JPH0747607B2 - Ultra high molecular weight propylene ethylene copolymer and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to an ultrahigh molecular weight propylene ethylene copolymer capable of forming polymer particles having a high molecular weight and a large bulk specific gravity, and a method for producing the same.

(Prior Art and Problems to be Solved by the Invention) In recent years, flexible olefin soft resins such as thermoplastic elastomers and ethylene propylene rubber have been widely used in automobile parts, electric wire fields, home electric appliances fields and the like. Conventionally, polyolefin having rubber-like flexibility has generally been produced by a solution polymerization method using a vanadium catalyst. However, vanadium catalysts have low polymerization activity and are significantly inferior to titanium-based catalysts in productivity, and the polymerization is carried out in a state in which the polymer produced is dissolved in a solvent by the solution polymerization method. The process was complicated and economically disadvantageous. Therefore, a method of producing particles in the same form as ordinary polypropylene by a propylene bulk polymerization method that is simplified in terms of a process using a titanium-based catalyst having excellent productivity is a more advantageous method. However, in general, when it is produced by propylene bulk polymerization, a low molecular weight component is generated, which is dissolved in a propylene solvent, the viscosity of the polymerization solution is significantly increased, and the stirring efficiency is reduced and the heat removal effect of the polymerization heat is reduced. In addition, this low molecular weight component causes mutual adhesion of particles. When mutual adhesion between particles occurs, the resulting polymer becomes lumpy,
Separation from the polymerization tank was difficult. Further, even if a particulate polymer that can be separated from the polymerization tank is obtained, the bulk specific gravity of the polymer particles produced when the ethylene composition becomes 20 to 45 mol% is achieved only at most about 0.20 g / cm ^3. However, the polymer particles having such a low bulk specific gravity are inferior in the fluidity of the particles, and it is difficult to transport the polymer in the process and the line is clogged. Is not preferable. Therefore, there has been a demand for a polymer having a high bulk specific gravity even in a region where the ethylene composition is high and giving polymer particles having excellent fluidity.

(Means for Solving the Problems) In view of the above problems, the present inventors have determined that the ethylene composition is 5 to 5
As a result of conducting a study to find polymer particles having a high bulk specific gravity in the range of 60 mol% and having excellent fluidity of particles, surprisingly, as a result, a region where the weight average molecular weight exceeds 1,000,000 is found. Thus, an ultra-high molecular weight propylene-ethylene copolymer that gives polymer particles having excellent particle properties with a bulk specific gravity of 0.35 g / cm ³ or more was successfully obtained, and the present invention was completed.

That is, the present invention provides: (A) 5 to 60 mol% of ethylene-based monomer units,
The monomer unit based on propylene is 95 to 40 mol%, (B) the weight average molecular weight is 1,000,000 or more, and (C) the component having a molecular weight of 10,000 or less measured by gel permeation chromatography is 1.0 or less. It is an ultrahigh molecular weight propylene-ethylene copolymer, characterized in that it is at most wt% and (D) at least 80 wt% is soluble when 1 g is dissolved in 100 ml of boiling decane.

The ultrahigh molecular weight propylene-ethylene copolymer of the present invention (hereinafter, also simply referred to as HMPE copolymer) has an ethylene-based monomer unit of 5 to 60 mol%, preferably 20 to 50 mol%.
And a random copolymer containing 95 to 40 mol%, preferably 80 to 50 mol% of a propylene-based monomer unit. When the content of the monomer unit based on ethylene is less than 5 mol%, the property as polypropylene becomes strong and sufficient flexibility and excellent impact resistance cannot be exhibited. On the other hand, when the content of the ethylene-based monomer unit exceeds 60%, the property as polyethylene becomes strong, and the tensile strength and heat resistance become insufficient, which is not preferable.

The HMPE copolymer of the present invention has a weight average molecular weight of 1 million or more, and is generally 1.5 million to 7 million, preferably 1.5 million to 300.
It has a molecular weight in the range of 10,000. When the weight average molecular weight is less than 1,000,000, polymer particles having a high bulk specific gravity cannot be obtained in the above-mentioned ethylene composition, and moreover, only a lumpy polymer can be obtained due to adhesion between the polymer particles, which is not preferable. The weight average molecular weight in the present invention is a value measured by gel permeation chromatography (hereinafter simply abbreviated as GPC).

