JP2677920B2 - Propylene-ethylene / butene block copolymer and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene-ethylene / butene block copolymer which is excellent in flexibility and transparency and has no stickiness.

[0002]

2. Description of the Related Art A conventional molded article made of ethylene-propylene rubber (hereinafter abbreviated as "EPR") has a problem that it has a sticky feeling. The EPR obtained by the polymerization of ethylene and propylene is a lump,
There was a defect that was difficult to handle. In order to solve the above problems, it has been proposed to increase the molecular weight of EPR.
However, the molded article made of this high molecular weight EPR has
There is a problem that heat resistance, moldability and mechanical strength are not sufficient.

Therefore, in order to solve the above problems, E
It is known to blend polypropylene with PR.

[0004]

[Problems to be Solved by the Invention] However, EPR
A molded article made of a mixture of polypropylene and polypropylene is white or milky white and is inferior in transparency as compared with other resins having equivalent flexibility such as linear low density polyethylene and soft polyvinyl chloride. Therefore, the above mixture of EPR and polypropylene cannot be used as a material for molded articles such as containers, sheets and films which are required to have transparency.

Therefore, the development of a material having good properties possessed by a mixture of EPR and polypropylene and having excellent transparency has been an issue.

[0006]

Means for Solving the Problems As a result of intensive research conducted by the inventors for the purpose of solving the above problems,
It was found that a propylene-ethylene / butene-based block copolymer containing a block component composed of a propylene-ethylene copolymer and a block component composed of polybutene is a material capable of achieving the object, and completed the present invention. Came to do.

That is, in the present invention, when the total polymer weight is 100% by weight, the block component (X) made of polybutene is 0.1 to 10% by weight, and the block component (Y) made of polypropylene is 0 to 30%. 60% by weight of the block component (Z) comprising a propylene-ethylene random copolymer having 15 to 60 mol% of ethylene monomer units and 85 to 40 mol% of propylene monomer units.
9.9% by weight, the weight average molecular weight is 600,000 or more, and the content of components having a molecular weight of 10,000 or less is 1.0% by weight.
The following is a powdery propylene-ethylene / butene-based block copolymer that is not substantially melt-processed or solution-processed. In the following, the propylene-ethylene / butene-based block copolymer may be abbreviated as "PE / B block copolymer".

The PE / B block copolymer of the present invention is
A block component consisting essentially of the above polybutene (hereinafter also referred to simply as "component X") and a block component consisting of a propylene-ethylene random copolymer having the above-mentioned specific composition (hereinafter also referred to simply as "component Z"). Each of the blocks). That is, when these block components are respectively X and Z, the PE / B block copolymer of the present invention is represented by XZ.

P-E / B of the present invention represented by X-Z
The block copolymer has a property such as fluidity of particles,
In order to further improve the tensile strength, heat resistance and the like of the processed product, a block component made of polypropylene (hereinafter, also simply referred to as “component Y”) is bonded between the component X and the component Z by block polymerization. You can That is, in the PE / B block copolymer of the present invention, when the above component Y is represented as Y, X-bonded with each block component.
It can also be indicated by YZ.

The PE / B block copolymer of the present invention can have sufficiently good physical properties by being essentially composed of the above component X and the above component Z, but the component X is a polypropylene component or If the polyethylene component is substituted, the physical properties of the molded product, such as transparency, will be insufficient and cannot be the object of the present invention.

The respective component ratios of the component X, the component Y and the component Z in the PE / B block copolymer of the present invention are
When the weight of the total polymer is 100% by weight, the component X is 0.1 to 10% by weight, the component Y is 0 to 30% by weight, and the component Z is 60 to 99.9% by weight. When the proportion of the component Y is 0% by weight, the PE / B block copolymer of the present invention corresponds to the above-mentioned X-Z. P
When the proportion of the component X in the -E / B block copolymer exceeds 10% by weight, the particle properties of the PE-B block copolymer, specifically, the bulk specific gravity is lowered, which is not preferable. On the other hand, when the proportion of the component X is less than 0.1% by weight, the transparency of the molded product is lost, which is not preferable.

Further, the embodiment of the PE-B / B block copolymer of the present invention containing the component Y not only improves the fluidity of the powder-like PE / B block copolymer, but also The tensile strength and heat resistance of the molded product obtained when the powdery PE / B block copolymer is molded are improved. However, if the proportion of the component X exceeds 30% by weight, the flexibility of the molded product is lowered and the transparency is deteriorated, so that the intended purpose cannot be achieved.

In the components X, Y and Z of the PE / B block copolymer of the present invention, the PE / E / B of the present invention is contained.
As long as the physical properties of the B block copolymer are not impaired, other α-
The olefin may be copolymerized and contained in a small amount, for example, in the range of 5 mol% or less.

The content ratio of the ethylene-based monomer unit and the propylene-based monomer unit in the component Z (block component consisting of a propylene-ethylene random copolymer) is based on the total of both monomer units. And the monomer unit based on ethylene is 15 to 60 mol%, preferably 20 to 50
Mol% and monomer units 85 to 4 based on propylene
It is 0 mol%, preferably 80 to 50 mol%. The content ratio of ethylene-based monomer units is less than 15 mol%, that is, the content ratio of propylene-based monomer units is 85%.
If it exceeds mol%, the flexibility and impact resistance of the molded product will be insufficient, which is not preferable. On the other hand, when the content ratio of ethylene-based monomer units exceeds 60 mol%, that is, when the content ratio of propylene-based monomer units is less than 40 mol%, the tensile strength and heat resistance of the molded product are It is not enough and is not preferable.

The PE / B block copolymer of the present invention is
Since it has the following peculiar properties, it is essential that it is in a powder state when it is not substantially melt-treated or dissolved.

That is, when the PE / B block copolymer of the present invention is once melted and made into pellets, the fluidity of the melt of the pellets is remarkably lowered. It becomes difficult to perform molding by using it. Such a behavior that the melt fluidity is lowered due to pelletization is a peculiar phenomenon that is not found in the conventional EPR having a molecular weight of about 200,000 to 300,000.

The PE / B block copolymer of the present invention also exhibits a unique behavior with respect to solubility in a solvent. That is, P-E / B of the present invention taken out from the polymerization tank
When the block copolymer is dissolved in 100 ml of boiling decane at a ratio of 1 g, it usually accounts for 80% by weight of the total powder.
As described above, 90% by weight or more, particularly 100% by weight in the examples described later, is dissolved, but decane is evaporated from the obtained decane solution of the P-E / B block copolymer or the solution is cooled. The recovered powder is boiling decane 1 again.
Even if an attempt is made to dissolve 1 g in 00 ml, only 40% by weight of the total powder is dissolved. Further, the powder-like PE / B block copolymer recovered here by cooling the solution has remarkably low fluidity at the time of melting, like the pellets.

Therefore, unless it is a powder which has substantially no melting treatment or dissolution treatment, for example, a state in which it is taken out from the polymerization tank and has good properties as described below, the powder of the present invention is used. It is difficult to mold the PE-B block copolymer of No. 1 by a general molding apparatus. Therefore,
It is important from the viewpoint of molding processability that the PE / B block copolymer of the present invention is in the form of powder that is not substantially melt-processed or melt-processed.

The cause of the unique behavior of the PE / B block copolymer of the present invention as described above has not yet been elucidated, but the present inventors presume as follows. That is, when the PE / B block copolymer of the present invention is once melted by heating or dissolved in a solvent, PE / B
It is presumed that the molecular chains of the block copolymer are entangled with each other, resulting in a structure as if they were crosslinked. For this reason, it is considered that it is difficult to melt or dissolve in a solvent once it is once melted or dissolved by heating again.

The PE / B block copolymer of the present invention comprises
It is characterized in that it is in a powder form in the state where it is not substantially melted or dissolved, that is, it has a particle property that the particles do not adhere to each other and that the fluidity is good. On the other hand, even if the particles are not subjected to the melting treatment or the dissolution treatment substantially, it is not preferable that the particles have a lumpy shape because the particles stick to each other and the fluidity of the lumps is poor.

