JP3035049B2 - Method for producing polyolefin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a polyolefin composition suitable as a material such as a conductive material or an electromagnetic shielding material, and more particularly, to a method in which a heterogeneous or irregular filler and a polyolefin are uniformly dispersed. In addition, the present invention relates to a method for efficiently producing a polyolefin-based composition in which characteristics caused by these fillers are stabilized.

[0002]

2. Description of the Related Art In general, polyethylene has been used for a wide range of applications because of its excellent properties. However, in order to further improve its properties and expand its applications, Various fillers have been formulated. In producing a composition in which a filler is blended and dispersed as described above, a method of mechanically kneading a desired filler and a resin is usually employed. However, this mechanical kneading method requires a large amount of kneading energy in order to uniformly disperse the filler, and has the disadvantage that the resin and the filler are deteriorated by the kneading. Furthermore, in the case of blending two or more fillers with different properties, shapes, and particle sizes, blending a large amount of fillers, or blending two fillers with significantly different blending amounts, the uniformity of the composition is improved. There is a problem that it is difficult to secure.

[0003] On the other hand, a method of blending a filler during the polymerization of ethylene is also known. Although this method has better dispersibility than the above-mentioned method of mechanically kneading, it is necessary to ensure uniform dispersion. Requires a little more kneading,
There is a disadvantage that the filler is easily separated from the obtained composition.

[0004] The applicant of the present invention has focused on the affinity of the filler to be used with polyethylene, and has previously contacted a filler having a low affinity among a plurality of types of fillers with a specific highly active catalyst component. In addition, by presenting this in an ethylene polymerization reaction system together with an untreated filler having an affinity equal to or higher than that of a method of obtaining a homogeneously dispersed composition even when different types of fillers are used. Proposal ( Sho 1)
-16403 ). However, in this method,
After contacting the catalyst with one of the fillers, the other filler is added, and then the polymerization is started.Therefore, two kinds of fillers are mixed before the polymerization, and the one filler is contacted in advance. Some of the catalyst migrates to the other filler and the polymerization is not uniform, resulting in a mixture of the composition containing the two fillers and the composition containing only the other filler. Also,
In the case of this method, since a composition containing only the other filler is prepared, control accuracy of the filler content of the composition containing the two fillers is reduced. Furthermore, in the case of this method, there is also a problem that the composition containing only the other filler is incorporated into the composition containing the two fillers, so that the particle size distribution of the composition is deteriorated.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional disadvantages, and a polyolefin-based material in which a plurality of fillers are uniformly dispersed and whose characteristics are stabilized by these fillers. It is an object of the present invention to provide a method for efficiently producing a composition. That is, the present invention contains a transition metal , is soluble in an organic solvent , and
Etch using the catalyst component and an organoaluminum compound
In low-pressure polymerization of ren, ethylene partial pressure 1 atm, transition gold
10g of polyethylene will be produced per 1g of genus atom
That a highly active catalyst component [A], treated obtained by previously contacting processes the filler (I), and using an organoaluminum compound [B], after performing the prepolymerization α- olefin, wherein Compared with filler (I),
An object of the present invention is to provide a method for producing a polyolefin-based composition, which comprises adding a filler (II) having an equivalent power or more and polymerizing an α-olefin.