Further, the HMPE copolymer of the present invention has a remarkably small amount of low molecular weight components. That is, in the HMPE copolymer of the present invention, the component having a molecular weight of 10,000 or less is 1.0% by weight or less, and further 0.5% by weight or less, in the elution curve measured by GPC. Therefore, the powder of the HMPE copolymer of the present invention prevents adhesion between particles and exhibits excellent fluidity. For example, the HMPE of the present invention
The angle of repose of the powder of the copolymer is generally 40 ° or less.

The HMPE copolymer of the present invention has boiling decane as described below.
When 1 g is dissolved in 100 ml, usually 80% by weight or more, more preferably 90% by weight or more, and particularly 100% by weight in Examples described later are dissolved in the total powder.

The HMPE copolymer of the present invention is obtained as a powder by polymerization. The bulk specific gravity of this powder is 0.35 g / cm ³ or more, and it is usually
Values range from 0.35 to 0.50 g / cm ³ .

The HMPE copolymer of the present invention is obtained as a powder having a relatively narrow particle size distribution. That is, the powder of the HMPE copolymer of the present invention,
The average particle (hereinafter abbreviated as D ₅₀ ) is 100 μm ≦ D ₅₀ ≦ 800 μm, and the particle body of 100 μm or less is 1% by weight or less and 1
The content of particles of 000 μm or more is 1% by weight or less.

The HMPE copolymer of the present invention exhibits the following behavior. It is known that the ultra-high molecular weight polymer has an extremely large molecular weight and therefore has extremely poor fluidity when melted. Ultra-high molecular weight polyethylene is difficult to mold with ordinary molding machines, such as screw extrusion molding or injection molding.
Efforts are being made to develop special molding machines.
It has been found that the ultra-high molecular weight propylene-ethylene copolymer of the present invention can be easily molded by a conventional molding machine without any difference from a polymer having a normal molecular weight, although the molecular weight is extremely large. This was completely unexpected from the knowledge of conventional molding methods for ultrahigh molecular weight polyethylene.

However, the ultra-high molecular weight propylene ethylene copolymer of the present invention is a conventional molding machine, when the particulate polymer isolated from the polymerization tank is once pelletized through a granulation process, the fluidity during melting is significantly reduced. It has been found that the molding becomes difficult, and the behavior which is not seen in a normal propylene ethylene copolymer having a molecular weight is exhibited. Also, regarding the solubility in solvents, HM isolated from the polymerization tank
PE copolymer, when dissolved 1 g in 100 ml of boiling decane,
Usually, 80% by weight or more, more preferably 90% by weight or more, especially 100% by weight in the examples described later are dissolved in the total powder. However, once the powder is recovered by evaporating or cooling decane after being dissolved, even if 1 g is dissolved in 100 ml of boiling decane, only 40% by weight of the total powder is dissolved. It was also confirmed that the reprecipitated polymer obtained by dissolving the particulate polymer isolated from the polymerization tank in boiling decane and then cooling the same behavior as granulated pellets.

The cause of the behavior of the HMPE copolymer of the present invention as described above has not been clarified yet, but the present inventors presume as follows. When the HMPE copolymer is once melted or dissolved by heat or a solvent, and when it solidifies again, the polymer chains are entangled and behave as if they were crosslinked. It is considered that this makes it difficult to perform thermal melting again or dissolution with a solvent again.

The HMPE copolymer of the present invention may be obtained by any method, but the following method is particularly preferably adopted.

The following components A, B and C A. Titanium compound B. Organoaluminum compound C. General formula [I] After the prepolymerization of propylene in the presence of the organosilicon compound shown in step D and using different organosilicon compounds in each prepolymerization step, D. Titanium-containing polypropylene obtained by the prepolymerization E. Organoaluminum compound F. This is a method of copolymerizing propylene and ethylene in the presence of the organosilicon compound represented by the above general formula [I]. As the titanium compound [A] used in the prepolymerization method, a compound known to be used for olefin polymerization can be used 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 one in which various halogen compounds, particularly titanium tetrachloride, are supported on various magnesium compounds. As a method for producing this catalyst, a known method is adopted without any limitation. For example, JP-A-56-155206 and JP-A-56-1368.
06, ibid 57-34103, ibid 58-8706, ibid 58-830 06, ibid 58-13870
8, Same 58-183709, Same 59-206408, Same 59-219311, Same 60-812
08, same 60-81209, same 60-186508, same 60-192708, same 61-211
309, 61-271304, 62-15209, 62-11706, 62-727
02, 62-104810, etc. are adopted.
Specifically, for example, a method of co-milling titanium tetrachloride with a magnesium compound such as magnesium chloride, a method of combining a titanium halide and a magnesium compound in the presence of an electron donor such as alcohol, ether, ester, ketone or aldehyde. Examples thereof include a method of co-milling, a method of contacting a titanium halide, a magnesium compound and an electron donor in a solvent.