The PE / B block copolymer of the present invention may be a powdery substance in which particles are not adhered to each other and can flow, and other properties of particles are not particularly limited, but the present invention is generally used. The properties of the PE / B block copolymer particles are as described below. That is, the average particle diameter (D ₅₀ ) is usually 100 to 1000 μm, preferably 100 to 800 μm.
m. Also, the particle size distribution is usually relatively narrow,
Specifically, the ratio of powdery material with a particle size of 100 μm or less is 1
It is not more than 1% by weight, and the proportion of the powdery material having a particle size of 8000 μm or more, preferably 1000 μm or more is 1% by weight or less. The bulk specific gravity is usually 0.35 g / cm.
³ or more, preferably 0.35 to 0.50 g / cm
The range is ³ . The angle of repose is usually 40 ° or less.

In order to obtain a powdery PE-B block copolymer having the above-mentioned particle properties in a state where it is not substantially melt-treated or dissolved, the amount of the low molecular weight component contained is Need to reduce. In the PE-B block copolymer of the present invention, in the elution curve measured by gel permeation chromatography (hereinafter abbreviated as "GPC"), the ratio of components having a molecular weight of 10,000 or less is usually 1.0.
By adjusting the amount to be not more than 0.5% by weight, preferably not more than 0.5% by weight, it is possible to maintain the above-mentioned powdery particle form. PE /
If the proportion of the component having a molecular weight of 10,000 or less contained in the B block copolymer exceeds 1.0% by weight, a powdery product having good particle properties cannot be obtained.

In the present invention, the weight average molecular weight is set to 600,000 or more in order to obtain a good particle size which facilitates the molding of the obtained PE / B block copolymer. P- of the present invention
The preferred weight average molecular weight of the E / B block copolymer is 1
It is, 000,000 or more, more preferably 1.5 to 7 million, and most preferably 1.5 to 3 million. When the weight average molecular weight is within the above-mentioned preferred range, the amount of the component having a molecular weight of 10,000 or less contained in the PE / B block copolymer becomes smaller, and the powder tends to have better properties. In addition,
The weight average molecular weight in the present invention is a value measured by GPC.

The method for identifying the PE / B block copolymer of the present invention is as follows, for example.

^{13 of the} PE / B block copolymer of the present invention
When the C-nuclear magnetic resonance (hereinafter referred to as "NMR") spectrum was measured, it was around 11 ppm, around 35 ppm, and 4
A peak is observed near 0.5 ppm. 11 pp
The peak near m is the following formula (i)

[0026]

Embedded image

It is derived from the C ¹ carbon of the butene monomer unit. The peak around 35 ppm is
It is derived from the C ² carbon of the above formula (i). Furthermore, the peak near 40.5 ppm is C in the above formula (i).
It is derived from the ^3rd carbon.

When the ¹³ C-NMR spectrum is measured, in addition to the above peaks, it is in the vicinity of 45.5 to 47.5 ppm, 3
Around 7 to 39 ppm, around 33 to 34 ppm, 24.5
A peak is observed at around 25.5 ppm. 4 above
The peak around 5.5 to 47.5 ppm has the following formula (ii)

[0029]

Embedded image

It is derived from the C ¹ carbon of the propylene-ethylene random copolymer part. Also, 37 to 3
The peak around 9 ppm is derived from the C ² carbon of the above formula (ii). Furthermore, the peak around 33 to 34 ppm is derived from the C ³ carbon of the above formula (ii). This peak is a peak that appears when the ethylene-based monomer unit (E) and the propylene monomer unit (P) are linked so as to be EPE. Furthermore, the peak around 24.5 to 25.5 ppm is derived from the C ⁴ carbon of the above formula (ii). This peak is a peak that appears when E and P are linked so as to be PEP. Therefore, by observing both the peak around 33 to 34 ppm and the peak around 24.5 to 25.5 ppm, it is confirmed that ethylene and propylene are randomly copolymerized.

^{13 of the} PE / B block copolymer of the present invention
From the C-NMR spectrum, the proportions of the component X (block component consisting of polybutene) and the component Z (block component consisting of an ethylene-propylene random copolymer), and the monomer unit based on ethylene in the component Z and propylene were determined. The respective proportions of the based monomer units are calculated.

Next, when the PE / B block copolymer of the present invention contains the component Y (block component made of polypropylene), the PE-B / B block copolymer is subjected to differential scanning calorimetry. (Hereinafter abbreviated as “DSC”), the peak derived from the melting of the component Y is 155 to 16
Appears in the range of 5 ° C. The magnitude of the heat of fusion obtained from the peak is determined by the content ratio of the component Y in the PE / B block copolymer, and when the component Y is contained in an amount of 30% by weight or less, the melting Heat is measured in the range of 30 mJ / mg or less. Therefore, if a calibration curve is prepared for the relationship between the weight of polypropylene and the heat of fusion, the heat of fusion determined from the weight of the sample used for DSC measurement and the peak appearing in the range of 155 to 165 ° C. using the calibration curve. The content ratio of the component Y can be obtained from

The PE / B block copolymer of the present invention comprises
It may be obtained by any method. A particularly suitably adopted method is, for example, a production method characterized by comprising a specific pre-polymerization step and a specific main polymerization step described below (hereinafter, also simply referred to as “production method of the present invention”). ) Is mentioned. Here, the specific pre-polymerization step,
In the presence of at least a titanium compound catalyst component (A) and an organoaluminum compound catalyst component (B), propylene is polymerized, or propylene or 1-butene is further polymerized following the polymerization of propylene to obtain the catalyst component ( A) A polymerization step for obtaining an active titanium catalyst component (E) containing an amount of the polymer in the range of 1 to 100 g per 1 g. The above-mentioned main polymerization step is a multi-step polymerization step in which any polymerization is performed in the presence of at least the above active titanium catalyst component (E) and organoaluminum compound catalyst component (B), and polymerization of 1-butene. And the random copolymerization of propylene and ethylene in this order to form the above block components (X) and (Z), or the polymerization of 1-butene, the polymerization of propylene and the random copolymerization of propylene and ethylene. This is a polymerization process which is performed in this order to form the block components (X), (Y) and (Z).

The characteristics of the above-mentioned production method of the present invention are at least the titanium compound catalyst component A (hereinafter also simply referred to as "catalyst component A") and the organoaluminum catalyst component B (hereinafter simply referred to as "catalyst component B"). ), And optionally propylene (and 1 in the presence of a known electron donor component).
-Butene) to carry out prepolymerization to obtain an active titanium catalyst component E (hereinafter also simply referred to as "catalyst component E") containing a specific amount of polymer (preliminary polymerization step), and then at least the catalyst component E. In the presence of the catalyst component B, 1-butene is polymerized and, if necessary, propylene is polymerized, and then propylene-ethylene random copolymerization is sequentially carried out (main polymerization step). When the above prepolymerization step is not carried out, it is difficult to obtain the PE / B block copolymer which is the object of the present invention, and in the main polymerization step, 1-butene polymerization and propylene-ethylene random copolymerization are performed. Even if the order of is reversed, it is difficult to obtain a powdery target product. This point can be clearly understood by comparing each of the examples of the present invention described later and the comparative example.

Further, in order to obtain the PE / B block copolymer of the present invention, as described above, the PE-B / B block copolymer having a molecular weight of 10,000 or less is contained in the PE / B block copolymer. It is necessary to control the ratio to be 1.0% by weight or less. For that purpose, the PE-B block copolymer may have a remarkably large molecular weight as compared with generally produced ethylene-propylene rubber having a molecular weight of 200,000 to 300,000 and crystalline polypropylene having a molecular weight of 100,000 to 500,000. This is one method. Specifically, the weight average molecular weight is at least 60.
10,000 or more, usually 800,000 or more, preferably 1 million or more, more preferably 1.5 to 7 million, most preferably 150 to 3
It is assumed to be one million.

