JPH02298540A - Polyolefin composition and its manufacture - Google Patents

Abstract

PURPOSE: To provide a compsn. which is prepd. by compounding a specified butene-1 (co)polymer and a hydrocarbon polymer and has large crystallization rate and remarkably good moldability and turns into a molded article with good mechanical strength and has little content of a catalyst residue and is efficiently obtd.

CONSTITUTION: 0.002-5 wt.% (hereinbelow described as %) polymer (A) prepd. by polymerizing preliminarily a hydrocarbon selected from 5-12C branched olefins and styrenes and 95-99.998% polymer (B) prepd. by polymerization in the presence of a solid catalyst ingredient wherein Mg halide, Ti and an electron-donating compd. are essential ingredients and being a butene-1 homopolymer or a butene-1 copolymer wherein other olefin monomer units are at most 25% with intrinsic viscosity (the measured value in decalin soln. at 135°C) in the range of 1.0-5.5 dl/g, are compounded. This is obtd. by polymerizing the above described two ingredients in the presence of the solid catalyst ingredients and the org. aluminum compd. at 50-100°C.

COPYRIGHT: (C)1990,JPO

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a polyolefin composition and a method for producing the same. A polyolefin composition that has good mechanical strength and a small amount of catalyst residual liquid and can be suitably used as a molding material for pipes, various films, etc., and a method for efficiently obtaining this polyolefin composition. The present invention relates to a method for producing a polyolefin composition.

[Prior Art and Problems to be Solved by the Invention] Butene-1 homopolymers or copolymers of butene-1 and other olefins, generally referred to as polybutene-1, have poor creep properties and compatibility with other resins. Because of its excellent compatibility, it is used in compositions that can be suitably used as materials for forming pipes and various molded products.

However, conventional polybutene-1 has the drawback of slow crystallization rate and extremely poor moldability.

Therefore, various attempts have been made to eliminate such drawbacks.

For example, in JP-A-59-6205, polybutene-1 is produced by prepolymerizing propylene using a highly active catalyst containing magnesium and titanium, and then performing gas phase polymerization at a temperature of 40 to 100°C. A method of manufacturing is disclosed.

However, since this method uses propylene as a prepolymer, the crystallization rate is insufficient.
Good 19. ,-Two □□, □, Yoa, □I have a problem.

In addition, in Japanese Patent Application Laid-open No. 55-1271109,
A catalyst composition mainly composed of titanium trichloride and an organoaluminum compound is brought into contact with ethylene to perform preliminary polymerization, and then polymerization is performed at a temperature of 35°C to form polybutene-1.
A method of manufacturing is disclosed.

However, in this method, titanium trichloride is used as a catalyst component and the polymerization is carried out at a relatively low temperature of 35° C., so the catalytic activity is extremely reduced.

On the other hand, in JP-A-55-123607, a magnesium compound, a titanium compound Th and an electron donor,
Further, in the presence of a highly active catalyst composition consisting of a reaction product of an organometallic compound of a group Ⅰ element, ethylene prepolymerization is performed, and then slurry polymerization is performed at a temperature of 40°C to produce polybutene-1. has been disclosed.

However, even in this method, slurry polymerization is carried out at a relatively low temperature of 40°C, so the intrinsic viscosity [
η] (measured value in a decalin solution at a temperature of 135°C) Only 5.9 dJL/g or more of polyphthene-1 can be obtained, and the catalytic activity is low, so it is difficult to obtain polybutene-1 with good moldability. Can not.

Furthermore, is there a known method of using a nucleating agent to increase the crystallization rate (U.S. Pat. No. 4,321,334)?
(see the specification), the dispersibility is inferior to that of the prepolymerization method, so it does not have sufficient effects. Particularly, in films made using polybutene-1 obtained by this method, there is a problem in that gels form and the appearance becomes poor.

Furthermore, even if polybutene-1 and poly-4-methyl-pentene-1 are mixed, the dispersibility is poor and the crystallization rate cannot be sufficiently increased.

The present invention has been made based on the above circumstances.

The object of the present invention is to provide a fast crystallization rate, extremely good moldability, and good mechanical strength of the molded product.
Furthermore, there is a polyolefin composition that has a small amount of catalyst residue and can be suitably used as a molding material for pipes, various films, etc., and a method for producing a polyolefin composition that can efficiently obtain this polyolefin composition. Our goal is to provide the following.

[Means to solve the problem] In order to solve the above problem, IJI Nagisa conducted extensive studies and found that a polyolefin composition prepared by introducing a specific component through prepolymerization has a remarkable crystallization rate. The molding properties are improved, the moldability is extremely good, the mechanical strength of the molded products is also good, and the amount of catalyst residue is small, so that it can be suitably used as a molding material for pipes, various films, etc. and such polyolefin compositions are prepared using specific solid catalyst components that include magnesium, halogen, titanium, and an electron donor as essential components.
The present invention was achieved by discovering that it can be efficiently produced by a specific method of polymerizing while achieving high catalytic activity at a temperature of 50 to 100°C.

The structure of the invention of claim 1 is a polymer obtained by prepolymerizing a hydrocarbon selected from the group consisting of branched olefins having 5 to 12 carbon atoms and styrenes.
~5% by weight, and a polymer obtained by polymerization in the presence of a solid catalyst component containing magnesium, halogen, titanium, and an electron-donating compound as essential components, and has an intrinsic viscosity [η]
The content of butene-1 homopolymer or other olefin monomer units with a value (measured in a decalin solution at a temperature of 135°C) ranging from 1.0 to 5.5 di/g or 2
Butene-1 copolymer 95-99.9% by weight or less
98% by weight of the solid catalyst component (A) and an organoaluminum compound (B) containing magnesium, halogen, titanium, and an electron-donating compound as essential components. After prepolymerization (prepolymerization amount 0.1 to 500 g/mnoi-Ti) with a hydrocarbon selected from the group consisting of branched olefins having 5 to 12 carbon atoms and styrenes in the presence of butene-1 or The method for producing a polyolefin composition according to claim 1, characterized in that a mixture of butene-1 and other olefins is polymerized at a temperature of 50 to 100C.

