JPH0725946A - Propylene polymer - Google Patents

Abstract

PURPOSE:To obtain a propylene polymer having specific physical properties, exhibiting excellent rigidity, heat-resistance and moistureproofing property and suitable for interior trim of automobile, etc. CONSTITUTION:This polymer has a melt flow rate(MFR) of 0.1-500g/10min at 230 deg.C under 2.16kg load, high stereoregularity determined by the absorption intensity of <13>C-NMR spectrum of a boiling heptane insoluble component, long meso-chain length (length of propylene unit chain having alpha-methyl carbons direction in the same direction) and a crystallinity of the boiling heptane insoluble component of >=60%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a propylene polymer, and more specifically, it has a high crystallinity of a boiling heptane-insoluble component, a high stereoregularity, and an extremely long meso chain (α-methyl carbon). It relates to a propylene polymer having propylene unit chains oriented in the same direction.

[0002]

BACKGROUND OF THE INVENTION Polyolefin such as crystalline polypropylene is a so-called Ziegler consisting of a compound of transition metal of Groups IV to VI of the periodic table and an organometallic compound of metal of Group I to III of the periodic table. It is well known that it can be obtained by polymerizing an olefin using a Natta catalyst. A method for obtaining a highly stereoregular crystalline polyolefin with high polymerization activity using such a catalyst has been studied.

For example, JP-A-61-209207, JP-A-62-104810, JP-A-62-104811, JP-A-62-104810.
-104812, JP 62-104813, JP 1-3111
JP-A No. 06-180180, JP-A No. 1-318011, JP-A No. 2-166104, etc., formed from a titanium-containing solid catalyst component containing titanium, magnesium, halogen and an electron donor, an organoaluminum compound and an electron donor. It is disclosed that when an olefin is polymerized with the catalyst, a polyolefin having high polymerization activity and high stereoregularity can be obtained.

Further, the present applicant has already made many proposals as described below for an olefin polymerization catalyst and an olefin polymerization method for obtaining a highly stereoregular crystalline polyolefin with high polymerization activity. (For example, JP-A-50-108385, JP-A-50-126590, JP-A-50-126590
51-20297, JP-A-51-28189, JP-A-51-645
86, JP-A-51-92885, JP-A-51-136625, JP-A-52-87489, JP-A-52-100596, JP-A-52-147688, JP-A-52-104593,
JP-A-53-2580, JP-A-53-40093, JP-A-5
3-40094, JP-A-53-43094, JP-A-55-1351
02, JP-A-55-135103, JP-A-55-152710, JP-A-56-811, JP-A-56-11908, JP-A-56-18606, JP-A-58-83006, JP-A-58
-138705, JP-A-58-138706, JP-A-58-138
707, JP 58-138708, JP 58-138709
Publication, JP-A-58-138710, JP-A-58-138715, JP-A-58-138720, JP-A-58-138721,
JP-A-58-215408, JP-A-59-47210, JP-A-59-117508, JP-A-59-117509, JP-A-59
-207904, JP 59-206410, JP 59-206
408, JP 59-206407 JP, JP 61-69815 JP, JP 61-69821 JP, JP 61-69822 JP,
JP 61-69823 JP, JP 63-22806 JP, JP Sho
63-95208, JP-A-63-199702, JP-A-63-19
9703, JP 63-202603, JP 63-202604
Publication, JP-A-63-223008, JP-A-63-223009, JP-A-63-264609, JP-A-64-87610,
JP 64-156305 A, JP 2-77407 A, JP
2-84404 JP, JP2-229807 JP, JP2-22980
By the way, crystalline polypropylene has high rigidity and generally has a high heat distortion temperature, melting point, and crystallization temperature, and therefore exhibits excellent heat resistance and a high crystallization rate. , Shows excellent properties such as high transparency. Therefore, it is preferably used for various applications such as containers and films. Since the rigidity and heat resistance of polypropylene increase as the degree of crystallinity increases, polypropylene having a high degree of crystallinity can be used in applications requiring higher rigidity and heat resistance. Further, when it is used for conventional applications, the product can be made thinner and the amount of filler such as talc can be reduced, so that the weight can be reduced.

Conventionally, in crystalline polypropylene, the crystallinity has been increased by blending a core material, etc., but in the conventional crystalline polypropylene, the isotactic pentad value by NMR measurement is about 90 to 95%. Therefore, there is a limit to the improvement of rigidity and heat resistance. Therefore, the advent of crystalline polypropylene having an extremely high isotactic pentad value, that is, crystalline polypropylene having an extremely high stereoregularity is desired.

Further, the conventional film made of crystalline polypropylene does not always have sufficient moisture proof property, so that the rigidity,
The advent of crystalline polypropylene that is excellent not only in heat resistance but also in moisture resistance is desired.

[0007]

OBJECTS OF THE INVENTION It is an object of the present invention to provide a propylene polymer having excellent rigidity and heat resistance as well as excellent moisture resistance.

[0008]

SUMMARY OF THE INVENTION The propylene polymer according to the present invention is 23
The melt flow rate (MFR) at 0 ° C and a load of 2.16 kg is in the range of 0.1 to 500 g / 10 minutes,
The value of the stereoregularity index [M ₅ ] obtained from the absorption intensity of Pmmmm and Pw in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component is 0.970 to 0.9.
¹³ C-NM with boiling heptane insoluble component in the range of 95
Pmmrm, Pmrmr, Pmrrr, Prmr in R spectrum
From the absorption intensities of r, Prmmr, Prrrr, and Pw, the following formula (2)
The value of the stereoregularity index [M ₃ ] obtained by
It is in the range of 20 to 0.0050, and is characterized in that the boiling heptane-insoluble component has a crystallinity of 60% or more.

[0009]

[Equation 3]

(Where Pmmmm is the absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously isotactically bonded, and Pw is the absorption intensity derived from the methyl group of the propylene unit. is there.)

[0011]

[Equation 4]

The propylene polymer according to the present invention contains a polymer having a constitutional unit derived from a compound represented by the following formula (i) or (ii) in an amount of 10 to 10,000 ppm. Is desirable.

[0013]

[Chemical 2]

[0014]

DETAILED DESCRIPTION OF THE INVENTION The propylene polymer according to the present invention will be specifically described below. In the present invention, the term "polymerization" may be used to mean not only homopolymerization but also copolymerization, and the term "polymer" refers to not only homopolymer but also copolymer. May be used in the inclusive sense.

The propylene polymer according to the present invention is a homopolymer of propylene. In such a propylene polymer, it is desirable that the melt flow rate (MFR) at 230 ° C. under a load of 2.16 kg is in the range of 0.1 to 500 g / 10 minutes, preferably 0.2 to 300 g / 10 minutes.

The melt flow rate (MFR) is A
Measured according to STM D1238-65T under the conditions of 230 ° C. and 2.16 kg load. The propylene polymer according to the present invention has a stereoregularity index [M ₅ ] determined by the following formula (1) from the absorption intensities of Pmmmm and Pw in the ¹³ C-NMR spectrum of a boiling heptane-insoluble component of 0.970 to 70.
It is in the range of 0.995, preferably 0.980 to 0.995, and more preferably 0.982 to 0.995.

[0017]

[Equation 5]

(In the formula, [Pmmmm]: Absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously isotactically bonded [Pw]: Absorption intensity derived from the methyl group of propylene unit. Next, the stereoregularity index [M ₅ ] used for evaluating the stereoregularity of the boiling heptane-insoluble component of the propylene polymer according to the present invention will be specifically described.

The propylene homopolymer can be represented, for example, by the following formula (A).

[0020]

[Chemical 3]

¹³ C derived from the methyl group (eg, Me ³ , Me ⁴ ) at the third unit in the propylene unit 5 chain represented by
The absorption intensity at -NMR spectrum and Pmmmm, when the absorption intensity derived from all methyl groups ^{(Me 1, Me 2, Me} 3 ...) in the propylene unit and Pw, polymers represented by the above formula (A) The stereoregularity can be evaluated by the ratio of Pmmmm and Pw, that is, the value [M ₅ ] obtained from the above formula (1).

Therefore, the stereoregularity of the boiling heptane-insoluble component of the propylene polymer according to the present invention is determined by the above formula (1) from the absorption intensity of Pmmmm and Pw in the ¹³ C-NMR spectrum of the insoluble component. It can be evaluated by the value of the sex index [M ₅ ].

In the propylene polymer according to the present invention, the value of the stereoregularity index [M ₅ ] of the boiling heptane-insoluble component determined by the above formula (1) is within the range of 0.970 to 0.995, and Pmmrm, Pmrmr, Pmrrr, Prmrr, P in ¹³ C-NMR spectrum of boiling heptane-insoluble component
The value of the stereoregularity index [M ₃ ] obtained from the absorption intensities of rmmr, Prrrr, and Pw by the following formula (2) is 0.0020 to
0.0050, preferably 0.0023 to 0.0045,
It is more preferably in the range of 0.0025 to 0.0040.

[0024]

[Equation 6]

In the above formula (2), [Pmmrm], [Pmrm]
r], [Pmrrr], [Prmrr], [Prmmr], [Prrr
r] is a methyl group of 5 consecutive propylene units in the chain of propylene units, 3 in the same direction, 2
It shows the absorption intensity derived from the methyl group of the third unit in the propylene unit 5 chain having a structure in which the individual units are oriented in the opposite direction (hereinafter sometimes referred to as “M ₃ structure”). That is, the stereoregularity index [M ₃ ] obtained by the above (2)
The value of indicates the proportion of the M ₃ structure in the propylene unit chain.

The propylene polymer of the present invention has a stereoregularity index [M ₅ ] of the boiling heptane-insoluble component determined by the above formula (1) in the range of 0.970 to 0.995, and the boiling heptane-insoluble component is insoluble. The value of the stereoregularity index [M ₃ ] obtained by the above formula (2) of the component is 0.0020 to 0.0
Since it is in the range of 050, it has an extremely long meso chain (a propylene unit chain in which α-methyl carbon points in the same direction).

Generally, in polypropylene, the smaller the value of the stereoregularity index [M ₃ ] is, the longer the mesochain is. However, when the value of the stereoregularity index [M ₅ ] is extremely large and the value of the stereoregularity index [M ₃ ] is very small, if the values of the stereoregularity index [M ₅ ] are almost the same, The larger the value of the regularity index [M ₃ ] is, the longer the meso chain may be.

[0028] For example a polypropylene having a structure (I) shown below, when compared with polypropylene having the structure (b), the polypropylene represented by the structure (a) having the M ₃ structure, the M ₃ structure It has a longer meso chain than the polypropylene represented by the structure (B) which does not have it. (However, the following structure (a) and structure (b) are
All are assumed to consist of 1003 units of propylene units. )

[0029]

[Chemical 4]

Polypropylene represented by the above structure (a)
Stereoregularity index [M_Five] Is 0.986, and
Stereoregularity index of polypropylene represented by structure (b)
[M _Five] Is 0.985 and is represented by structure (a)
Polypropylene and polypropylene represented by the structure (b)
Ren's stereoregularity index [M_Five] Values are almost equal
is there. However, M₃Table with structure (a) with structure
In the case of polypropylene, the propylene contained in the meso chain
The average len unit is 497 units, and M₃Contains structure
In the polypropylene represented by the non-structure (b),
The average number of propylene units in the chain is 250 units.
It That is, the stereoregularity index [M_Five] Is extremely large
In the case of polypropylene, it is included in the propylene unit chain.
The ratio of the structure shown by r (racemo) is extremely small
Therefore, the structure indicated by r (racemo) is concentrated.
Polypropylene (M₃Polypropylene having a structure
The structure represented by r (racemo) exists in the
Polypropylene (M₃Polypropylene without structure
N) will have a longer meso chain.

