclic compounds such as piperidines, quinolines, isoquinolines, etc.: Tetrahydrofuran , 1.4-cineole, 1. Cyclic oxygenated compounds such as cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, coumaran, phthalan, tetrahydropyran, pyran, ditedropyran; methanol, ethanol, propatool, pentanol, hexanol, octatool, 2 - Alcohols with 1 to 18 carbon atoms such as ethylhexanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol, propyl Phenol, nonylphenol, cumylphenol, phenols having 6 to 20 carbon atoms that may have a lower alkyl group such as cuff; acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, acetylacetone, benzoquinone, etc. Ketones having 3 to 15 carbon atoms; Aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; Methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate , octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate,
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, lobutyl maleate, 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,
2,1]-hebutane, diphenyldimethoxysilane, isopropyl-1-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 , acid anhydrides such as benzoic anhydride, etc. are used.

Further, as an electron donor, a [II[] 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 AI! zos, 5iO
z, B2O3, MgO1CaO1T i O2, ZnO
.

Resins such as Z n O2, Snow, BaO1ThO and styrene-divinylbenzene copolymer, MgC7,
, Mg(OH)t, Mg CO2, Mg(OE'
t) t, magnesium stearate, and the like.

Among these carrier compounds, SiO2, Af
20. , MgO1Zn○, ZnO2, etc.

[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, a pretreatment with a reaction aid may be performed. 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, or an aromatic hydrocarbon.

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

(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 at least a magnesium compound and an alkoxytitanium with a titanium compound, an electron donor, and, if necessary, a silicon compound containing nitrogen.

(lO) A method in which a non-reducing liquid magnesium compound and an organoaluminium 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 (lO) 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, but for example, the amount of the electron donor is 0.01 to 5 mol per 1 mol of the magnesium compound. , 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 10, and the magnesium/titanium (atomic ratio) is preferably about 1 to 100, preferably about 2 to 50.

In the method for producing a propylene copolymer according to the present invention, prior to propylene polymerization, the above [A] solid titanium catalyst component and the following [B] organometallic catalyst component are used,
A reactive monomer is prepolymerized to produce [I] a prepolymerized catalyst.

[B] As the organometallic catalyst component, an organometallic compound of a metal from Group 1 to Group II of the periodic table is used, and specifically, the following compounds are used.

(1) R’YAA (OR2), H,X.

(In the formula, R1 and R2 usually have 1 to 15 carbon atoms,
Preferably it is a hydrocarbon group containing 1 to 4, and these may be the same or different from each other. X represents a halogen atom, O<m≦3, n is 0≦n3, p is O≦p<3, q
is a number such that 0≦q<3, and m+n+p+q=3
An organoaluminum compound represented by

(2) A complex alkylated product of a Group 1 metal and aluminum represented by M'A A R'4 (wherein Ml is Li, Na, or Ni, and R] is the same as above).

(3) R'R2M2 (wherein, R1 and R2 are the same as above. H2 is M
A dialkyl compound of Group 1 or Group 2 represented by Zn or Cd).

Examples of the organoaluminum compounds that belong to the above (1) include the following compounds.

-Formula R', AI (OR2) s-.

In formula C, R1 and R2 are the same as above. m is preferably a number of 1.5≦m≦3), -Formula R1 A I X 2-.

(In the formula, R1 is the same as above. X is halogen, m is preferably 0<m<3), - Formula R', A I H3-.

(In the formula, R1 is the same as above. m is preferably 2≦m<3
), general formula R', Aj7 (OR2). Xl (wherein, R1
and R2 are the same as above. X is halogen, 0<m≦3.
0≦n<3.0≦q<3, m + n + q =
Examples include compounds represented by 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. Alkoxide; Alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, R'25Aj2 (OR2). Partially alkoxylated alkyl aluminum having an average composition such as Alkylaluminum sesquihalides such as bromides; partially halogenated alkylaluminums such as alkylaluminum cybarides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide; dialkylaluminums such as diethylaluminum hydride, dibutylaluminum hydride Hydrides: Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dikudride, propylaluminum dikudride; moieties such as ethylaluminum ethoxychloride, butylaluminum butoxychloride, ethylaluminum ethoxybromide Particularly alkoxylated and halogenated alkyl aluminums can be mentioned.