The polyolefin composition according to claim 1 has 5 to 5 carbon atoms.
a prepolymer of a hydrocarbon selected from the group consisting of 12 branched olefins and styrenes; a butene-1 homopolymer or a butene-1 copolymer having a content of other olefin monomer units of 25% by weight or less; Consisting of

One of the polymer particles of the prepolymer is a hydrocarbon selected from the group consisting of branched olefins having 5 to 12 carbon atoms and styrenes, and specifically, for example, 3-methylphthene-1,3-cyclohexyl rutsten. -1,3-phenylphthene-1,4-methyl-benzone-1,4,
4-dimethyl-pentene-1,3-methyl-pentene-
1,3-methyl-hexene-1,4-methyl-hexene-1,5-methyl-hexene-1,5,5,-dimethylhexene, vinylcyclohexane, styrene, alkyl group having 1 to 5 carbon atoms Examples include substituted alkyl-substituted styrene.

Among these, particularly preferred are 4-methyl-pentene-1,3-methyl-pentene-1 and styrene.

These may be used alone or in combination of two or more.

When the prepolymer does not contain one kind of polymer, or a hydrocarbon selected from the group consisting of branched olefins having 5 to 12 carbon atoms and styrenes, for example, a linear chain such as butene-1, pentene-1, hexene-1, etc. If it is an olefin or propylene, it is impossible to improve the crystallization rate.

The butene-1 copolymer is a copolymer in which the content of olefin monomer units other than butene-1 units is 25% by weight or less.

If the content of the other olefin monomer units exceeds 25% by weight, the molded product obtained using the polyolefin composition of the present invention may become sticky, or it may be difficult to mold it into a film. .

Examples of the olefin constituting the other olefin monomer unit include linear monoolefins such as propylene, ethylene, hexene-1, and octene-1, branched monoolefins such as 4-methyl-pentene-1, and tutadiene. Examples include dienes.

These may be used alone or in combination of two or more, and propylene and ethylene are particularly preferred in the present invention.

In the present invention, the intrinsic viscosity [η] of the butene-1 homopolymer or the butene-1 copolymer (temperature 135°C
(measured value in decalin solution) or 1.0 to 5.5
It is important that it is within the range of dfL/g. This intrinsic viscosity [η] is 1. If it is less than Od/g, the mechanical strength, especially the impact resistance, of the molded article obtained using the polyolefin composition will decrease. On the other hand, when it exceeds 5.5611 g, the moldability of the polyolefin composition decreases.

In the polyolefin composition of the present invention, the blending ratio of the prepolymer is 0.002 to 5% by weight, and the blending ratio of the butene-1 homopolymer or the butene-1 copolymer is 95 to 99.998%. Weight%.

If the blending ratio of the prepolymer is less than o, ooz% by weight, the crystallization rate of the butene-1 homopolymer or the butene-1 copolymer will not be sufficiently improved; When a gas phase polymerization method is employed to produce the -1 homopolymer or the above-mentioned phthene-1 copolymer, the bulk density of the resulting polymer decreases. On the other hand, if the blending ratio of the prepolymer exceeds 5% by weight, molded articles obtained using this composition will generate more gel or have lower strength.

The polyolefin composition of the present invention has a fast crystallization rate, excellent moldability, good mechanical strength of molded products, and has a small amount of catalyst residue, making it suitable for use in pipes, various films, etc. o** Engineering. 1st □t s , = , = ;6, Ah.

The polyolefin composition according to claim 1 having such excellent properties can be efficiently obtained by the production method according to claim 2.

In the production method according to claim 2, as shown in FIG. Prepolymerization with a hydrocarbon selected from the group consisting of branched olefins having 5 to 12 carbon atoms and styrenes (prepolymerization amount ())
, 1 to 500 g/mu+o-Ti).

Regarding one solid catalyst component (8) - The solid catalyst component (8) to be used is prepared from a non-layered catalyst component obtained by contacting a magnesium compound, a tetravalent titanium halide, and an electron-donating compound. I can do that. If a solid catalyst component other than this is used, such as a titanium trichloride catalyst, the catalyst activity will be low and the amount of residual chlorine in the produced polymer will increase, which may cause problems such as corrosion of the molding machine.

Specifically, the non-layered catalyst component is prepared by, for example, chlorinating at least one magnesium compound with at least one chlorinating agent to obtain a carrier, and then treating this carrier in the presence of an electron-donating compound with - It can be obtained by bringing a tetravalent titanium halide and an electron-donating compound into contact at a temperature within the range of 25°C to +180°C.

Examples of the magnesium compound include the following formula.

MgR' R2 (wherein, R1 and R2 each have 1 carbon number
-20 alkyl groups, and R1 and R2 may be the same or different. ) It is difficult to list organomagnesium compounds represented by

More specifically, diethylmagnesium, ethylbutylmagnesium, ethylhexylmagnesium, ethyloctylmagnesium, diethylmagnesium, butylhexylmagnesium, butyloctylmagnesium,
Examples include alkylmagnesium compounds such as cyclohexylmaxnesium.