The propylene polymer of the present invention is a highly crystalline polypropylene having an M ₃ structure as shown in the above structure (a), and the value of the stereoregularity index [M ₅ ] of the boiling heptane-insoluble component is 0. It is in the range of 0.970 to 0.995, and the value of the stereoregularity index [M ₃ ] of the boiling heptane-insoluble component is in the range of 0.0020 to 0.0050. The propylene polymer of the present invention having such a structure has high rigidity, heat resistance and moisture resistance as compared with the conventional highly crystalline polypropylene, although the reason is not clear.

If the value of the stereoregularity index [M ₃ ] of the boiling heptane-insoluble component deviates from the range of 0.0020 to 0.0050, the above characteristics may be deteriorated. In the present invention, the boiling heptane-insoluble component of the propylene polymer is
It is prepared as follows. That is, with a stirring device 1
In a liter flask, 3 g of polymer sample, 2,6-di tert-
Butyl-4-methylphenol 20mg, n-decane 500
Add ml and heat to dissolve on an oil bath at 145 ° C. After the polymer sample has dissolved, cool to room temperature over about 8 hours,
Then, it is kept on a water bath at 23 ° C. for 8 hours. The n-decane suspension containing the precipitated polymer (decane insoluble component at 23 ° C) was added to G-
After separation by filtration with a 4 (or G-2) glass filter and drying under reduced pressure, 1.5 g of the polymer was subjected to Soxhlet extraction with heptane for 6 hours or longer, and a boiling heptane-insoluble component was used as a sample. The boiling heptane-insoluble component amount of the propylene polymer according to the present invention is usually 80% by weight or more, preferably 90% by weight or more.
The content is preferably at least wt%, more preferably at least 94 wt%, even more preferably at least 95 wt%, particularly preferably at least 96 wt%. The amount of the boiling heptane-insoluble component is 2
The 3 ° C. decane-soluble component is calculated on the assumption that it is also soluble in boiling heptane.

In the present invention, the NMR measurement of the boiling heptane-insoluble component of the propylene polymer is carried out, for example, as follows. That is, 0.35 g of the insoluble component is heated and dissolved in 2.0 ml of hexachlorobutadiene. This solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added, and the solution is placed in an NMR tube having an inner diameter of 10 mm. And JEOL GX-500 type NM
¹³ C-NMR measurement is performed at 120 ° C. using an R measuring device. The number of times of integration is 10,000 or more. The values of the stereoregularity indexes [M ₅ ] and [M ₃ ] can be determined from the peak intensities or the sum of peak intensities based on the respective structures obtained by the above measurement.

The crystallinity of the boiling heptane-insoluble component of the propylene polymer according to the present invention is 60% or more, preferably 6
It is desirable to be 5% or more, and more preferably 70% or more.

The crystallinity is measured as follows.
That is, the sample is 1 mm thick with a pressure molding machine at 180 ° C.
Rotorflex RU3 manufactured by Rigaku Denki Co., Ltd. using a press sheet obtained by immediately cooling with water after molding into a rectangular plate
00 measuring device (output 50 kV, 250 mA). As a measuring method at this time, a transmission method is used, and the measurement is performed while rotating the sample.

The propylene polymer according to the present invention contains a polymer having a constitutional unit derived from a compound represented by the following formula (i) or (ii) in an amount of 10 to 10000 ppm, preferably 100 to 5000 ppm. It is desirable to contain in.

[0037]

[Chemical 5]

In the above formula (i), the cycloalkyl group represented by X includes a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like, and the aryl group includes a phenyl group, a tolyl group, a xylyl group and a naphthyl group. Groups and the like.

In the above formula (i) or (ii),
As the hydrocarbon group represented by R ¹ , R ² and R ³ ,
Examples thereof include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group, an aryl group such as a phenyl group and a naphthyl group, and a norbornyl group. Furthermore, R ¹ ,
The hydrocarbon group represented by R ² and R ³ may contain silicon or halogen.

Specific examples of the compound represented by the above formula (i) or (ii) include 3-methyl-1-butene and 3
-Methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-
1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, allylnaphthalene , Allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalene, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes and the like. Among these, 3-methyl-1-butene, 3-methyl-
1-pentene, 3-ethyl-1-hexene, vinylcyclohexane, allyltrimethylsilane, preferably contains dimethylstyrene and the like, 3-methyl-1-butene,
It is more preferable to contain vinylcyclohexane and allyltrimethylsilane, and it is particularly preferable to contain 3-methyl-1-butene.

The propylene polymer according to the present invention may contain a small amount of a structural unit derived from an olefin other than propylene having 20 or less carbon atoms or a diene compound having 4 to 20 carbon atoms.

As described above, even when the propylene polymer contains a small amount of a monomer component other than propylene, the value of the stereoregularity index [M ₅ ] and the value of the stereoregularity index [M ₃ ] are substantially affected. Does not give.

The propylene polymer according to the present invention has a density of 0.900 to 0.936 g / cm ³ , preferably 0.91.
It is preferably in the range of 0 to 0.936 g / cm ³ . Further, in the propylene polymer according to the present invention, the amount of the decane-soluble component at 23 ° C. is 3.0% or less, preferably 2.5% or less, more preferably 2.0% or less, particularly preferably 1.5%.
% Or less is desirable.

The amount of the 23 ° C. decane-soluble component of the propylene polymer is measured as follows. That is,
In a 1 liter flask equipped with a stirrer, 3 g of the polymer sample,
2,6-di tert-butyl-4-methylphenol 20mg, n-
Add 500 ml of decane and heat to dissolve on an oil bath at 145 ° C. After the polymer sample has dissolved, it is cooled to room temperature over about 8 hours and then held on a 23 ° C. water bath for 8 hours.
The precipitated polymer and the n-decane suspension containing the dissolved polymer are separated by filtration with a G-4 (or G-2) glass filter. The solution obtained is dried at 10 mmHg and 150 ° C. until a constant weight is obtained, and the weight is measured to obtain the amount of the soluble component of the polymer in the mixed solvent, which is calculated as a percentage with respect to the weight of the sample polymer. .

The half-crystallization time at 135 ° C. of the boiling heptane-insoluble component of the propylene polymer according to the present invention is 500 seconds or less, preferably 100 seconds or less, more preferably 80 seconds or less, and particularly preferably 70 seconds or less. Is desirable.

The half crystallization time of the boiling heptane-insoluble component of the propylene polymer at 135 ° C. is measured as follows. That is, by using a differential heat meter manufactured by Perkin Elmer Co., the relationship between the heating value due to the crystallization of the boiling heptane-insoluble component of the polymer at 135 ° C. and the time was measured, until the heating value reached 50% of the total heating value. The time required for crystallization is defined as the half-crystallization time.

In the propylene polymer according to the present invention, the difference between the melting point and the crystallization temperature of the boiling heptane-insoluble component is 45 ° C.
The temperature is preferably 43 ° C or lower, more preferably 40 ° C or lower.

135 ° C. of the propylene polymer according to the present invention
The intrinsic viscosity [η] measured in decalin is usually 30
~ 0.001 dl / g, preferably 10-0.01 dl / g,
Particularly preferably, it is desirable to be in the range of 8 to 0.05 dl / g.

Such a propylene polymer according to the present invention includes, for example, a solid titanium catalyst component (a) containing [Ia] magnesium, titanium, a halogen and an electron donor as essential components, and [II] an organic metal. Catalyst component (b)
If, [III] formula silicon compound represented by (iii) (c) or a compound having two or more ether linkages present through the atom (d) and _{^{R a n Si (OR b)}} 4- _n ... (iii) (In the formula, n is 1, 2 or 3, and when n is 1, R
^a is a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one R ^a is a secondary or tertiary hydrocarbon group, and R ^a is the same or different. R ^b is a hydrocarbon group having 1 to 4 carbon atoms,
When n is 2 or 3, R ^b may be the same or different. In the presence of an olefin polymerization catalyst formed from the above), a solid titanium catalyst component (a) preferably containing [Ib] magnesium, titanium, halogen and an electron donor as essential components, and an organometallic catalyst component (b). A prepolymerization catalyst component obtained by prepolymerizing at least one olefin selected from the olefins represented by the following formula (i) or (ii) in the presence of

[0050]

[Chemical 6]

[II] The organometallic catalyst component (b) and [II
I] Propylene in the presence of an olefin polymerization catalyst formed from the silicon compound (c) represented by the above formula (iii) or the compound (d) having two or more ether bonds existing through a plurality of atoms, It can be produced by polymerizing.

1 and 2 show the steps for preparing an olefin polymerization catalyst used for producing a propylene polymer according to the present invention. Each component forming the olefin polymerization catalyst used for producing the propylene polymer according to the present invention will be specifically described below.

The solid titanium catalyst component (a) can be prepared by bringing the following magnesium compound, titanium compound and electron donor into contact with each other. Specific examples of the titanium compound used for preparing the solid titanium catalyst component (a) include a tetravalent titanium compound represented by the following formula.

Ti (OR) _g X _4-g (In the formula, R is a hydrocarbon group, X is a halogen atom, and g is 0≤g≤4.) As such a titanium compound, Specifically, TiC
Tetrahalogenated titanium such as l ₄ , TiBr ₄ and TiI ₄ ;
Ti (OCH ₃ ) Cl ₃ , Ti (OC ₂ H ₅ ) Cl ₃ , Ti (On-C ₄ H
₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃ , Ti (O-iso-C ₄ H ₉ ) Br ₃
Trihalogenated alkoxy titanium such as; Ti (OCH ₃ )
₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti (On-C ₄ H ₉ ) ₂ Cl ₂ ,
Ti (OC ₂ H ₅₎ dihalogenated dialkoxy titanium, such as _{2 Br 2; Ti (OCH 3} ) 3 Cl, Ti (OC 2 H 5) 3 Cl, Ti
Monohalogenated trialkoxy titanium such as (On-C ₄ H ₉ ) ₃ Cl and Ti (OC ₂ H ₅ ) ₃ Br; Ti (OCH ₃ ) ₄ and Ti (O
_{C 2 H 5) 4, Ti} (On-C 4 H 9) 4, Ti (O-iso-C 4 H 9) 4,
Examples thereof include tetraalkoxy titanium such as Ti (O-2-ethylhexyl) ₄ .

Of these, halogen-containing titanium compounds are preferable, titanium tetrahalides are more preferable, and titanium tetrachloride is particularly preferable. These titanium compounds may be used alone or in combination of two or more. Further, these titanium compounds may be diluted with a hydrocarbon compound or a halogenated hydrocarbon compound.