In order to obtain the desired product, it is necessary to preferably select the polymerization conditions, the combination of catalysts used, the polymerization sequence, etc. in the prepolymerization step and the main polymerization step in the above-mentioned production method of the present invention as described below. is there.

Such preferable conditions and the like will be described below.

First, the prepolymerization step will be described. As the catalyst component A used in the prepolymerization step, a titanium compound known to be used for olefin polymerization is adopted without any limitation. In particular, a titanium compound containing titanium, magnesium and halogen and having high catalytic activity is preferable. Such a titanium compound having high catalytic activity is obtained by supporting a titanium halide, particularly titanium tetrachloride, on various magnesium compounds. As a method for producing this catalyst, a known method is employed without any limitation. For example, JP-A-56-155206 and JP-A-56-13680.
6, Same 57-34103, Same 58-8706, Same 58-
83006, 58-138708, 58-1837.
09, same 59-206408, same 59-219311,
Same 60-81208, same 60-81209, same 60-1
86508, 60-192708, 61-2113
09, 61-271304, 62-15209, 62-11706, 62-72702, 62-10.
For example, the method shown in US Pat. Specifically, for example, a method of co-milling titanium tetrachloride with a magnesium compound such as magnesium chloride, a method of co-milling titanium halide with a magnesium compound in the presence of an electron donor such as alcohol, ether, ester ketone or aldehyde. A method of pulverizing or a method of bringing a titanium halide, a magnesium compound and an electron donor into contact with each other in a solvent can be mentioned.

As the catalyst component A, well-known α, β, γ, or δ-titanium trichloride may be suitably used in addition to the above-mentioned supported catalyst. The method for preparing these titanium compounds is described, for example, in JP-A-47-34478 and 50-1265.
90, 50-114394, 50-93888, 50-123091, 50-74594, 50-1.
04191, 50-98489, 51-13662.
5, the method shown in the same 52-30888, the same 52-35283, etc. are adopted.

As the organoaluminum compound catalyst component B used in the prepolymerization, compounds known to be used in the polymerization of olefins are used without any limitation. For example, trimethyl aluminum, triethyl aluminum, tri-n propyl aluminum, tri-n butyl aluminum, tri-i butyl aluminum, tri-n hexyl aluminum, tri-n octyl aluminum, tri-n.
Trialkyl aluminums such as decyl aluminum:
Diethyl aluminum monohalides such as diethyl aluminum monochloride and diethyl aluminum bromide: alkyl aluminum halides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride and ethyl aluminum dichloride. Other alkoxy aluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can be used. Among them, triethylaluminum is most preferred.

When the above-mentioned supported catalyst is used as the catalyst component A, in addition to the above catalyst component B, an organosilicon compound catalyst component C represented by the following general formula (I) is generally used as an electron donor. Also referred to as "catalyst component C".)
And, it is preferable to add an iodine compound catalyst component D represented by the following general formula (II) (hereinafter, also simply referred to as “catalyst component D”), if necessary. Of course, even when the catalyst component A is not of a supported type, the use of the catalyst component C or C, D is effective.

Organosilicon compound catalyst component C: R _n Si (OR ′) _4-n (I) (wherein R is an alkyl group having 1 to 6 carbon atoms and 2 to 7 carbon atoms)
Is an alkenyl group, a phenyl group, a cyclohexyl group or a norbornene group, R'is an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 3. ) Iodine compound catalyst component D: R ″ -I (II) (wherein R ″ is an iodine atom, a carbon atom, an alkyl group having 1 to 7 carbon atoms or a phenyl group).
As the above, when the above α, β, γ or δ-titanium trichloride is used, it is preferable to further add an electron donor to the catalyst component B before use.

As the catalyst component A, as the catalyst component C which is preferably added when the above-mentioned supported catalyst is used, the compound represented by the general formula (I) is adopted without any limitation. R in the general formula (I) is a methyl group, an ethyl group, a propyl group,
Butyl group, a heptyl group, an alkyl group of C ₁ -C _6, such as a hexyl group, a phenyl group; a cyclohexyl group vinyl group, an allyl group, a butylene group, pentene group, an alkenyl group of C ₂ -C ₇ such as hexene group; Alternatively, a norbornene group is preferably used. As R ', the same C ₁ -C ₆ alkyl group as described above is used. These groups may be substituted and, for example, those substituted with an alkyl group can be preferably used. Particularly, as the above alkyl group, an alkyl group having 1 to 4 carbon atoms is preferable. Examples of the organosilicon compound that is preferably used in the present invention are as follows. For example, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane. Methoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, allyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, cyclohexyltriethoxysilane, 6-triethoxysilyl2-norbornene and the like.

Further, as the catalyst component D which is preferably added in the embodiment where the above-mentioned supported catalyst is used as the medium component A, the compound represented by the general formula (II) can be used without any limitation. Here, in the general formula (II), the alkyl group represented by R ″ may be the same alkyl group as exemplified for R in the general formula (I), and the phenyl group may have a substituent. Substituted phenyl groups are preferred, and the iodine compounds that can be preferably used in the present invention are as follows: for example, iodine, methyl iodide, erodiiodide, propyl iodide, butyl iodide. , Iodobenzene,
p-toluene iodide and the like. Methyl iodide and ethyl iodide are particularly preferable. When the catalyst component D is used in combination with the catalyst component C, not only the bulk specific gravity of the particles of the PE / B block copolymer obtained is further increased, but also the low molecular weight polymer such as a polymer having a molecular weight of 10,000 or less is obtained. There is an advantage that the amount is remarkably reduced and high fluidity can be imparted to the PE / B block copolymer.

Each catalyst component A in the prepolymerization step,
Since the amounts of B, C and D used differ depending on the type of catalyst and the conditions of the prepolymerization, the optimum amount may be determined in advance in accordance with each of these conditions. An example of the range generally used preferably is as follows.

In general, as will be described later, it is often effective that the prepolymerization step is not necessarily carried out only once but is carried out plural times (preliminary). The following blending ratios have been exemplified as suitable criteria for the usage ratio of each catalyst component used in one prepolymerization.

That is, the suitable use ratio of the catalyst component B is 1 to 100, preferably 2 to 20 in terms of Al / Ti (molar ratio) with respect to the type of the catalyst component A. In addition, a suitable usage ratio of the catalyst component C, which is preferably used when the supported catalyst component A is used, is 0.1 to 100, preferably 0 in terms of Si / Ti (molar ratio) with respect to the catalyst component A. ．
It is in the range of 5 to 10. Further, at this time, a suitable use ratio of the catalyst component D used as necessary is 0.1 to 100, preferably 0.5 to 50 in terms of I / Ti (molar ratio) with respect to the catalyst component A. is there.

The pre-polymerization step in the present invention is an important factor in controlling the shape and physical properties of the PE-B block copolymer obtained. Moreover, in order to obtain a powdery P-E / B block copolymer having good fluidity and excellent transparency, it is often expected that favorable results will be obtained by carrying out the preliminary polymerization a plurality of times, for example, 2 to 5 times. To be done. When carrying out the preliminary polymerization a plurality of times, it is possible to carry out the preliminary polymerization by adding a compound corresponding to the mixing ratio of each catalyst component described above in each preliminary polymerization. It is also possible to mix the required amount of each catalyst component and to carry out without newly adding the catalyst component after the second time, or to newly add only the specific catalyst component after the second time. . However, regarding the catalyst component C among the above-mentioned catalyst components, the reason and action are not yet clear at present, but it is advantageous to use different types in each prepolymerization when carrying out a plurality of prepolymerizations. It has a preferable effect in that the formation of the low molecular weight polymer in the P-E / B block copolymer can be controlled. In particular, as the catalyst component C, it is preferable to use a compound in which at least one of R and R'in the general formula (I) is a bulky hydrocarbon group such as a phenyl group, a cyclohexyl group or a norbornyl group. It is preferable because a PE / B block copolymer having a small molecular weight component can be obtained. However, the order of using the catalyst component C used in each prepolymerization step is not particularly limited.