As the chlorinating agent, mention may be made of chlorine gas and alkyl chloride. In the method of the present invention, it is preferable to use chloride gas and tutyl chloride in combination.

The above chlorination is usually carried out at a temperature of 0 to 100°C, preferably 2
It is carried out at a temperature of 0 to 60°C, particularly preferably 20 to 40°C.

Through this chlorination, some of the alkyl groups bonded to the magnesium atoms are replaced with chlorine atoms. Moreover, since at least some of the alkyl groups remain, the action of the remaining alkyl groups prevents the formation of a normal crystal lattice, resulting in a very small crystal size with appropriate surface area and pore volume. A non-layered material is formed.

The non-layered material thus obtained is treated with alcohol, if necessary, and then treated with a tetravalent titanium halide in the presence of an electron-donating compound. Further, in the method of the present invention, the treatment with a tetravalent titanium halide may be performed again in the absence of an electron-donating compound. If, according to the prior art, the treatment with an electron-donating compound is carried out before the treatment of tetravalent titanium with a halide, or if the treatment with an electron-donating compound is carried out during or after the second or later treatment of tetravalent titanium with a halide, Otherwise, a very inferior catalyst component may be obtained.

Treatment of tetravalent titanium with halides is usually -25
It is carried out at a temperature within the range of 8C to +180C.

Examples of the tetravalent titanium halides include tetrahalogenated titanium, trihalogenated alkoxytitanium, dihalogenated alkoxytitanium, and monohalogenated trialkoxytitanium.

These may be used alone or in combination of two or more.

Among these, highly halogen-containing materials are preferred, and titanium tetrachloride is particularly preferred.

As the electron-donating compound, an organic compound containing oxygen, nitrogen, phosphorus, or sulfur can be used.

More specifically, amines, amides, ketones, nitriles, phosphines, phosphoramides, esters, ethers, thioesters, thioethers, acid anhydrides, acid halides, acid amides, aldehydes kind,
Examples include organic acids.

Among these, esters, ethers, ketones, and acid anhydrides are preferred; specific examples include n-phthyl benzoate, ethyl p-methoxybenzoate, and p-ethoxybenzoic acid. Examples include ethyl, methyl toluate, cyisobutylphthalate, pentuquinone, benzoic anhydride, ethylene glycol buttyl ether, and the like.

For example, the solid catalyst component (
A) is the content ratio of halogen and titanium or the molar ratio of halogen/titanium, which is usually 3 to 200, preferably 4 to 1.
00, and the content ratio of magnesium and titanium or the molar ratio of magnesium/titanium is usually 1 to 90, preferably 5 to 70.

- About the organoaluminum compound (B) The organoaluminum compound (B) used in the method of the present invention is not particularly limited, and for example, the following general formula: % formula % In the formula, R3 is an alkyl group, a cycloalkyl group, or an aryl group having 1 to 1 carbon atoms, m is a number satisfying 1≦m≦3, and X is a halogen atom such as chlorine or bromine. ) can be suitably used.

Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisophtylaluminium, trioctylaluminum, etc.: diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum Dialkylaluminum sesquihalides such as monochloride and alkylaluminum sesquihalides such as ethylaluminum sesquichlorite and the like can be mentioned.

Among these, preferred is trialkylaluminum, and particularly preferred is trisophthylaluminum.

Regarding one-child polymerization, in the method of the present invention, in the presence of the solid catalyst component (A) and the organoaluminum compound (B), Prepolymerization using a hydrocarbon (preliminary polymerization amount: 0.1 to 500 g/mmo-Ti) is carried out.

Further, in the method of the present invention, an electron donor (C) may be present together with the solid catalyst component (A) and the organoaluminum compound (B) during prepolymerization.

The electron donor (C) may have a cyclic group or an open chain as long as it contains - or more heteroatoms, and is not particularly limited, but is particularly represented by the following formula: Heterocyclic compounds can be preferably used.

(In the formula, R4 and R7 are hydrocarbon groups.

Preferred R4 and R7 are hydrocarbon groups having 2 to 5 carbon atoms, and RS, R6 and R8 are each a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms. ), 1 Among the heterocyclic compounds represented by the above formula, preferred are, for example, 1,4-cineole,
(2) Cineoles such as 8-cineole and m-cineole. Furthermore, it is also possible to use a hetero compound other than the heterocyclic compound represented by the above formula, such as a silicon compound, or an arylalkoxysilane such as diphenyldimethoxysilane.

Prepolymerization may be carried out using the liquid agglomerate itself as a medium, or may be carried out using an inert solvent as a medium.

Examples of inert solvents that can be used include carbon atoms with a carbon number of 3.
~12 aliphatic hydrocarbons may be mentioned.

More specifically, propane, silane, pentane, 2-methylbutane, hexane, 2-methylpentane, 2,2-
dimethylbutane, heptane, octane, 2,2.3-
)limethylbentane, nonane, 2.2.5-)limethylhexane, decane, dodecane and the like.

In prepolymerizing, a hydrocarbon polymer (hereinafter sometimes simply referred to as a mercury) selected from the group consisting of the branched olefins having 5 to 12 carbon atoms and styrenes is used.

), the solid catalyst component (A) and the organoaluminum compound (R), and optionally the electron donor (C
) (hereinafter, these may be simply referred to as catalysts) means that the weight ratio of monomer/solid catalyst component (A) is 0.04.
-200, preferably 0.1-50. The amount of the solid catalyst component (A), the organoaluminum compound (B), and the electron donor (C) used as necessary in the prepolymerization is determined by the amount of aluminum in the organoaluminum compound (B) and the solid catalyst component (A). ) is 0.1 to 200,
The amount is preferably 0.5 to 50, and the molar ratio of aluminum to electron donor (C) in the organoaluminum compound (B) is 0.1 to 1,000, preferably 1 to 500. be.