Examples of the magnesium compound used for preparing the solid titanium catalyst component (a) include a magnesium compound having a reducing property and a magnesium compound having no reducing property.

Examples of the reducing magnesium compound include magnesium compounds having a magnesium-carbon bond or a magnesium-hydrogen bond. Specific examples of such a magnesium compound having a reducing property include dimethyl magnesium, diethyl magnesium, dipropyl magnesium,
Examples include dibutyl magnesium, diamyl magnesium, dihexyl magnesium, didecyl magnesium, ethyl magnesium chloride, propyl magnesium chloride, butyl magnesium chloride, hexyl magnesium chloride, amyl magnesium chloride, butyl ethoxy magnesium, ethyl butyl magnesium, butyl magnesium hydride. it can. These magnesium compounds may be used alone or may form a complex compound with an organic metal compound described later. Further, these magnesium compounds may be liquid, solid, or may be derived by reacting metallic magnesium with a corresponding compound. It can also be derived from magnesium metal using the above method during catalyst preparation.

Specific examples of the magnesium compound having no reducing property include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride;
Alkoxy magnesium halides such as ethoxy magnesium chloride, isopropoxy magnesium chloride, butoxy magnesium chloride, octoxy magnesium chloride;
Allyloxy magnesium halides such as phenoxy magnesium chloride, methylphenoxy magnesium chloride;
Ethoxymagnesium, isopropoxymagnesium,
Butoxy magnesium, n-octoxy magnesium, 2-
Examples thereof include alkoxy magnesium such as ethylhexoxy magnesium; allyoxy magnesium such as phenoxy magnesium and dimethylphenoxy magnesium; magnesium carboxylates such as magnesium laurate and magnesium stearate.

The non-reducing magnesium compound may be a compound derived from the above-mentioned reducing magnesium compound or a compound derived during preparation of the catalyst component. In order to derive a non-reducing magnesium compound from a reducible magnesium compound, for example, a reductive magnesium compound can be used as a halogen, a polysiloxane compound, a halogen-containing silane compound, a halogen-containing aluminum compound, an alcohol, an ester. It may be contacted with a compound having an active carbon-oxygen bond, such as a ketone, an aldehyde or the like.

In the present invention, the magnesium compound may be a complex compound, a complex compound or a complex compound of the above-mentioned magnesium compound with another metal, in addition to the above-mentioned magnesium compound having a reducing property and the magnesium compound having no reducing property. It may be a mixture with a metal compound. Furthermore, you may use the said compound in combination of 2 or more types.

As the magnesium compound used for preparing the solid titanium catalyst component (a), many magnesium compounds other than those mentioned above can be used, but in the finally obtained solid titanium catalyst component (a), , Preferably in the form of a halogen-containing magnesium compound,
Therefore, when a halogen-free magnesium compound is used, it is preferable to react it with a halogen-containing compound during the preparation.

Among the above-mentioned magnesium compounds, a magnesium compound having no reducing property is preferable, a halogen-containing magnesium compound is more preferable, and magnesium chloride, alkoxy magnesium chloride, and aryloxy magnesium chloride are particularly preferable.

The solid titanium catalyst component (a) used in the present invention is formed by contacting the above-mentioned magnesium compound with the above-mentioned titanium compound and electron donor.

Specific examples of the electron donor used in the preparation of the solid titanium catalyst component (a) include the following compounds. Methylamine, ethylamine,
Dimethylamine, diethylamine, ethylenediamine,
Amines such as tetramethylenediamine, hexamethylenediamine, tributylamine, tribenzylamine;
Pyrroles such as pyrrole, methylpyrrole and dimethylpyrrole; pyrroline; pyrrolidine; indole; pyridine, methylpyridine, ethylpyridine, propylpyridine, dimethylpyridine, ethylmethylpyridine, trimethylpyridine, phenylpyridine, benzylpyridine,
Pyridines such as pyridine chloride; nitrogen-containing cyclic compounds such as piperidines, quinolines, isoquinolines; tetrahydrofuran, 1,4-cineole, 1,8-cineole, pinolfuran, methylfuran, dimethylfuran, diphenylfuran, benzofuran, Cyclic oxygen-containing compounds such as coumaran, phthalane, tetrahydropyran, pyran and ditedropyran; methanol, ethanol, propanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol,
C1-C18 alcohols such as oleyl alcohol, benzyl alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, isopropylbenzyl alcohol; phenol, cresol, xylenol, ethylphenol, propylphenol,
Nonylphenol, cumylphenol, naphthol, and other phenols having 6 to 20 carbon atoms which may have a lower alkyl group; acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, acetylacetone, benzoquinone and the like having 3 to 15 carbon atoms Ketones; aldehydes having 2 to 15 carbon atoms such as acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, Ethyl propionate, methyl butyrate, ethyl valerate,
Methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, cyclohexyl benzoate, phenyl benzoate, benzoate Acid benzyl, methyl toluate, ethyl toluate, amyl toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, din-hexyl cyclohexenecarboxylic acid, diethyl nadic acid, tetrahydrophthalic acid Diisopropyl, diethyl phthalate, diisobutyl phthalate, di-n-butyl phthalate,
Di2-ethylhexyl phthalate, γ-butyrolactone, δ-
C2-30 organic acid esters such as valerolactone, coumarin, phthalide, and ethyl carbonate; acid halides having 2 to 15 carbon atoms such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl Ether, isopropyl ether,
Butyl ether, amyl ether, anisole, diphenyl ether epoxy-p-menthane, etc. with 2 to 2 carbon atoms
0 ethers; 2-isopentyl-2-isopropyl-1,3-
Dimethoxypropane, 2,2-isobutyl-1,3-dimethoxypropane, 2,2-isopropyl-1,3-dimethoxypropane, 2-cyclohexylmethyl-2-isopropyl-1,3-dimethoxypropane, 2,2-isopentyl -1,3-dimethoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,
3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 1,2-bis-methoxymethyl-bicyclo
-[2,2,1] -Heptane, diphenyldimethoxysilane, isopropyl-t-butyldimethoxysilane, 2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-isopentyl-
Diethers such as 2-isopropyl-1,3-dimethoxycyclohexane; Acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; Nitriles such as acetonitrile, benzonitrile, tolunitrile; Acetic anhydride, phthalic anhydride, anhydrous An acid anhydride such as benzoic acid is used.

As the electron donor, a silicon compound represented by the general formula (iii) described below can be used. When the titanium compound, the magnesium compound and the electron donor as described above are brought into contact with each other, the carrier compound as described below can be used to prepare the carrier-supported solid titanium catalyst component (a).

Examples of such carrier compounds include Al
₂ O ₃ , SiO ₂ , B ₂ O ₃ , MgO, CaO, TiO ₂ , Z
Examples thereof include resins such as nO, ZnO ₂ , SnO ₂ , BaO, ThO, and a styrene-divinylbenzene copolymer. Among these carrier compounds, SiO ₂ , Al ₂ O ₃ , MgO, ZnO, ZnO _{2 and the} like are preferable.

The above components may be contacted in the presence of other reaction agents such as silicon, phosphorus and aluminum. The solid titanium catalyst component (a) can be produced by bringing the above-mentioned titanium compound, magnesium compound and electron donor into contact with each other, and any known method can be adopted. it can.

A few specific examples of the method for producing the solid titanium catalyst component (a) will be briefly described below. (1) A method in which a solution of a magnesium compound, an electron donor and a hydrocarbon solvent is contact-reacted with an organometallic compound to precipitate a solid, or while being precipitated, a titanium compound is contact-reacted.

(2) A method in which a complex consisting of a magnesium compound and an electron donor is brought into contact with an organometallic compound to cause a reaction, and then a titanium compound is brought into a catalytic reaction. (3) For the contact product between the inorganic carrier and the organic magnesium compound,
A method of catalytically reacting a titanium compound and preferably an electron donor. At this time, the contact product may be previously contact-reacted with a halogen-containing compound and / or an organometallic compound.

(4) A magnesium compound-supported inorganic or organic carrier is obtained from a mixture of a solution containing a magnesium compound, an electron donor, and optionally a hydrocarbon solvent, and an inorganic or organic carrier. How to contact.

(5) magnesium compound, titanium compound,
A method for obtaining a solid titanium catalyst component carrying magnesium and titanium by contacting a solution containing an electron donor, and optionally a hydrocarbon solvent, with an inorganic or organic carrier.

(6) A method in which a liquid state organomagnesium compound is subjected to a catalytic reaction with a halogen-containing titanium compound. At this time, the electron donor is used at least once. (7) A method of contacting a titanium compound after a liquid reaction of an organomagnesium compound with a halogen-containing compound.
At this time, the electron donor is used at least once.

(8) A method of catalytically reacting an alkoxy group-containing magnesium compound with a halogen-containing titanium compound. At this time, the electron donor is used at least once. (9) A method of reacting a complex of an alkoxy group-containing magnesium compound and an electron donor with a titanium compound.

(10) A method in which a complex comprising an alkoxy group-containing magnesium compound and an electron donor is contacted with an organometallic compound and then reacted with a titanium compound. (11) A method of contacting and reacting a magnesium compound, an electron donor, and a titanium compound in any order. In this reaction, each component may be pretreated with an electron donor and / or a reaction aid such as an organometallic compound or a halogen-containing silicon compound. In this method, it is preferable to use the electron donor at least once.

(12) A method of reacting a liquid magnesium compound having no reducing ability with a liquid titanium compound, preferably in the presence of an electron donor, to precipitate a solid magnesium-titanium complex.

(13) A method of further reacting the reaction product obtained in (12) with a titanium compound. (14) A method of further reacting the reaction product obtained in (11) or (12) with an electron donor and a titanium compound.

(15) A method of treating a solid material obtained by pulverizing a magnesium compound, preferably an electron donor and a titanium compound with any of halogen, a halogen compound and an aromatic hydrocarbon. In this method,
It may include a step of pulverizing only the magnesium compound, the complex compound consisting of the magnesium compound and the electron donor, or the magnesium compound and the titanium compound. Further, after pulverization, pretreatment with a reaction auxiliary agent and then treatment with halogen or the like may be performed. Examples of the reaction aid include organic metal compounds and halogen-containing silicon compounds.

(16) A method of pulverizing a magnesium compound and then contacting and reacting with the titanium compound. At this time, it is preferable to use an electron donor or a reaction aid during pulverization and / or contact / reaction.

(17) A method of treating the compound obtained in (11) to (16) above with halogen or a halogen compound or an aromatic hydrocarbon. (18) A method of bringing a contact reaction product of a metal oxide, an organomagnesium and a halogen-containing compound into contact with an electron donor and a titanium compound.

(19) A method of reacting a magnesium compound such as a magnesium salt of an organic acid, alkoxy magnesium, or aryloxy magnesium with a titanium compound and / or a halogen-containing hydrocarbon and preferably an electron donor.

(20) A method of bringing a hydrocarbon solution containing at least a magnesium compound and alkoxytitanium into contact with a titanium compound and / or an electron donor. At this time, it is preferable to coexist with a halogen-containing compound such as a halogen-containing silicon compound.

(21) A liquid magnesium compound having no reducing ability is reacted with an organometallic compound to precipitate a solid magnesium-metal (aluminum) composite,
Then, a method of reacting an electron donor and a titanium compound.

