DESCRIPTION

Title of Invention

METHOD FOR PRODUCING PROPYLENE-ETHYLENE- 1 -BUTENE TERPOLYMER

Technical Field

The present invention relates to a method for producing a propylene-ethylene- 1 -butene terpolymer. More specifically, it relates to a method for producing a propylene-ethylene- 1 -butene terpolymer, which can produce a propylene-ethylene- 1 -butene terpolymer having a low hexane-soluble content and chlorine content and having a low melting point, at a high catalyst activity.

Background Art

A propylene-ethylene- 1 -butene terpolymer has been widely used as a CPP (non-extended) film, a heat-seal film, or the like utilizing characteristics such as high transparency and low melting point as compared with a propylene homopolymer.

The propylene-ethylene- 1 -butene terpolymer has been hitherto produced mainly by a slurry polymerization method using a solvent. The slurry polymerization method is a production method which needs a solvent-treating process or the like and, from an economic reason and a reason of reducing environmental burden, it is desired to shift it to a vapor-phase polymerization method which does not need a solvent.

However, in the slurry polymerization method, at the time of separating the polymer from the solvent, an oligomer (normal hexane-soluble content at 50°C defined in Food and Drug Administration (FDA)) is extracted into a solvent and removed, and the amount of the oligomer in the polymer was reduced. But, in the vapor-phase polymerization method, since the oligomer remains in the polymer, there is a concern of becoming unsuitable as a food film.

Moreover, when the oligomer remains in a large amount in the polymer, the oligomer bleeds out on the surface of the polymer powder and fluidity of the polymer powder is remarkably deteriorated, so that the oligomer sometimes becomes a serious obstacle to continuous operation.

For such a problem, there are proposes described in Patent Literatures 1 to 4, etc. Patent Literature 1 discloses a method for producing a ternary polymer of propylene, ethylene, and another oc-olefin using a catalyst which has been treated with an organosilicon compound after a pre-polymerization treatment of a Ziegler-Natta catalyst.

Moreover, Patent Literature 2 discloses a method for producing a propylene-ethylene- 1-butene terpolymer using a Ziegler-Natta catalyst that uses an electron donor compound composed of a combination of a succinic acid salt and a 1 ,3-diether.

Patent Literature 3 also discloses a method for producing a propylene-ethylene- 1-butene terpolymer using a Ziegler-Natta catalyst in the absence of a solvent.

In addition, Patent Literature 4 also discloses a method for producing a propylene-ethylene- 1-butene terpolymer having a low chlorine content using a Ziegler-Natta catalyst.

Citation List

Patent Literature

PTL 1 : WOOO/42081

PTL 2: JP-T-2016-513167

(the term "JP-T" as used herein means a published Japanese translation of a PCT patent application)

PTL 3: JP-A-06-073132

PTL 4: JP-A-04-225005

Summary of Invention

The propylene-ethylene- 1 -butene terpolymer obtained by the method according to Patent Literature 1 has a considerably excellent nature that a hexane-soluble content is reduced but, in order to suppress the formation of the oligomer soluble in hexane sufficiently, it becomes necessary to increase a treating amount of the organosilicon compound after the pre-polymerization and catalytic activity of the catalyst for propylene polymerization has been sacrificed. Also, it was found that time-dependent degradation of the catalytic activity is large when the catalyst is treated with an organosilicon compound after the pre-polymerization treatment. Thus, the method is insufficient for producing a propylene-ethylene- 1-butene terpolymer for 1 day or more.

Moreover, the terpolymer obtained by the method according to Patent Literature 2 has a reduced xylene-soluble content but exhibits a high melting point in spite of the contents of ethylene and 1 -butene contained and higher ethylene content and butene content are required for lowering the melting point, so that the terpolymer is not sufficiently satisfactory in view of copolymerization properties and costs and there is a concern that a gas is condensed and production becomes difficult depending on the mode of vapor phase polymerization.

In the method of Patent Literature 3, the catalytic activity was not enough and it was difficult to produce a propylene-ethylene- 1-butene terpolymer having a low chlorine content. Moreover, the catalytic activity decreased as the butene content increased and hence a production cost of a propylene-ethylene- 1-butene terpolymer having a melting point of 130°C or lower was very high.

In the method of Patent Literature 4, chlorine content derived from the catalyst is lowered by mixing silica as a carrier but, for compensating the decrease in the activity, the ratio of the content of ethylene that exhibits a high reaction rate is increased. However, when the ratio of the ethylene content is increased, a non-crystalline component increases and thus xylene-soluble content that corresponds the hexane-soluble content increases. As a result of Patent Literature 4, the xylene-soluble content is so high as 8 wt% or more and hence application to food uses was difficult.

As above, there has not yet been achieved a method for producing a propylene-ethylene- 1-butene terpolymer having a low chlorine content wherein a catalyst for propylene polymerization has a high catalytic activity and the resulting propylene-ethylene- 1-butene terpolymer has a low solvent-soluble content, is excellent in copolymerization properties, and has a low melting point. An object of the present invention is to provide a method for producing a propylene-ethylene- 1-butene terpolymer wherein a catalyst for propylene polymerization has a high catalyst activity and the resulting terpolymer has a low hexane-soluble content and chlorine content, is excellent in copolymerization properties, and has a low melting point. A method for producing a propylene-ethylene- 1-butene terpolymer of the present invention, comprises copolymerizing propylene, ethylene and 1-butene in a vapor phase, in the presence of a catalyst for propylene polymerization containing the following components (A) and (B), or the following components (A), (B), and (C), in which the propylene-ethylene- 1-butene terpolymer has a chlorine content of 3 to 16 mass ppm:

Component (A): a solid catalyst component containing titanium, magnesium and chlorine as essential components, and having a titanium content of 0.5% by mass or more and 2.4% by mass or less;

Component (B): an organoaluminum compound;

Component (C): an organosilicon compound.

Also, a method for producing a propylene-ethylene- 1 -butene terpolymer of the present invention, comprises copolymerizing propylene, ethylene and 1-butene in a vapor phase, in the presence of a catalyst for propylene polymerization containing the following components (A) and (B), or the following components (A), (B), and (C), in which the terpolymer has a chlorine content of 3 to 14 mass ppm:

Component (A): a solid catalyst component containing titanium, magnesium and chlorine as essential components, having a titanium content of 0.5% by mass or more and 2.4% by mass or less, and having a chlorine content of 55% by mass or more and 65% by mass or less;

Component (B): an organoaluminum compound;

Component (C): an organosilicon compound.

In the method for producing a propylene-ethylene- 1 -butene terpolymer of the present invention, it is preferable that the component (A) is a solid catalyst component obtained by bringing the following components (Al), (A2) and (A3) into contact:

Component (Al): a solid component containing titanium, magnesium and chlorine as essential components;

Component (A2): a vinyl silane compound;

Component (A3): at least one compound selected from the group consisting of an organosilicon compound having an alkoxy group and a compound having two ether bonds.

In the method for producing a propylene-ethylene- 1-butene terpolymer of the present invention, it is preferable that the component (A) is a solid catalyst component obtained by bringing the components (Al), (A2), (A3) and the following component (A4) into contact:

Component (A4): an organoaluminum compound. In the method for producing a propylene-ethylene- 1-butene terpolymer of the present invention, it is preferable that the vinylsilane compound of the component (A2) is a compound represented by the following general formula (1):

wherein X represents a halogen, R ¹ represents hydrogen or a hydrocarbon group, R ² represents hydrogen, a hydrocarbon group, or an organosilicon group, and m>l , 0<n<3, 0<j<3, 0<k<2, and m+n+j+k=4.

In the method for producing a propylene-ethylene- 1 -butene terpolymer of the present invention, it is preferable that the organosilicon compound having an alkoxy group of the component (A3) is a compound represented by the following general formula (2):

wherein R ³ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group, R ⁴ represents hydrogen, a halogen, a hydrocarbon group, or a heteroatom-containing hydrocarbon group, R ⁵ represents a hydrocarbon group, and 0<a<2, l<b<3, and a+b=3.

In the method for producing a propylene-ethylene- 1-butene terpolymer of the present invention, it is preferable that the compound having two ether bonds of the component (A3) is a compound represented by the following general formula (3):

R ⁸ 0-C(R ⁷ ) ₂ -C(R ⁶ ) ₂ -C(R ⁷ ) ₂ - OR ⁸ ... (3)

wherein R ⁶ and R ⁷ each independently represent hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group and R ⁸ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. In the method for producing a propylene-ethylene- 1-butene terpolymer of the present invention, it is preferable that removal of heat of polymerization is performed using heat of vaporization of liquefied propylene.

In the method for producing a propylene-ethylene- 1-butene terpolymer of the present invention, it is preferable to use, as a polymerization reactor, a horizontal -type polymerization reactor equipped with stirring vanes rotating around a horizontal axis.

In the method for producing a propylene-ethylene- 1-butene terpolymer of the present invention, it is preferable that the propylene-ethylene- 1-butene terpolymer has an ethylene content ranging from 0.5 to 5.0% by mass and a 1-butene content ranging from 0.5 to 18.0% by mass. In the method for producing a propylene-ethylene- 1-butene terpolymer of the present invention, it is preferable that the propylene-ethylene- 1-butene terpolymer has a hexane-soluble content at 50°C ranging from 0.1 to 3.0% by mass.

In the method for producing a propylene-ethylene- 1-butene terpolymer of the present invention, it is preferable that the propylene-ethylene- 1 -butene terpolymer has an MFR measured at 230°C and 21.18 N of 1.0 g/10 minutes or more and 30.0 g/10 minutes or less.

A propylene-ethylene- 1-butene terpolymer of the present invention, satisfies the following items of 1) to 5):

1) ethylene content is 0.5 to 5.0% by mass and 1-butene content is 0.5 to 18.0% by mass

2) Tm is 115 to 145°C

3) hexane-soluble content at 50°C is 0.1 to 3.0% by mass

4) MFR measured at 230°C and 21.18 N is 1.0 g/10 minutes or more and 30.0 g/10 minutes or less, and

5) chlorine content is 3 to 14 mass ppm.

According to the present invention, there can be provided a method for producing a propylene-ethylene- 1-butene terpolymer wherein a catalyst for propylene polymerization has a high catalyst activity, copolymerization properties are excellent, and the resulting terpolymer has a low hexane-soluble content and chlorine content, is excellent in copolymerization properties, and has a low melting point.

Brief Description of the Drawings

[Fig. 1] Fig. 1 is a schematic view showing an example of a process flow in the case of using one horizontal-type polymerization reactor in the production method of the present invention.

[Fig. 2] Fig. 2 is a schematic view showing an example of a process flow in the case of using two horizontal-type polymerization reactors in the production method of the present invention.

Description of Embodiments

The method for producing a propylene-ethylene- 1-butene terpolymer of the present invention is a method for producing a propylene-ethylene- 1-butene terpolymer having a chlorine content of 3 to 16 mass ppm, wherein

propylene, ethylene, and 1-butene in a vapor phase are copolymerized in the presence of a catalyst for propylene polymerization containing the following components (A) and (B) or the following components (A), (B), and (C):

Component (A): a solid catalyst component containing titanium, magnesium and chlorine as essential components, and having a titanium content of 0.5% by mass or more and 2.4% by mass or less;

Component (B): an organoaluminum compound;

Component (C): an organosilicon compound.

The following will describe the method for producing a propylene-ethylene- 1-butene terpolymer of the present invention in detail. [I] Catalyst for Propylene Polymerization

The catalyst for propylene polymerization to be used in the present invention contains the following components (A) and (B) or the following components (A), (B), and (C):

Component (A): a solid catalyst component containing titanium, magnesium, and chlorine as essential components where titanium content is 0.5% by mass or more and 2.4% by mass or less;

Component (B): an organoaluminum compound;

Component (C): an organosilicon compound. 1. Component (A): Solid catalyst component containing titanium, magnesium and chlorine as essential components, and having of a titanium content of 0.5% by mass or more and 2.4%) by mass or less.

In the present invention, the component (A) is a solid catalyst component containing titanium, magnesium and chlorine as essential components, and having a titanium content of 0.5% by mass or more and 2.4% by mass or less.

Moreover, in the present invention, the component (A) is preferably a solid catalyst component obtained by bringing the following components (Al), (A2), and (A3) into contact with one another:

Component (Al): a solid component containing titanium, magnesium and a chlorine as essential components;

Component (A2): a vinylsilane compound;

Component (A3): at least one compound selected from the group consisting of an organosilicon compound having an alkoxy group and a compound having two ether bonds.

The above component (A) may be a solid catalyst component obtained by further bringing another optional component such as the following component (A4) into contact with the components (Al), (A2), and (A3) by an arbitrary method:

Component (A4): an organoaluminum compound.

The following will describe individual constituent components in detail.

(1) Component (Al): Solid component containing titanium, magnesium, and chlorine as essential components

In the present invention, as the component (Al), titanium, magnesium, and chlorine are contained as essential components and an electron donor can be used as an optional component. Incidentally, when the titanium content of the solid component of the component (Al) is 0.5% by mass or more and 2.4% by mass or less, the solid component can be used as the solid catalyst component of the above component (A).

Here, the phrase "contained as essential components" means that, besides the mentioned three components, any component may be contained in any form in the range where the advantages of the present invention are not impaired.