The prepolymerization time is usually in the range of 1 second to 30 minutes, and the temperature is usually 0 to 100°C, preferably 20 to 70°C.
It is ℃. □ The prepolymerized catalyst may then be washed with an inert solvent or dried. Further, the prepolymerized catalyst can be stored as it is or after being washed and dried.

In addition, in the method of the present invention, preliminary polymerization may be performed in a gas phase atmosphere.

The amount of prepolymerization in the prepolymerization using the monomer carried out in this way is 0.1 to 500 in terms of titanium atoms.
g/mmoJ1. The amount of this prepolymerization is 0.1 g.
/[lllo-Ti is less than the butene-1
The crystallization rate of the homopolymer or the phthene-1 copolymer is not sufficiently improved, and a gas phase polymerization method is adopted for producing the butene-1 homopolymer or the butene-1 copolymer. Sometimes the bulk density of the resulting polymer is reduced. On the other hand, if the amount of prepolymerization exceeds 500 g/m2o-Ti, the molded product obtained using this composition will generate more gel or its strength will decrease.

In the method of the present invention, after preliminary polymerization, main polymerization, which will be described in detail below, is performed.

Regarding monopolymerization In the method of the present invention, the main polymerization with butene-1 or a mixture of butene-1 and other olefins is carried out using the catalyst composition obtained by the prepolymerization. There, the solid catalyst component (A), the organoaluminum compound CB) and the electron donor used as desired (
In addition to C), a prepolymerized polymer is present on the catalyst surface, but in the main polymerization, an organoaluminum compound (II) or an electron donor (C) may be further added.

In the main polymerization, the amount of the solid catalyst component (8), the organoaluminum compound (b), and the electron donor (C) used if desired is determined by the amount of the organoaluminum compound (B).
), the molar ratio (AM/Ti') of aluminum in the solid catalyst component (A) to titanium in the solid catalyst component (A) is 0.1 to 500, preferably 0.5 to 200, and the organic aluminum compound (B
) is the molar ratio of aluminum and electron donor (C) 0?
．． 1-1. The amount is such that [l[lO, preferably 1-500.

For the main polymerization, a gas phase polymerization method or a solution polymerization method may be employed.

In any case, in the method of the present invention, 50 to 100
It is important to carry out the main polymerization at a temperature of .degree.

When the polymerization temperature is lower than 50°C, the activity is extremely reduced. Furthermore, in the gas phase polymerization method, butene-1 tends to liquefy, which may lead to the formation of lumps, and in the solution polymerization method, the polymer tends to precipitate. On the other hand, 100℃
At higher temperatures, the polymerization operation becomes difficult as the tendency for the polymer particles to stick to each other and agglomerate, or for the polymer particles to stick to the walls of the reactor or the stirrer, increases significantly. Furthermore, the catalyst activity also decreases, making it impossible to carry out a smooth polymerization operation.

Next, a case where a gas phase polymerization method is employed will be explained.

When employing the gas phase polymerization method, the polymerization temperature is usually 50 to
The temperature is 70°C, preferably 50-65°C.

The partial pressure of butene-1 varies depending on the polymerization temperature, but
It may be within a range in which liquefaction does not substantially occur, and is usually about 1 to 15 kg/cm2.

In the method of the present invention, main polymerization may be carried out in the presence of a molecular weight regulator such as hydrogen gas.

By using a molecular weight regulator, it is possible to conveniently obtain polymers having various melt flows depending on the purpose.

For example, when hydrogen gas is used, the hydrogen/butene-1 molar ratio is preferably in the range of 0.001 to 0.2. If it is outside this range, the catalytic activity will decrease, the amount of residual halogen in the polymer will increase, and the moldability of the polymer will deteriorate.

Furthermore, in the process of the present invention, inert gases less sensitive than butene-1, such as nitrogen, methane, ethane,
The main polymerization can also be carried out in the presence of propane or the like.

The presence of these inert gases reduces the tendency of the polymer to agglomerate and also facilitates the removal of the heat of polymerization. The effective amount of inert gas present is 0.2 times or more mole based on butene-1.

Gas phase polymerization can be carried out using a fluidized bed or an agitated fluidized bed, or can be carried out without passing the gas component through a tubular polymerization vessel.

In the process of the present invention, it is possible to produce a homopolymer of Phthene-1 or a random copolymer of Phthene-1 with other olefins or a so-called turquoise copolymer.

When producing a homopolymer, butene is
What is necessary is to supply only 1 together with hydrogen etc. to a polymerization vessel and polymerize it by a conventional method.

When producing a lantum copolymer, butene-1 and other olefins as monomers are supplied to a polymerization vessel together with hydrogen etc. so that the content of other olefins in the copolymer is 25% by weight or less. , may be copolymerized.

When producing a so-called turoc copolymer, butene-
After the first stage polymerization treatment in which olefins other than 1 are homopolymerized, in the second stage 1), phten- Copolymerization of 1 or butene-1 with other olefins is carried out. In this case as well, conditions are set so that the content of other olefins in the resulting copolymer is 25% by weight or less.

Here, as the olefin other than butene-1, those similar to those exemplified in the olefin composition according to claim 1 can be used, but in order to obtain a polymer with preferable physical properties, , propylene or ethylene can be suitably used.

When the gas phase polymerization method is adopted, the step of recovering the polymerization solution can be omitted and the step of drying the produced polymer can be greatly simplified.