The total amount of the polymer obtained in the prepolymerization step carried out in the presence of each of the above catalyst components varies depending on the number of prepolymerizations, the prepolymerization conditions, etc., but is generally 1 for 1 g of the titanium compound catalyst component A. It is sufficient to select from the range of up to 100 g. In addition, the amount of the polymer obtained by pre-polymerization per one time is 0.1 per 1 g of the titanium compound catalyst component A.
It is preferable to set a range of 1 to 100 g, preferably 2 to 50 g as a reference. The amount of (preliminary) polymer obtained in each prepolymerization or total prepolymerization can be confirmed by analyzing the prepolymer obtained after the completion of each stage or finally. Regarding the monomer used in each prepolymerization, propylene is used in the first prepolymerization,
Either propylene or 1-butene may be used in the second and subsequent prepolymerizations. Propylene or 1 used at this time
-Butene is a P-obtainable to be used alone-
It is suitable for controlling the physical properties of the E / B block copolymer, but within a range that does not adversely affect the physical properties of the block copolymer, for example, 5 mol% or less of other α-olefins such as ethylene, propylene, 1 -Butene, 1-Pentene, 1
Mixing hexene, 4-methylpentene-1 etc. is acceptable. It is also possible to make hydrogen coexist at the stage of each prepolymerization step.

Each prepolymerization in the above prepolymerization step is
Usually, it is preferable to apply slurry polymerization, and as the solvent, saturated aliphatic hydrocarbons or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, and toluene can be used alone, or a mixed solvent thereof can be used. The temperature of each prepolymerization is preferably −20 to 100 ° C., particularly preferably 0 to 60 ° C. When the prepolymerization is carried out in plural times, each step may be carried out under different temperature conditions. Each prepolymerization time may be appropriately determined depending on the prepolymerization temperature and the amount of polymerization in the prepolymerization, and the pressure in each prepolymerization is not limited, but in the case of slurry polymerization, it is generally from atmospheric pressure to 5 kg. / Cm ² G or so. Each prepolymerization may be carried out by any of batch, semi-batch and continuous methods. The catalyst component E obtained in the above prepolymerization step has the polymerization activity in the main polymerization step to be described later as it is.

In the production method of the present invention, following the prepolymerization step, any polymerization is a multi-step polymerization step in which at least the above active titanium catalyst component (E) and organoaluminum compound catalyst component (B) are present. , 1-butene polymerization and random copolymerization of propylene and ethylene in this order to form the block components (X) and (Z), or 1-butene polymerization, propylene polymerization and propylene and ethylene. The main polymerization step, which is a polymerization step for forming the block components (X), (Y) and (Z) by carrying out random copolymerization with the above in this order, is carried out under suitable conditions. It is as follows.

That is, the polymerization of 1-butene, which is the first stage polymerization in the main polymerization step, can be carried out as it is after the completion of the prepolymerization, but in general, the catalyst component E obtained in the prepolymerization step is used. Is preferably washed with a solvent that can be used in the above-mentioned prepolymerization and then subjected to 1-butene polymerization in the main polymerization step.

In the main polymerization step, 1-butene is first polymerized, then propylene is polymerized if necessary, and then propylene-ethylene random copolymerization is conducted. Each polymerization (main polymerization) in the main polymerization step is preferably performed by newly adding the catalyst component B to the catalyst component E obtained in the preliminary polymerization step. Further, the catalyst component C
It is a preferred embodiment that an electron donor such as or D is appropriately added. The combination of the catalyst components at this time is not particularly limited as long as it includes the catalyst component E and the catalyst component B,
It is preferred to use the same combination of catalyst components as used in the prepolymerization (with the exception that catalyst component A replaces catalyst component E). That is, in the preliminary polymerization step, the catalyst component A
When a combination of B and B (and an electron donor as necessary) is adopted, it is preferable to use a combination of catalyst components E and B (and an electron donor as necessary).
When a combination of catalyst components A, B and C and, if necessary, D is used in the prepolymerization step, the catalyst component E,
It is preferable to use a combination of B, C and, if necessary, D.

As the catalyst component B used in the main polymerization,
Although the one used for the above-mentioned prepolymerization can be used without limitation,
Most preferably, it is triethylaluminum. The amount of the catalyst component B used is Al based on the titanium atom in the catalyst component E.
/ Ti (molar ratio), 10 to 1000, preferably 50
~ 500.

As the catalyst component C used in the main polymerization, those used in the above-mentioned prepolymerization can be used without limitation, and the amount used is generally Si / Ti relative to the Ti atom in the catalyst component E.
(Molar ratio) 0.1 to 1000, preferably 0.5 to 5
00.

Further, the catalyst component D optionally used can be the catalyst component used in the above-mentioned prepolymerization without limitation, and the amount of the catalyst component D used is I / Ti (based on the titanium atom in the catalyst component E). 0.1 to 100, preferably 0.5
~ 50.

In the main polymerization step, 1-butene is first polymerized in the presence of the above catalyst components. The polymerization of 1-butene may be carried out by gas phase polymerization, but generally slurry polymerization may be carried out in the solvent. The polymerization temperature is -20 to
A temperature of 100 ° C, especially 0 to 60 ° C, is preferred. The polymerization time may be appropriately determined depending on the temperature and the amount of polymerization, but generally it may be selected from the range of 15 minutes to 3 hours. The polymerization pressure is not particularly limited, and in the case of slurry polymerization, it is generally from atmospheric pressure to about 5 kg / cm ² G.

The polymerization conditions are preferably determined in advance so that the block component (component X) composed of polybutene in the obtained PE / B block copolymer is in the range of 0.1 to 10% by weight.

In the measurement by DSC and the measurement by NMR described above, the components X and Y contained in the PE / B block copolymer were produced in the prepolymerization process and in the main polymerization process. I can't tell things apart.
However, since the amount of the polymer polymerized in the prepolymerization step can be confirmed by pre-analyzing the catalyst component E used in the main polymerization step, as in Examples described later, the main polymerization In the polymerization of 1-butene and the polymerization of propylene described below in the step, the total weight is considered in consideration of the amounts of polypropylene and polybutene contained in the catalyst component E (including these amounts in the components X and / or Y). It may be adjusted so that the ratio of each component to the combined weight is within the above range.

The PE / B block copolymer obtained in the present invention is powdery and has a large bulk specific gravity. For this reason, it is most preferable that the 1-butene is a homopolymer. However, within the range where the shape is not adversely affected, 1
Α-olefins other than butene such as ethylene, propylene, 3-methylbutene, 4-methyl-1-pentene,
It is acceptable to copolymerize 1-hexene or the like in a mixed state. The permissible amount varies depending on various polymerization conditions, but it is generally preferable to select such that the mixing ratio of other α-olefin is 5 mol% or less. Further, in the polymerization of 1-butene, hydrogen can be allowed to coexist as a molecular weight modifier, if necessary.

After the above-mentioned polymerization of 1-butene, or after the polymerization of propylene, which will be described later, if necessary, random copolymerization of propylene-ethylene is carried out. The random copolymerization may be carried out by purging unreacted monomers after the completion of the polymerization of 1-butene or propylene and supplying a mixture of propylene and ethylene instead. In addition, in the case of the propylene-ethylene random copolymerization, an electron donor such as an ether compound, an amide compound, an ester compound, an ionic compound, a phosphorus compound and an acid anhydride is newly added as a catalyst component, if necessary. It is often the preferred mode.

In the propylene-ethylene random copolymer, the propylene-based monomer unit is 40 to 85 mol%.
Preferably 40-80 mol% and 15-60 mol% of monomer units based on ethylene, preferably 20-60 mol%
Propylene and ethylene may be mixed so as to be in the range. For that purpose, it is preferable to select the mixing ratio of propylene and ethylene such that the ethylene concentration in the gas state is 7 to 50 mol%, preferably 10 to 40 mol%.