The solid component itself containing titanium, magnesium, and chlorine as essential components is known and will be described below in detail. (Ala): Titanium

As a titanium compound to be a titanium source, an arbitrary titanium compound can be used. As representative examples thereof, there can be mentioned compounds disclosed in JP-A-3-234707. With regard to the valency of titanium, it is possible to use a titanium compound having arbitrary valent titanium, i.e., tetravalent, trivalent, bivalent, or 0-valent titanium, but it is desirable to use preferably a tetravalent or trivalent titanium compound, further preferably a tetravalent titanium compound.

Specific examples of the tetravalent titanium compound may include halogenated titanium compounds typified by titanium tetrachloride, alkoxytitanium compounds typified by tetrabutoxytitanium, condensed compounds of alkoxytitanium having a Ti-O-Ti bond typified by tetrabutoxytitanium dimer (BuO) ₃ Ti-0-Ti(OBu) ₃ , organometallic titanium compounds typified by dicyclopentadienyltitanium dichloride, and the like. Of these, titanium tetrachloride and tetrabutoxytitanium are particularly preferred.

Moreover, specific examples of the trivalent titanium compound may include halogenated titanium compounds typified by titanium trichloride. As titanium trichloride, it is possible to use compounds produced by any known methods, such as hydrogen reduction type one, metal aluminum reduction type one, metal titanium reduction type one, and organoaluminum reduction type one.

As for the above titanium compounds, it is possible to use not only the compound solely but also a plurality of the compounds in combination.

Moreover, it is possible to use mixtures of the above titanium compounds, compounds in which the average compositional formula is a formula formed by mixing them (e.g., a compound such as Ti(OBu) _m Cl _4-m ; 0<m<4), complexes with another compound such as a phthalic acid ester (e.g., a compound such as Ph(C0 ₂ Bu) ₂ iCl ₄ ), and the like.

(Alb): Magnesium

As a magnesium compound to be a magnesium source contained in the component

(A), an arbitrary magnesium compound can be used.

As representative examples thereof, there can be mentioned compounds disclosed in JP-A-3-234707.

In general, it is possible to use halogenated magnesium compounds typified by magnesium chloride, alkoxymagnesium compounds typified by diethoxymagnesium, metal magnesium, oxymagnesium compounds typified by magnesium oxide, hydroxymagnesium compounds typified by magnesium hydroxide, Grignard compounds typified by butylmagnesium chloride, organomagnesium compounds typified by butylethylmagnesium, magnesium salt compounds of inorganic and organic acids typified by magnesium carbonate and magnesium stearate, and mixtures thereof and compounds in which the average compositional formula is a formula formed by mixing them (e.g., compounds such as Mg(OEt) _m Ch- _m ; 0<m<2), and the like. Of these, magnesium chloride, diethoxymagnesium, metal magnesium, and butylmagnesium chloride are particularly preferred.

(Ale): Chlorine

The chlorine to be contained in the component (A) is generally supplied from the above titanium compounds and/or magnesium compounds but it can be also supplied from another compound.

Representative examples thereof may include chlorinated silicon compounds typified by silicon tetrachloride, chlorinated aluminum compounds typified by aluminum chloride, chlorinated organic compounds typified by 1 ,2-dichloroethane and benzyl chloride, chlorinated borane compounds typified by trichloroborane, chlorinated phosphorus compounds typified by phosphorus pentachloride, chlorinated tungsten compounds typified by tungsten hexachloride, chlorinated molybdenum compounds typified by molybdenum pentachloride, and the like. These compounds can be not only used solely but also used in combination. Of these, silicon tetrachloride is particularly preferred. (Aid): Electron Donor (Internal Donor)

The component (Al) to be used in the component (A) may contain an electron donor as an optional component.

As representative examples of the electron donor, there can be mentioned compounds disclosed in JP-A-2004- 124090.

In general, it is preferred to use organic and inorganic acids and their derivatives

(esters, acid anhydrides, acid halides, amides) compounds, ether compounds, ketone compounds, aldehyde compounds, alcohol compounds, amine compounds, and the like.

As the organic acid compounds that can be used as electron donors, there can be exemplified aromatic polybasic carboxylic acid compounds typified by phthalic acid, aromatic carboxylic acid compounds typified by benzoic acid, aliphatic polybasic carboxylic acid compounds typified by malonic acid having one or two substituents at the 2-position such as 2-n-butylmalonic acid or succinic acid having one or two substituents at the 2-position or one or more substituents at each of the 2- and 3 -positions such as 2-n-butylsuccinic acid, and aliphatic carboxylic acid compounds typified by propionic acid; aromatic and aliphatic sulfonic acid compounds typified by benzenesulfonic acid and methanesulfonic acid; and the like.

Whether these carboxylic acid compounds and sulfonic acid compounds are aromatic ones or aliphatic ones, they may have any number of unsaturated bond(s) at any position in the molecule, like maleic acid.

As derivative compounds of the organic acids that can be used as electron donors, there can be exemplified esters, acid anhydrides, acid halides, amides, and the like of the above organic acids.

As the alcohol that is a constituent element of the ester, aliphatic and aromatic alcohols can be used. Of these alcohols, an alcohol composed of an aliphatic free group having 1 to 20 carbon atoms such as an ethyl group, a butyl group, an isobutyl group, a heptyl group, an octyl group, or a dodecyl group is preferred. Further, an alcohol composed of an aliphatic free group having 2 to 12 carbon atoms is preferred. Moreover, it is also possible to use an alcohol composed of an alicyclic free group such as a cyclopentyl group, a cyclohexyl group, or a cycloheptyl group. As the halogen that is a constituent element of the acid halide, fluorine, chlorine, bromine, iodine, or the like can be used. Of these, chlorine is most preferred. In the case of a polyhalide of a polybasic organic acid, a plurality of the halogens may be the same or different.

As the amine that is a constituent element of the amide, aliphatic and aromatic amines can be used. Of these amines, there can be exemplified ammonia, aliphatic amines typified by ethylamine and dibutylamine, amines having an aromatic free group in the molecule, typified by aniline and benzylamine, as preferred compounds.

As the inorganic acid that can be used as the electron donor, there can be exemplified carbonic acid, phosphoric acid, silic acid, sulfuric acid, nitric acid, and the like.

As the derivative compounds of these inorganic acids, esters thereof are desirably used. Tetraethoxysilane (ethyl silicate), tetrabutoxysilane (butyl silicate), and the like may be mentioned as specific examples. As the ether compounds that can be used as electron donors, there can be exemplified aliphatic ether compounds typified by dibutyl ether, aromatic ether compounds typified by diphenyl ether, aliphatic polyvalent ether compounds typified by 1,3-dimethoxypropanes having one or two substituents at 2-position, such as 2-isopropyl-2-isobutyl- 1 ,3-dimethoxypropane and 2-isopropyl-2-isopentyl-l,3-dimethoxypropane, polyvalent ether compounds having an aromatic free group in the molecule typified by 9,9-bis(methoxymethyl)fluorene, and the like.

Preferable examples of the polyhydric ether compounds are compounds each having two ether bonds to be mentioned later and can be selected from the examples disclosed in JP-A-3-294302 and JP-A-8-333413.

As the ketone compounds that can be used as electron donors, there can be exemplified aliphatic ketone compounds typified by methyl ethyl ketone, aromatic ketone compounds typified by acetophenone, polyvalent ketone compounds typified by 2,2,4,6,6-pentamethyl-3,5-heptanedione, and the like.

As the aldehyde compounds, there can be exemplified aliphatic aldehyde compounds typified by propionaldehyde, aromatic aldehyde compounds typified by benzaldehyde, and the like.

As the alcohol compounds that can be used as electron donors, there can be exemplified aliphatic alcohol compounds typified by butanol and 2-ethylhexanol, phenol derivative compounds typified by phenol and cresol, aliphatic or aromatic polyhydric alcohol compounds typified by glycerol and l,l'-bi-2-naphthol, and the like.

As the amine compounds that can be used as electron donors, there can be exemplified aliphatic amine compounds typified by diethylamine, nitrogen-containing alicyclic compounds typified by 2,2,6,6-tetramethyl-piperidine, aromatic amine compounds typified by aniline, nitrogen-containing aromatic compounds typified by pyridine, polyvalent amine compounds typified by l,3-bis(dimethylamino)-2,2-dimethylpropane, and the like.

Further, as the compound to be used as the electron donor, it is also possible to use a compound containing a plurality of the above functional groups in the same molecule. As examples of such compounds, it is possible to mention ester compounds having an alkoxy group in the molecule typified by acetic acid-(2-ethoxyethyl) and ethyl 3-ethoxy-2-t-butylpropionate, keto ester compounds typified by ethyl 2-benzoyl-benzoate, keto ether compounds typified by (l-t-butyl-2-methoxyethyl) methyl ketone, amino ether compounds typified by N,N-dimethyl-2,2-dimethyl-3-methoxypropylamine, halogeno ether compounds typified by epoxychloropropane, and the like.

As for these electron donors, it is possible to use not only the compound solely but also a plurality of the compounds in combination. Of these, preferred are phthalic acid ester compounds typified by diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate and diheptyl phthalate, phthalic acid halide compounds typified by phthaloyl dichloride, malonic acid ester compounds having one or two substituents at the 2-position, such as diethyl 2-n-butylmalonate, succinic acid ester compounds having one or two substituents at the 2-position or one or more substituents at each of the 2- and 3-positions, such as diethyl 2-n-butylsuccinate, aliphatic polyvalent ether compounds typified by a 1,3-dimethoxypropane having one or two substituents at the 2-position, such as 2-isopropyl-2-isobutyl- 1 ,3-dimethoxypropane and 2-isopropyl-2-isopentyl- 1,3-dimethoxypropane, polyvalent ether compounds having an aromatic free group in the molecule typified by 9,9-bis(methoxymethyl)fluorene, and the like.

The amount of each component constituting the component (Al) to be used in the component (A) in the present invention may be arbitrary in the range where the advantages of the present invention are not impaired but, in general, the following range is preferred.

The amount of the titanium compound to be used is, relative to the amount of the magnesium compound to be used, in terms of a molar ratio (number of moles of the titanium compound/number of moles of the magnesium compound), preferably in the range of 0.0001 to 1,000, particularly preferably in the range of 0.01 to 10.

In the case where a compound to be a chlorine source is used besides the magnesium compound and the titanium compound, the amount of the compound to be used is, relative to the amount of the magnesium compound to be used, in terms of a molar ratio (number of moles of the compound to be a chlorine source/number of moles of the magnesium compound), preferably in the range of 0.01 to 1 ,000, particularly preferably in the range of 0.1 to 100, whether each of the magnesium compound and the titanium compound contains a chlorine or not.

In the case where an electron donor is used as an optional component at the time of preparing the component (Al ), the amount of the electron donor to be used is, relative to the amount of magnesium compound to be used, in terms of a molar ratio (number of moles of the electron donor/number of moles of the magnesium compound), preferably in the range of 0.001 to 10, particularly preferably in the range of 0.01 to 5. The component (Al ) to be used in the component (A) in the present invention is obtained by bringing the above-described constituting components into contact in the amounts mentioned above. As the contact conditions for the components, in the absence of a substantially harmful substance, any conditions can be used in the range where the advantages of the present invention are not impaired. In general, the following conditions are preferred.

The contact temperature is about -50 to 200°C, preferably 0 to 100°C.

As the contact method, a mechanical method by a rotary ball mill, a vibration mill, etc., a method of achieving the contact by stirring in the presence of an inert diluent, and the like can be exemplified.

At the time of preparing the component (Al), washing may be performed with an inert solvent in the middle or at the end.

As preferable inert solvent species, aliphatic hydrocarbon compounds such as heptane, aromatic hydrocarbon compounds such as toluene, halogen-containing hydrocarbon compounds such as 1 ,2-dichloroethylene and chlorobenzene and the like can be exemplified.

As a method for preparing the component (Al) to be used in the component (A) in the present invention, any methods can be used. Specifically, the following methods can be exemplified. However, the present invention is not limited at all by the following examples.

(i) Method of bringing titanium-containing compound into contact with chlorine-containing magnesium compound typified by magnesium chloride If necessary, an optional component such as an electron donor or a chlorinated silicon compound may be brought into contact. On this occasion, the optional component may be brought into contact simultaneously with the titanium-containing compound or may be brought into contact separately.

(ii) Method of dissolving chlorine-containing magnesium compound typified by magnesium chloride using alcohol compound, epoxy compound, phosphoric acid ester compound, and the like and bringing magnesium compound into contact with chlorine-containing titanium compound typified by titanium tetrachloride.

Before the contact with a chlorine-containing, titanium compound, particle formation may be performed using spray drying or a method of dropwise addition to a poor solvent such as a cooled hydrocarbon solvent.

Moreover, if necessary, an optional component such as an electron donor or a chlorinated silicon compound may be brought into contact.

On this occasion, the optional component may be brought into contact simultaneously with the chlorine-containing titanium compound or may be brought into contact separately.

(iii) Method of bringing chlorine-containing magnesium compound typified by magnesium chloride into contact with alkoxy group-containing titanium compound typified by tetrabutoxytitanium and specific polymer silicon compound component to obtain solid component and bringing solid component into contact with at least one compound selected from the group consisting of chlorine-containing titanium compound typified by titanium tetrachloride and chlorine-containing silicon compound typified by silicon tetrachloride.