Next, as the organoaluminum compound [B], a compound known to be used for polymerization of olefin is adopted without any limitation. For example, trimethyl aluminum, triethyl aluminum, tri-n propyl aluminum, tri-
n-butyl aluminum, tri-i-butyl aluminum,
Trialkyl aluminums such as tri-n-hexyl aluminum, tri-n octyl aluminum, and tri-n decyl aluminum; diethyl aluminum monohalides such as diethyl aluminum monochloride; methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum dichloride, etc. Alkyl aluminum halides of Other alkoxy aluminums such as monoethoxydiethylaluminum and diethoxymonoethylaluminum can be used. Of these, triethylaluminum is most preferable. The amount of organoaluminum compound used in each prepolymerization step is Al / Ti relative to the Ti atom in the titanium compound.
The (molar ratio) is 1 to 100, preferably 2 to 20.

Furthermore, the organosilicon compound [C] is a compound represented by the above general formula [I].
The compound represented by is adopted without any limitation. R and R'in the general formula [I] are an alkyl group, an alkenyl group,
It is a hydrocarbon group such as an alkynyl group and an aryl group. Examples of the organosilicon compound preferably used in the present invention are as follows. For example, trimethylmethoxysilane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, diphenyldiethoxysilane, ethyltrimethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane. , Phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, vinyltriethoxysilane, butyltriethoxysilane, phenyltriethoxysilane, 6-triethoxysilyl2-norbornene and the like.

The amount of the organosilicon compound used in each prepolymerization step is 0.1 to 10 in terms of Si / Ti (molar ratio) with respect to Ti atoms in the titanium compound.
It is 0, preferably 0.5 to 10.

In the present invention, the above titanium compound [A], organoaluminum compound [B] and organosilicon compound [C] are used.
In addition to the following general formula [II] The use of the iodine compound [D] represented by not only increases the bulk specific gravity of the resulting HMPE copolymer particles,
It is preferable because the amount of low molecular weight components having a molecular weight of 10,000 or less is remarkably reduced and high fluidity is achieved.

In the general formula [II], the hydrocarbon group represented by R ″ is a hydrocarbon group such as an alkyl group, an alkenyl group, an alkynyl group or an aryl group. Specific examples of iodine compounds that can be preferably used in the present invention are as follows. Is as follows: For example,
Examples include iodine, methyl iodide, ethyl iodide, propyl iodide, butyl iodide, iodobenzene, p-iodine toluene and the like. Of these, methyl iodide and ethyl iodide are preferred. The amount of the iodine compound used in each prepolymerization step is I / Ti (molar ratio) with respect to the titanium atom in the titanium compound,
It is 0.1 to 100, preferably 0.5 to 50.

In the present invention, the term "preliminary polymerization carried out in multiple steps" means that titanium obtained by prepolymerizing propylene in the presence of the above components [A], [B], [C] and optionally [D]. Containing polypropylene and the above [B], [C]
Further, it means that the preliminary polymerization of propylene is further repeated in the presence of each component of [D] which is optionally used. The prepolymerization is preferably performed in the range of 2 to 5 times. Each of the above-mentioned components used in each prepolymerization may be added sequentially or may be used as a mixture. The amount of propylene polymerized in each prepolymerization step is 1 g of the titanium compound,
The range is 0.1 to 100 g, preferably 1 to 100 g, and industrially the range is 2 to 50 g.

Different types of organosilicon compounds are used in each prepolymerization stage. As the organosilicon compound, 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 an HMPE copolymer having a small amount of HMPE can be obtained. The order of using the organosilicon compound used in each prepolymerization step is not particularly limited.