Examples of 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 (C2Hs) 2Aj'OAf
(C2H6)2, (C4H9) 2AIOAA (C4
H9) 2, (C2H5)zAINAA' (C2H5)
In addition to 22Hs, aluminoxanes such as methylaluminoxane can be mentioned.

Examples of compounds belonging to the above (2) include LiAβ(C2H6)4 and LIA1(C7HI5)4.

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

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

In the prepolymerization, it is possible to use a considerably higher concentration of catalyst in the system 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 inert hydrocarbon medium 11 described below. It is desirable to do so.

[B] The amount of organometallic catalyst component is [0.1 to 1000 g per 1 g of Al solid titanium catalyst component, preferably 0.3
The amount may be such that ~500g of polymer is produced;
[A] Usually about 0.1-100 mmol, preferably about 0.5 mmol per mole of titanium atoms in the solid titanium catalyst component.
It is desirable that the amount be in the range of ~50 mmol.

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,5i(OR')4-11+
・+ [Iaco [wherein R and Ro are hydrocarbon groups, and 0xn<4] As the organosilicon compound represented by the above general formula [Ia], specifically, is trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyljethoxysilane, diisopropyldimethoxysilane, t-butylmethyldimethoxysilane, t-
Butylmethyljethoxysilane, t-amylmethyljethoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, diphenyljethoxysilane, bis0-)lyldimethoxysilane, bism-)lyldimethoxysilane, bisI)-)lyl dimethoxysilane,
Bis p-tolyljethoxysilane, bisethyl phenyldimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyljethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, t-butyltriethoxy Silane, n-butyltriethoxysilane, 1so-butyltriethoxysilane, phenyltriethoxysilane, γ-aminopropyltriethoxysilane, chlortriethoxysilane, ethyltriisopropoxysilane, vinyltriptoxysilane, cyclohexyltrimethoxysilane, Cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane, 2-norbornanemethyldimethoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriaryloxysilane, vinyltris(β) -methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane, and the like.

Further, as an electron donor (al), the following general formula [
]Ia] can also be used.

S +R'R2+-(OR") 2-0 -=[II
a] [In the formula, 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, and R3 is a hydrocarbon group. Yes, m is 0≦m≦2. ] In the above formula [I[al, R1 is a cyclopentyl group or a cyclopentyl group having an alkyl group, and R
Examples of 1 include, in addition to the cyclopentyl group, cyclopentyl groups having an alkyl group such as 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, and 2,3-dimethylcyclopentyl group.

Further, in formula [IIa], R2 is an alkyl group, a cyclopentyl group, or a cyclopentyl group having an alkyl group, and R2 is, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, An alkyl group such as a hexyl group, or a cyclopentyl group and a cyclopentyl group having an alkyl group as exemplified as R1 can be similarly mentioned.

Further, in the formula [I[al], 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; dicyclopentyl Dialkoxysilanes such as dimethoxysilane, bis(2-methylcyclobentyl)dimethoxysilane, bis(2,3-dimethylcyclopentyl)dimethoxysilane, dicyclopentyljethoxysilane, nitricyclopentylmethoxysilane, tricyclopentylethoxysilane, Examples include monoalkoxysilanes such as cyclopentylmethylmethoxysilane, 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.

The 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 inert hydrocarbon media used at this time include propane, butane, pentane, hexane, heptane, octane, decane, dodecane, aliphatic hydrocarbons such as kerosene, didiclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene, and their contact materials. Among these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons.

The reaction temperature of the prepolymerization may be such that the prepolymer produced is not substantially dissolved in the inert hydrocarbon medium, and is usually about -20 to +100'C1, preferably about -2
It is desirable that the temperature is in the range of 0 to +8°C1, more preferably 0 to +40°C.

In addition, in the prepolymerization, a molecular weight regulator such as hydrogen can also be used. Such a molecular weight modifier is 1
Intrinsic viscosity of the polymer obtained by prepolymerization measured in decalin at 35°C [η, about 0.2 dl/g or more,
Preferably, it is used in an amount of about 0.5 to 10 di/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 preferable to conduct the process so as to produce 500 g of polymer. If the amount of prepolymerization is too large, the production efficiency of propylene copolymer in main polymerization may decrease.
When a film or the like is formed from the resulting propylene copolymer, fish eyes may easily occur.