The polymer silicon compound is suitably one represented by the following general formula (a):

[-Si(H)(R)-0-] _q ... (a)

wherein R is a hydrocarbon group having 1 to about 10 carbon atoms, q represents such a polymerization degree that the viscosity of the polymer silicon compound becomes 1 to about 100 centistokes.

As specific examples of the compound, methyl hydrogen polysiloxane, phenyl hydrogen polysiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and the like can be mentioned. Moreover, if necessary, an optional component such as an electron donor may be brought into contact. On this occasion, the optional component may be brought into contact simultaneously with the chlorine-containing titanium compound and the chlorine-containing silicon compound or may be brought into contact separately.

(iv) Method of bringing alkoxy group-containing magnesium compound typified by diethoxymagnesium into contact with alkoxy group-containing titanium compound typified by tetrabutoxytitanium and subsequently bringing product into contact with chlorinating agent or chlorine-containing titanium compound typified by titanium tetrachloride.

If necessary, an optional component such as an electron donor may be brought into contact. On this occasion, the optional component may be brought into contact simultaneously with the chlorinating agent or the chlorine-containing titanium compound or may be brought into contact separately. (v) Method of bringing alkoxy group-containing magnesium compound typified by diethoxymagnesium into contact with chlorine-containing titanium compound typified by titanium tetrachloride.

If necessary, an optional component such as an electron donor or a chlorinated silicon compound may be brought into contact. On this occasion, the optional component may be brought into contact simultaneously with the chlorine-containing titanium compound or may be brought into contact separately.

(vi) Method of bringing metal magnesium into contact with alcohol and, if necessary, iodine-containing compound typified by iodine and subsequently bringing product into contact with chlorine-containing titanium compound typified by titanium tetrachloride.

If necessary, an optional component such as an electron donor or a chlorinated silicon compound may be brought into contact. On this occasion, the optional component may be brought into contact simultaneously with the titanium-containing compound or may be brought into contact separately.

(vii) Method of bringing an organomagnesium compound such as Grignard reagent typified by butylmagnesium chloride with titanium-containing compound.

As the titanium-containing compound, an alkoxy group-containing titanium compound typified by tetrabutoxytitanium, a chlorine-containing titanium compound typified by titanium tetrachloride, or the like can be used. If necessary, an optional component such as an electron donor, an alkoxy group-containing titanium compound typified by tetrabutoxytitanium, and a chlorinated silicon compound may be brought into contact. On this occasion, the optional component may be brought into contact simultaneously with the titanium-containing compound or may be brought into contact separately.

The amount of titanium contained in the component (A) in the case where the component (A) is not preliminary polymerized or before pre-polymerization in the case where the component (A) is preliminary polymerized may be 0.5% by mass or more and 2.4% by mass or less. The amount is preferably 0.5% by mass or more and 1.8% by mass or less, more preferably 0.6% by mass or more and 1.0% by mass or less.

When the amount exceeds 2.4% by mass, since atactic polypropylene is prone to be formed at the time of producing the propylene-ethylene- 1 -butene terpolymer, it is necessary to use the method described in WO00/42081. When the method is used, there is a concern of a remarkable decrease in the catalytic activity. Moreover, the organosilicon compound remaining in the solvent coordinates to an active point of the catalyst with the passage of the time, so that the activity decreases and chain transfer behavior of hydrogen changes. Thereby, since operation controllability changes, it becomes difficult to control polymer structures such as MFR, ethylene content, and 1 -butene content steadily.

When the amount is less than 0.5% by mass, there is a concern of no exhibition of the activity of the catalyst.

The above titanium content in the component (A) is a value when the pre-polymerization is not performed.

In the above (i) to (vii) methods, it is common to control the titanium content in conventional Ziegler-Natta catalyst to more than 2.4% by mass and 4.0% by mass or less so as to have a suitable catalytic potential.

In order to make the Ti content in the component (A) fall within a predetermined range, further, when the Ti content in the component (A) is high, there may be mentioned a method of reducing the addition amount of the titanium compound, a method of reducing titanium on magnesium chloride by repeating strong washing and high-temperature washing with an aliphatic hydrocarbon compound such as heptane, an aromatic hydrocarbon compound such as toluene, and a halogen-containing hydrocarbon compound such as 1 ,2-dichloroethylene or chlorobenzene, a method of treatment with a vinylsilane, and the like.

The method of treatment with a vinylsilane is preferable as compared with the method of reducing the addition amount of the titanium compound, which method is slightly inferior in view of easy aggregation of the titanium compounds themselves in the production process of the component (A), and the method of reducing titanium on magnesium chloride by repeating strong washing and high-temperature washing with an aliphatic hydrocarbon compound such as heptane, an aromatic hydrocarbon compound such as toluene, and a halogen-containing hydrocarbon compound such as 1 ,2-dichloroethylene or chlorobenzene, which method is slightly inferior in view of efficiency and the amount of an organic waste liquid to be disposed.

In the case where the Ti content in the component (A) is insufficient, there is a method of increasing the addition amount of the titanium compound, and the like.

The chlorine content in the component (A) is preferably 55% by mass or more and 65% by mass or less.

In the above (i) to (vii) methods, the content is controlled by the addition amount of magnesium chloride.

(2) Component (A2): Vinylsilane Compound

As the component (A2): vinylsilane compound to be used in the present invention, compounds disclosed in JP-A-3-234707 and JP-A-2003-292522, and the like can be used. The vinylsilane compound is a compound having a structure in which at least one hydrogen atom of monosilane (SiH ₄ ) is replaced with a vinyl group and a part or all of the remaining hydrogen atom(s) are replaced with other free group(s), and can be represented by the following general formula (1):

[CH ₂ =CH-] _m SiX _n R'j(OR ² )k ... (1)

wherein X represents a halogen, R ¹ represents hydrogen or a hydrocarbon group, R ² represents hydrogen, a hydrocarbon group, or an organosilicon group, and m≥l , 0<n<3,

0<j<3, 0<k<2, and m+n+j+k=4. In the general formula (1), m represents the number of vinyl group(s) and is a value of 1 or more and 4 or less. More preferably, the value of m is desirably 1 or 2, particularly preferably 2.

In the general formula (1), X represents a halogen and fluorine, chlorine, bromine, iodine, and the like can be exemplified. In the case that a plurality of the X groups are present, they may be the same or different from each other. Of these, chlorine is particularly preferred, n represents the number of the halogen and is a value of 0 or more and 3 or less. More preferably, the value of n is desirably 0 or more and 2 or less, particularly preferably 0.

In the general formula (1), R ¹ represents hydrogen or a hydrocarbon group, preferably hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, more preferably hydrogen or a hydrocarbon group having 1 to 12 carbon atoms. Preferable examples of R ¹ may include hydrogen, alkyl groups typified by a methyl group or a butyl group, cycloalkyl groups typified by a cyclohexyl group, aryl groups typified by a phenyl group, and the like. Particularly preferable examples of R ¹ may include hydrogen, a methyl group, an ethyl group, a phenyl group, and the like, j represents the number of R ¹ and is a value of 0 or more and 3 or less. The value of j is more preferably 1 or more and 3 or less, further preferably 2 or more and 3 or less, particularly preferably 2. In the case where the value of j is 2 or more, a plurality of the R ¹ groups may be the same or different from each other.

In the general formula (1), R ² represents hydrogen, a hydrocarbon group, or an organosilicon group. In the case where R ² is a hydrocarbon group, it can be selected from the same compound group as that of R ¹ . In the case where R ² is an organosilicon group, it is preferably an organosilicon group having a hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of the organosilicon group that can be used as R ² may include alkyl group-containing silicon groups typified by a trimethylsilyl group, aryl group-containing silicon groups typified by a dimethylphenylsilyl group, vinyl group-containing silicon groups typified by a dimethylvinylsilyl group, silicon groups obtained by combining them, such as a propylphenylvinylsilyl group, and the like.

k represents the number of R ² groups and is a value of 0 or more and 2 or less.

In the case of a compound where the value of k corresponds 3, such as vinyltriethoxysilane, the performance as the component (A2): vinylsilane compound in the present invention is not exhibited and the performance as the organosilicon compound having an alkoxy group in the present invention is exhibited, so that the case is not preferred. This is because the compound behaves like t-butyltriethoxysilane that is structurally close to the compound (as mentioned later, the t-butyltriethoxysilane is effective as an organosilicon compound having an alkoxy group in the present invention). More preferably, the value of k is desirably 0 or more and 1 or less, particularly preferably 0. In the case where the value of k is 2, two R ² groups may be the same or different from each other. Further, regardless of the value of k, R ¹ and R ² may be the same or different. As for the vinylsilane compound, it is possible to use not only the compound solely but also a plurality of the compounds in combination.

Preferable examples of the compound may include CH ₂ =CH-SiMe ₃ , [CH ₂ =CH-] ₂ SiMe ₂ , CH ₂ =CH-Si(Cl)Me ₂ , CH ₂ =CH-Si(Cl) ₂ Me, CH ₂ =CH-SiCl ₃ , [CH ₂ =CH-] ₂ Si(Cl)Me, [CH ₂ =CH-] ₂ SiCl ₂ , CH ₂ =CH-Si(Ph)Me , CH ₂ =CH-Si(Ph) ₂ Me, CH ₂ =CH-SiPh ₃ , [CH ₂ =CH-] ₂ Si(Ph)Me, [CH ₂ =CH-] ₂ SiPh ₂ , CH ₂ =CH-Si(H)Me ₂ , CH ₂ =CH-Si(H) ₂ Me, CH ₂ =CH-SiH ₃ , [CH ₂ =CH-] ₂ Si(H)Me, [CH ₂ =CH-] ₂ SiH ₂ , CH ₂ =CH-SiEt ₃ , CH ₂ =CH-SiBu ₃ , CH ₂ =CH-Si(Ph)(H)Me, CH ₂ =CH-Si(Cl)(H)Me, CH ₂ =CH-Si(Me) ₂ (OMe), CH ₂ =CH-Si(Me) ₂ (OSiMe ₃ ), CH ₂ =CH-Si(Me) ₂ -0-Si(Me) ₂ -CH=CH ₂ , and the like. Of these, CH ₂ =CH-SiMe ₃ and [CH ₂ =CH-] ₂ SiMe ₂ are preferred and [CH ₂ =CH-] ₂ SiMe ₂ is most preferred.

In the compounds, the "Me" represents a methyl, the "Et" represents an ethyl, the "Bu" represents a n-butyl, sec-butyl or t-butyl, and the "Ph" represents a phenyl.

(3) Component (A3): At least one compound selected from group consisting of organosilicon compound having alkoxy group and compound having two ether bonds.

(A3a): Organosilicon compound having alkoxy group

As the organosilicon compound having an alkoxy group to be used in the present invention, compounds disclosed in JP-A-2004- 124090 and the like can be used.

In general, it is desirable to use a compound represented by the following general formula (2):

R ³ R ⁴ _a Si(OR ⁵ )b ... (2)

wherein R ³ represents a, hydrocarbon group or a heteroatom-containing hydrocarbon group, R ⁴ represents an arbitrary free group selected from hydrogen, a halogen, a hydrocarbon group, or a heteroatom-containing hydrocarbon group, R ⁵ represents a hydrocarbon group, and 0<a<2, l<b<3, and a+b=3.

In the general formula (2), R ³ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group.

The hydrocarbon group that can be used as R ³ is generally one having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms.

Specific examples of the hydrocarbon group that can be used as R ³ may include linear aliphatic hydrocarbon groups typified by an n-propyl group, saturated hydrocarbon groups, branched aliphatic groups typified by an i-propyl group and a t-butyl group, alicyclic hydrocarbon groups typified by a cyclopentyl group and a cyclohexyl group, aromatic hydrocarbon groups typified by a phenyl group, and the like.

More preferably, a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group is desirably used as R ³ and, especially, an i-propyl group, an i-butyl group, a t-butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, or the like is desirably used.

In the case where R ³ is a heteroatom-containing hydrocarbon group, the heteroatom is desirably selected from nitrogen, oxygen, sulfur, phosphorus, and silicon. Especially, it is desirable to be nitrogen or oxygen.

As the backbone structure of the heteroatom-containing hydrocarbon group of R ³ , it is desirable to select from the examples in the case where R ³ is a hydrocarbon group. Especially, an Ν,Ν-diethylamino group, a quinolino group, an isoquinolino group, and the like are preferred. In the general formula (2), R ⁴ represents hydrogen, a halogen, a hydrocarbon group, or a heteroatom-containing hydrocarbon group.

As the halogen atom that can be used as R ⁴ , fluorine, chlorine, bromine, iodine, and the like may be exemplified. In the case where R ⁴ is a hydrocarbon group, it is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms.

Specific examples of the hydrocarbon group that can be used as R ⁴ may include linear aliphatic hydrocarbon groups typified by a methyl group and an ethyl group, branched aliphatic groups typified by an i-propyl group and a t-butyl group, alicyclic hydrocarbon groups typified by a cyclopentyl group and a cyclohexyl group, aromatic hydrocarbon groups typified by a phenyl group, and the like. Of these, it is desirable to use a methyl group, an ethyl group, a propyl group, an i-propyl group, an i-butyl group, an s-butyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, or the like.