In addition, when employing a solution polymerization method using Futhene-1 itself as a medium, the polymerization temperature is 50 to 90'C1 pressure, 1
5〜′°“′°””,,IJ″″″′−”I or′°
It is preferable to carry out the reaction under conditions of ~200 gel.

In the method of the present invention, post-polymerization treatments can be carried out according to conventional methods.

For example, to explain the post-processing when gas phase polymerization is adopted, after gas phase polymerization, the polymer powder taken out from the polymerization vessel is passed through an air stream to remove olefins etc. contained therein. It's okay. Further, if desired, it may be pelletized using an extruder, and at that time, a small amount of water, alcohol, etc. may be added to completely deactivate the catalyst.

The manufacturing method of the present invention having the above configuration can be suitably used for manufacturing the polyolefin composition according to claim 1, and the resulting polyolefin composition has a significantly improved crystallization rate and , the amount of catalyst residue is reduced.

[Example] Next, Examples and Comparative Examples of the present invention will be shown to further specifically explain the present invention.

(Example 1) ■Preparation of solid catalyst component (A) Butyloctylmaxnesium (20% hebutane solution) was charged into a 5-tubular flask equipped with a mechanical stirrer, a reflux condenser, a gas supply valve, and a thermometer. A solid catalyst component (A) was prepared as follows. That is, the suspension was kept in an inert atmosphere by bubbling nitrogen through it. Butyl chlorite was added via addition funnel at room temperature. Then, apply chlorine gas for 100 m
Chlorination was added at a rate of M/min.

Then, at 25-35°C, silicone oil was added and then ethanol was added into the mixture. During the addition of ethanol, a thick layer of chlorinated precipitate was deposited. The mixture was then stirred at 40°C for 1 hour. Then reduce the temperature to 75-80
℃ and the solution was left at this temperature overnight.

This hot solution was gently added with a siphon to an excess amount of TiCJlj 4 (-25°C) cooled to low temperature, containing shiisobutylphthalate as an electron donating compound, and the reaction intermediate was precipitated in low temperature T1Cu 4. I let it happen.

The mixture was then warmed to room temperature. Thereafter, di-isobutyl phthalate was added as an electron-donating compound, the temperature was raised to 100-110°C, and the mixture was kept at this temperature for 1 hour. After settling the precipitate, add 5 to 6 ml of hebutane at 85°C.
After washing twice, the solution was transferred to another container using a siphon. A further excess of TiC was added and the mixture was stirred at +10°C for 1 hour.

After settling the precipitate and moving the solution through a siphon, the generated catalyst component was washed several times with butane (5 to 6 times at 80°C) and dried under weak vacuum to obtain a solid catalyst component (A). .

■ I Sarato Kyuen 1 N-heptane dried on a molecular sheet 14 times, triisobutylaluminum [TIBA, organoaluminum compound (B)] 333 mmoM and 1,8-cineole [electron donor (C)] 133 mmoJ1 Prepolymerization tank with stirrer filled with active gas (N2) (
(capacity: 20 sentences).

To this, 67 u of the solid catalyst component (A) obtained in the above
+a+oJJ (titanium atom equivalent) was added. The mixture was left at room temperature for about 10 minutes with gentle stirring.

Then, 640 g of 4-methyl-pentene-1 (1,000 grams for prepolymerization) was slowly added.

After reacting this mixture at 30'C for 15 minutes while stirring lightly, stirring was stopped and the supernatant liquid was taken out.
12! Washing was performed three times with 1 liter of hexane.

The amount of prepolymerization calculated from the weight measured after extracting a part of the slurry and drying it was 9.4 in terms of titanium atoms.
g/ml1oJ1-Ti.

The results are shown in Table 1.

■ Support 1 Plan 1 Diameter 30 with 2 kg of polybutene-1 powder added in advance
hm, using a fluidized bed polymerization vessel with a volume of 100M,
The prepolymerized catalyst obtained was fed from a catalyst supply tank at a rate of 0.15 mmoM/hr in terms of titanium atoms, triisobutylaluminum was fed at a flow rate of 1 mmo/hr, and 1,8-cineole was fed at a rate of 0. Each was supplied to the polymerization vessel at a flow rate of .5 ft/hr.

The partial pressure of Futen-1 is 3 kg/cm2, and the partial pressure of nitrogen is 4.
kg/cm2 and the partial pressure of hydrogen were adjusted to 0.1 kg/cm2, respectively, and the mixed gas was circulated at a superficial gas velocity of 35 cn+/sec. The discharge of the polymer was adjusted so that the amount of polymer in the polymerization vessel remained constant.

The polymerization temperature was 55°C.

The following additives were added to the resulting polymer, and the mixture was granulated using an extruder to obtain a sample.

Calcium stearate: 10100pp,
6-tert-phthyl-4-methylphenol...500ppImtetrakis-[methylene-3-(3',5'-tert-phthyl-4'-hydroxyphenyl)propionate comethane... Table 1 shows the intrinsic viscosity [η], residual titanium, 1/2 crystallization time, Izod impact strength, film formability, gel formation, etc. of the obtained polymer.

In addition, evaluation of each item was performed as follows.

Intrinsic viscosity [η], measured in a decalin solution at a temperature of 135°C.

Titanium content: Calculated backward from the activity.

1/2 crystallization time: A polymer melted at a temperature of 190°C was rapidly cooled to 30°C and crystallized, and the time required for 1/2 crystallization was measured using a depolarized light intensity method.

Izot impact strength Samples with a thickness of 31111 were prepared by nibless molding and notched, and measured at a temperature of 0°C according to ASTM 0256-81.

Film formability.