The amount of each component used in preparing the solid titanium catalyst component (a) varies depending on the preparation method and cannot be specified unconditionally. For example, the amount of electron donor is 0.01 per mol of the magnesium compound. It is used in an amount of -10 to 10 mol, preferably 0.1 to 5 mol, and the titanium compound is used in an amount of 0.01 to 1000 mol, preferably 0.1 to 200 mol.

The solid titanium catalyst component (a) thus obtained contains magnesium, titanium, halogen and an electron donor as essential components. In this solid titanium catalyst component (a), the halogen / titanium (atomic ratio) is in the range of about 2-200, preferably about 4-100, and the electron donor / titanium (molar ratio) is about 0.0.
1 to 100, preferably about 0.02 to 10, magnesium / titanium (atomic ratio) is about 1 to 100,
It is desirable that it is preferably in the range of about 2 to 50.

Such solid titanium catalyst component (a)
(Catalyst component [Ia]) is a [Ib] prepolymerization catalyst component obtained by prepolymerizing an olefin in the presence of the solid titanium catalyst component (a) and the following organometallic catalyst component (b). It is desirable to use it for polymerization.

[Ib] As the organometallic catalyst component (b) used for preparing the prepolymerization catalyst component, an organometallic compound of Group I to Group III metal of the periodic table is used, and specifically, Compounds such as

(B-1) General formula R ¹ _m Al (OR ² ) _n H _p X _q (In the formula, R ¹ and R ² are carbonized usually containing 1 to 15, preferably 1 to 4 carbon atoms. Hydrogen groups, which may be the same or different, X represents a halogen atom,
0 <m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ p <3, and q is 0
≦ q <3, and m + n + p + q = 3. ) An organoaluminum compound represented by.

[0088] (b-2) the general formula M ¹ AlR ¹ ₄ (wherein, M ¹ is Li, Na, a K, R ¹ is as defined above.) Group I metals and aluminum represented by Complex alkylated with.

(B-3) General formula R ¹ R ² M ² (wherein R ¹ and R ² are the same as above, and M ² is M
g, Zn or Cd. ) A dialkyl compound of Group II or Group III represented by:

Examples of the organoaluminum compound belonging to the above (b-1) include the following compounds. It is represented by the general formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as defined above, and m is preferably a number of 1.5 ≦ m ≦ 3). A compound, a compound represented by the general formula R ¹ _m AlX _3-m (wherein R ¹ is the same as defined above, X is a halogen, and m is preferably 0 <m <3), Formula R ¹ _m AlH _3-m (In the formula, R ¹ is as defined above, and m is preferably 2 ≦
m <3. ), A compound represented by the general formula R ¹ _m Al (OR ² ) _n X _q (wherein R ¹ and R ² are the same as defined above, X is halogen, 0 <m ≦ 3, 0 ≦ n < 3, 0 ≦ q <3, and m + n + q = 3).

Specific examples of the aluminum compound belonging to (b-1) include trialkylaluminums such as triethylaluminum and tributylaluminum; trialkenylaluminums such as triisoprenylaluminum; diethylaluminum ethoxide and dibutylaluminum butoxide. Dialkyl aluminum alkoxides such as; ethyl aluminum sesquiethoxide,
Butyl aluminum sesquibutoxide and other alkyl aluminum sesquialkoxides; R ¹ _2.5 Al (OR ² )
Partially alkoxylated alkyl aluminum having an average composition represented by _0.5, etc .; Dialkyl aluminum halides such as diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide; ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesqui Alkyl aluminum sesquihalides such as bromide;
Partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide; Dialkyl aluminum hydride such as diethyl aluminum hydride, dibutyl aluminum hydride; ethyl aluminum dihydride, propyl aluminum Alkyl aluminums such as dihydrides Other partially hydrogenated alkyl aluminums such as dihydrides; Partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxycyclolide, ethyl aluminum ethoxy bromide Can be mentioned.

Examples of the compound similar to (b-1) include an organoaluminum compound in which two or more aluminum atoms are bound via an oxygen atom or a nitrogen atom. Examples of such a compound include (C ₂ H ₅ ) ₂ Al
_{OAl (C 2 H 5) 2} , (C 4 H 9) 2 AlOAl (C
_{4 H 9) 2, (C} 2 H 5) 2 AlN (C 2 H 5) Al (C
_{In addition to 2} H ₅ ) _{2 and the} like, aluminoxanes such as methylaluminoxane can be mentioned.

Compounds belonging to the above (b-2) include Li
Examples thereof include Al (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Of these, organoaluminum compounds are preferably used. As the olefin used for preparing the prepolymerization catalyst component [Ib], the compound represented by the above formula (i) or (ii) is preferably used, and specifically, 3-methyl-1-butene, 3-methyl -1-pentene, 3-ethyl
-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3 -Ethyl-1-hexene, allylnaphthalene, allylnorbornane, styrene, dimethylstyrenes, vinylnaphthalene, allyltoluenes, allylbenzene, vinylcyclohexane, vinylcyclopentane, vinylcycloheptane, allyltrialkylsilanes, etc. And an olefin having Among these, 3-methyl-1-butene, 3-methyl-
1-Pentene, 3-ethyl-1-hexene, vinylcyclohexane, allyltrimethylsilane, dimethylstyrene and the like are preferable, 3-methyl-1-butene, vinylcyclohexyne and allyltrimethylsilane are more preferable, and 3-methyl
-1-Butene is particularly preferred.

In addition to these, linear olefins such as ethylene, propylene, 1-butene, 1-octene, 1-hexadecene and 1-eicosene can be used in combination. In the prepolymerization, the catalyst can be used at a much higher concentration than the catalyst concentration in the system in the main polymerization of propylene.

The concentration of the solid titanium catalyst component (a) in the prepolymerization is usually about 0.01-200 mmol, preferably about 0.05-0.5, in terms of titanium atom, per liter of an inert hydrocarbon medium described later. It is preferably in the range of 100 mmol.

The amount of the organometallic catalyst component (b) may be such that 0.1 to 1000 g, preferably 0.3 to 500 g of a polymer is produced per 1 g of the solid titanium catalyst component (a). The amount is usually about 0.1 to 100 mmol, preferably about 0.5 to 50 mmol, per mol of titanium atom in the solid titanium catalyst component (a).

When carrying out the prepolymerization, an electron donor (e) may be used in addition to the solid titanium catalyst component (a) and the organometallic catalyst component (b). As the electron donor (e), specifically, the electron donor used in the preparation of the solid titanium catalyst component (a), the silicon compound (c) represented by the formula (iii) described later, and A compound (d) having two or more ether bonds existing through a plurality of atoms,
Further, an organic silicon compound represented by the following formula (ci) can be given.

R _n Si (OR ′) _4-n ... (ci) (wherein R and R ′ are hydrocarbon groups, and 0 <n <4
It should be noted that the organosilicon compound represented by the formula (ci) does not include the silicon compound (c) represented by the formula (iii) described later.

Specific examples of the organosilicon compound represented by the general formula (ci) include trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diisopropyldimethoxysilane, diphenyldimethoxysilane, Phenylmethyldimethoxysilane, diphenyldiethoxysilane, bis o-tolyldimethoxysilane, bis m-tolyldimethoxysilane, bis p-tolyldimethoxysilane, bis p-tolyldiethoxysilane, bisethylphenyldimethoxysilane, ethyltrimethoxysilane, Ethyltriethoxysilane, vinyltrimethoxysilane, methyltrimethoxysilane, n-propyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane,
Phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, n-butyltriethoxysilane, phenyltriethoxysilane,
γ-aminopropyltriethoxysilane, chlorotriethoxysilane, ethyltriisopropoxysilane, vinyltributoxysilane, ethyl silicate, butyl silicate,
Trimethylphenoxysilane, methyltriaryloxy (a
llyloxy) silane, vinyltris (β-methoxyethoxysilane), vinyltriacetoxysilane, dimethyltetraethoxydisiloxane and the like.

These electron donors (e) can be used alone or in combination of two or more kinds. The electron donor (e) is used in an amount of 0.1 to 50 mol, preferably 0.5 to 3 mol, per mol of titanium atom in the solid titanium catalyst component (a).
It is used in an amount of 0 mol, more preferably 1 to 10 mol.

The prepolymerization is preferably carried out under mild conditions by adding the olefin represented by the above formula (i) or (ii) and the above catalyst component to an inert hydrocarbon medium. Specific examples of the inert hydrocarbon medium used at this time include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene; cyclopentane, cyclohexane, methylcyclopentane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethylene chloride and chlorobenzene; and contact products thereof. Of these inert hydrocarbon media, it is particularly preferable to use aliphatic hydrocarbons.

The reaction temperature in the prepolymerization may be a temperature at which the produced prepolymer does not substantially dissolve in the inert hydrocarbon medium, and is usually about -20 to + 100 ° C, preferably about-. 20 to + 80 ° C, more preferably 0 to +
It is preferably in the range of 40 ° C. In the prepolymerization, a molecular weight modifier such as hydrogen can be used.

It is desirable that the prepolymerization is carried out so that about 0.1 to 1000 g, preferably about 0.3 to 500 g of a polymer is produced per 1 g of the solid titanium catalyst component (a) as described above. If the amount of prepolymerization is too large, the production efficiency of the (co) polymer in the main polymerization may decrease, and fish eyes are likely to occur when a film or the like is formed from the obtained (co) polymer. There is.

Such prepolymerization can be carried out batchwise or continuously. The olefin polymerization catalyst used for producing the propylene polymer according to the present invention comprises the above-mentioned [Ia] solid titanium catalyst component or [Ib] prepolymerization catalyst component,
[II] An organometallic catalyst component and [III] a silicon compound (c) or a compound (d) having two or more ether bonds existing through a plurality of atoms.

As the [II] organometallic catalyst component, the same as the (b) organometallic catalyst component used in the preparation of the above-mentioned [Ib] prepolymerization catalyst component can be used. The [III] silicon compound (c) is a compound represented by the following formula (iii).

[0107] In _{^{R a n -Si- (OR b)}} 4-n ... (iii) ( wherein, n is 1, 2 or 3, when n is 1, R
^a is a secondary or tertiary hydrocarbon group, and when n is 2 or 3, at least one R ^a is a secondary or tertiary hydrocarbon group, and R ^a is the same or different. R ^b is a hydrocarbon group having 1 to 4 carbon atoms,
When n is 2 or 3, R ^b may be the same or different. ) In the silicon compound (c) represented by the formula (iii), the secondary or tertiary hydrocarbon group is a cyclopentyl group, a cyclopentenyl group, a cyclopentadienyl group, a group having these substituents or Si. And a hydrocarbon group in which the carbon adjacent to is a secondary or tertiary carbon group.
More specifically, the substituted cyclopentyl group, 2-methylcyclopentyl group, 3-methylcyclopentyl group, 2-ethylcyclopentyl group, 2-n-butylcyclopentyl group,
2,3-dimethylcyclopentyl group, 2,4-dimethylcyclopentyl group, 2,5-dimethylcyclopentyl group, 2,3-diethylcyclopentyl group, 2,3,4-trimethylcyclopentyl group, 2,3,5-trimethylcyclopentyl group Examples thereof include a cyclopentyl group having an alkyl group such as a group, a 2,3,4-triethylcyclopentyl group, a tetramethylcyclopentyl group, and a tetraethylcyclopentyl group.