In the case where R ⁴ is the heteroatom-containing hydrocarbon group, it is desirable to select from the examples in the case where R ³ is a heteroatom-containing hydrocarbon group. Especially, an Ν,Ν-diethylamino group, a quinolino group, an isoquinolino group, and the like are preferred.

In the case where the value of a is 2, two R ⁴ groups may be the same or different. Further, regardless of the value of a, R ⁴ and R ³ may be the same or different.

In the general formula (2), R ⁵ represents a hydrocarbon group.

The hydrocarbon group that can be used as R ⁵ is generally one having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, further preferably 1 to 5 carbon atoms.

Specific examples of the hydrocarbon group that can be used as R ⁵ may include linear aliphatic hydrocarbon groups typified by a methyl group and an ethyl group, branched aliphatic groups typified by an i-propyl group and a t-butyl group, and the like. Of these, a methyl group and an ethyl group are most preferred. In the case where the value of b is 2 or more, a plurality of the R ⁵ groups may be the same or different. Preferable examples of the alkoxysilane compound to be used in the present invention may include t-Bu(Me)Si(OMe) ₂ , t-Bu(Me)Si(OEt) ₂ , t-Bu(Et)Si(OMe) ₂ , t-Bu(n-Pr)Si(OMe) ₂ , c-Hex(Me)Si(OMe) ₂ , c-Hex(Et)Si(OMe) ₂ , c-Pen ₂ Si(OMe) ₂ , i-Pr ₂ Si(OMe) ₂ , i-Bu ₂ Si(OMe) ₂ , i-Pr(i-Bu)Si(OMe) ₂ , n-Pr(Me)Si(OMe) ₂ , t-BuSi(OEt) ₃ , (Et ₂ N) ₂ Si(OMe) ₂ , Et ₂ N-Si(OEt) ₃ ,

[Chem 1

, and the like. In the compounds above, the "Me" represents a methyl, the "Et" represents an ethyl, the "Ph" represents a phenyl, the "t-Bu" represents t-butyl, the "Pr" represents a propyl, the "Hex" represents a hexyl, and the "Pen" represents a pentyl.

As for the organosilicon compound, it is possible to use not only the compound solely but also a plurality of the compounds in combination.

(A3b): Compounds Having Two Ether Bonds

As the compound having two ether bonds that can be used in the present invention, compounds disclosed in JP-A-3-294302 and JP-A-8-333413 can be used.

In general, it is desirable to use a compound represented by the following general formula (3):

R ⁸ 0-C(R ⁷ ) ₂ -C(R ⁶ ) ₂ -C(R ⁷ ) ₂ -OR ⁸ ... (3)

wherein, R ⁶ and R ⁷ represent an arbitrary free group selected from hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group, and R ⁸ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group.

In the general formula (3), R ⁶ represents an arbitrary free group selected from hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group.

The hydrocarbon group that can be used as R ⁶ is generally one having 1 to 20 carbon atoms, preferably one having 1 to 10 carbon atoms.

Specific examples of the hydrocarbon group that can be used as R ⁶ may include linear aliphatic hydrocarbon group typified by an n-propyl group, branched aliphatic groups typified by an i-propyl group and a t-butyl group, alicyclic hydrocarbon groups typified by a cyclopentyl group and a cyclohexyl group, aromatic hydrocarbon groups typified by a phenyl group, and the like. More preferably, a branched aliphatic hydrocarbon group or an alicyclic hydrocarbon group is desirably used as R ⁶ and, especially, an i-propyl group, an i-butyl group, an i-pentyl group, a cyclopentyl group, a cyclohexyl group, or the like is desirably used.

Two R ⁶ groups may be combined to form one or more rings. At this time, it is also possible to form a cyclopolyene-based structure containing two or three unsaturated bonds in the ring structure.

Also, it may be condensed with another cyclic structure.

Regardless of monocyclic, polycyclic, or presence or absence of condensation, one or more hydrocarbon groups may be present on the ring as substituent(s). The substituent on the ring is generally one having 1 to 20 carbon atoms, and preferably one having 1 to 10 carbon atoms. Specific examples thereof may include linear aliphatic hydrocarbon group typified by an n-propyl group, branched aliphatic groups typified by an i-propyl group and a t-butyl group, alicyclic hydrocarbon groups typified by a cyclopentyl group and a cyclohexyl group, aromatic hydrocarbon groups typified by a phenyl group, and the like.

In the general formula (3), R ⁷ represents an arbitrary free group selected from hydrogen, a hydrocarbon group, and a heteroatom-containing hydrocarbon group. Specifically, R ⁷ can be selected from the examples of R ⁶ . R ⁷ is preferably hydrogen.

In the general formula (3), R ⁸ represents a hydrocarbon group or a heteroatom-containing hydrocarbon group. Specifically, R ⁸ can be selected from the examples in the case where R ⁶ is a hydrocarbon group. Preferably, R ⁸ is desirably a hydrocarbon group having 1 to 6 carbon atoms, more preferably an alkyl group. Most preferred is a methyl group.

In the case where R ⁶ to R ⁸ are each a heteroatom-containing hydrocarbon group, the heteroatom is desirably selected from nitrogen, oxygen, sulfur, phosphorus, and silicon. Moreover, whether R ⁶ to R ⁸ are each a hydrocarbon group or a heteroatom-containing hydrocarbon group, they may arbitrarily contain a halogen. In the case where R ⁶ to R ⁸ contain a heteroatom and/or a halogen, the backbone structure is desirably selected from the examples in the case of a hydrocarbon group. Further, eight substituents of R ⁶ to R ⁸ may be the same as or different from one another.

Preferable examples of the compound having two ether bonds that can be used in the present invention may include 2,2-diisopropyl-l ,3-dimethoxypropane, 2,2-diisobutyl-l ,3-dimethoxypropane, 2,2-diisobutyl-l ,3-diethoxypropane,

2-isobutyl-2-isopropyl-l ,3-dimethoxypropane,

2-isopropyl-2-isopentyl-l,3-dimethoxypropane, 2,2-dicyclopentyl-l ,3-dimethoxypropane, 2,2-dicyclohexyl-l,3-dimethoxypropane, 2-isopropyl-l ,3-dimethoxypropane, 2-tert-butyl- 1 ,3-dimethoxypropane, 2,2-dipropyl- 1 ,3-dimethoxypropane,

2-methyl-2-phenyl-l,3-dimethoxypropane, 9,9-bis(methoxymethyl)fluorene, 9,9-bis(methoxymethyl)- 1 ,8-dichlorofluorene,

9,9-bis(methoxymethyI)-2,7-dicyclopentylfluorene, 9,9-bis(methoxymethyl)- 1 ,2,3 ,4-tetrahydrofluorene, 1 , 1 -bis( 1 '-butoxyethyl)cyclopentadiene, 1 , 1 -bis(a-methoxybenzyl)indene, 1 , 1 -bis(phenoxymethyl)-3 ,6-dicyclohexylindene,

1 , 1 -bis(methoxymethyl)benzonaphthene, 7,7-bis(methoxymethyl)-2,5-norbornadiene, and the like.

Of these, particularly preferred are 2,2-diisopropyl-l,3-dimethoxypropane,

2,2-diisobutyl-l,3-dimethoxypropane, 2-isobutyl-2-isopropyl-l,3-dimethoxypropane, 2-isopropyl-2-isopentyl-l ,3-dimethoxypropane, 2,2-dicyclopentyl-l ,3-dimethoxypropane, and 9,9-bis(methoxymethyl)fluorene.

As for the compound having two ether bonds, it is possible to use not only the compound solely but also a plurality of the compounds in combination. It may be the same as or different from the polyvalent ether compound to be used as an optional component ((Aid): electron donor) in the component (Al).

(4) Component (A4): Organoaluminum Compound

The component (A) in the present invention is preferably a solid catalyst component obtained by bringing the component (Al): solid component, the component (A2): vinylsilane compound, and at least one compound selected from the component (A3): organosilicon compound having an alkoxy group and the compound having two ether bond, and further another optional component may be brought into contact in a range where the advantages of the present invention are not impaired. As such an optional component, an organoaluminum compound may be mentioned.

As the organoaluminum compound to be used as an optional component at the time of preparing the component (A) in the present invention, compounds disclosed in JP-A-2004- 124090, and the like can be used.

In general, it is desirable to use a compound represented by the following general formula (4):

R ⁹ _c AlXd(OR ¹⁰ )e ... (4)

wherein R ⁹ represents a hydrocarbon group, X represents a halogen or hydrogen, R ¹⁰ represents a hydrocarbon group, and c>l, 0<d<2, 0<e< 2, and c+d+e=3.

In the general formula (4), R ⁹ represents a hydrocarbon group, and it is desirable to use one having preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, particularly preferably 1 to 6 carbon atoms. Specific examples of R ⁹ may include a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a hexyl group, an octyl group, and the like. Of these, a methyl group, an ethyl group, and an isobutyl group are most preferred.

In the general formula (4), X represents a halogen or hydrogen. As the halogen that can be used as X, fluorine, chlorine, bromine, iodine, and the like may be exemplified. Of these, chlorine is particularly preferred.

In the general formula (4), R ¹⁰ is a hydrocarbon group. In the case where R ¹⁰ is a hydrocarbon group, R ¹⁰ can be selected from the same group as the examples of the hydrocarbon group of R ⁹ .

Examples of the compound that can be used as the organoaluminum compound may include trimethylaluminum, triethylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum chloride, ethylaluminum dichloride, diethylaluminum ethoxide, and the like. Of these, triethylaluminum and triisobutylaluminum are preferred.

As for the organoaluminum compound, it is possible to use not only the compound solely but also a plurality of the compounds in combination.

2. Preparation Method of Component (A)

The component (A) in the present invention is preferably a solid catalyst component obtained by bringing into contact with the component (Al): solid component, the component (A2): vinylsilane compound, and at least one compound selected from the component (A3): organosilicon compound having an alkoxy group and the compound having two ether bonds. At this time, another optional component such as the component (A4): organoaluminum compound or the like may be brought into contact by an arbitrary method in a range where the advantages of the present invention are not impaired.

As the contact conditions for the constitutional components of the component (A), any conditions can be used in the range where the advantages of the present invention are not impaired although it is necessary that oxygen is made absent. In general, the following conditions are preferred.

The contact temperature is about -50 to 200°C, preferably -10 to 100°C, more preferably 0 to 70°C, particularly preferably 10 to 60°C.

As the contact method, a mechanical method by a rotary ball mill, a vibration mill, etc., a method of achieving the contact by stirring in the presence of an inert diluent, and the like can be exemplified. Preferably, it is desirable to use a method of achieving the contact by stirring in the presence of an inert diluent. The ratio of the amount of individual components to be used which constitute the component (A) in the present invention may be arbitrary in the range where the advantages of the present invention are not impaired but, in general, the following ranges are preferred.

It is desirable that the amount of the vinylsilane compound as the component (A2) to be used is, in terms of a molar ratio to the titanium component constituting the component (Al) (number of moles of the vinylsilane compound/number of moles of the titanium atom), preferably in the range of 0.001 to 1,000, particularly preferably in the range of 0.01 to 100.

In the case of using the organosilicon compound having an alkoxy group as the component (A3), it is desirable that the amount thereof to be used is, in terms of a molar ratio to the titanium component constituting the component (Al) (number of moles of the organosilicon compound having an alkoxy group/number of moles of the titanium atom), preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.01 to 100.

In the case of using the compound having two ether bonds as the component (A3), it is desirable that the amount thereof to be used is, in terms of a molar ratio to the titanium component constituting the component (Al) (number of moles of the compound having two ether bonds/number of moles of the titanium atom), preferably in the range of 0.01 to 1,000, particularly preferably in the range of 0.01 to 100.

In the case of using the organoaluminum compound as an optional component, it is desirable that the amount thereof to be used is, in terms of a molar ratio of aluminum to the titanium component constituting the component (Al) (number of moles of the aluminum atom/number of moles of the titanium atom), preferably in the range of 0.1 to 100, particularly preferably in the range of 1 to 50.

With respect to the contact procedure of the component (Al), the component (A2), and the component (A3), any procedure may be used. Specific examples include the following procedures (i) to (iii).

Procedure (i): a method of bringing the component (A2) into contact with the component (Al) and subsequently bringing the component (A3) into contact. Procedure (ii): a method of bringing the component (A3) into contact with the component (Al) and subsequently bringing the component (A2) into contact.

Procedure (iii): a method of bringing all the compounds into contact at the same time.

Of these, the procedure (i) and the procedure (iii) are preferred.

Further, it is also possible to bring the component (Al) into contact with any of the component (A2) and the component (A3) at arbitrary number of times. On this occasion, as for any of the component (A2) and the component (A3), compounds to be used in multiple times of the contact may be the same or different from each other.

Also in the case of using the component (A4): organoaluminum compound as the optional component, the contact can be performed in any order as mentioned above. Especially, the following procedures (iv) to (vi) are mentioned. Procedure (iv): a method of bringing the component (A2) into contact with the component (Al), then bringing the component (A3) into contact, and subsequently bringing the component (A4) into contact.