Film molding was performed using a mini-cast molding machine with a screw diameter of 20 mII+ under conditions of a resin temperature of 210°C and a chill roll temperature of 30°C, and evaluation was made.

Gel generation: The obtained film was visually evaluated. Ta.

(Example 2) The same procedure as in Example 1 was carried out, except that 1 to ethylaluminum was used in place of triisophthylaluminium in the main polymerization of (2).

The results are shown in Table 1.

(Example 3) In the above Example 1, 0.2 ml/hr of Schiffer dimethoxysilane was used instead of 0.5 ml/hr of 1,8-cineole in the main polymerization of (2). It was carried out in the same manner as in 1.

The results are shown in Table 1.

(Example 4) The same procedure as in Example 1 was carried out, except that the hydrogen partial pressure in the main polymerization in Example 1 was changed from 0.1 kg/cm2 to 0.3 kg/c112.

The results are shown in Table 1.

(Example 5) In the above Example 1, the hydrogen partial pressure in the main polymerization in (2) was changed from 0.1 kg/cm 2 to 0.01 kg/cm 2 .

The results are shown in Table 1.

(Example 6) In the above-mentioned Example 1, the partial pressure in the main polymerization of (1) was changed from the partial pressure of butene-1 of 3 kg/cn+2 to the partial pressure of butene-1 of 2.4 kg/c+n2 and propylene of 0.5 kg/cn+2.
The same procedure as in Example 1 was carried out except that the weight was changed to 6 kg/cm2.

The propylene content in the obtained copolymer was 13C-NM
As a result of measurement with R, it was found to be 18.7% by weight.

The results are shown in Table 1.

(Example 7) In Example 1, the partial pressure in the main polymerization of (1) was changed from the partial pressure of butene-1 to 3 kg/cm2 of butene-1.
Partial pressure of 1 3kg IC+12 and ethylene 0.03kg
Same as in Example 1 except that /cm2 was changed to 1
. Aya, huh?

The ethylene content in the obtained copolymer was determined by '3C-NMR
As a result of the measurement, it was found to be 1.3% by weight.

The results are shown in Table 1.

(Example 8) In the above Example 1, the solid catalyst component (A) in the prepolymerization of (2), 1-liisobutylaluminum [organoaluminum compound! tlJI(B)] and 1,8
-The amount of cineole [electron donor (C)] used was reduced to 1/10, and the amount of 4-methyl-pentene-1 (
The amount used for prepolymerization was changed from 640g to 1200g.
The procedure was carried out in the same manner as in Example 1 except that g was changed.

The results are shown in Table 1.

(Example 9) In Example 1, the amount of 4-methyl-pentene-1 (monomer for prepolymerization) used in the prepolymerization of
The same procedure as in Example 1 was carried out except that the amount was changed from 40 g to 25 g.

The results are shown in Table 1.

(Example 10) In Example 1, the temperature in the prepolymerization of (1) was changed to 3
The experiment was carried out in the same manner as in Example 1 except that the temperature was changed from 0°C to 55°C.

The results are shown in Table 1.

(Example 11) In Example 1, 640 g of 4-methyl-pentene-1 (substitute for prepolymerization) was replaced with 3-methyl-phtene-1 without using 14 g of n-hebutane in the prepolymerization of (1). (For prepolymerization) Instead of 500 g, feed 2 kg/C [I12] over 1 hour in the form of scraps, and reduce the temperature to 30
The polymerization was carried out in the same manner as in Example 1, except that the temperature was changed from .degree. C. to 50.degree. C. and preliminary polymerization was carried out in the gas phase.

The results are shown in Table 1.

(Example 12) In the above Example 1, 640 g of 4-methyl-pentene-1 (monomer for prepolymerization) in the prepolymerization of (1)
Example 1 was carried out in the same manner as in Example 1, except that 640 g of styrene (monomer for prepolymerization) was used and the prepolymerization time was changed from 15 minutes to 30 minutes.

The results are shown in Table 1.

(Example 13) Butene-12000 was added to an autoclave with a stirrer for 5 minutes.
g and maintained at 708C.

In this autoclave, l isotutyl aluminum 2[IIIfiO, 1,8-cineole]-3mmo
Then, 0.02 m+SO (in terms of Ti atoms) of the prepolymerized solid catalyst component prepared in the same manner as in Example 1 was injected in this order, and hydrogen was further added at 0.5 kg/cl.
It was injected so that the pressure was +2.

After polymerization was carried out for 1 hour at 70° C. with stirring, methanol was injected to stop the polymerization.

Thereafter, the contents were taken out into a flash tank and unreacted butene-1 was purged to obtain amorphous polyphthene-1. The yield was 331 g.

Note that the obtained solution polymer was pulverized using a pulverizer, and then a sample was prepared in the same manner as in Example 1 above.

The results are shown in Table 1.

(Example 14) In Example 13, 1700 g of Futhene-1 and 300 g of Propylene were used instead of 12000 g of Butene-1.
The same procedure as in Example 13 was carried out except that g was used. The yield was 359g. In addition, the content of propylene in the copolymer was measured by 13C-NMR, and was found to be 21
．． It was 2% by weight.

The results are shown in Table 1.

(Example 15) In the above Example 13, the above Example 1 was added to the prepolymerization catalyst.
In addition to using the hydrogen obtained in step 2, the amount of hydrogen injection was increased from the amount to pressurize 0.5 kg/cm2 to 0.05 kg/cm2.
The same procedure as in Example 13 was carried out except that the amount of pressurization was changed to cm2. The yield was 289g.

The results are shown in Table 1.