The substituted cyclopentenyl group includes 2-methylcyclopentenyl group, 3-methylcyclopentenyl group,
2-ethylcyclopentenyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentenyl group, 2,4-dimethylcyclopentenyl group, 2,5-dimethylcyclopentenyl group, 2,3,4-trimethyl Examples include cyclopentenyl group, cyclopentenyl group having an alkyl group such as 2,3,5-trimethylcyclopentenyl group, 2,3,4-triethylcyclopentenyl group, tetramethylcyclopentenyl group, and tetraethylcyclopentenyl group. it can.

Examples of the substituted cyclopentadienyl group include 2-
Methylcyclopentadienyl group, 3-methylcyclopentadienyl group, 2-ethylcyclopentadienyl group, 2-n-butylcyclopentenyl group, 2,3-dimethylcyclopentadienyl group, 2,4-dimethyl Cyclopentadienyl group, 2,5-
Dimethylcyclopentadienyl group, 2,3-diethylcyclopentadienyl group, 2,3,4-trimethylcyclopentadienyl group, 2,3,5-trimethylcyclopentadienyl group, 2,
3,4-triethylcyclopentadienyl group, 2,3,4,5-tetramethylcyclopentadienyl group, 2,3,4,5-tetraethylcyclopentadienyl group, 1,2,3,4, Examples thereof include a cyclopentadienyl group having an alkyl group such as a 5-pentamethylcyclopentadienyl group and a 1,2,3,4,5-pentaethylcyclopentadienyl group.

Examples of the hydrocarbon group in which the carbon adjacent to Si is a secondary carbon include i-propyl group, s-butyl group, s-amyl group and α-methylbenzyl group. Examples of the hydrocarbon group whose carbon adjacent to is a tertiary carbon include a t-butyl group, a t-amyl group, an α, α′-dimethylbenzyl group, and an admantyl group.

When n is 1, the silicon compound (c) represented by the formula (iii) includes cyclopentyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane, and 2,3-dimethylcyclopentyltrimethoxysilane. Trialkoxysilanes such as silane, cyclopentyltriethoxysilane, iso-butyltriethoxysilane, t-butyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, 2-norbornanetrimethoxysilane, 2-norbornanetriethoxysilane Is exemplified.

When n is 2, dicyclopentyldiethoxysilane, t-butylmethyldimethoxysilane,
Examples of dialkoxysilanes include t-butylmethyldiethoxysilane, t-amylmethyldiethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, and 2-norbornanemethyldimethoxysilane.

When n is 2, the silicon compound (c) represented by the formula (iii) is preferably a dimethoxy compound represented by the following formula (iv).

[0114]

[Chemical 7]

In the formula, R ^a and R ^c are each independently a cyclopentyl group, a substituted cyclopentyl group, a cyclopentenyl group, a substituted cyclopentenyl group, a cyclopentadienyl group, a substituted cyclopentadienyl group, or
A hydrocarbon group in which the carbon adjacent to Si is secondary carbon or tertiary carbon is shown.

Examples of the silicon compound represented by the formula (iv) include dicyclopentyldimethoxysilane, dicyclopentenyldimethoxysilane, dicyclopentadienyldimethoxysilane, di-t-butyldimethoxysilane and di (2- Methylcyclopentyl) dimethoxysilane, di (3-methylcyclopentyl) dimethoxysilane, di (2-ethylcyclopentyl) dimethoxysilane,
Di (2,3-dimethylcyclopentyl) dimethoxysilane,
Di (2,4-dimethylcyclopentyl) dimethoxysilane,
Di (2,5-dimethylcyclopentyl) dimethoxysilane,
Di (2,3-diethylcyclopentyl) dimethoxysilane,
Di (2,3,4-trimethylcyclopentyl) dimethoxysilane, di (2,3,5-trimethylcyclopentyl) dimethoxysilane, di (2,3,4-triethylcyclopentyl) dimethoxysilane, di (tetramethylcyclopentyl) dimethoxysilane , Di (tetraethylcyclopentyl) dimethoxysilane, di (2-methylcyclopentenyl) dimethoxysilane, di (3-methylcyclopentenyl) dimethoxysilane, di (2-ethylcyclopentenyl) dimethoxysilane, di (2-n-butylcyclo) Pentenyl) dimethoxysilane, di (2,3-dimethylcyclopentenyl) dimethoxysilane, di (2,4-dimethylcyclopentenyl) dimethoxysilane, di (2,5-dimethylcyclopentenyl) dimethoxysilane, di (2,3, 4-trimethylcyclopentenyl)
Dimethoxysilane, di (2,3,5-trimethylcyclopentenyl) dimethoxysilane, di (2,3,4-triethylcyclopentenyl) dimethoxysilane, di (tetramethylcyclopentenyl) dimethoxysilane, di (tetraethylcyclopentenyl) dimethoxy Silane, di (2-methylcyclopentadienyl) dimethoxysilane, di (3-methylcyclopentadienyl) dimethoxysilane, di (2-ethylcyclopentadienyl) dimethoxysilane, di (2-n-butylcyclopentenyl) ) Dimethoxysilane, di (2,3-dimethylcyclopentadienyl) dimethoxysilane, di (2,4-dimethylcyclopentadienyl) dimethoxysilane, di (2,5-dimethylcyclopentadienyl) dimethoxysilane, di (2,3-diethylcyclopentadienyl) dimethoxysilane, di (2,3,4-trimethyl) Dicyclopentadienyl) dimethoxysilane, di (2,3,5-trimethylcyclopentadienyl) dimethoxysilane, di (2,3,4-triethylcyclopentadienyl) dimethoxysilane, di (2,3,4 , 5-Tetramethylcyclopentadienyl) dimethoxysilane, di (2,3,4,5-tetraethylcyclopentadienyl) dimethoxysilane, di (1,2,3,4,5-pentamethylcyclopentadienyl) ) Dimethoxysilane, di (1,2,
3,4,5-Pentaethylcyclopentadienyl) dimethoxysilane, di-t-amyl-dimethoxysilane, di (α, α'-dimethylbenzyl) dimethoxysilane, di (admantyl) dimethoxysilane, admantyl-t-butyldimethoxy Examples thereof include silane, cyclopentyl-t-butyldimethoxysilane, diisopropyldimethoxysilane, dis-butyldimethoxysilane, dis-amyldimethoxysilane, and isopropyl-s-butyldimethoxysilane.

When n is 3, tricyclopentylmethoxysilane, tricyclopentylethoxysilane, dicyclopentylmethylmethoxysilane, dicyclopentylethylmethoxysilane, dicyclopentylmethylethoxysilane, cyclopentyldimethylmethoxysilane, cyclopentyldiethylmethoxysilane, Examples include monoalkoxysilanes such as cyclopentyldimethylethoxysilane.

Of these, dimethoxysilanes, particularly dimethoxysilanes represented by the formula (iv), are preferable, and specifically, dicyclopentyldimethoxysilane, di-t-butyldimethoxysilane, di (2-methylcyclopentyl) dimethoxysilane. , Di (3-methylcyclopentyl) dimethoxysilane and di-t-amyldimethoxysilane are preferable.

Two or more kinds of these silicon compounds (c) can be used in combination. In the compound (d) having two or more ether bonds existing through a plurality of atoms used in the present invention (hereinafter sometimes referred to as a polyether compound), the atoms existing between these ether bonds are carbon and silicon. , At least one selected from the group consisting of oxygen, sulfur, phosphorus, and boron, and the number of atoms is 2 or more. Of these, a relatively bulky substituent at an atom between ether bonds, specifically, a substituent having 2 or more carbon atoms, preferably 3 or more, having a linear, branched or cyclic structure, and more preferably a branched substituent. Those in which a substituent having a ring-like or cyclic structure is bonded are desirable. Further, a compound in which a plurality of carbon atoms, preferably 3 to 20, more preferably 3 to 10 and particularly preferably 3 to 7 carbon atoms are contained in an atom existing between two or more ether bonds is preferable.

As such a polyether compound,
For example, a compound represented by the following formula can be given.

[0121]

[Chemical 8]

In the formula, n is an integer of 2 ≦ n ≦ 10, and R
^{1 to} R ²⁶ are carbon, hydrogen, oxygen, halogen, nitrogen, sulfur,
At least one selected from phosphorus, boron and silicon
R ^{1 to} R ²⁶ , preferably R ^{1 to} R ²ⁿ , which are substituents having a certain element, may jointly form a ring other than a benzene ring, and an atom other than carbon in the main chain. May be included.