In each preliminary polymerization, it is preferable to polymerize propylene alone, but α-other than propylene such as ethylene, 1-butene, 1-pentene, 1-hexene, and 4-methylpentene-1.
You may copolymerize 5 mol% or less of olefins and propylene. It is also possible to coexist with hydrogen at each prepolymerization stage.

For each prepolymerization, it is usually preferable to apply slurry polymerization, and as the solvent, saturated aliphatic hydrocarbon or aromatic hydrocarbon such as hexane, heptane, cyclohexane, benzene and toluene is used alone or a mixed solvent thereof is used. You can Each prepolymerization temperature is −20 to 100.
C., especially 0 to 60.degree. C., is preferred, and each step of the prepolymerization may be carried out under different temperature conditions. The pre-polymerization time may be appropriately determined depending on the pre-polymerization temperature and the amount of polymerization in the pre-polymerization, and the pressure in the pre-polymerization is not limited, but in the case of slurry polymerization, it is generally atmospheric pressure to 5 kg / cm. It is about ² G. Each prepolymerization is batch, semi-batch,
Any continuous method may be used. After the completion of each prepolymerization, it is preferable to wash with saturated aliphatic hydrocarbons or aromatic hydrocarbons such as hexane, heptane, cyclohexane, benzene, and toluene alone or with a mixed solvent thereof. It is preferably 5 to 6 times.

After the preliminary polymerization, main polymerization is carried out. The main polymerization is carried out in the presence of the titanium-containing polypropylene, organoaluminum compound and organosilicon compound obtained by the above-mentioned prepolymerization.

As the organoaluminum compound used in the main polymerization, those used in the above-mentioned prepolymerization can be used, and triethylaluminum is most preferable. The amount of the organic aluminum compound used is 10 to 1000, preferably 50 to 500, in terms of Al / Ti (molar ratio) with respect to the titanium atom in the titanium-containing polypropylene.
Is.

Further, as the organosilicon compound, the compound represented by the above general formula [I] is adopted without any limitation. The amount of the organosilicon compound used in the main polymerization is 0.1 to 1000, preferably 0.5 to 500, in terms of Si / Ti (molar ratio) with respect to Ti atoms in the titanium-containing polypropylene.

Other polymerization conditions, as long as the effect of the present invention is observed
Although not particularly limited, the following conditions are generally preferable. The polymerization temperature is in order to make the particles of the HMPE copolymer of high bulk specific gravity,
It is preferable that the temperature is as low as possible, for example, 80 ° C or lower,
Further, it is preferable to adopt from the range of 20 to 70 ° C.
Hydrogen may be allowed to coexist as a molecular weight regulator. 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 main polymerization, propylene and ethylene are copolymerized. To control the stereoregularity of propylene, ethers, amines, amides, sulfur-containing compounds, nitriles, carboxylic acids,
An electron donor such as acid amide, acid anhydride, or acid ester can coexist.

After the completion of the main polymerization, the monomer can be evaporated from the polymerization system to obtain a particulate polymer. This particulate polymer has a higher bulk density when subjected to known washing or countercurrent washing with a hydrocarbon having a carbon number of 7 or less.

The HMPE copolymer of the present invention can be molded into various shapes by various molding methods such as injection molding, extrusion molding and press molding.

At the time of molding, various additives and molding aids used in conventional polyolefins may be added to the HMPE copolymer of the present invention.

(Effect) The HMPE copolymer of the present invention can be polymer particles having an ultrahigh molecular weight and a high bulk specific gravity even when the ethylene composition is increased. Further, the HMPE copolymer of the present invention has high fluidity in a powder state. For this reason,
The HMPE copolymer of the present invention does not cause hanging in the hopper of the molding machine, and easily penetrates the screen of the molding machine. Therefore, according to the present invention, a propylene-ethylene copolymer having sufficient mechanical strength and heat resistance due to an ultra-high molecular weight can be easily prepared by injection molding or extrusion molding which is adopted for molding a usual thermoplastic resin. Can be molded into Therefore, it is possible to easily obtain a molded product of a propylene copolymer having excellent properties due to the ultrahigh molecular weight.

The HMPE copolymer of the present invention can be used as a raw material for machine parts such as gears, packings, caskets, etc .; automobile parts such as radiator tanks, washer tanks, inner panels; sports equipment materials; and various lining materials.