Procedure (v): a method of bringing the component (A2) and the component (A3) into contact with the component (Al) and subsequently bringing the component (A4) into contact.

Procedure (vi): a method of bringing all the compounds into contact at the same time.

It is also possible to bring the organoaluminum compound to be used as the component (A4) into contact at arbitrary number of times. On this occasion, the organoaluminum compounds to be used in multiple times may be the same or different from each other.

At the time of preparing the component (A), washing may be performed with an inert solvent in the middle or at the end.

As preferable solvent species, there can be exemplified aliphatic hydrocarbon compounds such as heptane, aromatic hydrocarbon compounds such as toluene, halogen-containing hydrocarbon compounds such as 1 ,2-dichloroethylene and chlorobenzene, and the like. The titanium content of the component (A) is preferably 0.5% by mass or more and 2.4% by mass or less, more preferably 0.5% by mass or more and 1.9% by mass or less, and further preferably 0.6% by mass or more and 1.0% by mass or less. 3. Component (B): Organoaluminum Compound

As the organoaluminum compound to be used as the component (B) in the catalyst for propylene polymerization to be used in the present invention, compounds disclosed in JP-A-2004- 124090 and the like can be used.

Preferably, it can be selected from the same group as the examples in the component (A4): organoaluminum compound that is an optional component at the time of preparing the component (A). On this occasion, the organoaluminum compound (B) that is used as the component (B) may be the same as or different from the organoaluminum compound that is used as the component (A4).

As for the organoaluminum compound to be used as the component (B), it is possible to use not only the compound solely but also a plurality of the compounds in combination.

The amount of the organoaluminum compound to be used as the component (B) is, in terms of a molar ratio of the titanium component constituting the component (A) (number of moles of the organoaluminum compound/number of moles of the titanium atom), preferably in the range of 1 to 1,000, particularly preferably in the range of 10 to 500.

Specific examples of the component (B) that can be used in the present invention include those represented by the following general formulae (b) to (c):

R ⁿ _3- sAlX _s ... (b) or

R ¹² _3- tAl(OR ¹³ )t ... (c)

wherein R ¹¹ and R ¹² each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom, R ¹³ represents a hydrocarbon group, X represents a halogen, and, as for s and t, 0<s<3, and 0<t<3.

Specifically, there are mentioned (i) trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and tri-n-decylaluminum, (ii) alkylaluminum halides such as diethylaluminum monochloride, diisobutylaluminum monochloride, ethylaluminum sesquichloride, and ethylaluminum dichloride,

(iii) alkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, and

(iv) alkylaluminum alkoxides such as diethylaluminum ethoxide and diethylaluminum phenoxide, and the like.

These organoaluminum compounds of (i) to (vi) can be also used in combination with the other organometallic compounds, for example, an aluminum alkoxide represented by the following general formula (d):

R ¹⁴ _3-u Al(O ¹⁵ )u ... (d)

wherein R ¹⁴ and R ¹⁵ are the same or different from each other and represent a hydrocarbon group having 1 to 20 carbon atoms, and, as for u, 0<u<3.

For example, there are mentioned a combination use of triethylaluminum and diethylaluminum ethoxide, a combination use of diethylaluminum monochloride and diethylaluminum ethoxide, a combination use of ethylaluminum dichloride and ethylaluminum diethoxide, a combination use of triethylaluminum, diethylaluminum ethoxide, and diethylaluminum monochloride, and the like.

4. Other Optional Components in Catalyst for Propylene Polymerization

In the present invention, it is an essential requirement to use the component (A) and the component (B) as the catalyst for propylene polymerization but, within the range where the advantages of the present invention are not impaired, optional components of the component (C): organosilicon compound and the component (D): compound having two ether bonds, the component (E): other compound to be described below can be used.

Component (C): Organosilicon compound

As the organosilicon compound to be used as an optional component in the catalyst for propylene polymerization to be used in the present invention, compounds disclosed in JP-A-2004- 124090 and the like can be used. Preferably, it can be selected from the same group as the examples in (A3a): organosilicon compound having an alkoxy group to be used as the component (A3) in the component (A). On this occasion, (A3a): organosilicon compound having an alkoxy group to be used as the component (A3) and the organosilicon compound that is used as the component (C) may be the same or different.

As for the organosilicon compound to be used as the component (C), it is possible to use not only the compound solely but also a plurality of the compounds in combination.

As preferable organosilicon compound, an organic silicic acid ester and the like may be mentioned.

A preferable organic silicic acid ester is an organosilicon compound represented by the following general formula (e):

R ¹⁶ vR ¹⁷ wSi(OR ^,8 ) _4- v-w - (e)

wherein R ¹⁶ represents a branched aliphatic hydrocarbon residual group having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms, or a cyclic aliphatic hydrocarbon residual group having 5 to 20 carbon atoms, preferably 6 to 10 carbon atoms, R ¹⁷ represents a branched or linear aliphatic hydrocarbon residual group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, R ¹⁸ represents an aliphatic hydrocarbon residual group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and v and w represent numerals of 0<v<3, 0<w<3, and v+w<3, respectively.

Incidentally, R ¹⁶ of the above general formula (e) is preferably one branched from the carbon atom adjacent to the silicon atom.

Component (D): Compound Having Two Ether Bonds

As the compound having two ether bonds to be used as the component (D) in the catalyst for propylene polymerization to be used in the present invention, preferably, it is selected from the same group as the examples in (A3b): compound having two ether bonds that is used as the component (A3) in the component (A). On this occasion, (A3b): compound having two ether bonds to be used as the component (A3) at the time of preparing the component (A) may be the same as or different from the compound having two ether bonds to be used as the component (D).

As for the compound having two ether bonds to be used as the component (D), it is possible to use not only the compound solely but also a plurality of the compounds in combination.

Component (E): Other Compound Unless the advantages of the present invention are impaired, a component other than the component (C) and the component (D) can be used as an optional component of the catalyst for propylene polymerization.

For example, as disclosed in JP-A-2004- 124090, by using a compound having a C(=0)N bond in the molecule, the formation of amorphous components such as CXS can be suppressed. In this case, tetramethylurea, l,3-dimethyl-2-imidazolidinone, l-ethyl-2-pyrrolidinone, and the like may be mentioned as preferable examples. Moreover, it is also possible to use an organometallic compound having a metal atom other than Al, such as diethylzinc.

5. Amount of Optional Component to be Used

The amount of the optional component to be used in the catalyst for propylene polymerization is arbitrary within the range where the advantages of the present invention are not impaired but, in general, the following ranges are preferable.

The amount of the organosilicon compound in the case of using the compound as the component (C) is, in terms of a molar ratio thereof to the titanium component constituting the component (A) (number of moles of the organosilicon compound/number of moles of the titanium atom), preferably in the range of 0.1 to 10,000, particularly preferably in the range of 0.5 to 500.

The amount of the compound having two ether bonds in the case of using the compound as the component (D) is, in terms of a molar ratio thereof to the titanium component constituting the component (A) (number of moles of the compound having two ether bonds/number of moles of the titanium atom), preferably in the range of 0.01 to 10,000, particularly preferably in the range of 0.5 to 500.

The amount of the compound having a C(=0)N bond in the molecule in the case of using the compound as the component (E) is, in terms of a molar ratio thereof to the titanium component constituting the component (A) (number of moles of the compound having a C(=0)N bond in the molecule/number of moles of the titanium atom), preferably in the range of 0.001 to 1 ,000, particularly preferably in the range of 0.05 to 500.

[II] Polymerization

1. Pre-polymerization Step

It is preferable that the component (A) in the present invention is used after a pre-polymerization treatment before the use in main polymerization. By forming a small amount of a polymer around the catalyst prior to the polymerization process, the catalyst becomes more uniform and the generation amount of fine powder can be suppressed. The pre-polymerization treatment can be performed in the presence of the same organoaluminum compound as the organoaluminum compound to be used as the component (B) in the main polymerization.

The addition amount of the organoaluminum compound to be used depends on the kind of the solid catalyst component to be used, but the organoaluminum compound is usually used in a range of 0.1 to 40 mol, preferably 0.3 to 20 mol, relative to 1 mol of the titanium atom and 0.1 to 100 g, preferably 0.5 to 50 g of a monomer per 1 g of the solid catalyst component is reacted in an inert solvent at a temperature of 10 to 80°C over a period of 10 minutes to 48 hours. In the pre-polymerization treatment, the same organosilicon compound as the component (C) to be used in the main polymerization may also be used as needed.

The organosilicon compound may be used in a range of 0.01 to 10 mol relative to 1 mol of the organoaluminum compound. As a monomer to be used in the pre-polymerization treatment of the component (A), compounds disclosed in JP-A-2004- 124090 and the like can be used.

Examples of the specific compound may include olefins typified by ethylene, propylene, 1-butene, 3-methylbutene-l, 4-methylpentene-l, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1 -octadecene, 1-eicosene, 4-methyl- 1-pentene, 3 -methyl- 1-pentene, and the like;

styrene analogous compound typified by styrene, ot-methylstyrene, allylbenzene, chlorostyrene, and the like; and

diene compounds typified by 1 ,3-butadine, isoprene, 1 ,3-pentadiene, 1,5-hexadiene, 2,6-octadiene, dicyclopentadiene, 1,3-cyclohexadiene, 1 ,9-decadiene, divinylbenzenes, and the like.

Of these, ethylene, propylene, 3-methylbutene-l, 4-methylpentene-l, styrene, divinylbenzenes, and the like are particularly preferable.

They may be used not only alone but also they may be used as a mixture of two or more compounds with other cc-olefin(s).

In addition, at polymerization thereof, to adjust molecular weight of a polymer formed in the polymerization, a molecular weight modifier such as hydrogen may be used in combination.

In the case of using preliminarily polymerized one as the component (A), the pre-polymerization can be performed in any procedure in the preparation procedure of the component (A). For example, the component (A2) and the component (A3) can be brought into contact after the component (Al) is preliminarily polymerized.

Moreover, the pre-polymerization can be performed after the component (Al), the component (A2), and the component (A3) are brought into contact.

Furthermore, the pre-polymerization can be performed at the time of bringing the component (Al), the component (A2), and the component (A3) into contact. As the reaction conditions of the component (A) and the above monomer, any conditions can be used within the range where the advantages of the present invention are not impaired. In general, the following ranges are preferable.

It is desirable that the amount of the pre-polymerization is preferably 0.1 to 100 g, preferably 0.5 to 50 g per 1 g of the component (A). The reaction temperature at the pre-polymerization is 10 to 80°C.

The temperature at the pre-polymerization treatment is desirably lower than the polymerization temperature at the main polymerization.

The reaction is preferably performed generally under stirring and, at the time, an inert solvent may be present.

The inert solvent to be used in the pre-polymerization treatment of the component

(A) is an inert solvent having no extreme influence on the polymerization reaction, e.g., a liquid saturated hydrocarbon such as hexane, heptane, octane, decane, dodecane, or liquid paraffin, silicone oil having a structure of dimethylpolysiloxane, or the like.

These inert solvents may be either a single solvent of one kind or a mixed solvent of two or more kinds. At the use of these inert solvents, it is preferable to use them after removing impurities such as moisture, a sulfur compound, and the like that adversely influence on the polymerization. The pre-polymerization treatment may be performed in multiple times, and a monomer to be used on this occasion may be the same or different. In addition, after the pre-polymerization treatment, washing of the component (A) may be performed with an inert solvent such as hexane, heptanes or the like.

After completion of pre-polymerization treatment, the component (A) after the pre-polymerization may be used as it is, in response to use form of the catalyst but, it may be dried as needed.

Furthermore, at the contact with the above each component or after the contact, a polymer such as polyethylene, polypropylene, or polystyrene or a solid inorganic oxide such as silica or titania may be present at the same time.

The amount of titanium contained in the component (A) after pre-polymerization is preferably 0.5% by mass or more and 2.4% by mass or less. The amount is more preferably 0.5% by mass or more and 1.8% by mass or less, further preferably 0.6% by mass or more and 1.0% by mass or less.

After pre-polymerization, the organosilicon compound is preferably not added again to the catalyst feeding tank. When the organosilicon compound is present in the catalyst feeding tank, the organosilicon compound coordinates to an active point of the catalyst with the passage of the time in the catalyst feeding tank, so that the activity may decrease and chain transfer behavior of hydrogen may change. Thereby, since operation controllability changes, it becomes complex to control polymer structures such as MFR, ethylene content, and 1-butene content steadily. 2. Polymerization Step (Main Polymerization Step)

The polymerization step of the present invention comprises at least a first stage polymerization (first step) and, from the viewpoint of improving catalytic activity, preferably comprises a first stage polymerization (first step) and a second stage polymerization (second step). The first stage polymerization and the second stage polymerization are preferably carried out in this order (first stage -> second stage).

3. Polymerization Mode

The production of the propylene-ethylene- 1-butene terpolymer according to the present invention is preferably produced by a vapor-phase polymerization method.

As long as a vapor phase polymerization method is performed, any of a fluidized bed reactor, a vertical-type reactor, and a horizontal -type reactor equipped with stirring vanes rotating around a horizontal axis (horizontal-type polymerization reactor) may be used but it is desirable to carry out the polymerization in a continuous manner using at least one horizontal-type reactor equipped with stirring vanes rotating around a horizontal axis, where the powder held in the reactor is efficiently replaced.