As the polyether compound as described above,
Specifically, 2- (2-ethylhexyl) -1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane, 2
-Butyl-1,3-dimethoxypropane, 2-s-butyl-1,3-dimethoxypropane, 2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-dimethoxypropane, 2-cumyl-1 , 3-Dimethoxypropane, 2- (2-phenylethyl) -1,3-dimethoxypropane, 2- (2-cyclohexylethyl) -1,3-dimethoxypropane, 2- (p-chlorophenyl) -1,3- Dimethoxypropane, 2- (diphenylmethyl) -1,3-dimethoxypropane, 2- (1-naphthyl) -1,3-
Dimethoxypropane, 2- (2-fluorophenyl) -1,3-
Dimethoxypropane, 2- (1-decahydronaphthyl) -1,3
-Dimethoxypropane, 2- (pt-butylphenyl) -1,3-
Dimethoxypropane, 2,2-dicyclohexyl-1,3-dimethoxypropane, 2,2-dicyclopentyl-1,3-dimethoxypropane, 2,2-diethyl-1,3-dimethoxypropane,
2,2-dipropyl-1,3-dimethoxypropane, 2,2-diisopropyl-1,3-dimethoxypropane, 2,2-dibutyl-1,3-
Dimethoxypropane, 2-methyl-2-propyl-1,3-dimethoxypropane, 2-methyl-2-benzyl-1,3-dimethoxypropane, 2-methyl-2-ethyl-1,3-dimethoxypropane,
2-methyl-2-isopropyl-1,3-dimethoxypropane, 2-
Methyl-2-phenyl-1,3-dimethoxypropane, 2-methyl
-2-Cyclohexyl-1,3-dimethoxypropane, 2,2-bis (p-chlorophenyl) -1,3-dimethoxypropane, 2,2-
Bis (2-cyclohexylethyl) -1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2- (2-ethylhexyl) -1,3-dimethoxypropane, 2 , 2-Diisobutyl-1,3-dimethoxypropane, 2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane, 2,2-bis (cyclohexylmethyl) -1, 3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobutyl-
1,3-dibutoxypropane, 2-isobutyl-2-isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-
Isopropyl-1,3-dimethoxypropane, 2- (1-methylbutyl) -2-s-butyl-1,3-dimethoxypropane, 2,2-di
-s-butyl-1,3-dimethoxypropane, 2,2-di-t-butyl-1,3-dimethoxypropane, 2,2-dineopentyl-1,3-
Dimethoxypropane, 2-isopropyl-2-isopentyl-
1,3-dimethoxypropane, 2-phenyl-2-isopropyl-
1,3-dimethoxypropane, 2-phenyl-2-s-butyl-1,3-
Dimethoxypropane, 2-benzyl-2-isopropyl-1,3-
Dimethoxypropane, 2-benzyl-2-s-butyl-1,3-dimethoxypropane, 2-phenyl-2-benzyl-1,3-dimethoxypropane, 2-cyclopentyl-2-isopropyl-1,3-dimethoxypropane, 2-Cyclopentyl-2-s-butyl-1,3-
Dimethoxypropane, 2-cyclohexyl-2-isopropyl-1,3-dimethoxypropane, 2-cyclohexyl-2-s-butyl-1,3-dimethoxypropane, 2-isopropyl-2-s-butyl-1,3-dimethoxy Propane, 2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2,3-diphenyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,2- Dibenzyl-1,4-diethoxybutane, 2,3-dicyclohexyl-1,4-diethoxybutane, 2,3-diisopropyl-1,4-diethoxybutane, 2,2
-Bis (p-methylphenyl) -1,4-dimethoxybutane, 2,
3-bis (p-chlorophenyl) -1,4-dimethoxybutane,
2,3-bis (p-fluorophenyl) -1,4-dimethoxybutane, 2,4-diphenyl-1,5-dimethoxypentane, 2,5-diphenyl-1,5-dimethoxyhexane, 2,4-diisopropyl -1,5-dimethoxypentane, 2,4-diisobutyl-1,5-dimethoxypentane, 2,4-diisoamyl-1,5-dimethoxypentane, 3-methoxymethyltetrahydrofuran, 3-methoxymethyldioxane, 1,3- Diisobutoxypropane, 1,2-diisobutoxypropane, 1,2-diisobutoxyethane, 1,3-diisoamyloxypropane, 1,3-diisoneopentyloxyethane, 1,3-dineopentyloxypropane , 2,2-tetramethylene-1,3-dimethoxypropane, 2,2
-Pentamethylene-1,3-dimethoxypropane, 2,2-hexamethylene-1,3-dimethoxypropane, 1,2-bis (methoxymethyl) cyclohexane, 2,8-dioxaspiro [5,
5] undecane, 3,7-dioxabicyclo [3,3,1] nonane, 3,7-dioxabicyclo [3,3,0] octane, 3,3-diisobutyl-1,5-oxononane, 6, 6-diisobutyldioxyheptane, 1,1-dimethoxymethylcyclopentane,
1,1-bis (dimethoxymethyl) cyclohexane, 1,1-bis (methoxymethyl) bicyclo [2,2,1] heptane, 1,1
-Dimethoxymethylcyclopentane, 2-methyl-2-methoxymethyl-1,3-dimethoxypropane, 2-cyclohexyl-
2-ethoxymethyl-1,3-diethoxypropane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxypropane,
2,2-diisobutyl-1,3-dimethoxycyclohexane, 2-
Isopropyl-2-isoamyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2-methoxymethyl-1,3-dimethoxycyclohexane, 2-isobutyl-2 -Methoxymethyl-1,3-dimethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-cyclohexyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-isopropyl-2- Ethoxymethyl-1,3-diethoxycyclohexane, 2-isopropyl-
2-ethoxymethyl-1,3-dimethoxycyclohexane, 2-
Isobutyl-2-ethoxymethyl-1,3-diethoxycyclohexane, 2-isobutyl-2-ethoxymethyl-1,3-dimethoxycyclohexane, tris (p-methoxyphenyl) phosphine, methylphenylbis (methoxymethyl) silane, diphenyl Bis (methoxymethyl) silane, methylcyclohexylbis (methoxymethyl) silane, di-t-
Butylbis (methoxymethyl) silane, cyclohexyl
-t-butylbis (methoxymethyl) silane, i-propyl-
Examples thereof include t-butylbis (methoxymethyl) silane.

Of these, 1,3-diethers are preferably used, and particularly 2,2-diisobutyl-1,3-dimethoxypropane, 2-isopropyl-2-isopentyl-1,3-dimethoxypropane, 2,2 2-dicyclohexyl-1,3-dimethoxypropane and 2,2-bis (cyclohexylmethyl) -1,3-dimethoxypropane are preferably used.

These polyether compounds (d) can be used in combination of two or more kinds. Next, the method for producing the propylene polymer according to the present invention will be described. The propylene polymer according to the present invention comprises: [Ia] the solid titanium catalyst component, [II] the organometallic catalyst component, [III] the silicon compound (c) or the polyether compound (of the formula (iii) above. In the presence of an olefin polymerization catalyst formed from (d), preferably [Ib] the prepolymerization catalyst component, [II] the organometallic catalyst component, and [III] the above formula (iii).
It can be obtained by polymerizing propylene (main polymerization) in the presence of an olefin polymerization catalyst formed from the silicon compound (c) or the polyether compound (d) represented by

When propylene is polymerized, a small amount of an olefin other than propylene or a small amount of a diene compound may coexist in the polymerization system in addition to propylene.

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

As the diene compound, 1,3-butadiene,
1,3-pentadiene, 1,4-pentadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 4-methyl-
1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene,
6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl-1,6-octadiene, 6-methyl-1,6-nonadiene, 7-methyl-1,6-nonadiene, 6-ethyl-1,6-nonadiene, 7-ethyl-1,6-nonadiene, 6-methyl-1,6-decadiene, 7-methyl-1,6-decadiene, 6-methyl-1,6-undecadiene, Examples thereof include diene compounds having 4 to 20 carbon atoms such as 1,7-octadiene, 1,9-decadiene, isoprene, butadiene, ethylidene norbornene, vinyl norbornene and dicyclopentadiene.

Polymerization of propylene is usually carried out in a gas phase or a liquid phase. When the polymerization takes the reaction form of slurry polymerization or solution polymerization, the above-mentioned [Ib] is used as the reaction solvent.
Inert hydrocarbons similar to the inert hydrocarbons used to prepare the prepolymerization catalyst component can be used.

In the polymerization system, the above-mentioned [Ia] solid titanium catalyst component or [Ib] prepolymerization catalyst component is the titanium atom in the [Ia] solid titanium catalyst component or [Ib] preliminary per 1 liter of polymerization volume. It is generally used in an amount of about 0.0001 to 50 mmol, preferably about 0.001 to 10 mmol, calculated as titanium atoms in the polymerization catalyst component. In the [II] organometallic catalyst component, the metal atom contained in the [II] organometallic catalyst component is usually about 1 to 2000 mol, preferably about 2 to 500 mol, relative to 1 mol of the titanium atom in the polymerization system. Used in such an amount that Further, the [III] silicon compound (c) or the polyether compound (d) is usually about 0.001 to 50 mol, preferably about 0.001 mol per mol of the metal atom in the [II] organometallic catalyst component.
It is used in an amount such that it is from 01 to 20 mol.

When hydrogen is used during the polymerization, a propylene polymer having a high melt flow rate is obtained, and the molecular weight of the propylene polymer obtained can be adjusted by adjusting the hydrogenation amount. Even in this case, in the present invention, the crystallinity and stereoregularity index of the obtained propylene polymer do not decrease, and the catalytic activity does not decrease.

In the present invention, the polymerization temperature of propylene is usually about -50 to 200 ° C, preferably about 20 to 1
The temperature is 00 ° C., and the pressure is usually atmospheric pressure to 100 kg / cm.
² , preferably about ² to 50 kg / cm ² . The polymerization can be carried out by any of batch method, semi-continuous method and continuous method.

When the propylene polymer is produced in this manner, the yield of the propylene polymer per unit amount of the solid catalyst component can be increased, so that the catalyst residue, particularly the halogen content, in the propylene polymer is relatively increased. Can be reduced to Therefore, the operation of removing the catalyst in the propylene polymer can be omitted, and at the time of molding a molded product using the obtained propylene polymer, rusting of the mold can be easily prevented.

Further, such a propylene polymer has a very small amount of amorphous components and therefore a small amount of hydrocarbon-soluble components, and a film formed from this propylene polymer has a low surface tackiness.

The production of the propylene polymer according to the present invention is
It is also possible to perform the reaction in two or more steps by changing the reaction conditions.
In this case, it is carried out in a gas phase or a liquid phase using 2 to 10 polymerization vessels.

When the polymerization takes the reaction form of slurry polymerization or solution polymerization, an inert hydrocarbon similar to the inert hydrocarbon used in the preparation of the above-mentioned [Ib] prepolymerization catalyst component is used as a reaction solvent. it can.

In such a polymerization method, propylene is polymerized in at least one or more of the above-mentioned two or more polymerization vessels (hereinafter, this polymerization may be referred to as "A polymerization"). Intrinsic viscosity [η] is 3-40
dl / g, preferably 5 to 30 dl / g, particularly preferably 7
~ 25 dl / g polymer is produced.

The isotactic pentad value ([M ₅ ]) determined by NMR measurement of the boiling heptane-insoluble component of the polymer obtained by this A-polymerization was 0.960 to 0.995,
It is preferably 0.970 to 0.995, more preferably 0.9.
980 to 0.995, more preferably 0.982
It is preferably 0.995.

The amount of the boiling heptane-insoluble component in the polymer is 80% or more, preferably 90% or more, more preferably 94% or more, further preferably 95% or more, particularly preferably 96% or more. .

The polymer obtained by such A polymerization is
0.1 to 55 in the propylene polymer finally obtained
%, Preferably 2-35%, particularly preferably 5-30%
It is desirable to be manufactured so that it is present in the ratio of.

When the propylene polymer is produced by using two or more polymerization vessels, propylene is polymerized in the remaining two or more polymerization vessels (hereinafter referred to as "B polymerization"). As a final product, a propylene polymer having a melt flow rate of 0.1 to 500 g / 10 min is obtained.

In the polymerization system of A polymerization and B polymerization, the solid titanium catalyst component [Ia] or [Ib] is used.
The prepolymerization catalyst component is [Ia] per liter of polymerization volume.
Converted to titanium atoms in the solid titanium catalyst component or titanium atoms in the [Ib] prepolymerization catalyst component, it is usually about 0.0001-50 mmol, preferably about 0.001-.
Used in an amount of 10 mmol. Further, the [II] organometallic catalyst component is [I] based on 1 mol of titanium atom in the polymerization system.
I] The metal atom contained in the organometallic catalyst component is usually about 1
~ 2000 mol, preferably about 2-500 mol. Further, the [III] silicon compound (c) or the polyether compound (d) is usually about 0.000 per mol of the metal atom in the [II] organometallic catalyst component.
It is used in an amount of 1 to 50 mol, preferably about 0.01 to 20 mol.

If necessary, in any polymerization vessel, [Ia] solid titanium catalyst component or [Ib] prepolymerization catalyst component, [II] organometallic catalyst component, [III] silicon compound (c) or The polyether compound (d) may be supplied. Further, the electron donor used when preparing the solid titanium catalyst component (a) and / or the organosilicon compound represented by the above formula (ci) may be supplied to any of the polymerization vessels.