The polymerization temperature in the propylene-ethylene random copolymer is preferably as low as possible in order to increase the bulk specific gravity of the PE / B block copolymer, for example, 80 ° C. or lower, further 20 to 70 ° C. It is suitable to adopt from the range. If necessary, hydrogen may be allowed to coexist as a molecular weight modifier. Further, the polymerization may be any method such as slurry polymerization using propylene and ethylene itself as a solvent, gas phase polymerization, solution polymerization and the like. The polymerization method may be a batch method, a semi-batch method, or a continuous method, and the polymerization can be carried out in two or more stages under different conditions. In the propylene-ethylene random copolymer, the weight average molecular weight of all the polymers is at least 600,000 or more, usually 800,000 or more, so that the finally obtained PE / B block copolymer is obtained in a powder form. Is 1 million or more, more preferably 1.5 to 7 million, most preferably 1.5 to 3 million, and each condition is set so that the amount of the component Z obtained by the copolymerization is 60 to 99.9% by weight. Is done. Further, if the weight average molecular weight is within this range, the condition that the amount of the polymer component having a molecular weight of 10,000 or less contained in all the polymers is 1.0 wt% or less is within the range of usual reaction conditions. It can be easily selected.

In the production method of the present invention, propylene may be polymerized between the above-mentioned 1-butene polymerization and propylene-ethylene random copolymerization. The advantage of carrying out the polymerization of the propylene is that the fluidity of the powdery PE-B / B block copolymer obtained as described above can be further improved, and that the processed PE-B / B copolymer is obtained. It is possible to improve tensile strength and heat resistance. Therefore, the above-mentioned propylene polymerization is a mode often adopted depending on the physical properties required for the PE / B block copolymer.

However, when the amount of the component Y (block component made of polypropylene) contained is large, the flexibility of the resulting block copolymer is poor and the transparency of the processed product is poor. Maximum content of ingredient Y is 3
It is necessary to keep it at 0 wt%. In addition, when the propylene is polymerized only in the preliminary polymerization, the component Y is very small, for example, 0.001 in the PE / B block copolymer.
The content is about 1.0 wt%.

The polymerization conditions for the propylene are the same as those for the propylene-ethylene random copolymerization described above, except that a monomer comprising propylene alone or a mixture of propylene and up to 5 mol% of another α-olefin is used. It can be carried out so that the content of is 0 to 30% by weight based on the total polymer. Generally, propylene polymerization conditions that are suitably adopted are, for example, 0 to 80 ° C., preferably 20.
It is a polymerization method such as slurry polymerization in which hydrogen is present as a molecular weight modifier as necessary at a polymerization temperature of up to 70 ° C. and propylene itself is used as a solvent, gas phase polymerization, or solvent polymerization using a solvent.

After the completion of the main polymerization step, the monomer can be evaporated from the polymerization system to obtain a powdery polymer in which the particles are not sticking to each other. This powdery polymer becomes a powder having a higher bulk specific gravity when it is subjected to known washing or countercurrent washing using a hydrocarbon solvent having a carbon number of 7 or less.

The PE / B block copolymer of the present invention comprises
Since it is obtained in the form of powder having good particle properties, molded articles having various shapes can be easily obtained by various molding methods such as injection molding, extrusion molding and press molding without pelletization.

In molding, it is often a preferred mode to add various additives and molding aids used in conventional polyolefins to the PE / B block copolymer of the present invention.

[0070]

EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

The measuring method used in the following examples will be described.

1) Weight average molecular weight, ratio of molecular weight of 10,000 or less GPC (gel permeation chromatography)
It was measured by the method. Waters GPC-150C
Was carried out at 135 ° C. using o-dichlorobenzene as a solvent. The column used was TSK gel GM manufactured by Tosoh Corporation.
H6-HT, gel size 10-15μ. The calibration curve has a weight average molecular weight of 950, 2900,
It was prepared using 10,000, 50,000, 49.8 million, 2.7 million and 6.75 million polystyrene.

2) The proportions of the propylene-ethylene random copolymer component and the polybutene component, and the proportions of the ethylene-based monomer unit and the propylene-based monomer unit in the propylene-ethylene random copolymer component, respectively. Measurement method It was calculated using a ¹³ C-NMR spectrum chart. That is, the respective proportions of the ethylene-based monomer units and the propylene-based monomer units in the propylene-ethylene random copolymer component are as follows: Polymer (Polymer) Vol. 29 (19)
88), p. 1848, to determine peak assignments, and then to Macromolecules (Macro
The ratio of the monomer unit based on ethylene and the monomer unit based on propylene was calculated by the method described in Volume 10 (1977) p. 773.

Then, the ratio of the weight of the monomer unit based on propylene to the weight of the polybutene component in the propylene-ethylene random copolymer component was calculated by the above ¹³ C--N
It was calculated using the chart of MR spectrum. That is, from the integrated intensity ratio of the peak due to the methyl carbon in the propylene-based monomer unit, and the peak due to the methyl carbon in the polybutene component, the weight of the propylene-based monomer unit and the weight of the polybutene component. Was calculated.

Using each of the above calculated ratios, PE
/ B block copolymer, the respective proportions of the propylene-ethylene random copolymer component and the polybutene component, and the ethylene-based monomer units and propylene-based monomer units of the propylene-ethylene random copolymer component. The ratio was calculated for each.

3) Bulk Specific Gravity It was carried out according to JIS K6721 (1977).

4) Angle of repose "Powder physical property measurement method" (written by Sohachiro Hayakawa), page 97.
That is, an inner diameter 68 having an outlet with a diameter of 10 mm in the center of the bottom
mm in a cylindrical container of 48 mm in height, 5 on the cylindrical container
After dropping the polymer from a funnel provided at a height of 0 mm and filling the cylindrical container, the outlet is opened to allow the stationary polymer to flow out, and the slope of the slope of the powder layer remaining in the container is used as the angle of repose. It was measured.

5) Shore A hardness A test piece was prepared according to JIS K6301, and the test piece was tested using an A type tester.

6) Tensile Strength at Break, Elongation According to JIS K6301, a test piece was prepared using a No. 3 dumbbell and measured at a speed of 200 mm / min.

7) Softening temperature Using TNA manufactured by Seiko Denshi Co., a temperature rising rate of 20 ° C./min.
The temperature was measured when a 49 g load and a 0.1 mm needle were inserted.

8) Bending elastic modulus: 12 by a Japan Steel Works J120SAII type injection molding machine.
A test piece of 7 mm x 12.7 mm x 3.1 mm was prepared and A
It carried out according to STM: G-790.

9) Izod impact value 63.
A test piece with a notch of 6 mm × 12.7 mm × 3.1 mm was prepared and measured at 23 ° C. according to ASTM G-256.

10) Amount of Soluble Content of Boiling Decane A slurry solution prepared by adding 1 g of polymer to 100 ml of n-decane at room temperature was heated with stirring and boiled for about 30 minutes. In this state, stirring was continued for another 30 minutes, and at this temperature, the gel-like substance was quickly filtered off. The soluble amount was obtained by completely concentrating the filtered n-decane solution.

11) Particle size distribution Opening 75,125,250,355,500,71
A 0.11 μm sieve was charged with about 5 g of the polymer, and the mixture was classified on a sieve shaker for 10 minutes.

12) Transparency (haze value) Japan Steel Works J120SAII type injection molding machine at resin temperature 230 ° C. 80.0 mm × 50.0 mm × 1.0 mm
After 48 hours from the formation of the plate, the measurement was performed according to JIS K6714.

13) Method for Measuring Ratio of Polypropylene Component Differential Scanning Cal
It was measured by orimetry (DSC). That is, the DSC was used to measure the heat of fusion at the temperature of the peak observed in the range of 155 to 165 ° C., and based on the graph showing the relationship between the content ratio of the polypropylene component and the heat of fusion prepared in advance, polypropylene The content ratio of the component was obtained.