In the present invention, the vapor phase polymerization method does not mean entire absence of a liquid. It is sufficient that the phase at which polymerization is performed is substantially a vapor phase and a liquid may be present in the range where the presence does not deviate from the gist of the present invention. As the liquid, not only liquefied propylene for heat removal but also an inert hydrocarbon such as hexane may be exemplified.

It is preferable that removal of heat of polymerization that generates at polymerization is performed using heat of vaporization of liquefied propylene of a raw material as fed, in view of a reduction of manufacturing cost.

4. First Step

The first stage polymerization (first step) is a step of producing a propylene-ethylene- 1-butene terpolymer by continuously polymerizing a mixture of propylene, ethylene, and butene in a substantially vapor phase state in the presence of the components (A) and (B) or in the presence of the components (A) to (C).

As for the monomer gas composition for obtaining the propylene-ethylene- 1-butene terpolymer, for example, the proportion of ethylene to the whole monomer gas is preferably

0.005 molar ratio or more and 0.06 molar ratio or less, more preferably 0.007 molar ratio or more and 0.021 molar ratio or less, and further preferably 0.007 molar ratio or more and 0.016 molar ratio or less, and the proportion of butene is preferably 0.01 molar ratio or more and 0.300 molar ratio or less, more preferably 0.032 molar ratio or more and 0.112 molar ratio or less.

Moreover, the proportion of hydrogen that is fed for controlling MFR of the product is preferably 0.010 molar ratio or more and 0.100 molar ratio or less, and more preferably 0.023 molar ratio or more and 0.084 molar ratio or less. The polymerization conditions such as temperature and pressure can be set arbitrary, as long as they do not impair the advantages of the present invention.

Specifically, the polymerization temperature is preferably 0°C or higher, further preferably 30°C or higher, and particularly preferably 40°C or higher, while preferably 100°C or lower, further preferably 90°C or lower, and particularly preferably 80°C or lower. Furthermore, in the case of a horizontal -type reactor equipped with stirring vanes rotating around a horizontal axis, it is desirable that a temperature difference ΔΤ1 (°C) between reaction temperature (Ta) of a region containing an upstream end of the reactor and reaction temperature (Tco) of a region containing a downstream end (=Τω-Τα) that is the temperature range described in JP-A-2011-153287 is 0.1 to 20°C and a temperature difference ΔΤ2 (°C) between reaction temperature (Tx) of a region containing a catalyst feeding part and the dew point (Tz) of the mixed gas in the reactor (=Tx-Tz) is 1 to 20°C. The polymerization pressure is atmospheric pressure or higher, preferably 600 kPa or higher, further preferably 1000 kPa or higher, and particularly preferably 1600 kPa or higher, while preferably 4200 kPa or lower, further preferably 3500 kPa or lower, and particularly preferably 3000 kP a or lower. However, the polymerization pressure should not be set at a pressure higher than the vapor pressure of propylene at polymerization temperature.

The residence time may be adjusted arbitrarily in response to a constitution of polymerization tanks or a product index. In general, it is set within a range of 30 minutes to 10 hours.

The ratio of the amount of the component (A) to the amount of the component (B) is, on the basis of the number of gram atoms of Ti in the component (A), usually Al/Ti = 1 to 500 (molar ratio), preferably 10 to 300 (molar ratio). In the present invention, on the basis of the number of gram atoms of Mg that is high in measurement accuracy, the operation is controlled usually at Al/Mg of 1 to 100. Preferably, it is 1 to 50 (molar ratio).

In the case of using the component (C), on the basis of the number of gram atoms of Al in the component (B), usually AI/Si is 1 to 100 (molar ratio), preferably 1 to 50 (molar ratio).

As for the catalytic activity of the catalyst for propylene polymerization in the first stage polymerization step, a lower limit value thereof is preferably 15,000 g/g-catalyst or more, further preferably 17,000 g/g-catalyst or more, and more preferably 18,000 g/g-catalyst or more. An upper limit value thereof is, for example, 150,000 g/g-catalyst or less.

In the case where the catalytic activity of the catalyst for propylene polymerization is too low, the particle diameter of the powder to be obtained in the first stage polymerization step becomes small and powder fluidity in the polymerization step decreases. The decrease in the powder fluidity may generate lumps. Further, there is a concern of causing an increase of the chlorine content in the polymer owing to a decrease in the activity.

In the case where the catalytic activity of the catalyst for propylene polymerization is too high, local heat removal of the catalyst feeding part becomes difficult and there is a concern that lumps and the like are prone to be generated.

A smaller amount of the lumps in the powder during operation is more preferable. The amount is preferably 1.0% by mass or less, more preferably 0.5% by mass or less. When the amount is 1.0% by mass or less, the production can be continued for a long period of time without causing clogging in a powder transferring pipeline.

5. Second Step

In the present invention, the second stage polymerization (second step) is not always needed. In the case of performing the second stage polymerization (second step), the step may be a step of producing a propylene-ethylene- 1-butene terpolymer, as in the first stage polymerization (first step).

As for the monomer gas composition and the polymerization temperature and polymerization pressure, the step is desirably performed in the same ranges as those in the first stage polymerization.

In order to obtain the objective index, the step may be performed while changing the monomer gas composition to a monomer gas composition different from that in the first stage polymerization.

Moreover, within the range where the advantages of the present invention are not impaired, in order to deactivate a short pass, the electron donor compound described and used in JP-A-2008- 150466 or the like may be added.

As for the catalytic activity of the catalyst for propylene polymerization in the second stage polymerization, a lower limit value thereof is preferably 5,000 g/g-catalyst or more, further preferably 10,000 g/g-catalyst or more, more preferably 15,000 g/g-catalyst or more and an upper limit value thereof is, for example, 150,000 g/g-catalyst or less.

In the case where the catalytic activity of the catalyst for propylene polymerization is too low, the production amount obtained in the second stage polymerization decreases and there is a concern of a decrease in economical efficiency.

In the case where the catalytic activity of the catalyst for propylene polymerization is too high, local heat removal of the catalyst feeding part becomes difficult and there is a concern that lumps and the like are prone to be generated.

In the powder during operation, a smaller amount of the lumps is more preferable. The amount is preferably 1.0% by mass or less, further preferably 0.5% by mass or less. When the amount is 1.0%» by mass or less, the production can be continued for a long period of time without causing clogging in a powder transferring pipeline.

6. Propylene-Ethylene- 1-Butene Terpolymer

The total of the ethylene content and the butene content in the propylene-ethylene- 1-butene terpolymer is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, further preferably 3.0% by mass or more and preferably 23% by mass or less, more preferably 21% by mass or less, further preferably 19% by mass or less.

When the total of the ethylene content and the butene content in the propylene-ethylene- 1-butene terpolymer exceeds 23% by mass, the bulk density of the terpolymer powder decreases and there is a concern of an increase in an amount of by-product of a low crystalline polymer that corresponds to the hexane-soluble content at 50°C.

The ethylene content in the propylene-ethylene- 1-butene terpolymer is preferably 0.5%) by mass or more, more preferably 0.9%) by mass or more, further preferably 1.5% by mass or more and preferably 5.0% by mass or less, more preferably 4.5% by mass or less, further preferably 4.0% by mass or less, particularly preferably 3.5% by mass or less.

When the content is less than 0.5% by mass, there is a concern that the terpolymer does not have physical properties as an objective product. When the content exceeds 5.0% by mass, there is a concern of an increase in the amount of by-product of a low crystalline polymer that corresponds to the hexane-soluble content at 50°C.

The butene content in the propylene-ethylene- 1-butene terpolymer is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, further preferably 1.5% by mass or more, more further preferably 1.8% by mass or more, particularly preferably 2.2% by mass or more, and preferably 18% by mass or less, more preferably 17.5% by mass or less, further preferably 15% by mass or less, more further preferably 8.2% by mass or less, particularly preferably 7.8% by mass or less.

When the content is less than 0.5% by mass, there is a concern that the terpolymer does not have physical properties as an objective product. When the content exceeds 18% by mass, there is a concern of occurrence of a decrease in the catalytic activity.

The melt flow rate (MFR) in the propylene-ethylene- 1-butene terpolymer can be controlled using a molecular weight modifier such as hydrogen.

The MFR of the propylene-ethylene- 1-butene terpolymer is set depending on the forming method and use application but is usually 0.1 g/10 minutes or more, preferably 1.0 g/10 minutes or more, further preferably 3.0 g/10 minutes or more, particularly preferably 5.0 g/10 minutes or more and is 100.0 g/10 minutes or less, preferably 50.0 g/10 minutes or less, further preferably 40.0 g/10 minutes or less, particularly preferably 30.0 g/10 minutes or less.

In the case where MFR is less than 0.1 g/10 minutes, the fluidity of the polymer decreases and, in the case where MFR exceeds 100.0 g/10 minutes, it becomes difficult to form a film that is a main use application.

In the present invention, MFR is a value measured under conditions of 230°C and 21.18 N in accordance with the method of JIS-K6921. The hexane-soluble content at 50°C of the propylene-ethylene- 1 -butene terpolymer is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably 0.3% by mass or more and preferably 3.0% by mass or less, more preferably less than 3.0% by mass, further preferably 2.9% by mass or less, more further preferably 2.8% by mass or less.

When the content exceeds 3.0% by mass, there is a concern of an increase in an amount of by-product of a low crystalline polymer that corresponds to the hexane-soluble content at 50°C and, through occurrence of deterioration of powder properties, long-term operation stability may not be obtained. Moreover, in the case of using the terpolymer as a film that is a main use application, there is a concern that the low crystalline polymer bleeds out onto the film surface and the appearance deteriorates.

The melting point (Tm) of the propylene-ethylene- 1-butene terpolymer is preferably 115°C or higher, more preferably 118°C or higher, further preferably 120°C or higher and preferably 145°C or lower, more preferably 143°C or lower, further preferably 140°C or lower. When the melting point is lower than 115°C, in the case of using the terpolymer as a film that is a main use application, there is a concern that the low crystalline polymer bleeds out onto the film surface and the appearance deteriorates. On the other hand, when the melting point becomes 145°C or higher, there is a concern that the heat seal effect is not sufficiently obtained.

The chlorine content of the propylene-ethylene- 1-butene terpolymer is 16 mass ppm or less, preferably 14 mass ppm or less, more preferably less than 9 mass ppm, further preferably 8 mass ppm or less. Since chlorine may cause a decrease in performance, for example, occurrence of operation failure by chlorine when a precision instrument is wrapped with the film, a lower content is more preferable, but the chlorine content may be 3 mass ppm or more, further, may be 4 mass ppm or more. Examples

Explanation will be given below in further detail on the present invention with reference to Examples but, the present invention should not be limited to these Examples.

Measurement methods of individual physical properties in the present invention are shown below.

(Measurement methods of various physical properties)

a) MFR (unit: g/10 minutes):

It was measured in accordance with the method of JIS-K6921 under conditions of 230°C and 21.18 N.

b) Content of a-olefin (% by mass):

It was measured by an infrared absorption spectral method.

c) Melting point (Tm) (unit: °C):

DSC manufactured by Seiko was used and 5.0 mg of a sample was collected. After it was kept at 200°C for 5 minutes, the sample was crystallized at a temperature-lowering rate of 10°C/minute until 40°C. Further, at the time when it was melted at a temperature-raising rate of 10°C/minute, melting peak temperature was taken as Tm.

d) Hexane-soluble content at 50°C (% by mass):

After a film having a thickness described in FDA section 177.1520(d) was prepared as a sample, the measurement was performed in accordance with the method of measuring hexane-soluble content at 50°C described in FDA section 177.1520(d)(3)(ii).

e) Ti content:

As for a catalyst brought into contact with a vinylsilane, the measurement was performed using a colorimetric method. A specific method was as follows:

Apparatus: an ultraviolet visible spectrophotometer UV-1650 manufactured by Shimadzu Corporation

The catalyst were accurately weighed and, after the catalyst was decomposed using sulfuric acid, an aqueous hydrogen peroxide was added thereto to develop color. From absorbance of a filtrate thereof and a calibration curve, the Ti content was determined.

As for a catalyst subjected to pre-polymerization alone, as a pretreatment, the catalyst were accurately weighed and, after the catalyst was decomposed using sulfuric acid and a dilution was carried out, the measurement was performed using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectro-metry). A specific method was as follows:

Apparatus: UOP-1 Mark II manufactured by Kyoto Koken Co., Ltd.

Measurement Condition

High-frequency output: 1.2 kW

Plasma gas: Kind of gas: Ar, Flow rate: 13 L/min

Auxiliary gas: Kind of gas: Ar, Flow rate: 0.8 L/min

Nebulizer gas: Kind of gas: Ar, Flow rate: 0.4 L/min

Observation height: 10 mm above coil

Measurement wavelength: 334.941 nm f) Mg content in catalyst:

As a pretreatment, the catalyst were accurately weighed and, after the catalyst was decomposed using sulfuric acid and a dilution was carried out, the measurement was performed using ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectro-metry). A specific method was as follows:

Apparatus: UOP-1 Mark II manufactured by Kyoto Koken Co., Ltd.