Prepolymerization can be carried out batchwise or continuously.

When a propylene copolymer is produced using such a [I] prepolymerized catalyst, a propylene copolymer having excellent rigidity, heat resistance, etc. can be obtained.

In the method for producing a propylene copolymer according to the present invention, in the presence of an olefin polymerization catalyst comprising the above-mentioned [I] prepolymerized catalyst, [III] an organometallic catalyst component, and [I] a silicon compound, Carry out polymerization of propylene. [II] As the organometallic catalyst component, the above-mentioned [I]
The same organic metal catalyst component [B] used in the preparation of the prepolymerized catalyst can be used.

The [II[] silicon compound used in the method for producing a propylene copolymer according to the present invention has the following formula, but the formula (
1), R1 and R2 each independently represent a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentagenyl group,
Indicates a substituted cyclopentadienyl group or a tertiary hydrocarbon group.

Examples of substituted cyclopentyl groups include cyclopentyl groups having an alkyl group, specifically 2-methylcyclopentyl groups, 3-methylcyclopentyl groups, 2-methylcyclopentyl groups, and 2-methylcyclopentyl groups.
-Ethylcyclopentyl group, 2-n-butylcyclopentyl group, 2.3-dimethylcyclopentyl group, 2.4-dimethylcyclopentyl group, 2,5-dimethylcyclopentyl group, 2.3-diethylcyclopentyl group, 2.3.
Examples include 4-trimethylcyclopentyl group, 2,3.5-trimethylcyclopentyl group, 2.3.4-triethylcyclopentyl group, tetramethylcyclopentyl group, and tetraethylcyclopentyl group.

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-)dimethylcyclopentenyl group, 2.3.5-)dimethylcyclopentenyl group, 2.3.4-)ethylcyclobentenyl group, tetramethylcyclopentenyl group, tetraethyl Examples include a cyclopentenyl group.

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-) Limethylcyclopentadienyl group, 2
．． 3.5-trimethylcyclopentadienyl group, 2.
3.4- triethylcyclopentadienyl group, 2.3
．． 4.5-tetramethylcyclopentadienyl group, 2.
3.4.5-tetraethylcyclopentadienyl group, 1
．． Examples include 2.3.4.5-pentamethylcyclopentadienyl group and 1.2.3.4.5-pentaethylcyclopentadienyl group.

Examples of the tertiary hydrocarbon group include t-butyl group, 1-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-) 1
dimethylcyclopentyl)dimethoxysilane, di(2,
3,4-)IJ ethylcyclopentyl)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)dimethoxysilane, di(2,3,4-trimethylcyclopentenyl)dimethoxysilane, di(2,3,
5-trimethylcyclopentenyl)dimethoxysilane,
Di(2,3,4-)ethylcyclopentenyl)dimethoxysilane, di(tetramethylcyclopentenyl)dimethoxysilane, di(tetraethylcyclopentenyl)dimethoxysilane, di(2-methylcyclopentadienyl)dimethoxysilane, di (3-Methylcyclopentadienyl)dimethoxysilane, di(2-ethylcyclopentajenyl)dimethoxysilane, di(2-n-butylcyclopentenyl)dimethoxysilane, di(2,3-dimethylcyclopentadienyl) Dimethoxysilane, di(2,
4-dimethylcyclopentagenyl)dimethoxysilane, di(2゜5-dimethylcyclopentagenyl)dimethoxysilane, di(2,3-diethylcyclopentagenyl)dimethoxysilane, di(2,3,4-trimethyl cyclopentadienyl)dimethoxysilane, di(2,3,
5-trimethylcyclopentadienyl)dimethoxysilane, di(2,3,4-)diethylcyclopentajenyl)dimethoxysilane, di(2,3,4,5-tetramethylcyclopentajenyl)dimethoxysilane, dimethoxysilane, (2,
3,4,5-tetraethylcyclopentadienyl)dimethoxysilane, di(1,2,3,4,5-pentamethylcyclopentadienyl)dimethoxysilane, di(1,2
, 3,4,5-pentaethylcyclopentadienyl)dimethoxysilane, di-t-myldimethoxysilane, di(α
, α°-dimethylpencyl)dimethoxysilane, di(atomantyl)dimethoxysilane, atmantyl-t-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.