In both the A-polymerization and the B-polymerization, the molecular weight of the polymer obtained by supplying or removing hydrogen can be easily adjusted. In this case, in the present invention, the crystallinity and stereoregularity index of the obtained propylene polymer do not decrease, and the catalytic activity does not decrease. The supply amount of hydrogen varies depending on various conditions, but may be such that the melt flow rate of the polymer finally obtained is in the range of 0.1 to 500 g / 10 minutes.

The value of [M ₅ ] of the boiling heptane-insoluble component is 0.975 to 0.995, preferably 0.980.
0.995, more preferably 0.982 to 0.995, and the value of [M ₃ ] is 0.0020 to 0.005.
It may be 0, preferably 0.0023 to 0.0045, and more preferably 0.0025 to 0.0040.

The polymerization temperature of propylene in the A polymerization and the B polymerization is usually about -50 to 200 ° C, preferably 20 to 100 ° C, and the pressure is usually from atmospheric pressure to 10 ° C.
The pressure is set to 0 kg / cm ² , preferably ² to 50 kg / cm ² . The polymerization can be carried out by any of batch method, semi-continuous method and continuous method.

The propylene polymer according to the present invention may contain a nucleating agent as described below. By blending the core material with the propylene polymer, the crystal grains can be made finer, the crystallization rate can be improved, and high-speed molding can be performed.

As the nucleating agent, various conventionally known nucleating agents can be used without particular limitation. Among them, as preferable nucleating agents, the following nucleating agents can be exemplified.

[0149]

[Chemical 9]

(In the formula, R ¹ is oxygen, sulfur, or a hydrocarbon group having 1 to 10 carbon atoms, R ² and R ³ are hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ^{3 s} may be the same or different, R ^{2 s} , R ^{3 s,} or R ^{2 s} and R ^{3 s} may be bonded to form a ring, and M is
It is a monovalent metal atom, and n is an integer of 1 to 3. ) Specifically, sodium-2,2'-methylene-bis (4,6-di-
t-Butylphenyl) phosphate, sodium-2,2'-
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis- (4,6-di-t-butylphenyl) phosphate, lithium-2,2 ' -Ethylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-ethylidene-bis (4-i-propyl-
6-t-Butylphenyl) phosphate, lithium-2,2'-
Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, lithium-2,2'-methylene-bis (4-ethyl-6-
t-Butylphenyl) phosphate, calcium-bis [2,2'-thiobis (4-methyl-6-t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis (4-ethyl-6) -t-butylphenyl) phosphate], calcium-bis [2,2'-thiobis- (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2'-thiobis (4, 6-di-t-butylphenyl) phosphate],
Magnesium-bis [2,2'-thiobis- (4-t-octylphenyl) phosphate], sodium-2,2'-butylidene-bis (4,6-di-methylphenyl) phosphate, sodium-2, 2'-butylidene-bis (4,6-di-t-butylphenyl) phosphate, sodium-2,2'-t-octylmethylene-bis (4,6-di-methylphenyl) phosphate, sodium-2 , 2'-t-octylmethylene-bis (4,6-
Di-t-butylphenyl) phosphate, calcium-
Bis- (2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate), magnesium-bis [2,2'-methylene-bis (4,6-di-t-butylphenyl) ) Phosphate], barium-bis [2,2'-methylene-bis (4,6-di-t-
Butylphenyl) phosphate], sodium-2,2'-
Methylene-bis (4-methyl-6-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4-ethyl-
6-t-Butylphenyl) phosphate, sodium (4,
4'-dimethyl-5,6'-di-t-butyl-2,2'-biphenyl) phosphate, calcium-bis [(4,4'-dimethyl-6,6'-
Di-t-butyl-2,2'-biphenyl) phosphate], sodium-2,2'-ethylidene-bis (4-m-butyl-6-t-butylphenyl) phosphate, sodium-2,2 ' -Methylene-bis (4,6-di-methylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-ethylphenyl) phosphate, potassium-2,2'-ethylidene-bis (4,6-Di-t-butylphenyl) phosphate, calcium-bis [2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate], magnesium-bis [2,2 ' -
Ethylidene-bis (4,6-di-t-butylphenyl) phosphate], barium-bis [2,2'-ethylidene-bis (4,6
-Di-t-butylphenyl) phosphate], aluminum-tris [2,2'-methylene-bis (4,6-di-t-butylfel) phosphate] and aluminum-tris [2,
2′-Ethylidene-bis (4,6-di-t-butylphenyl) phosphate] and mixtures of two or more thereof. Particularly preferred is sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate.

[0151]

[Chemical 10]

(In the formula, R ⁴ is hydrogen or has 1 to 1 carbon atoms.
It is a hydrocarbon group of 0, M is a metal atom with a valence of 1 to 3, and n is an integer of 1 to 3. ) Specifically, sodium-bis (4-t-butylphenyl)
Phosphate, sodium-bis (4-methylphenyl) phosphate, sodium-bis (4-ethylphenyl) phosphate, sodium-bis (4-i-propylphenyl) phosphate, sodium-bis (4-t-
Octylphenyl) phosphate, potassium-bis (4
-t-Butylphenyl) phosphate, calcium-bis (4-t-butylphenyl) phosphate, magnesium
-Bis (4-t-butylphenyl) phosphate, lithium-bis (4-t-butylphenyl) phosphate, aluminum-bis (4-t-butylphenyl) phosphate and mixtures of two or more thereof can do. Particularly, sodium-bis (4-t-butylphenyl) phosphate is preferable.

[0153]

[Chemical 11]

(In the formula, R ⁵ is hydrogen or has 1 to 1 carbon atoms.
It is a hydrocarbon group of 0. ) Specifically, 1,3,2,4-dibenzylidene sorbitol, 1,
3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3- p-Ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4
-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-methylbenzylidene sorbitol,
1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,
3,2,4-di (p-ethylbenzylidene) sorbitol, 1,3,
2,4-di (pn-propylbenzylidene) sorbitol, 1,
3,2,4-di (pi-propylbenzylidene) sorbitol,
1,3,2,4-di (pn-butylbenzylidene) sorbitol,
1,3,2,4-di (ps-butylbenzylidene) sorbitol,
1,3,2,4-di (pt-butylbenzylidene) sorbitol,
1,3,2,4-di (2 ', 4'-dimethylbenzylidene) sorbitol, 1,3,2,4-di (p-methoxybenzylidene) sorbitol, 1,3,2,4-di (p- Ethoxybenzylidene) sorbitol, 1,3-benzylidene-2-4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4- p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-
Methylbenzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di (p-chlorobenzylidene) sorbitol and these And a mixture of two or more of 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di (p-methylbenzylidene) sorbitol, 1,3,2,4-di ( p-Ethylbenzylidene) sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3,2,4-di (p-chlorobenzylidene) sorbitol, and mixtures of two or more thereof. Is preferred.

Examples of the other nucleating agent include metal salts of aromatic carboxylic acids and aliphatic carboxylic acids.
Aluminum benzoate, aluminum pt-butylbenzoate, sodium adipate, sodium thiophenecarboxylate, sodium pyrrolecarboxylate and the like can be mentioned.

Inorganic compounds such as talc described later can also be exemplified. In the propylene polymer according to the present invention, the nucleating agent is 0.001 to 10 parts by weight, preferably 0.001 part by weight, based on 100 parts by weight of the propylene polymer.
It is desirable that the blending amount be 01 to 5 parts by weight, particularly preferably 0.1 to 3 parts by weight.

By blending the nucleating agent in the above amount in the propylene polymer, a propylene polymer having fine crystal particles and improved crystallinity can be obtained without impairing the excellent characteristics originally possessed by the propylene polymer. To be

The propylene polymer according to the present invention contains a rubber component for improving impact strength, a heat stabilizer, a weather stabilizer, an antistatic agent, a slip agent, an antiblocking agent, an antifog agent and a lubricant. , Dyes, pigments, natural oils, synthetic oils, waxes and the like can be added, and the mixing ratio is an appropriate amount.

Further, to the extent that the object of the present invention is not impaired, propylene polymer is added to silica, diatomaceous earth, alumina, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate. , Dolomite, calcium sulfate, potassium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass fiber, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, molybdenum sulfide, boron Fillers such as fibers, silicon carbide fibers, polyethylene fibers, polypropylene fibers, polyester fibers and polyamide fibers may be blended.

Such a propylene polymer of the present invention is
It is used without particular limitation in the fields where polypropylene has been used conventionally, but it is particularly preferably used for applications such as an extruded sheet, an unstretched film, a stretched film, a filament, an injection molded product, and a blow molded product.

The shape and product type of the extruded product made of the propylene polymer of the present invention are not particularly limited, but specifically, a sheet, a film (unstretched film), a pipe, a hose, a wire coating, a filament and the like can be used. Named
It is particularly preferably used as a sheet, a film (unstretched film), a filament and the like.

When extrusion-molding a sheet, film (unstretched film) or the like from the propylene polymer of the present invention,
A conventionally known extrusion device can be used. For example,
It can be produced by extruding a molten propylene polymer from a T-die using a single screw extruder, kneading extruder, ram extruder, gear extruder or the like. Further, as the molding conditions, conventionally known conditions can be adopted.

Such an extruded sheet or film (unstretched film) is excellent in rigidity and heat resistance and is also excellent in moisture resistance. The stretched film can be produced using a sheet or film made of the above-mentioned propylene polymer by a conventionally known stretching device. For example, a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), simultaneous biaxial stretching method, uniaxial stretching method and the like can be mentioned. The stretching ratio of the stretched film is usually 20 to 70 in the case of a biaxially stretched film.
It is preferably double, and in the case of a uniaxially stretched film, usually 2 to 10 times. Further, the thickness of the stretched film is usually preferably 5 to 200 μm.

Such a stretched film has excellent rigidity and heat resistance as well as moisture resistance. An inflation film can also be produced from the propylene polymer of the present invention.

The sheet, unstretched film and stretched film made of the propylene polymer of the present invention are excellent in heat resistance, transparency, see-through property, gloss, rigidity, moisture resistance, gas barrier property, etc. It can be widely used for Especially, because of its excellent moisture resistance, it is a press-through pack (pr
Suitable for ess through pack).

The filament made of the propylene polymer of the present invention can be produced, for example, by extruding a molten propylene polymer through a spinneret. The filament thus obtained may be further stretched. The extent of this stretching may be such that the propylene polymer is effectively imparted with at least uniaxial molecular orientation, and the stretching ratio is usually preferably 5 to 10 times.

Such a filament has excellent rigidity and heat resistance. The injection-molded article made of the propylene polymer of the present invention can be produced by a conventionally known injection-molding apparatus. Further, as the molding conditions, conventionally known conditions can be adopted. Such an injection-molded article is excellent in rigidity, heat resistance, impact resistance, surface gloss, chemical resistance, abrasion resistance, etc., and is used for automobile interior trim materials, automobile exterior materials,
It can be widely used in housings and containers for home appliances.

The blow molded product of the propylene polymer of the present invention can be manufactured by a conventionally known blow molding device. Further, as the molding conditions, conventionally known conditions can be adopted. For example, in the case of extrusion blow molding,
A tubular parison is extruded from a die in a molten state at a resin temperature of 100 ° C to 300 ° C, and then the parison is held in a mold having a shape to be imparted, and then air is blown into the resin to make the resin temperature 130 ° C to 300 ° C. Then, it is attached to a mold to obtain a hollow molded product. The draw ratio is 1.5 to the transverse direction.
It is desirable to be 5 times.