Measurement Condition

High-frequency output: 1.2 kW

Plasma gas: Kind of gas: Ar, Flow rate: 13 L/min

Auxiliary gas: Kind of gas: Ar, Flow rate: 0.8 L/min

Nebulizer gas: Kind of gas: Ar, Flow rate: 0.4 L/min

Observation height: 10 mm above coil

Measurement wavelength: 279.553 nm

g) CI content in catalyst:

As a pretreatment, the catalyst were accurately weighed and, after the catalyst was decomposed using sulfuric acid and a dilution was carried out, the measurement was performed using a silver nitrate titration method.

h) Content of organosilicon compound in catalyst after pre-polymerization after subjected to contact with vinylsilane and organosilicon compound:

Specific apparatus and method are as follows:

Apparatus: a gas chromatograph GC-2014AF manufactured by Shimadzu Corporation

Measuring conditions

Analysis time: 10 minutes

Column temperature: 100°C

Inlet temperature: 200°C

Outlet temperature: 200°C

A catalyst was accurately weighed and was decomposed with methanol. A supernatant thereof was analyzed by the gas chromatograph. Using a calibration curve prepared from standard samples, the concentration of the organosilicon compound in the obtained methanol solution was determined.

From the concentration of the organosilicon compound in the methanol and the mass of the sample, the content of the organosilicon compound contained in the sample was calculated. As for a sample after pre-polymerization, the content was calculated using the mass excluding the preliminary polymerized polymer,

i) CI content in polymer

Specific apparatus and method are as follows:

Apparatus: a scanning fluorescent X-ray analyzer ZSX Primus II manufactured by Rigaku Corporation

Measuring conditions

Tube voltage: 40 kV

Tube current: 90 mA

Detecting 2Θ angle: 89.618°

Integrating time: 60 s

Detector: Flow Proportional Counter

Dispersive crystal: RX9

After mixed with BHT that is an antioxidant, a sample was melted in a hot press to prepare a test piece. Thereafter, it was measured by the above apparatus under the above conditions,

j) Catalytic activity

By a weight-measuring device of a powder silo existing at or after pipelines 6 and 13 in Fig. 1 , a production amount per unit time was measured and a value obtained by dividing the amount by the catalyst feed amount per unit time was taken as catalytic activity.

The activity in the present specification was calculated from a production amount and catalyst feed amount at an operation time after attaining a target polymer composition. With regard to an estimation of a decrease in activity, a case that the activity of from 24 hours to 25 hours after a start of operation is 90% or more of the activity of from 1 hour to 2 hours after a start of operation was estimated as no decrease in activity: "no", and a case that the activity of from 24 hours to 25 hours after a start of operation is less than 90% of the activity of from 1 hour to 2 hours after a start of operation was estimated as a decrease in activity: "yes".

k) Measurement method of generation amount of lumps

Lumps were collected with a vibrating sieve of 4750 μηι disposed before a powder silo existing at or after pipelines 6 and 13 in Fig. 1 and the amount of the lumps contained in the amount of production were measured. Example 1

1 ) Preparation of Component (A)

As the component (Al), THC-C-125 purchased from Toho Titanium Co., Ltd. was used. The analysis of the purchased catalyst component (Al) was performed, and as a result, the component (Al) contained 1.9% by mass of Ti, 20.2% by mass of Mg and 63.7% by mass of CI.

Next, an autoclave with a volume of 20 L, equipped with a stirring apparatus, was sufficiently replaced with nitrogen, into which 100 g of a slurry of the above component (Al) was introduced as a component (Al).

Purified n-heptane was introduced and adjustment was performed so that the concentration of the component (Al) became 25 g/L.

Then, 50 ml of silicon tetrachloride was added thereto and a reaction was performed at 90°C for 1 hr.

A reaction product was sufficiently washed with purified n-heptane.

Thereafter, purified n-heptane was introduced to adjust the liquid level to 4 L. Therein, there was prepared an n-heptane diluted solution of triethylaluminum compound, which contained 30 ml of dimethyldivinylsilane as a vinylsilane compound (component (A2)), 30 ml of diisopropyldimethoxysilane as an organosilicon compound (component (A3)-A3a), and 80 g of triethylaluminum as an organoaluminum compound (component (A4)), and a reaction was performed at 40°C for 2 hr.

A reaction product was sufficiently washed with purified n-heptane and a part of the resulting slurry was sampled and dried.

As an analysis result, the obtained component (A) contained 0.88% by mass of Ti, 8.0%) by mass of diisopropyldimethoxysilane, and 63.7% by mass of chlorine.

2) Pre-polymerization

Using the component (A) obtained in the above, pre-polymerization was performed by the following procedure.

Purified n-heptane was introduced into the above slurry to adjust the concentration of the component (A) so as to be 20 g/L.

After the slurry was cooled to 10°C, there was prepared an n-heptane diluted solution of triethylaluminum, which contained 10 g of triethylaluminum, and 280 g of propylene was fed over a period of 4 hr. After the feed of propylene was completed, the reaction was further continued for 30 minutes.

Then, the vapor phase part was sufficiently replaced with nitrogen and a reaction product was sufficiently washed with purified n-heptane.

The resulting slurry was taken out from the autoclave and vacuum drying was performed to obtain a component (A) after pre-polymerization.

The component (A) after pre-polymerization contained 2.0 g of polypropylene per g of the solid component.

After the component (A) after pre-polymerization was subjected to a slurrying by n-hexane, the amount as used in a continuous operation of about one week was fed to a catalyst feeding tank, and no additional feeding was performed during an operation.

3) First Stage Polymerization Step

Fig. 1 is a schematic view showing an example of a process flow in the case where one horizontal -type polymerization reactor (horizontal -type reactor) in the production method of the present invention. Hereinafter, explanation will be given with reference to the process flow shown in Fig. 1.

Into a horizontal-type polymerization reactor 5 (L/D=4.3, inner volume of 100 L), having a stirring vane, there was continuously fed a catalyst for propylene polymerization which was prepared so that the above component (A) after pre-polymerization was fed with

0.14 g/hr and triethylaluminum as an organoaluminum compound (component (B)) was such an amount as to attain an Al/Mg molar ratio of 10 relative to Mg in the component (A) after pre-polymerization.

The reaction temperature was controlled to 58°C, 61°C, and 64°C from the upstream side at each volume of the polymerization reactor equally divided into three portions.

While maintaining conditions of a reaction pressure of 1.90 MPa and a stirring speed of 28 rpm, hydrogen gas and ethylene were continuously fed from a circulation pipeline 2 and 1-butene from a pipeline 3, so as to maintain hydrogen concentration in the vapor phase in the polymerization reactor at the hydro gen/(ethylene+propylene+ 1-butene) molar ratio shown in Table 1, ethylene concentration at the ethylene/(ethylene+propylene+ 1-butene) molar ratio shown in Table 1, and 1-butene concentration at the l-butene/(ethylene+propylene+ 1-butene) molar ratio shown in Table 1 , thereby adjusting the MF , ethylene content, and 1 -butene content of the first stage polymer.

Reaction heat was removed by vaporization heat of raw material liquefied propylene fed from a pipeline 3. Unreacted gas exhausted from the polymerization reactor was cooled and condensed outside the reactor system through a pipeline 4, to be recycled to the polymerization reactor 5 by a pipeline 3.

A formed polymer of the first stage polymerization was continuously taken out from the polymerization reactor 5 through a pipeline 6 so that a holding level of the polymer of 50% by volume of the reactor volume was attained.

At this time, a part of the polymer was intermittently collected from the pipeline 6 and, after unreacted monomers were removed, the propylene-ethylene- 1 -butene terpolymer was used as a sample for measuring MFR, ethylene content, and 1 -butene content.

The MFR, ethylene content, 1 -butene content, melting point, n-hexane-soluble content at 50°C and chlorine conetnt of the resulting propylene-ethylene- 1 -butene terpolymer were as described in Table 1.

The production speed (production rate) of the propylene-ethylene- 1 -butene terpolymer at this time was about 10 kg/h and catalytic activity of the catalyst for propylene polymerization to be determined from the catalyst feed amount per hour (0.14 g/h) and the production speed of the propylene-ethylene- 1 -butene terpolymer (10 kg/h) was about 79,000 g/g-catalyst. The generation amount of lumps was also small and a decrease in activity during operation did not also occur.

Example 2

Operation was performed under the same conditions as in Example 1 except that the catalyst feed amount, hydrogen concentration, ethylene concentration, and 1 -butene concentration were changed to the conditions described in Table 1, thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1, a terpolymer having a lower melting point as in Example 1 was produced without a decrease in activity while suppressing the generation amount of lumps to 1.0% by mass or less.

Example 3 Operation was performed under the same conditions as in Example 1 except that the catalyst feed amount, hydrogen concentration, ethylene concentration, and 1-butene concentration were changed to the conditions described in Table 1 , thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1, a terpolymer having a further lower melting point than that in Examples 1 and 2 was produced without a decrease in activity while suppressing the generation amount of lumps to 1.0% by mass or less.

Example 4

3) First Stage Polymerization Step

Operation was performed under the same conditions as in Example 3.

4) Second State Polymerization Step

Fig. 2 is a schematic view showing an example of a process flow in the case of using two horizontal-type polymerization reactors in the production method of the present invention. The second stage polymerization step will be explained with reference to the process flow shown in Fig. 2.

Into a horizontal-type polymerization reactor 12 (L/D=4.3, inner volume of 100 L), having a stirring vane, there was received the propylene-ethylene- 1-butene terpolymer from the first stage polymerization tank via a pipeline 8, and under conditions of a stirring speed of 28 rpm, a temperature of 65°C, and a pressure of 1.85 MPa, hydrogen gas and ethylene were continuously fed from a circulation pipeline 9 and 1-butene from a pipeline 10, so as to maintain gas composition in the vapor phase at the hydrogen/(ethylene+propylene+ 1-butene) molar ratio shown in Table 1, ethylene concentration at the ethyl ene/(ethylene+propylene+ 1-butene) molar ratio shown in Table 1, and 1-butene concentration at the 1 -butene/(ethylene+propylene+ 1-butene) molar ratio shown in Table 1, thereby adjusting the MFR, ethylene content, and 1-butene content of the second stage polymer.

The heat of the reaction was removed by the heat of vaporization of raw material liquefied propylene fed from a pipeline 10.

Unreacted gas exhausted from the polymerization reactor was cooled and condensed outside the reactor system through a pipeline 11 , to be recycled to the polymerization reactor 12. A propylene-ethylene- 1 -butene terpolymer formed in the second polymerization step was continuously taken out from the polymerization reactor 12 through a pipeline 13, so that a holding level of the polymer of 50% by volume of the reactor volume was attained.

At this time, a part of the polymer was intermittently collected from the pipeline 13 and, after unreacted monomers were removed, the propylene-ethylene- 1 -butene terpolymer was used as a sample for measuring MFR, ethylene content, and 1 -butene content. The MFR, ethylene content, 1-butene content, melting point, n-hexane-soluble content at 50°C, and chlorine content of the propylene-ethylene- 1-butene terpolymer and the catalytic activity were as described in Table 1.

Example 5

Operation was performed under the same conditions as in Example 1 except that diisopropyldimethoxysilane was fed as an organosilicon compound (component (C)) from the pipeline 1 in Fig. 1 so as to attain an Al/Si molar ratio of 9.0 and the catalyst feed amount, hydrogen concentration, ethylene concentration, and 1 -butene concentration were changed to the conditions described in Table 1, thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1 , a terpolymer having a melting point equal to that in

Example 3 or 4 was produced without a decrease in activity while suppressing the generation amount of lumps to 1.0% by mass or less and a propylene-ethylene- 1-butene terpolymer having a n-hexane-soluble content at 50°C lower than those in Examples 3 and 4 could be produced.

Example 6

Operation was performed under the same conditions as in Example 1 except that diisopropyldimethoxysilane was fed as an organosilicon compound (component (C)) from the pipeline 1 in Fig. 1 so as to attain an Al/Si molar ratio of 11.0 and the catalyst feed amount, hydrogen concentration, ethylene concentration, and 1-butene concentration were changed to the conditions described in Table 1, thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1 , a terpolymer having a melting point equal to that in Example 2 was produced without a decrease in activity while suppressing the generation amount of lumps to 1.0% by mass or less and a propylene-ethylene- 1-butene terpolymer having a n-hexane-soluble content at 50°C lower than that of the polymer in Example 2 could be produced.

Example 7

Operation was performed under the same conditions as in Example 1 except that diisopropyldimethoxysilane was fed as an organosilicon compound (component (C)) from the pipeline 1 in Fig. 1 so as to attain an Al/Si molar ratio of 14.0 and the catalyst feed amount, hydrogen concentration, ethylene concentration, and l.-butene concentration were changed to the conditions described in Table 1, thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1 , a terpolymer having a melting point equal to that in Example 1 was produced without a decrease in activity while suppressing the generation amount of lumps to 1.0% by mass or less and a propylene-ethylene- 1-butene terpolymer having a n-hexane-soluble content at 50°C lower than that of the polymer in Example 1 could be produced.