(Examples) Hereinafter, the present invention will be described with reference to Examples and Comparative Examples.
The invention is not limited to these examples.

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

1) Weight average molecular weight and proportion of components having a molecular weight of 10,000 or less
It was measured by GPC (gel permeation chromatography) method. Waters company GPC-150C o-
It was carried out at 135 ° C. using dichlorobenzene as a solvent. The column used was TSK gel GMH6-HT manufactured by Toso, gel size 10-1.
It is 5μ. The calibration curve was prepared by using polystyrene having a weight average molecular weight of 950,29,900,10,000, 50,000,498,000,2.77,675,750,000 as a standard sample.

2) Ethylene content The ethylene content was measured using JEOL GSX-270 and a ¹³ C-NMR spectrometer.

3) Bulk specific gravity It was performed according to JIS K6721 (1977).

4) Angle of repose “Powder physical properties measurement method” (written by Sohachiro Hayakawa), page 97. That is, an inner diameter of 68 mm and a height of 4 mm with an outlet of 10 mm in diameter at the bottom center.
In a cylindrical container of 8 mm, the polymer was dropped from a funnel provided at a height of 50 mm on the cylindrical container, and after filling the cylindrical container, the outlet was opened to allow the stationary polymer to flow out and remain in the container. The inclination of the slope of the powder layer was measured as the angle of repose.

5) Shore A hardness, Shore D hardness Prepare test pieces according to JIS K 6301, and use the A type tester and D
It was performed using a shape tester.

6) Tensile strength at break, elongation According to JIS K 6301, 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 KK, the temperature at a temperature rising rate of 20 ° C./min, a load of 49 g and a 0.1 mm needle was measured.

8) Flexural modulus Japan Steel Works J120SA II type injection molding machine 12.7mm × 12.7m
A test piece of m × 3.1 mm was prepared and the test was performed according to ASTM: G-790.

9) Izod impact value 63.6mm × 12.7m by Japan Steel Works J120SA II type injection molding machine
A test piece with a m × 3.1 mm notch was prepared and measured at 23 ° C. according to ASTM G-256.

10) Boilable decane-soluble content 1 g of the polymer was added to 100 ml of room temperature n-decane to raise the temperature of the slurry solution while stirring, and the solution was 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 For sieves with openings of 75,125,250,355,500,710,1180 μm,
About 5 g of the polymer was loaded, and the mixture was classified on a sieve shaker for 10 minutes.

Example 1 [Preparation of titanium compound] The titanium component was prepared according to the method of Example 1 in JP-A-58-83006. That is, 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 (3.75 m) of phthalic anhydride was added to this solution.
mol) 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, the whole amount was dropwise added to 40 ml (0.36 mol) of titanium tetrachloride kept at 120 ° C 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 the mixture was stirred at the same temperature for 2 hours. Held down. After the completion of the reaction for 2 hours, a solid portion was collected by hot filtration, and the solid portion was removed with a T of 200 mm.
After resuspending in iCl ₄ , heating reaction was performed again at 110 ° C. for 2 hours. After completion of the reaction, the solid portion was collected again by hot filtration and washed sufficiently with decane and hexane until no free titanium compound was detected in the washing liquid. The solid Ti catalyst component prepared by the above production method was stored as a heptane slurry. The composition of the solid Ti catalyst component is titanium 2.
The content was 1% by weight, 57% by weight chlorine, 18.0% by weight magnesium, and 21.9% by weight diisobutyl phthalate.

[Preliminary polymerization]

Purified heptane 20 in 1 autoclave with N ₂ substitution
After charging 0 ml, triethylaluminum 50 mmol, diphenyldimethoxysilane 10 mmol, ethyl iodide 50 mmol and solid Ti catalyst component 5 mmol in terms of Ti atom, propylene was continuously added for 5 hours to 1 g solid Ti catalyst component 1 g. Was introduced into the reactor and the first prepolymerization was performed. The temperature during this period was kept at 15 ° C. After 1 hour, 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 6 times with purified heptane.

Furthermore, this solid component was charged into a N ₂ -substituted 1-autoclave, and purified heptane 200 ml, triethylaluminum 50 mmol, 6-triethoxysilyl 2-norbornene 10 was added.
After adding 1 mmol of ethyl iodide and 10 mmol of ethyl iodide, propylene was continuously introduced into the reactor for 1 hour so as to be 5 g with respect to 1 g of the solid Ti catalyst component, 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.