In the first polymerization step, propylene is homopolymerized, or propylene is copolymerized with ethylene and/or an α-olefin having 4 to 2 carbon atoms.

Specifically, the α-olefin having 4 to 20 carbon atoms includes 1-butene, 1-pentene, 1-hexene,
4-Methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 3-methyl-1-butene, 1-decene, ■-dodecene, ■-tetradecene, 1-hexadecene, 1-octadecene, 1 -Eicosene, cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene, 2-methyl-1°4.5. Dimethano-1, 2, 3, 4, 4a, 5.8
．． Examples include α-olefins such as 8a-octahydronaphthalene.

The first polymerization step is usually carried out in a gas phase or a liquid phase.

When the reaction mode is polymerization, slurry polymerization or solution polymerization, the above-mentioned inert hydrocarbons can be used as the reaction solvent.

In the first polymerization system, the [I] prepolymerization catalyst is usually about 0.001 to 50 mmol, preferably about It is used in amounts of 0.01 to 10 mmol. [n] Organometallic catalyst component, per mole of titanium atom in the polymerization system, the amount of metal atoms contained in [III] organometallic catalyst component is usually about 1 to 500 moles, preferably about 2 to 500 moles.
It is used in an amount of 200 moles. Furthermore [I]
The silicon compound is usually about 0.001 to 10 mol, preferably about 0, in terms of silicon atom in the [111] silicon compound per mol of metal atom in the organometallic catalyst component [III].
．． It is used in an amount of 0.1 to 5 moles.

If hydrogen is used during the first polymerization, the molecular weight of the resulting propylene polymer can be adjusted.

In the first polymerization step, the polymerization temperature is usually about -50
~200″C1 preferably about 20~100°C,
The pressure is usually set at normal pressure to 100 kg/ad, preferably about 2 to 50 kg/crl. Polymerization can be carried out in any of the batch, semi-continuous and continuous methods.

In the propylene polymer obtained in the first polymerization step as described above, the content of structural units derived from ethylene and/or α-olefin having 4 to 10 carbon atoms is preferably 0 to 20 mol%. is 0 to 15 mol%, particularly preferably 0 to 10 mol%.

The intrinsic viscosity [η] of the propylene polymer obtained in the first polymerization step measured in decalin at 135°C is 40 to 0.001 dI! /g, preferably 30
~0.01 dl/g, particularly preferred +-120
-0.05di/g.

Further, the isotactic pentad value determined by NMR measurement of the propylene polymer obtained in the first polymerization step is 95% or more, preferably 97% or more, particularly preferably 98% or more.

In addition, in the first polymerization step, in addition to propylene, the ethylene and/or the α-olefin having 4 to 20 carbon atoms, a small amount of a diene compound is added to the polymerization system, and a structural unit derived from the diene compound is added. may be introduced into the propylene polymer obtained in the first polymerization step.

As the diene compound, 1,3-butadiene, 1,3-
Pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-1,4-hexadiene, 5-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, 6-zocadien, 6-methyl-1,6
- Diene compounds having 4 to 20 carbon atoms such as undecadiene, 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidenenorbornene, vinylnorbornene and dicyclopentadiene, among which are preferred , 1.4-hexadiene, 1.5-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, ethylidenenorbornene,
Diene compounds having 5 to 12 carbon atoms such as vinylnorbornene may be mentioned.

In the method for producing a propylene copolymer according to the present invention, following the first polymerization step, in the presence of the propylene polymer obtained in the first polymerization step, ethylene and 2 selected from α-olefins of
Copolymerization with more than one type of monomer is carried out.

Here, as the α-olefin having 3 to 20 carbon atoms, the above-mentioned α-olefin having 4 to 12 carbon atoms can be exemplified in addition to propylene.

The second polymerization step is usually carried out in a gas phase or a liquid phase.