(Example 16) In the above Example 7, the above Example 12 was added to the prepolymerization catalyst.
Example 7 was carried out in the same manner as in Example 7, except that the obtained product was used.

The results are shown in Table 1.

(Comparative Example 1) In Example 13, the amount of hydrogen injection was changed to 0.5 kg/
Polybutene-1 was obtained in the same manner as in Example 13, except for changing the amount from crn2 pressure to 0.02 kg/cm2 pressure. The yield was 240g.

The results are shown in Table 1.

(Comparative Example 2) Polybutene- 1
I got it.

The results are shown in Table 1.

(Comparative Example 3) In Example 13, instead of 2000 g of Futhene-1, 1600 g of Butene-1 and 420 g of Propylene were used.
Polybutene-1 was obtained in the same manner as in Example 13 except that . The yield was 399g. Further, the content of propylene in the copolymer was determined to be 29.5% by weight as a result of 13C-NMR measurement.

The results are shown in Table 1.

(Comparative Example 4) In Example 1, the solid catalyst component (A), triisophthylaluminium [organoaluminium compound (B)] and 1,8-cineole [electron donor (C)] in the prepolymerization of (1) Polybutene-1 was prepared in the same manner as in Example 1, except that the amount used was reduced to 1/20 of each, and the amount of 4-methyl-pentene-1 (submerged for prepolymerization) was changed from 640 g to 1900 g. I got 1.

The results are shown in Table 1.

(Comparative Example 5) In Example 1, the amount of 4-methyl-pentene-1 (substitute for prepolymerization) used in the prepolymerization of (1) was changed to 6
Polybutene-1 was obtained in the same manner as in Example 1 except that the amount was changed from 40 g to 4 g.

The results are shown in Table 1.

(Comparative Example 6) In Example 1, 640 g of 4-methyl-pentene-1 (monomer for prepolymerization) in the prepolymerization of (1) was replaced with 640 g of propylene over 1]) minutes. Polybutene-1 was obtained in the same manner as in Example 1.

The results are shown in Table 1.

(Comparative Example 7) In Example 1, 640 g of 4-methyl-pentene-1 (prepolymerization catalyst) in the prepolymerization of (1)
Prepolymerization was carried out in the same manner as in Example 1, except that 1,640 g of phthene was added over 10 minutes instead of. The prepolymerized catalyst obtained was highly viscous and could not be used for polymerization.

The results are shown in Table 1.

(Comparative Example 8) Solid catalyst component 6 obtained in the same manner as in Example 1 (■)
7 mmo structure (titanium atom equivalent) was dried to form triisophthylaluminum [organoaluminum compound (B)].
120011110 and 1,8-cineole [electron donor (C)] 80 n++ aou powder sprinkled with 500 g of polyphthene powder were added to a 20 ml prepolymerization tank.

1640 g of gaseous butene was fed into this prepolymerization tank over 30 minutes at a temperature of 40° C. under stirring, and the partial pressure of nitrogen was 2 kg/cm2 and the partial pressure of butene-1 was 2 kg/cm2.
Preliminary polymerization was carried out under the following conditions.

Using this preliminary polymerization catalyst, main polymerization was carried out in the same manner as in Example 1 (2) to obtain polybutene-1.

The results are shown in Table 1.

(Comparative Example 9) In Example 13, the polymerization temperature was changed from 70°C to 40°C.
Polybutene-1 was obtained in the same manner as in Example 13 except that The yield was 41g.

The results are shown in Table 1.

1 (Comparative Example 1°) When polybutene-1 was produced in the same manner as in Example 1 except that the preliminary polymerization was not performed, lumps were generated during polymerization.

The results are shown in Table 1.

(Comparative Example 11) Polybutene-1 was obtained in the same manner as in Example 13, except that preliminary polymerization was not performed. The yield was 213g.

The results are shown in Table 1.

(Comparative Example 12) 100 mJ of n-heptane dried with molecular sheets
1, diethylaluminum chloride 27ynvnol,
Highly active titanium trichloride catalyst (manufactured by Marubeni Solvay, Lot N
o, TTM-10) 1.8a+IIloM (in terms of titanium atoms) and 11.6 g of 4-methyl-pentene were placed in a 200 m bottle filled with inert gas (N2 gas), and the mixture was stirred gently. It's 30 degrees Celsius and 15
Prepolymerization was performed by reacting for a minute.

Thereafter, a polymer was produced using the entire amount of the mixture containing this prepolymer in accordance with Example 13 without adding triisobutylaluminum and 1,8-cineole. The yield was 319g.

The results are shown in Table 1.

(Comparative Example 13) Commercially available polybutene-1 [Shell Oil Company acid.'
0200J], the intrinsic viscosity [η], 1/2 crystallization time, Izod impact strength and film formability were evaluated in the same manner as in Example 1.゛The results are shown in Table 1.

(Comparative Example 14) Commercially available polybutene-1 [Shell Oil Company acid:
ro 200. ] and polystyrene [manufactured by Idemitsu Petrochemical ■: "Idemitsu Styrene HM-30"] in a ratio of 22% by weight, the intrinsic viscosity [η], 1/2 crystallization was carried out in the same manner as in Example 1 above. Time, Izot impact strength, film formability and gel formation were evaluated.

The results are shown in Table 1.

(Comparative Example 15) Commercially available polybutene-1 [Shell Oil Company acid:
ro 200. ] Nucleating agent [manufactured by Adeka Argus:
Intrinsic viscosity [η], 1/2 crystallization time, Izot impact strength, film formability, and gel strength were measured in the same manner as in Example 1 for 1.000-weight IPPM granulated product of rNA-10,]. We evaluated the generation.