14) Falling seconds 100 ml of powder was put into a metal funnel having an outlet of 10 mm at the center of the bottom, a height of 175 mm, an upper cylindrical portion having an inner diameter of 68 mm, and a cylindrical portion having a height of 60 mm. The powder was discharged while applying a vibration of 2 mm width in the lateral direction, and the time required for discharging all the powder was measured.

Example 1 [Preparation of titanium compound catalyst component] 0.95 g (10 mmol) of anhydrous magnesium chloride, 10 ml of decane, and 4.7 ml (30 mmol) of 2-ethylhexyl alcohol were heated and stirred at 125 ° C. for 2 hours, and then, 0.55 g of phthalic anhydride (3.
75 mmol) was added, and the mixture was further stirred and mixed at 125 ° C. for 1 hour to obtain a uniform solution. After cooling to room temperature,
40 ml of titanium tetrachloride (0.36
(mmol) over 1 hour. After the completion of charging, the temperature of this mixed solution was raised to 110 ° C. over 2 hours, and when it reached 110 ° C., 0.54 ml (2.5 mmol) of diisophthalate was added, and 2
It was kept under stirring at the same temperature for a time. After the completion of the reaction for 2 hours, a solid part was collected by hot filtration, and the solid part was collected with a T
After resuspending in iCl ₄ , again at 110 ° C. for 2 hours,
A heating reaction was performed. After the completion of the reaction, the solid portion was collected again by hot filtration, and sufficiently washed with decane and hexane until no free titanium compound was detected in the washing solution. The solid Ti catalyst component (corresponding to the titanium compound catalyst component A, hereinafter abbreviated as "cat.A") prepared by the above production method was stored as a heptane slurry. ca
t. The composition of A is 2.1% by weight of titanium, 57% by weight of chlorine,
The amount of magnesium was 18.0% by weight, and the amount of diisobutylphthalate was 21.9% by weight.

[Preliminary Polymerization Step] 200 ml of purified heptane was added to a 1 liter autoclave substituted with N ₂ and 50 mmol of triethylaluminum was used as the organoaluminum compound catalyst component (B).
10 mmol of diphenyldimethoxysilane as the organosilicon catalyst component (C), 50 mmol of ethyl iodide as the iodine compound catalyst component (D), and cat. A to T
5 mmol was charged in terms of i atom. Then, propylene was added to the cat. The first pre-polymerization was carried out by continuously introducing into the reactor for 1 hour so that the amount of A was 5 g. The temperature during this period was kept at 15 ° C. One hour later, the introduction of propylene was stopped, and the inside of the reactor was sufficiently replaced with N ₂ . The solid portion of the resulting slurry was washed six times with purified heptane.

Further, this solid component was charged into a 1 liter autoclave which had been replaced with N ₂ and purified heptane 20 was added.
After adding 0 ml, triethylaluminum 50 mmol, 6-triethoxysilyl 2-norbornene 10 mmol, and ethyl iodide 10 mmol, propylene was further added to c.
at. A1 g was continuously introduced into the reactor for 1 hour so that the amount was 5 g, and the second preliminary polymerization was performed. The temperature during this period was kept at 15 ° C. The solid portion of the obtained slurry was washed 6 times with purified heptane to obtain a titanium-containing polypropylene (active titanium catalyst component E).

[Main Polymerization Step] [Polymerization of 1-butene] 1000 ml of purified heptane was added to a 2-liter autoclave subjected to N ₂ substitution, and 50 mmol of triethylaluminum was used as the organoaluminum compound catalyst component B.
After charging 50 mmol of diphenyldimethoxysilane as the organosilicon catalyst component C and 1.0 mmol of the active titanium catalyst component E obtained by prepolymerization in terms of Ti atom, 1-butene was added as cat. A 1 g of 200 g was continuously introduced into the reactor for 1 hour to polymerize 1-butene. The temperature during this period was kept at 20 ° C.
Obtained polymer (hereinafter referred to as titanium-containing polybutene)
Was washed 5 times with purified heptane under N ₂ atmosphere. The cat. It was 203 g with respect to A1 g.

[Propylene-ethylene Copolymerization] 200 L of propylene was charged into a 400 L autoclave which had been subjected to N ₂ substitution, and 125 mmol of triethylaluminum and 1 diphenyldimethoxysilane were added.
Ethylene was supplied so that the concentration of 25 mmol and the ethylene gas concentration would be 18 mol%, and the internal temperature of the autoclave was adjusted to 50
The temperature was raised to 0 ° C., and 0.5 mmol of titanium-containing polybutene was added in terms of titanium atom. Then, the internal temperature of the autoclave was raised to 55 ° C., and propylene-ethylene copolymerization was carried out for 1 hour. The polymerization pressure was 26 kg / cm ² , and the temperature during this period was kept at 55 ° C. The ethylene concentration was kept at 18 mol while being confirmed by a gas chromatograph. After 1 hour, a white granular polymer was obtained. No polymer adhesion was observed in the polymerization tank or on the stirring blades. The yield was 15 kg, and the polymerization activity at this time was 13157 g-polymer / g-cat. It was A / hr.

As a result, a chart of ¹³ C-NMR spectrum of the obtained PE / B block copolymer is shown in FIG.

The properties and physical properties of the obtained PE / B block copolymer were as shown in Tables 1 and 2.

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

[0099]

[Table 5]

Examples 2 and 3 In the polymerization of 1-butene of Example 1, the polymerization amount of 1-butene was adjusted to cat. The same operation as in Example 1 was performed except that 100 g and 500 g per 1 g of A were used. As a result, 101 g and 520 g of 1-butene were polymerized, respectively. The results are shown in Tables 1 and 2.

Examples 4 and 5 In the propylene-ethylene copolymerization of Example 1, the same operation as in Example 1 was performed except that the ethylene gas concentrations were 26 mol% and 12 mol%. The results are shown in Tables 1 and 2.

Examples 6 and 7 In the propylene-ethylene copolymerization of Example 1, hydrogen gas was added at a gas concentration of 0.01 mol% (Example 6), 0.
The same operation as in Example 1 was carried out except that the content was changed to 02 mol% (Example 7). The results are shown in Tables 1 and 2.

Examples 8 to 10 In the prepolymerization of Example 1, the organosilicon compound catalyst component C used in the second prepolymerization was replaced by phenyltriethoxysilane (instead of 6-triethoxysilyl-2-norbornene). Example 8), methylphenyldiethoxysilane (Example 9), butyltriethoxysilane (Example 1)
The same operation as in Example 1 was performed except that 0) was used. The results are shown in Tables 1 and 2.

Example 11 [Preparation of titanium compound catalyst component] 100 g of aluminum trichloride (anhydrous) and 29 g of magnesium hydroxide were reacted while being pulverized at 250 ° C. for 3 hours in a vibration mill. After completion of heating, the mixture was cooled under a nitrogen stream to obtain a solid product (SP-1).

Purified decane 1 in a glass flask.
5 ml, 2.5 g of a solid product (SP-1), 8.5 g of n-butyl orthotitanate, and 9.8 g of 2-ethyl-1-hexanol were mixed and stirred at 130 ° C. for 1.5.
The mixture was heated for a period of time to dissolve to form a uniform solution. 7 of the solution
After the temperature was set to 0 ° C., ethyl p-toluate 1.8 was added and reacted for 1 hour, 26 g of silicon tetrachloride was added dropwise over 2 hours with stirring to precipitate a solid, and the mixture was further stirred at 70 ° C. for 1 hour. The solid was separated from the solution and washed with purified hexane to obtain a solid product (SP-II).