[Overlap]

Autoclave having a content volume of 400 subjected to N ₂ substitution was charged with propylene 200, triethylaluminum 274mmo
l, Diphenyldimethoxysilane (274 mmol) and ethylene were fed so that the ethylene gas concentration became 18 mol%, the internal temperature of the autoclave was raised to 45 ° C., and 1.1 mmol of titanium-containing polypropylene was charged as titanium atoms. Then, the internal temperature of the autoclave was raised to 50 ° C., and propylene and ethylene were copolymerized for 1 hour. Polymerization pressure is 24 Kg / cm ²
During this period, the temperature was kept at 50 ° C., and the ethylene concentration was kept at 18 mol% while checking the gas concentration with a gas chromatograph. After 1 hour, unreacted propylene was purged to obtain a white granular polymer. The yield was 37.5 g, and the polymerization activity at this time was 15000 g-PP / g-Gat · Hr.

The results are shown in Tables 1 and 2. Further, a chart of ¹² C-nuclear magnetic resonance spectrum (using GSX270 manufactured by JEOL) is shown in FIG.

The measurement conditions are as follows.

Measurement solvent o-dichlorobenzene / deuterium benzene Measurement temperature 120 ° C. Integration number 4000 times Pulse repetition time 15 seconds Examples 2 to 5 In the polymerization of Example 1, ethylene gas concentration was 14 mol%.
The same operation as in Example 1 was performed except that (Example 2), 24 mol% (Example 3), 28 mol% (Example 4), and 34 mol% (Example 5) were used. The results are shown in Tables 1 and 2.

Examples 6 and 7 In the polymerization of Example 1, hydrogen gas was added at a gas concentration of 0.01 mol.
The same operation as in Example 1 was carried out except that charging was performed so that the amounts were 1% (Example 6) and 0.02 mol% (Example 7). Table of results
1, shown in Table 2.

Examples 8 to 10 In the prepolymerization of Example 1, phenyltriethoxysilane (Example 8) and methylphenyl were used instead of 6-triethoxysilyl-2-norbornene in the second prepolymerization. Diethoxysilane (Example 9),
The same operation as in Example 1 was performed except that butyltriethoxysilane (Example 10) was used. The results are shown in Tables 1 and 2.

Example 11 [Preparation of Titanium Compound] The titanium compound was prepared according to the method of Example 1 in JP-A-62-104810. That is, 100 g of aluminum trichloride (anhydrous) and 29 g of magnesium hydroxide were reacted while being crushed by a vibration mill at 250 ° C. for 3 hours. After completion of heating, the mixture was cooled in a nitrogen stream to obtain a solid product (I).

In a glass flask, 15 ml of purified decane, 2.5 g of solid product (I), 8.5 g of n-butyl orthotitanate, and 9.8 g of 2-ethyl-1-hexanol were mixed, and stirred while stirring.
The mixture was heated to ℃ for 1.5 hours and dissolved to obtain a uniform solution. The solution was heated to 70 ° C., 1.8 g of ethyl p-toluate 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 (II).

30 ml of 1,2-dichloroethane in the total amount of the solid product (II)
And 30 ml of titanium tetrachloride with diisobutyl phthalate
After adding 1.5 g and reacting at 100 ° C for 2 hours with stirring, the liquid phase part was removed by decantation at the same temperature,
30 ml of 1,2-dichloroethane, 30 ml of titanium tetrachloride, and 1.5 g of diisobutyl phthalate were added again, and the mixture was heated to 100 ° C. with stirring.
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 fixed product (III).

The solid product (III) is spherical and has an average particle size of 15 μm.
The particle size distribution was extremely narrow. This solid product (III) was used as a solid Ti catalyst component.