The results are shown in Table 1.

(Laikong, hereafter blank) (Evaluation) As is clear from Table 1, the method of the invention of claim 2 has high catalytic activity, and the polyolefin composition of claim 1 produced by this method has crystallization. It was confirmed that despite the improved conversion rate, it was possible to make a molded product with a small amount of residual titanium, good Izot impact strength and film formability, and little gel formation.

[Effects of the invention] (1) According to the invention of claim 1, the number of carbon atoms is 5 to 12.
A specific polymer obtained by prepolymerizing a specific monomer selected from the group consisting of branched olefins and styrenes in the range of .

Intrinsic viscosity [η
] is in the range of 1.0 to 5.5 or a specific butene-1 copolymer having a content of other olefins of 25% by weight or less in a specific proportion. As a result, the crystallization rate has been significantly improved, the moldability has been significantly improved, and the mechanical strength of the molded product has also been improved.

Furthermore, it is possible to provide a polyolefin composition that has little catalyst residue and can be suitably used as a molding material for pipes, various films, and the like.

(2) According to the invention of claim 2, in the presence of a specific solid catalyst component and an organoaluminum compound, a specific monomer selected from the group consisting of branched olefins and styrenes having a carbon number ranging from 5 to 12. After prepolymerization, butene-1 or a mixture of butene-1 and other olefins is polymerized at a specific temperature of 50 to 100°C, which has high catalytic activity and prevents agglomeration and adhesion of polymer particles. A method for producing a polyolefin composition, which can be suitably used to efficiently produce the industrially useful olefin composition according to claim 1, which does not generate can be provided.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram showing catalyst preparation and polymerization treatment in the present invention. Patent Applicant: Idemitsu Petrochemical Co., Ltd. ○ 9 9 w 4 ”ae Procedural Amendment 1 Description of the Case Patent Application No. 333856 of 1988 2 Name of the Invention Polyolefin Composition and Process for Producing the Same 3 Amendment Patent applicant address: 1-1 Marunoshiratama-chome, Chiyoda-ku, Tokyo Name: Idemitsu Petrochemical Co., Ltd. Representative: Mutsumi Mizugo 4 Agent address: 18-20 Nishi-Shinjuku 7-chome, Shinjuku-ku, Tokyo Building 6th floor Telephone 03-361-2738 Name Patent attorney (8759) Naoki Fukumura 5 Date of amendment order Sent date: spontaneous) 6 Subject of amendment
"Detailed Description of the Invention" column □ 7 Contents of amendment (1) r2f stated on page 21, line 5 of the specification
ltl” is corrected to “40 mouths”. (2) “3” stated on the 21st page, line 16 of the specification
Correct "0 minutes" to "6 hours". (3) "Electron donor (C)" described in page 23, line 1 O of the specification may be replaced with "electron donor (C) (these may be the same as those used in prepolymerization, or (which may be different or different) is amended to j. (4) "15
" is corrected to "10". (5) "Liquid)" written on page 28, line 20 of the specification is amended to "liquid 300g." (6) "Butyl chlorite" written on page 29, line 4 of the specification is corrected to "butyl chlorite 1 to 5 sentences." (7) "Silicon oil" written on page 29, line 7 of the specification is corrected to "silicone oil 2.5 or 1.""Ethanol" is corrected to "Ethanol 113ml". (9) "Then, add the mixture" in page 29, line 18 of the specification, "then add the mixture" to "then add the mixture while stirring." (10) "In addition," written in page 29, line 20 of the specification, is amended to "in addition," (11) "After the precipitate is precipitated" in the first line of page 30 of the specification is amended to "after the reaction product is precipitated." (12) From the 2nd line on page 30 of the specification to the 3rd line on the same page
"Washed and then transferred the solution to another container using a siphon. Further" in the row was corrected to "Washed. Then, further." (13) [1m stated on page 31, line 13 of the specification]
Correct uJ to r4mn+ouJ. (14) “0.
Correct 5muJ to r3m+5ouJ. (15) “0.5” stated on page 34, line 9 of the specification
Correct "m sentence" to "r3m+io sentence". (16) [0,
2mfLJ to rO, 9mmo! ;Correct to LJ. (17) "Styrene HM-30J" described on page 45, line 13 of the specification.
Correct to J. (18) Table 1 on page 47 of the specification is replaced with Table 1 on the attached sheet. (19) Table 1 listed on page 48 of the specification (continued)
Replace with Table 1 (continued) of the attached sheet. that's all

Claims (2)

[Claims] (1) 0.002 to 5% by weight of a polymer obtained by prepolymerizing a hydrocarbon selected from the group consisting of branched olefins having 5 to 12 carbon atoms and styrenes, magnesium, halogen, titanium, and electron donating properties. A polymer obtained by polymerization in the presence of a solid catalyst component containing a compound as an essential component, which has an intrinsic viscosity [η] (measured value in a decalin solution at a temperature of 135°C) of 1.0 to 5.5 dl/
95 to 99.998% by weight of a butene-1 homopolymer or a butene-1 copolymer having a content of other olefin monomer units of not more than 25% by weight. (2) In the presence of a solid catalyst component (A) containing magnesium, halogen, titanium, and an electron-donating compound as essential components and an organoaluminum compound (B),
Prepolymerization with a hydrocarbon selected from the group consisting of branched olefins and styrenes (prepolymerization amount 0.1 to 5
00 g/mmol-Ti), then butene-1 or a mixture of butene-1 and other olefins was added to
Claim 1 characterized in that the polymerization is carried out at a temperature of 100°C.
A method for producing a polyolefin composition as described in .