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 second polymerization system, [I] a prepolymerization catalyst, [II] an organometallic catalyst component, and an [In]silane compound can be added as necessary, and the [I] prepolymerization catalyst has a polymerization volume of 1 ! ! [I] Normally about 0.00 to 50 mmol, preferably about 0.00 mmol, in terms of titanium atoms in the prepolymerized catalyst [I]. Amounts of 1 to 10 mmol of O may be added. [III] The organometallic catalyst component is usually about 1 to 2,000 mol, preferably about 2 to 2,000 mol of the metal atoms contained in the [n] organometallic catalyst component per 1 mol of titanium atom added to the polymerization system. An amount such as 500 moles can be added. Furthermore, [I] silicon compound was added []I]
Usually about 0.001 to 1 mole of metal atom in the organometallic catalyst component, calculated as silicon atom in the [III] silicon compound.
Amounts such as 10 moles, preferably about 0.01 to 5 moles can be used.

If hydrogen is used during the main polymerization, the molecular weight of the resulting propylene copolymer can be adjusted, and a propylene copolymer with a high melt flow rate can be obtained. Even in this case, in the present invention, the catalytic activity of the propylene copolymer obtained does not decrease.

In the second polymerization step, the polymerization temperature is usually about -50
-200°C, preferably about 20-100°C, and the pressure is usually normal pressure -100 kg/ad, preferably about 2
It is set to ~50kg10f. Polymerization can be carried out in any of the batch, semi-continuous and continuous methods.

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

Note that in the second polymerization step as well, a small amount of a diene compound may be introduced into the reaction system as in the first polymerization step described above.

In the propylene copolymer obtained by the above manufacturing method, the content of crystalline polymer is 50 to 95 mol%.
and preferably 60 to 90 mol%.

The propylene copolymer according to the present invention is characterized in that it can be obtained by the above-mentioned production method.

The intrinsic viscosity [η] of the propylene copolymer according to the present invention measured in decalin at 135°C is 30 to 0°001.
dl/g, preferably 10 to 0.01 dl/g
The amount is particularly preferably 5 to 0.05 dllg.

In addition, the n-decane soluble portion at 23°C is 5 to 7
0% by weight, preferably 8 to 55% by weight, particularly preferably 10 to 45% by weight, and the main monomer units constituting the 23° Cn-decane soluble portion are 20 to 8% by weight.
0% by weight, preferably 30 to 70% by weight, particularly preferably 40 to 60% by weight.

The 23° Cn-decane soluble components were measured by the following method. That is, in a II flask equipped with a stirrer, 5 g of copolymer sample, 0.3 g of 2°6-dite
Add rt-butyl-4-methylphenol and 50 ml of n-decane and boil in an oil bath at 130°C.

After dissolution, the mixture is allowed to cool naturally at room temperature for about 3 hours, and then cooled on a 23°C water bath for 8 hours or more. The n-decane solution containing the precipitated copolymer and the dissolved polymer was separated by filtration using a G-4 glass filter, the solution was dried at 150° C. in 10 mmt (g), its weight was measured, and the mixture The amount of the copolymer soluble in the solvent was calculated and determined as a percentage of the weight of the sample copolymer.

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

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

Among them, preferred nucleating agents are listed below (in the above formula, R1 is oxygen, sulfur, or a hydrocarbon group having 1 to 10 carbon atoms, and R2 and R2 are hydrogen or a carbonized group having 1 to 10 carbon atoms). There is a hydrogen group, and R2 and R2 may be the same or different types, and R2 and R3 or R2 and R3 may be bonded together to form a ring,
M is a monovalent to trivalent metal atom, and n is an integer of 1 to 3. ) 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, t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis(4-1-propyl-6-t-butylphenyl) phosphate, lithium-2°2'-methylene-bis(4-
Methyl-6-tert-butylphenyl) phosphate, lithium-2,2”-methylene-bis(4-ethyl-6-
t-butylphenyl)fusulfate, calcium-bis-[2,2°-thiobis(4-methyl-6-t-butylphenyllucium-bis-[2.2'-thiobis(4-ethyl-6-t) -butylphenylbis-[2. 2'-thiobis-(4.6-di-t-butylphenyl) phosphate], magnesium-bis-[2. 2'-thiobis(4.6-di-t-butylphenyl) phosphate 1, magnesium-bis [2.
2'-thiobis-(4-t-octylphenyl) phosphate], sodium-2,2°-butylidene-his(4,6-di-methylphenyl) phosphate, sodium-2. 2'-butylidene-bis(4,6-
di-t-butylphenyl) phosphate, sodium-2. 2'-cutylmethylene-bis(4.6-
di-methylphenyl)phosphate, sodium-2
．． 2°-t-octylmethylene-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], barium-bis-[2,2-methylene-bis(4,6-di-t-butylphenyl)phosphate 1, 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-1 -], sodium-2,2-ethylidene-bis(4-m-butyl-6-t-butylphenyl)
phosphate, sodium-2,2-methylene-bis(4,6-di-methylphenylmethylene-bis(4,6-cy-nitylphenyl) phosphate, 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)phosphate 1, barium-
Bis[2,2'-ethylidene-bis(4,6-di-t-
butylphenyl) phosphate 1, aluminum
Tris-[2,2°-methylene-bis(4,6-dit)
-butylphenyl) phosphate 1 and aluminumtris-[2,2-ethylidene-bis(4,6-di-t-butylphenyl) phosphate 1 and mixtures of two or more thereof may be mentioned.