1.2% of the total amount of the solid product (SP-II)
-Dichloroethane 30 ml and titanium tetrachloride 30 ml
Diisobutyl phthalate (1.5 g) was added together with the mixture, and the mixture was reacted at 100 ° C. for 2 hours while stirring, the liquid phase portion was removed by decantation at the same temperature, and 1,2-dichloroethane (30 ml), titanium tetrachloride (30 ml) and phthalic acid were added again. Add 1.5 g of diisobutyl acid and stir to 100 ° C for 2
After reacting for hours, the solid part was collected by hot filtration, washed with purified hexane, and dried under reduced pressure at 25 ° C. for 1 hour to obtain a solid product (SP-III).

The solid product (SP-III) was spherical and had an average particle size of 15 μm, and its particle size distribution was extremely narrow. This solid product (SP-III) was treated with cat. A.

The cat. The composition analysis result of A is T
i 3.0% by weight (hereinafter referred to as%), Cl 56.2%,
The content was Mg 17.6%, Al 1.7%, diisobutyl phthalate 20.1%, butoxy group 1.1%, 2-ethylhequinoxy group 0.2%, and p-toluate 0.1%. Hereinafter, prepolymerization and polymerization were performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 12 [Preparation of Titanium Compound Catalyst Component] A 500-ml glass three-necked flask (with a thermometer and a stirrer) having an internal volume of 500 ml, which had been purged with nitrogen, had 50 ml of purified heptane, 50 ml of titanium tetrabutoxide and 7.0 g of anhydrous water. Add magnesium chloride. Then place the flask at 90
The temperature was raised to 0 ° C., and magnesium chloride was completely dissolved in 2 hours. Next, the flask was cooled to 40 ° C., and 10 ml of methylhydrogen polysiloxane was added to deposit a magnesium chloride-titanium tetrabutoxide complex. This was washed with purified heptane to give an off-white solid.

50 ml of a heptane slurry containing 10 g of the precipitated solid obtained above was introduced into a glass three-necked flask (equipped with a thermometer and a stirrer) with an inner volume of 300 ml which had been purged with nitrogen. Then, 20 ml of a heptane solution containing 5.8 ml of silicon tetrachloride was added at room temperature over 30 minutes, and an additional 30
The reaction was carried out at 0 ° C for 45 minutes. The reaction was further carried out at 90 ° C. for 1.5 hours, and after completion of the reaction, the product was washed with purified heptane. Next, 50 ml of a heptane solution containing 1.5 ml of diheptyl phthalate was added and reacted at 50 ° C. for 2 hours, then washed with purified heptane, further 25 ml of titanium tetrachloride was added and reacted at 90 ° C. for 2 hours. It was washed with purified heptane and washed with cat. A was obtained. cat. The titanium content in A was 30.4% by weight. Thereafter, prepolymerization and polymerization were carried out in the same manner as in Example 1. The results are shown in Tables 1 and 2.

Example 13 Example 8 was repeated except that vinyltriethoxysilane was used instead of phenyltriethoxysilane in Example 8.
The same operation as described above was performed. The results are shown in Tables 1 and 2.

Example 14 The same operation as in Example 8 was carried out except that cyclohexyltriethoxysilane was used instead of phenyltriethoxysilane in Example 8. The results are shown in Tables 1 and 2.

Example 15 In the prepolymerization of Example 1, the same operation as in Example 1 was carried out except that iodine was used in place of the methyl iodide used in the first prepolymerization and the second prepolymerization. The results are shown in Tables 1 and 2.

Example 16 The same operation as in Example 1 was carried out except that the ethylene gas concentration was changed to 33 mol%. The results are shown in Tables 1 and 2.

Comparative Examples 1 to 3 In Example 1, 1-butene was not polymerized (Comparative Example 1). 5 g per 1 g of A was polymerized (Comparative Example 2), cat. The same operation as in Example 1 was carried out except that 2000 g was polymerized per 1 g of A (Comparative Example 3). As a result, the cat. 1-butene 5.0 per 1g of A
g (Comparative Example 2) and 2400 g (Comparative Example 3) were polymerized. The results are shown in Tables 3 and 4.

[0116]

[Table 6]

[0117]

[Table 7]

[0118]

[Table 8]

[0119]

[Table 9]

[0120]

[Table 10]

Comparative Examples 4 and 5 The same as Example 1 except that hydrogen gas was introduced so that the gas concentrations were 0.08 mol% and 0.12 mol% in the propylene-ethylene copolymerization of Example 1. The operation was performed. As a result, the obtained polymer was not a powder. The results are shown in Tables 3 and 4.

Comparative Examples 6 to 8 Instead of polymerizing 1-butene of Example 1, cat. A1
200 g of propylene per g (Comparative Example 6), 500 g of the same
(Comparative Example 7) and the same operation as in Example 1 was carried out except that 200 g of ethylene (Comparative Example 8) was polymerized. As a result, c
at. 203 g of propylene per 1 g of A (Comparative Example 6),
520 g (Comparative Example 7) and 203 g of ethylene (Comparative Example 8) were polymerized. The results are shown in Tables 3 and 4.

Comparative Example 9 The procedure of Example 1 was repeated except that ethylene was fed so that the ethylene gas concentration in the propylene-ethylene copolymerization of Example 1 was 5 mol%. The polymer obtained as a result had a low ethylene content, and its physical properties were not sufficiently satisfactory. The results are shown in Tables 3 and 4.

Comparative Example 10 Polymerization of 1-butene and copolymerization of propylene-ethylene in Example 1 were carried out in reverse order. That is, after the preliminary polymerization, random copolymerization of propylene-ethylene was first carried out, and then polymerization of 1-butene was carried out. The physical properties of the obtained polymer are shown in Tables 3 and 4.

Comparative Examples 11 to 13 To 100 parts by weight of the propylene-ethylene random copolymer obtained in Comparative Example 1, 0.5 parts by weight of polybutene-1 (M8010 manufactured by Mitsui Petrochemical Co., Ltd.), 1 part by weight, 5 parts by weight. Parts were mixed and the physical properties were evaluated. Table 5 shows the results.

[0126]

[Table 11]

Examples 17 and 18 The same procedure as in Example 1 was carried out except that polypropylene was polymerized by the following operation between the polymerization of 1-butene and the propylene / ethylene random copolymerization in the main polymerization of Example 1. .

That is, after the polymerization of 1-butene of Example 1 was completed, 200 liters of propylene, 125 mmol of triethylaluminum and 125 mmol of diphenyldimethoxysilane were charged into a 400 liter autoclave which had been subjected to N ₂ substitution, and the autoclave was charged. Internal temperature of 70
The temperature was raised to 0 ° C., and 0.5 mmol of titanium-containing polybutene was added in terms of titanium atom. 20 minutes at 70 ° C. (Example 1
7), propylene was polymerized for 45 minutes (Example 18). Then, the internal temperature of the autoclave was rapidly lowered to 55 ° C., and at the same time ethylene gas concentration was 20 mol%.
And propylene / ethylene were subjected to random copolymerization for 60 minutes. During this period, the temperature was maintained at 55 ° C., and the ethylene gas concentration was maintained at 24 mol% while confirming with a gas chromatograph.

After completion of the polymerization, the unreacted monomer was purged,
A white granular polymer was obtained. No polymer adhesion was observed in the polymerization tank or on the stirring blades.

The yield was 16.3 kg (Example 1)
7) and 18.1 kg (Example 18), the polymerization activity was 1
4300 g-polymer / g-cat. A (Example 17)
And 15880 g-polymer / g-cat. It is A (Example 18).

Separately, when only the above-mentioned propylene polymerization was carried out, at 70 ° C. for 20 minutes, the cat. A
1100 g-polymer / g-cat. A
And 2600 g-polymer / g-in 45 minutes at 70 ° C.
cat. A. Therefore, the amount of polypropylene component in each of the obtained block copolymers is 7.7 wt%
(Example 17) and 16.4 wt% (Example 18).

The results are shown in Tables 6 and 7. Further, D using the PE / B block copolymer obtained in Example 17 was used.
The SC chart is shown in FIG.