The compositional analysis result of the solid Ti catalyst component was as follows: Ti 3.0% by weight (hereinafter referred to as%), Cl 56.2%, Mg 17.6%, Al 1.7%, diisobutyl phthalate 20.1%, butoxy group 1.1%. The content was 0.2% of 2,2-ethylhexynoxy group and 0.1% of ethyl p-toluate. 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] The titanium compound was prepared according to the method of Example 1 of JP-A-62-11706. That is, 50 ml of purified heptane, 50 ml of titanium tetrabutoxide, and 7.0 g of anhydrous magnesium chloride were added to a 500-ml glass three-necked flask (with a thermometer and a stirrer) having a nitrogen atmosphere.
Then, the flask was heated to 90 ° C. and the 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 precipitate 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 (with a thermometer and a stirrer) having an inner volume of 300 ml 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 the mixture was further reacted at 30 ° C. for 45 minutes. 90 ° C
After reacting for 1.5 hours, the reaction mixture was washed with purified heptane after completion of the reaction. Next, add 50 ml of a heptane solution containing 1.5 ml of diheptyl phthalate and react at 50 ° C. for 2 hours, then wash with purified heptane and add 25 ml of titanium tetrachloride.
The reaction was carried out at 90 ° C for 2 hours. This was washed with purified heptane to obtain a solid Ti catalyst component. The titanium content in the solid Ti catalyst component was 3.04% 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.

Comparative Example 1 In the prepolymerization of Example 1, the same operation as in Example 1 was performed except that the second prepolymerization was not performed. The results are shown in Tables 3 and 4.

Comparative Examples 2 and 3 In the polymerization of Example 1, hydrogen gas was added at a gas concentration of 0.08 mol.
The same operation as in Example 1 was carried out except that the charging amount was changed to 1% (Comparative Example 2) and 0.12 mol% (Comparative Example 3). Table of results
3, shown in Table 4.

Comparative Example 4 The same operation as in Comparative Example 1 was performed using the solid Ti catalyst component obtained in Example 11. The results are shown in Tables 3 and 4.

Comparative Example 5 Using the solid Ti catalyst component obtained in Example 12, the same operation as in Comparative Example 1 was performed. The results are shown in Tables 3 and 4.

Reference Example 1 20 × 20 × 2 (mm) from the polymer powder obtained in Example 1
Sheets were made by press molding. 1.0g of this sheet
Only 1.8% by weight was soluble in 100 ml of boiling decane, and a swollen gel-like substance remained as an insoluble matter.

Reference Example 2 The polymer powder obtained in Example 1 was granulated with an extruder to form pellets. The softening temperature of the pellets was 157 ° C., the soluble content of 1.0 g of the pellets in 100 ml boiling decane was 1.3% by weight, and the swollen gel-like substance remained as an insoluble content.

Reference Example 3 1.0 g of the polymer powder obtained in Example 1 was boiled with n-decane.
It was completely dissolved in 100 ml, cooled to room temperature, and then mixed in a large amount of methanol to obtain a white powdery polymer.

An attempt was made again to dissolve 1.0 g of the obtained polymer in 100 ml of boiling n-decane, but only 22% by weight was soluble, and a swollen gel-like substance remained as an insoluble matter.

[Brief description of drawings]

FIG. 1 is a ¹³ C-nuclear magnetic resonance spectrum chart of the ultrahigh molecular weight propylene ethylene copolymer of the present invention obtained in Example 1. FIG. 2 is a flow chart diagram for clarifying the production process of the ultrahigh molecular weight propylene ethylene copolymer of the present invention. In Fig. 2, * 1 and * 2 represent the following matters. * 1: Different organosilicon compounds are used at each prepolymerization stage. * 2: Preliminary polymerization is carried out in multiple stages (two or more stages).

Claims (2)

[Claims] 1. A monomer unit based on (A) ethylene is 5
-60% by mole, propylene-based monomer unit is 95-40% by mole, (B) weight average molecular weight is 1,000,000 or more, and (C) molecular weight of 10,000 or less measured by gel permeation chromatography. An ultrahigh molecular weight propylene ethylene copolymer, characterized in that the content of the component is 1.0% by weight or less and (D) 80% by weight or more is soluble when 1 g is dissolved in 100 ml of boiling decane. 2. The following components A, B and C A. Titanium compound B. Organoaluminum compound C. General formula [I] After the prepolymerization of propylene in the presence of the organosilicon compound shown in step D and using different organosilicon compounds in each prepolymerization step, D. Titanium-containing polypropylene obtained by the prepolymerization E. Organoaluminum compound F. Ultra-high molecular weight propylene-ethylene copolymer according to claim (1), wherein propylene and ethylene are copolymerized in the presence of the organosilicon compound represented by the general formula [I]. Manufacturing method.