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 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-( 4-1-propylphenyl) phosphate, sodium bis-
(4-octylphenyl)phosphate, potassium-bis-(4-t-butylphenyl)phosphate, calcium-bis-(4-t-butylphenyl)phosphate, magnesium-bis(4-t-butylphenyl)phosphate, -butylphenyl)phosphate, lithium-bis-(4-1
-butylphenyl) phosphate, aluminum-bis-(4-1-butylphenyl) phosphate, and mixtures of two or more thereof. Particularly sodium-bis~(4-t-)ethylphenyl H (In the above formula, R5 is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms.) Specifically, 1, 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, 1. 3-p-methylbenzylidene-2.
4-p-ethylbenzylidene sorbitol, 1. 3-
p-Ethylbenzylidene-2. 4-p-methylbenzylidene sorbitol, 1. 3, 2. 4-di(p-
methylbenzylidene) sorbitol, 1, 3. 2.
4-di(p-ethylbenzylidene)sorbitol, 1
．． 3, 2. 4-di(pn-propylbenzylidene)sorbitol, 1. 3, 2. 4-di(pi)
-propylbenzylidene) sorbitol, 1, 3,
2. 4-di(p-n-butylbenzylidene)sorbitol, 1. 3. 2. 4-di(p-s-butylbenzylidene) sorbitol, 1, 3, 2. 4-ji (
pt-butylbenzylidene) sorbitol, 1,3
, 2. 4-di(2°,4′-dimethylbenzylidene)sorbitol, ■,3.

2,4-di(p-methoxybenzylidene)sorbitol, 1, 3, 2. 4-di(p-ethoxybenzylidene)sorbitol, 1.3-benzylidene-2-4-p
- Chlorbenzylidene sorbitol, 1. 3-p-chlorobenzylidene-2.4-benzylidene sorbitol, 1. 3-p-chlorobenzylidene-2. 4-p-
Methylbenzylidene sorbitol, 1, sp-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-
Examples include di(p-chlorobenzylidene)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, 1. 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, and thiophenecarboxylic acid. Examples include sodium acid, sodium pyrrolecarboxylate, and the like.

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

In the propylene copolymer composition according to the present invention, the nucleating agent is 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, based on 100 parts by weight of the propylene copolymer.
It is desirable that it be added in an amount of 0.05 to 3 parts by weight, particularly preferably 0.05 to 3 parts by weight.

By adding the nucleating agent in the above amount to the propylene copolymer of the present invention, the excellent properties inherent to the propylene copolymer of the present invention are not impaired, and the crystal particles are fine and crystallized. A propylene copolymer composition with improved strength is obtained.

In addition to the above-mentioned propylene copolymer and nucleating agent, the propylene copolymer composition of the present invention may contain a rubber component that improves impact strength, a heat stabilizer, a weather stabilizer, and an antistatic stabilizer. Preventive agents, slip agents, anti-blocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, etc. can be blended, and the blending ratios are appropriate. For example, as a stabilizer that may be added as an optional component, tetrakis[methylene-3(3,5-
Di-t-butyl-4-hydroxyphenyl)propionate 1 Methane, β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid alkyl ester, 2
．． 2-Oxamidobis[ethyl-3(3,5-di-t-
butyl-4-hydroxyphenyl)] phenolic antioxidants such as propionate, fatty acid metal salts such as zinc stearate, calcium stearate, and calcium 12-hydroxystearate, glycerin monostearate, glycerin monolaurate, glycerin distearate, Examples include fatty acid esters of polyhydric alcohols such as pentaerythritol monostearate, pentaerythritol distearate, and pentaerythritol tristearate. These may be blended alone or in combination; for example, tetrakis[methylene-3(3,5-dyl-t-butyl-4
A combination of -hydroxyphenyl)propionate 1methane, calcium stearate and glycerin monostearate can be exemplified.