[0133]

[Table 12]

[0134]

[Table 13]

[0135]

[Table 14]

[0136]

[Table 15]

[0137]

[Table 16]

Example 19 In the propylene-ethylene random copolymerization of Example 18, the same operation as in Example 18 was carried out except that the hydrogen gas concentration was supplied at 0.06 mol% and the polymerization was carried out. As a result, the yield was 19.8 kg, and the polymerization activity was 17400 kg.
g-polymer / g-cat. A. As a result, the polypropylene component in the block copolymer was 14.9w.
It can be seen that it is t%.

The results are shown in Tables 6 and 7.

Example 20 [Preliminary Polymerization Step] A glass autoclave reactor having an internal volume of 1 liter equipped with a stirrer was sufficiently replaced with nitrogen gas, and then 400 ml of heptane was inserted. Keep the temperature in the reactor at 20 ℃,
14.5 mmol of diethyl aluminum chloride and titanium trichloride ("TOS-1" manufactured by Marubeni Solvay Chemical Co., Ltd.
7 ") 18.1 mmol was added, and then propylene was added to TO.
S-17 (cat.A) 1 g to be 3 g per 1 g
It was continuously introduced into the reactor for an hour. The temperature during this period was kept at 20 ° C. After stopping the supply of propylene, the inside of the reactor was sufficiently replaced with nitrogen gas, and the obtained titanium-containing polypropylene (corresponding to the active titanium catalyst component E) was obtained.
Was washed 4 times with purified heptane. As a result of the analysis, cat.
2.9 g of propylene was polymerized per 1 g of A.

[Main Polymerization Step] [Polymerization of 1-butene] A stainless steel autoclave reactor having an internal volume of 2 liter and equipped with a stirrer was sufficiently replaced with nitrogen gas, and then 1000 ml of heptane was inserted. Keeping the temperature inside the reactor at 20 ° C, diethylaluminum chloride 0.70mmo
l, titanium-containing polypropylene obtained by prepolymerization (active titanium catalyst component E) as titanium trichloride 0.087
After adding mmol, 1-butene was added to cat. It was continuously introduced into the reactor for 2 hours so that 30 g per 1 g of A was obtained. The temperature during this period was kept at 20 ° C. After the supply of 1-butene was stopped, the inside of the reactor was replaced with nitrogen gas to obtain a titanium-containing poly-1-butene polymer. Poly 1 obtained
-Butene was washed twice with purified heptane under nitrogen atmosphere. As a result of the analysis, cat. 28 g of 1-butene had been polymerized per 1 g of A.

[Polymerization of Propylene and Copolymerization of Propylene Ethylene] 1 liter of propylene and 0.70 mmol of diethylaluminum chloride were added to a 2 liter autoclave subjected to N ₂ substitution, and the internal temperature of the autoclave was adjusted to 70
The temperature was raised to ° C. 0.087 mmol of titanium-containing poly-1-butene was added as titanium trichloride, and propylene was polymerized at 70 ° C. for 30 minutes. Then, the inner temperature of the autoclave was rapidly lowered to 55 ° C, and at the same time, 0.35 mmol of ethylaluminum diethoxide was added, and then ethylene was supplied so that the ethylene gas concentration became 7 mol%, and the temperature was kept at 55 ° C for 90 minutes. Copolymerization of propylene and ethylene was performed. During this period, the ethylene gas concentration was maintained at 10 mol% while confirming with a gas chromatograph. After completion of the polymerization, unreacted monomers were purged to obtain a polymer on white granules.

No adhesion was observed in the polymerization tank or on the stirring blade. The yield was 110 g, and the polymerization ratio of all polymers was 5730 g-polymer / g-cat. A.

Separately, as a result of the above-mentioned polymerization of only propylene, the cat. 340 g of propylene was polymerized per 1 g of A. As a result, the polypropylene component in the block copolymer was 5.
It can be seen that it is 9 wt%. The results are shown in Tables 6 and 7.

Comparative Example 14 An example of propylene polymerization and propylene ethylene copolymerization of Example 17 except that propylene was polymerized at 70 ° C. for 60 minutes and propylene ethylene was copolymerized at 55 ° C. for 30 minutes. The same operation as (Part 2) was performed.

The yield was 9.2 kg and the polymerization activity was 8
100 g-polymer / g-cat. A. From another experiment, in the above propylene polymerization at 70 ° C. for 60 minutes,
cat. A per gram of 3200 g-polymer / g-ca
t. From the fact that A was polymerized, it was found that the polypropylene component in the block copolymer was 39.5%.
This block copolymer was inferior in flexibility.

The results are shown in Tables 6 and 7.

[0148]

EFFECT OF THE INVENTION The PE / B block copolymer of the present invention becomes polymer particles having a high bulk density despite having a high ethylene composition. In addition, PE / B of the present invention
The block copolymer has high fluidity in a powder state. Therefore, the PE / B block polymer of the present invention does not cause hanging in the hopper of the molding machine, and
It easily bites into the screw of the molding machine. Therefore, the PE / B block copolymer of the present invention can be easily molded by injection molding or extrusion molding that is used for molding a usual thermoplastic resin.

Furthermore, since the PE / B block copolymer of the present invention has no stickiness in the molded article and has high transparency, it can be used in various fields where conventional thermoplastic elastomers are used. It can be preferably used.

For example, in the field of injection molding, bumpers, mat guards, lamp packings for automobile parts, and various packings for home electric appliances, ski shoes, grips, roller skates, etc. can be mentioned. On the other hand, in the field of extrusion molding, various automotive interior materials, various insulating sheets for home appliances and electric wire materials, coating materials for cords and cables, and waterproof sheets, waterproof materials for civil engineering and building materials,
It can be suitably used as a joint material.

[Brief description of the drawings]

1 is a chart of a ¹³ C-NMR spectrum of the PE / B block copolymer of the present invention obtained in Example 1. FIG.

2 is a DSC chart of the PE / B block copolymer of the present invention obtained in Example 17. FIG.

FIG. 3 is a flow chart diagram of a method for suitably producing the PE / B block copolymer of the present invention. However, * 1 to * 3 in the figure mean the following, respectively. * 1: (Pre) polymerization of propylene or 1-butene may be carried out in multiple stages. * 2: A value including the amount of polybutene in the prepolymer. * 3: A value including the amount of polypropylene in the prepolymer.

Claims (2)

(57) [Claims] 1. When the total polymer weight is 100% by weight, the block component (X) composed of polybutene is 0.1 to 0.1%.
10% by weight, 0 to 30% by weight of the block component (Y) made of polypropylene, 15 to 60 mol% of ethylene monomer units and 85 to 4 of propylene monomer units.
The content of a component having a weight average molecular weight of 600,000 or more and a molecular weight of 10,000 or less, comprising 60 to 99.9% by weight of a block component (Z) consisting of 0 mol% of a propylene-ethylene random copolymer. Is 1.0% by weight or less, and a powdery propylene-ethylene / butene-based block copolymer which is not substantially melt-processed or solution-processed. 2. The method for producing a propylene-ethylene / butene block copolymer according to claim 1, which comprises the following prepolymerization step and the following main polymerization step. [Preliminary Polymerization Step] Propylene is polymerized in the presence of at least a titanium compound catalyst component (A) and an organoaluminum compound catalyst component (B), or propylene or 1-butene is further polymerized following the polymerization of propylene. A polymerization step for obtaining an active titanium catalyst component (E) containing an amount of the polymer in the range of 1 to 100 g per 1 g of the catalyst component (A). [Main Polymerization Step] Any polymerization step is a multi-step polymerization step carried out in the presence of at least the active titanium catalyst component (E) and the organoaluminum compound catalyst component (B), and comprises 1-butene polymerization and propylene and ethylene. The block copolymers (X) and (Z) according to claim 1, wherein the random copolymerization is carried out in this order.
Or the block component (X) according to claim 1, wherein 1-butene polymerization, propylene polymerization and random copolymerization of propylene and ethylene are carried out in this order.
Polymerization step of forming (Y) and (Z).