In the case of injection blow molding, the resin temperature is 10
The propylene polymer is injected into a mold at 0 ° C. to 300 ° C. to form a parison, and then the parison is held in a mold having a shape to be imparted, and then air is blown into the mold to obtain a resin temperature of 120.
It is attached to a mold at a temperature of ℃ to 300 ℃ to obtain a hollow molded article. The stretching ratio is preferably 1.1 to 1.8 times in the machine direction and 1.3 to 2.5 times in the cross direction.

Such a blow-molded article is excellent in rigidity and heat resistance, and is also excellent in moisture resistance. The propylene polymer of the present invention can be used as a base material in a method (mold stamping molding) for producing a molded body in which the skin material and the base material are simultaneously press-molded to form a composite and integrated body. The mold stamping molding obtained by this molding method is suitably used as an interior material for automobiles such as door trim, rear package trim, seat back garnish, instrument panel and the like.

Such a mold stamping molding has excellent rigidity and heat resistance.

[0172]

EFFECT OF THE INVENTION The propylene polymer according to the present invention has high crystallinity of the boiling heptane-insoluble component, high stereoregularity, and a long meso chain. Along with being excellent, it has excellent moisture resistance.

[0173]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited to these examples.

[0174]

Example 1 [Preparation of Solid Titanium Catalyst Component (A)] 95.2 g of anhydrous magnesium chloride, 442 ml of decane and 390.6 g of 2-ethylhexyl alcohol were heated at 130 ° C. for 2 hours to prepare a uniform solution. Phthalic anhydride 2 in solution
1.3 g was added, and the mixture was further stirred and mixed at 130 ° C. for 1 hour to dissolve phthalic anhydride. After cooling the homogeneous solution thus obtained to room temperature,
5 ml was added dropwise to 200 ml of titanium tetrachloride kept at -20 DEG C. over 1 hour. After the charging is completed, the temperature of this mixed solution is raised to 110 ° C. over 4 hours to reach 110 ° C.
Diisobutyl phthalate (DIBP)
5.22 g was added, and the mixture was kept stirring at the same temperature for 2 hours. After the completion of the reaction for 2 hours, a solid part was collected by hot filtration, and the solid part was resuspended in 275 ml of titanium tetrachloride, and then heated and reacted again at 110 ° C. for 2 hours. After completion of the reaction, the solid part was collected again by hot filtration, and thoroughly washed with decane and hexane at 110 ° C. until no free titanium compound was detected in the solution. The solid titanium catalyst component (A) prepared by the above operation was stored as a decane slurry, and a part of this was dried for the purpose of examining the catalyst composition. The composition of the solid titanium catalyst component (A) thus obtained is titanium; 2.4% by weight,
Chlorine; 60% by weight, magnesium; 20% by weight, DIB
P; 13.0% by weight.

[Preliminary Polymerization of Solid Titanium Catalyst Component (A)] Purified hexane (500 ml) and 3-methyl-1-butene (57.5) were placed in a 2-liter autoclave equipped with a stirrer under a nitrogen atmosphere.
After adding 50 g of triethylaluminum, 50 mmol of trimethylmethoxysilane, and 5.0 mmol of the above solid titanium catalyst component (A) in terms of titanium atom, the reaction was carried out for 2 hours. The polymerization temperature was kept at 20 ° C.

After completion of the reaction, the inside of the reactor was replaced with nitrogen, and the washing operation consisting of removal of the supernatant and addition of purified hexane was carried out 3 times, and then resuspended in purified hexane to transfer the whole amount to a catalyst bottle. Thus, 5.7 g of poly-3-methyl-1-butene was produced per 1 g of the solid titanium catalyst component (A), which was the prepolymerized catalyst (B).

[Polymerization] An autoclave having an internal volume of 2 liters was charged with 750 ml of purified n-hexane, and 0.75 mmol of triethylaluminum and dicyclopentyldimethoxysilane (DCPM) were added in a propylene atmosphere at 60 ° C.
S) (0.75 mmol) and the prepolymerization catalyst (B) were charged in an amount of 0.015 mmol Ti in terms of titanium atom.

After introducing 1200 ml of hydrogen and raising the temperature to 70 ° C., this was kept for 2 hours to carry out propylene polymerization. The pressure during the polymerization was kept at 7 kg / cm ² -G. After completion of the polymerization, the slurry containing the produced solid was filtered to separate a white powder and a liquid phase part. The yield of the white powdery polymer after drying is 3
03.2 g, MFR was 12.5 g / 10 minutes, and apparent bulk specific gravity was 0.45 g / ml. Further, the obtained white powder was once dissolved in decane, and then slowly cooled to obtain a powder having a boiling heptane-insoluble component ratio of 96.9% and a boiling heptane-insoluble component crystallinity of 71.0%. It was

On the other hand, the liquid phase portion was concentrated to obtain 2.0 g of a solvent-soluble polymer. Therefore, the activity is 20,300 g-
It was PP / mM-Ti, and the boiling heptane-insoluble component ratio in the whole was 96.3%. The results are shown in Table 1.

[0180]

Example 2 Example 1 except that the polymerization temperature was 80 ° C.
Polymerization was carried out in the same manner as in. The results are shown in Table 1.

[0181]

Example 3 Example 1 except that the polymerization temperature was 90 ° C.
Polymerization was carried out in the same manner as in. The results are shown in Table 1.

[0182]

Example 4 [Polymerization] An autoclave having an internal volume of 2 liters was charged with 500 g of propylene and 6 liters of hydrogen, heated to 60 ° C., 0.6 mmol of triethylaluminum, 0 of dicyclopentyldimethoxysilane (DCPMS). 0.6 mmol and the prepolymerization catalyst (B) were charged in an amount of 0.006 mmol Ti in terms of titanium atom.

After the temperature was raised to 70 ° C., this was kept for 40 minutes to carry out propylene polymerization. The reaction was completed by adding a small amount of ethanol, the unreacted propylene was depressurized, and the white powdery polymer was dried under reduced pressure. The polymerization results are shown in Table 1.

[0184]

Example 5 Example 4 except that the polymerization temperature was 80 ° C.
Polymerization was carried out in the same manner as in. The results are shown in Table 1.

[0185]

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 except that 0.075 mmol of cyclopentylmethyldimethoxysilane was used instead of DCPMS and 500 ml of hydrogen was added. The results are shown in Table 1.

[0186]

Comparative Example 2 In place of DCPMS, 0.075 mmol of diphenyldimethoxysilane was used, and 700 ml of hydrogen was added.
Polymerization was carried out in the same manner as in Example 1 except that the components were added. The results are shown in Table 1.

[0187]

[Comparative Example 3] [Preparation of solid titanium catalyst component (C)] n-hexane 50
1.2 mol of diisoamyl ether was added dropwise to 0 ml of 0.5 mol of diethylaluminum chloride at 25 ° C. over 2 minutes, and the mixture was reacted for 10 minutes.

4.0 mol of titanium tetrachloride was added to a 2 liter reactor purged with nitrogen, the temperature was raised to 35 ° C., the above reaction solution was added dropwise thereto over 3 hours, and the temperature was kept at the same temperature for 30 minutes. I kept it. Then, the temperature was raised to 75 ° C. and the reaction was further performed for 1 hour. This was cooled to room temperature, the supernatant was removed, and then 1 liter of hexane was added to wash the produced solid. This washing operation was repeated three more times.

100 g of the obtained solid was added to n-hexane 2
Suspended in liter, 20 ℃ diisoamyl ether 80
g and 180 g of titanium tetrachloride were added at room temperature for 1 minute and reacted at 65 ° C. for 1 hour. After completion of the reaction, the mixture was cooled to room temperature, the supernatant was removed by decantation, and 2 liters of hexane was added to wash the produced solid. Then
This washing operation was repeated 3 times to obtain a solid titanium catalyst component (C).

[Prepolymerization of solid titanium catalyst component (C)] To a 2 liter autoclave equipped with a stirrer, 1 liter of purified hexane, 30 mmol of diethylaluminum chloride and 3 g of the above solid titanium catalyst component (C) were added under a nitrogen atmosphere. Then add 2 liters of hydrogen,
Propylene was fed to the reactor to carry out prepolymerization for 5 minutes. The pressure during the reaction was kept at 5 kg / cm ² -G.

After completion of the reaction, unreacted propylene and hydrogen were removed, the inside of the reactor was replaced with nitrogen, and the washing operation consisting of removal of the supernatant and addition of purified hexane was repeated 3 times to carry out prepolymerization catalyst (D). Got The prepolymerized catalyst (D) was resuspended with purified decane and stored.

[Polymerization] 750 ml of purified n-hexane was charged into an autoclave with a stirrer having an internal volume of 2 liters,
In a propylene atmosphere at 0 ° C., 0.75 mmol of diethylaluminum chloride, 0.75 mmol of methyl p-toluate and 1.1 g of the prepolymerization catalyst (D) were charged.

After introducing 8 liters of hydrogen and raising the temperature to 70 ° C., this was kept for 4 hours to polymerize propylene. The pressure during the polymerization was kept at 7 kg / cm ² -G. After completion of the polymerization, 200 ml of methanol was added and the temperature was raised to 80 ° C. After 30 minutes, 1 ml of a 20% aqueous sodium hydroxide solution was added and the pressure was released.

After removing the aqueous phase, deionized water is added to 300 m.
l In addition, it was washed with water for 20 minutes, the aqueous phase was extracted, and then the hexane slurry was filtered, washed and dried to obtain polypropylene powder. The results are shown in Table 1.

[0195]

[Table 1]

[Brief description of drawings]

FIG. 1 is an explanatory view showing a process for preparing an olefin polymerization catalyst used for producing a propylene polymer according to the present invention.

FIG. 2 is an explanatory view showing a process for preparing an olefin polymerization catalyst used for producing a propylene polymer according to the present invention.

Claims (2)

[Claims] 1. A melt flow rate (MFR) at 230 ° C. under a load of 2.16 kg of 0.1 to 500 g / 10.
The value of the stereoregularity index [M ₅ ] obtained from the absorption intensity of Pmmmm and Pw in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component by the following formula (1) is 0.970 to 0.9.
In the range of 95, Pmmrm, Pmrmr, Pmrrr, Prmrr, Prmmr, Prrrr in the ¹³ C-NMR spectrum of the boiling heptane-insoluble component
The value of stereoregularity index [M ₃ ] obtained from the absorption intensity of Pw by the following formula (2) is in the range of 0.0020 to 0.0050, and the crystallinity of the boiling heptane-insoluble component is 60% or more. A propylene polymer characterized by the following; (In the formula, [Pmmmm]: absorption intensity derived from the methyl group of the third unit at the site where 5 units of propylene units are continuously isotactically bonded, [Pw]: absorption intensity derived from the methyl group of propylene unit. (2) 2. A polymer comprising a structural unit derived from a compound represented by the following formula (i) or (ii) is 10 to 1
The propylene polymer according to claim 1, which is contained in an amount in the range of 0000 ppm;