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

Such fatty acid esters of polyhydric alcohols include:
Specifically, glycerin monostearate, glycerin monolaurate, glycerin monomyristate, glycerin monopalmitate, glycerin distearate,
Glycerin fatty acid esters such as 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 propylene copolymer composition 1.
The fatty acid ester of polyhydric alcohol 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 propylene copolymer composition. 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, polyethylene fiber, propylene copolymer fiber,
Fillers such as polyester fibers and polyamide fibers may also be blended.

The propylene copolymer and propylene copolymer composition according to the present invention as described above have a high degree of crystallinity. Molded objects obtained from such propylene copolymers or propylene copolymer compositions have high rigidity, which allows products to be made thinner, and the amount of fillers such as talc added can be reduced, resulting in lower product density. can be reduced. In addition, highly crystalline propylene copolymers and compositions thereof generally have high heat distortion temperatures, melting points, and crystallization temperatures, and therefore exhibit excellent heat resistance. Furthermore, since the crystallization rate of the highly crystalline propylene copolymer of the present invention and its composition is improved compared to conventional products, high-speed molding is possible. Furthermore, the highly crystalline propylene copolymer of the present invention and its composition have high transparency and are therefore suitable for use in various applications.

The highly crystalline propylene copolymer or composition thereof of the present invention can be used without any particular restriction in the fields in which propylene copolymers have been conventionally used, but particularly in applications as injection molded articles or stretched films. suitable for

The injection molded article obtained using the highly crystalline propylene copolymer or its composition of the present invention has good surface hardness, abrasion resistance, surface gloss, and stability at high temperatures, and can be used for automobile parts,
Widely used as parts for home appliances.

The highly crystalline propylene copolymer or composition thereof of the present invention can also be used for film applications.

Effects of the Invention As explained above, according to the present invention, it is possible to provide a propylene copolymer having the characteristics of having excellent rigidity, heat resistance, and impact resistance. By providing such a propylene copolymer or a composition of a propylene copolymer and a nucleating agent, it becomes possible to produce products of excellent quality.

[Examples] The present invention will be described 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, 442 ml of decane and 390°6 g of 2-ethylhexyl alcohol were heated at 130°C for 2 hours to form a homogeneous solution. 21.3 g of phthalic anhydride was added to this solution, and the mixture was stirred and mixed at 130° C. for 1 hour to dissolve phthalic anhydride in this homogeneous solution. After cooling the homogeneous solution thus obtained to room temperature, 75 ml of this homogeneous solution was dropped into 200 ml of titanium tetrachloride maintained at -20"C over a period of 1 hour. After the charging was completed, the mixture was mixed. The temperature of the liquid was raised to 110'C over 4 hours, and when it reached 110'C, 5.22g of diisobutyl phthalate (DIBP) was added, and the mixture was maintained at the same temperature for 2 hours with stirring. After 2 hours of reaction, the solid part was collected by hot filtration, and this solid part was resuspended in 275+nl of titanium tetrachloride.
The heating reaction was carried out again at 110°C for 2 hours. After the reaction was completed, the solid portion was again collected 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 procedure was stored as a decane slurry, or a portion of it 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, 60% by weight of chlorine, 20% by weight of magnesium, and 13.0% of DIBP.
% by weight.

(Preparation of prepolymerization catalyst [I]) 2I! Purified hexane II at 20°C under a nitrogen atmosphere in a pressure-resistant autoclave! , triethylaluminum 100 mmol, methyltrimethoxysilane (TMMS) 100
After adding 10 mmol of the above solid titanium catalyst component [A] in terms of titanium atoms and stirring and mixing, 115 g of 3-methyl-1-butene (3MB-1) was added and 20 mmol of the solid titanium catalyst component [A] was added.
A prepolymerization reaction was carried out under stirring for 2 hours while maintaining 'C. 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 [I]. Poly(3MB-1) in this prepolymerized catalyst [I] was produced at a ratio of 5.5 g to Ig of solid titanium catalyst component (A).