Example 8

Operation was performed under the same conditions as in Example 1 except that diisopropyldimethoxysilane was fed as an organosilicon compound (component (C)) from the pipeline 1 in Fig. 1 so as to attain an Al/Si molar ratio of 10.0 and, pressure, temperature, the catalyst feed amount, hydrogen concentration, ethylene concentration, and 1-butene concentration were changed to the conditions described in Table 1 , thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1 , a terpolymer having a melting point equal to that in Example 1 was produced without a decrease in activity while suppressing the generation amount of lumps to 1.0% by mass or less and a propylene-ethylene- 1-butene terpolymer having a n-hexane-soluble content at 50°C lower than that of the polymer in Example 1 could be produced while reducing the low crystalline component by decreasing ethylene content. Example 9

Operation was performed under the same conditions as in Example 1 except that diisopropyldimethoxysilane was fed as an organosilicon compound (component (C)) from the pipeline 1 in Fig. 1 so as to attain an Al/Si molar ratio of 10.0 and, pressure, temperature, the catalyst feed amount, hydrogen concentration, ethylene concentration, and 1-butene concentration were changed to the conditions described in Table 1 , thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1 , a terpolymer having a melting point equal to that in Example 2 was produced without a decrease in activity while suppressing the generation amount of lumps to 1.0% by mass or less and a propylene-ethylene- 1 -butene terpolymer having a n-hexane-soluble content at 50°C lower than that of the polymer in Example 2 could be produced while reducing the low crystalline component by decreasing ethylene content.

Example 10

Operation was performed under the same conditions as in Example 1 except that diisopropyldimethoxysilane was fed as an organosilicon compound (component (C)) from the pipeline 1 in Fig. 1 so as to attain an Al/Si molar ratio of 10.0 and, pressure, temperature, the catalyst feed amount, hydrogen concentration, ethylene concentration, and 1-butene concentration were changed to the conditions described in Table 1, thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1, a propylene-ethylene- 1-butene terpolymer having a melting point and a n-hexane-soluble content at 50°C equal to those in Example 1 could be produced without a decrease in activity while suppressing the generation amount of lumps to 1.0% by mass or less.

Example 11

1) Pre-polymerization

Using THC-C-125 purchased from Toho Titanium Co., Ltd. as the component (Α') similar to the Example 1 , pre-polymerization was performed by the following procedure.

An autoclave with a volume of 3 L, equipped with a stirring apparatus, was sufficiently replaced with nitrogen.

Then, 1.5 L of purified n-heptane was added to 90 g of the above component (Α') and the resulting slurry in which the concentration of the component (Α') became 60 g/L was introduced into the autoclave.

There was prepared an n-heptane diluted solution of triethylaluminum, which contained 10 g of triethylaluminum, and 270 g of propylene was fed over a period of 3 hr.

After the feed of propylene was completed, the reaction was further continued for 10 minutes.

The resulting slurry was taken out from the autoclave and a reaction product was sufficiently washed with purified n-heptane. Then, vacuum drying was performed to obtain a component (A) after pre-polymerization.

The component (A) after pre-polymerization contained 2.0 g of polypropylene per g of the solid component.

2) Polymerization Step

Operation was performed under the same conditions as in Example 1 except that diisopropyldimethoxysilane was fed as an organosilicon compound (component (C)) from the pipeline 1 in Fig. 1 so as to attain an Al/Si molar ratio of 1.5 and, the catalyst feed amount, hydrogen concentration, ethylene concentration, and 1-butene concentration were changed to the conditions described in Table 1, thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1, a propylene-ethylene- 1-butene terpolymer having a melting point and a n-hexane-soluble content at 50°C equal to those in Example 2 could be produced while further reducing the generation amount of lumps. Example 12

Operation was performed under the same conditions as in Example 11 except that the catalyst feed amount, hydrogen concentration, ethylene concentration, and 1-butene concentration were changed to the conditions described in Table 1, thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1 , a propylene-ethylene- 1-butene terpolymer having a melting point lower than that in Example 11 could be steadily produced. Example 13

First Stage polymerization Step

Operation was performed under the same conditions as in Example 11 except that the catalyst feed amount, hydrogen concentration, ethylene concentration, and 1-butene concentration were changed to the conditions described in Table 1.

Second Stage polymerization Step

Operation was performed under the same conditions as in Example 4 except that the hydrogen concentration, ethylene concentration, and 1-butene concentration were changed to the conditions described in Table 1 , thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1, a propylene-ethylene- 1-butene terpolymer having a melting point and a n-hexane-soluble content at 50°C equal to those in Example 4 was produced without a decrease in activity while suppressing the generation amount of lumps to 1.0% by mass or less.

Comparative Example 1

1 ) Pre-polymerization

Using THC-C-121 purchased from Toho Titanium Co., Ltd. as the component (Α'), pre-polymerization was performed by the following procedure. The analysis of the purchased catalyst component (Α') was performed, and as a result, the component (Α') contained 2.5% by mass of Ti, 18.6% by mass of Mg and 59.3% by mass of CI.

An autoclave with a volume of 20 L, equipped with a stirring apparatus, was sufficiently replaced with nitrogen, and 100 g of slurry of the above component (Al) was introduced as component (Α'). The concentration of the solid component was adjusted so as to attain 20 g/L by introducing purified n-heptane.

After the slurry was cooled to 10°C, there was prepared an n-heptane diluted solution of triethylaluminum, which contained 10 g of triethylaluminum, and 280 g of propylene was fed over a period of 4 hr.

After the feed of propylene was completed, the reaction was further continued for 30 minutes.

Then, the vapor phase part was sufficiently replaced with nitrogen and a reaction product was sufficiently washed with purified n-heptane.

The resulting slurry was taken out from the autoclave and vacuum drying was performed to obtain a component (Α') after pre-polymerization.

The component (Α') after pre-polymerization contained 1.9 g of polypropylene per g of the solid component. 2) Addition of Organosilicon Compound

After the component (Α') after pre-polymerization was transformed into a slurry with n-hexane, diisopropyldimethoxysilane was added as an organosilicon compound (component (C)) to a catalyst feeding tank in an amount of 11 mmol/L relative to n-hexane and the whole was stirred for 30 minutes to obtain a catalyst component for main polymerization.

3) Polymerization Step

Operation was performed under the same conditions as in Example 1 except that there was added, from the pipeline 1 , a catalyst for propylene polymerization in which triethylaluminum was prepared as an organoaluminum compound (component (B)) so as to attain an Al/Mg molar ratio of 6 relative to Mg in the component (A) after pre-polymerization and diisopropyldimethoxysilane was adjusted as an organosilicon compound (component (C)) so as to attain an Al/Si molar ratio of 1.5 relative to the organoaluminum compound (component (B)) and, the catalyst feed amount, reaction temperature, hydrogen concentration, ethylene concentration, and 1-butene concentration were changed to the conditions described in Table 1, thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1, catalytic activity comparable to that in Example 11 was obtained but a decrease in the activity during the operation occurred. Further, the melting point was comparable to those in Examples 1 , 7, and 10 but and the n-hexane-soluble content at 50°C also increased.

Comparative Example 2

Operation was performed under the same conditions as in Comparative Example 1 except that diisopropyldimethoxysilane was not fed as an organosilicon compound (component (C)) after the component (A ¹ ) after pre-polymerization was transformed into a slurry with n-hexane and the catalyst feed amount, hydrogen concentration, ethylene concentration, and 1 -butene concentration were changed to the conditions described in Table 1 , thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1 , the activity increased as compared with Comparative Example 1 but the n-hexane-soluble content at 50°C also increased. Since the organic silicon donor was not added before the polymerization reactor, the reaction immediately after the introduction into the polymerization reactor was increased and the lump generation rate also remarkably increased. By the increase in the lump generation rate, continuation of the operation was difficult. Comparative Example 3

Operation was performed under the same conditions as in Comparative Example 1 except that the catalyst feed amount, hydrogen concentration, ethylene concentration, and 1-butene concentration were changed to the conditions described in Table 1, thereby obtaining the terpolymer and the catalytic activity of the catalyst for propylene polymerization described in Table 1.

As understood from Table 1, a propylene-ethylene- 1-butene terpolymer having a melting point further lower than that in Example 1 could be produced while suppressing the generation amount of lumps to 1.0% by mass or less, but the n-hexane-soluble content at 50°C was remarkably increased and a propylene-ethylene- 1-butene terpolymer satisfactory as a product could not be produced.

Comparative Example 4

In a state that 220 g of a polypropylene powder of 300 μπ or less was placed as a bed powder in an autoclave with an internal volume of 3 L, equipped with a stirring apparatus and a temperature-controlling apparatus, the autoclave was sufficiently replaced with propylene and then temperature was raised to the polymerization temperature: 65°C described in Table 2. In a state of maintaining the temperature, the catalyst described in Example 1 and triethylaluminum were added so as to attain an Al/Mg molar ratio of 10 relative to Mg in the component (A) after pre-polymerization and then ethylene, hydrogen, and propylene gases were pressurized to the pressure described in Table 2 so as to attain the gas composition described in Table 2, followed by polymerization for 2 hours.

As a result, as described in Table 2, the yield of a powder after the bed powder was removed was 190 g and the catalytic activity was 12,500 g/g-Cat. As understood from Comparative Example 4, even when polymerization was performed using the catalyst to be used in the present invention in a fluid-bed vapor phase reactor, a sufficient activity was not exhibited, and it is difficult to obtain a propylene-ethylene- 1-butene terpolymer having a low chlorine content. Also, the terpolymer is produced in a fluid-bed vapor phase reactor or the like, production costs remarkably increase.

Comparative Example 5

Polymerization was performed under the same conditions as in Comparative Example 4 except that ethylene, hydrogen, propylene gases were changed to the conditions described in Table 2 to obtain the results described in Table 2. As described in Table 2, when a propylene-ethylene- 1-butene terpolymer having a low melting point was polymerized, activity decreases and, since the catalytic activity and production rate are decreased when a propylene-ethylene- 1-butene terpolymer having a low melting point of 130°C or lower is produced in a fluid-bed vapor phase reactor or the like, production costs remarkably increase.

Comparative Example 6

Polymerization of propylene-ethylene- 1-butene terpolymer was performed using a fluidized bed reactor having inner volume of 2, 190 L.

After the reaction temperature, a monomer pressure (absolute pressure) consisting of propylene, ethylene and 1-butene, and superficial gas velocity were controlled to 65°C, 1.90 MPa, and 0.35 m/s, respectively, hydrogen gas and ethylene were continuously fed so as to maintain molar ratios of ethylene concentration, hydrogen concentration, propylene concentration and 1-butene concentration as shown in Table 3.

Further, there was continuously fed the same catalyst for propylene polymerization as in the Example 1 with 2.30 g/hr, which was prepared so that triethylaluminum as an organoaluminum compound (component (B)) was such an amount as to attain an Al/Mg molar ratio of 10 relative to Mg in the component (A) after pre-polymerization.

A powder polymerized in the reactor was continuously extracted to a vessel so as to control a holding powder quantity in the reactor to 40 kg, to obtain propylene-ethylene- 1 -butene terpolymer.

The production speed (production rate) of the propylene-ethylene- 1-butene terpolymer at this time was about 20 kg/h and catalytic activity of the catalyst for propylene polymerization to be determined from the catalyst feed amount per hour (2.3 g/h) and the production speed of the propylene-ethylene- 1 -butene terpolymer (20 kg/h) was about 8,700 g/g-catalyst.

As understood from this result, even when polymerization was performed using the same catalyst as in the Example 1, in a fluid-bed vapor phase reactor, a sufficient activity was not exhibited and it was difficult to obtain a propylene-ethylene- 1 -butene terpolymer having a low chlorine content.

Comparative Example 7

Polymerization was performed under the same conditions as in Comparative Example 6 except that the catalyst feed amount, hydrogen concentration, ethylene concentration, propylene concentration, and 1 -butene concentration were changed to the conditions described in Table 3 to obtain the results described in Table 3.

Since the catalytic activity are greatly decreased when a propylene-ethylene- 1-butene terpolymer having a low melting point of 130°C or lower is produced in a fluid-bed vapor phase reactor, production costs remarkably increase.

[Table 1]

Table 1

Table 1 Continued

[Table 3]

Table 2

[Table 4]

Table 3

Industrial Applicability

According to the present invention, by polymerizing propylene, ethylene, and 1 -butene in the presence of a solid catalyst component (Ziegler-Natta catalyst) containing titanium, magnesium, and chlorine as essential components where titanium content is 0.5% by mass or more and 2.4% by mass or less, as a component (A), and a component (B) or a components (B) and (C), there can be produced a propylene-ethylene- 1 -butene terpolymer wherein a catalyst for propylene polymerization has a high catalyst activity and the hexane-soluble content and chlorine content of the resulting terpolymer are suppressed, and copolymerization properties are excellent. Thus, the present invention is industrially highly applicable.

The present application claims benefit of Japanese Patent Application No. 2017-093990 filed on May 10, 2017; the entire contents of which are incorporated herein by reference.

Reference Signs List 1 : Catalyst component feeding pipeline (pipeline)

2, 9: Raw material mixed gas-feeding pipeline (circulation pipeline)

3, 10: Raw material propylene, 1-butene feeding pipeline (pipeline)

4, 11 : Unreacted gas-extracting pipeline (pipeline)

5, 12: Polymerization reactor (horizontal-type polymerization reactor) 6, 13 : Downstream end of a reactor

7: Gas shutting off tank

8: Upstream end of a reactor