(Polymerization) An autoclave with an internal volume of 17 f was replaced with propylene, and 4 kg of propylene and 18 I of hydrogen were added. Introducing 60°
After raising the temperature to C, 5 mmol of triethylaluminum, 5 mmol of dicyclopentyldimethoxysilane (DCPMS), and 0.05 mmol of the above solid titanium catalyst component [A] were added, and polymerization was carried out at 8°C for 1 hour. After removing the liquid propylene, add 100 I each of ethylene and propylene mixed gas at 60°C! , 150ff to 150
Added in minutes. Remove unreacted mixed gas, white powder 2
゜1 kg was obtained. The analysis results are shown in Table 1.

(Granulation, injection molding of test pieces and evaluation of physical properties) Tetrakis (methylene (3,5-
0.05 parts by weight of di-t-butyl-4-hydroxy)hydrocinnamate) methane, 0.05 parts by weight of tris(mixed mono&dinonylphenyl phosphite), and 0.1 parts by weight of calcium stearate were mixed. 2 of the mixture
The mixture was granulated at 50°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 flexural modulus was measured.

The results are shown in Table 1.

Example 2 (Granulation, injection molding of test pieces and evaluation of physical properties) 0.3 parts by weight of sodium-2,2°-methylene-bis(4,6-di-t-butylphenyl) phosphate was added as a nucleating agent. The procedure was carried out in the same manner as in Example 1 except for using the following.

The results are shown in Table 1.

Comparative Example 1 (Prepolymerization) 150 ml of purified hexane, 15 mmol of triethylaluminum, 3 mmol of DCPMS and [A] were placed in a 400 ml four-glass reactor equipped with a stirrer under a nitrogen atmosphere.
After adding 1.5 mmol of the solid titanium catalyst component in terms of Ti atoms, propylene was fed to the reactor at a rate of 3.21/hour at 20'C for 1 hour. When the supply of propylene was finished, the inside of the reactor was purged with nitrogen, and a washing operation consisting of removing the supernatant and adding purified hexane was performed twice, and then resuspended in purified hexane and transferred the entire amount to a catalyst bottle. A prepolymerized catalyst [IV] was obtained.

(Polymerization) 0.5 mmol of cyclohexylmethyldimethoxysilane (CMMS) was used instead of DCPMS, and 10 mmol of hydrogen was used.
1! Polymerization was carried out in the same manner as in Example 1 except that
2.3 kg of white powder was obtained.

The analysis results are shown in Table 1.

(Granulation, injection molding of test piece, and measurement of physical properties) The same procedure as in Example 1 was carried out except that the above copolymer was used.

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 method for producing a propylene copolymer 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 the first polymerization step, propylene is homopolymerized in the presence of an olefin polymerization catalyst consisting of a silicon compound represented by In the second polymerization step, two or more monomers selected from ethylene and α-olefins having 3 to 20 carbon atoms are copolymerized to produce a crystalline polymer. A method for producing a propylene copolymer, which comprises producing a propylene copolymer by producing a crystalline or amorphous copolymer. (2) [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 the first polymerization step, propylene is homopolymerized in the presence of an olefin polymerization catalyst consisting of a silicon compound represented by By copolymerizing with ethylene to produce a crystalline polymer, and in the second polymerization step, copolymerizing two or more monomers selected from ethylene and α-olefins having 3 to 20 carbon atoms. A propylene copolymer that can be produced. (3) [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 the first polymerization step, propylene is homopolymerized in the presence of an olefin polymerization catalyst consisting of a silicon compound represented by By copolymerizing with ethylene to produce a crystalline polymer, and in the second polymerization step, copolymerizing two or more monomers selected from ethylene and α-olefins having 3 to 20 carbon atoms. A propylene copolymer composition comprising a propylene copolymer that can be produced and a nucleating agent in an amount of 0.001 to 10 parts by weight based on 100 parts by weight of the propylene copolymer. (4) A stretched film comprising the propylene copolymer composition according to claim 2 or the propylene copolymer composition according to claim 3. (5) An injection molded article comprising the propylene copolymer composition according to claim 2 or the propylene copolymer composition according to claim 3.