[0006] In the present invention, if the transition metal is contained
Both are soluble in organic solventsAnd the catalyst component and an organic
Low pressure polymerization of ethylene with aluminum compounds
And 1 atm of ethylene partial pressure, 1 g of transition metal atom,
Can produce 10 kg or more of polyethyleneHighly active catalyst component
(Soluble catalyst component)(Hereinafter, simply referred to as highly active catalyst component)
Sometimes. )[A] and the filler (I) are contacted in advance
Process to obtain a processed product. If the transition metal is contained here
Both are highly active catalyst components soluble in organic solvents [A]
The following are specific examples, and various methods
Can be prepared. That is, it can be used in organic solvents.
As a soluble high activity catalyst component,Magnesium or ma
Salt of gangan with higher fatty acids having 10 or more carbon atoms, magnesi
Or manganese and higher alcohols with 10 or more carbon atoms
Salt or magnesium or manganese with 6 or more carbon atoms
A salt with phosphoric acid having a long-chain aliphatic hydrocarbon group,Chita
Reaction products obtained by adding and reacting Transition
Transfer metal compound and aluminoxane, or Transition metal compound
Reacts with the transition metal in the transition metal compound to form an ion.
Compounds that can form an acidic complex. For example
For the catalyst component containing titanium as a transition metal,
Magnesium or manganese and high-grade fats with 10 or more carbon atoms
Salts with fatty acids (hereinafter referred to as magnesium or manganese
It is called a fatty acid salt. ), With magnesium or manganese
Salts with higher alcohols having 10 or more carbon atoms (hereinafter referred to as Magneto
It is referred to as higher alcohol salts of calcium or manganese. )
Or magnesium or manganese and a long chain with 6 or more carbon atoms
Salts with phosphoric acid having an aliphatic hydrocarbon group (hereinafter
Containing long-chain aliphatic hydrocarbon groups of calcium or manganese
Called phosphate. )General formula [I]

[0007]

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[Wherein, R ¹ represents an alkyl group or an acyl group having 1 to 10 carbon atoms, and X ¹ represents a halogen atom. Further, n is a real number from 0 to 4 inclusive. The reaction product obtained by adding and reacting the titanium compound represented by formula (1) is used. In particular, a reaction product obtained by adding a titanium compound to an organomagnesium compound, for example, a higher fatty acid salt of magnesium and reacting the same, is preferable. At this time, the addition amount of the titanium compound is not particularly limited, but is usually 0 to the above-mentioned higher fatty acid salt of magnesium or manganese, higher alcohol salt or phosphate having a long-chain aliphatic hydrocarbon group. 0.5 or less (molar ratio), preferably 0.02
It is selected in the range of ~ 0.2 (molar ratio). If the amount of the titanium compound exceeds 0.5 (molar ratio), the catalytic activity is remarkably reduced, which is not preferable. Here, the higher fatty acid or higher alcohol constituting the salt may be saturated or unsaturated as long as it has 10 or more carbon atoms.
Six or more are preferred. Specific examples thereof include higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid, and higher alcohols such as decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, and stearyl alcohol. Can be mentioned. The phosphoric acid constituting the phosphate having a long-chain aliphatic hydrocarbon group may be phosphorous acid, and phosphoric acid or a mono- or dialkyl ester of phosphorous acid (ROPH ₂ O ₃ , (R
O) ₂ PHO ₂ , ROPH ₂ O ₂ ) or mono- or dialkyl (sub) phosphoric acid (RPH ₂ O ₃ , R ₂ PH)
O ₂ , RPH ₂ O _2, etc.). The long-chain aliphatic hydrocarbon group may be a saturated or unsaturated group as long as it has 6 or more carbon atoms, and particularly preferably has 8 or more carbon atoms. Specific examples of these include a hexyl group,
Examples include heptyl, octyl, 2-ethyl-hexyl, nonyl, decyl, lauryl, myristyl, heptadecyl, stearyl, octadecenyl and the like. These higher fatty acid, higher alcohol or magnesium salt or manganese salt of phosphoric acid having a long-chain hydrocarbon group can be obtained by various methods, or a commercially available product may be used by drying as it is. The magnesium salt can be easily produced from a higher fatty acid, a higher alcohol or phosphoric acid having a long-chain hydrocarbon group and an alkyl magnesium. Further, the above-mentioned magnesium salt or manganese salt (ie, a higher fatty acid salt of magnesium or manganese, a higher alcohol salt or the above-mentioned phosphate) may form a double salt with another metal.

On the other hand, the titanium compound used here is represented by the general formula [I] as described above, and specifically, a titanium tetrahalide such as TiCl ₄ , TiBr ₄ , or TiI ₄ ; (OCH ₃ ) Cl ₃ , Ti (O
C ₂ H ₅ ) Cl ₃ , Ti (OiC ₃ H ₇ ) Cl ₃ ,
Ti (OC ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br ₃
Trihalogenated monoalkoxy titanium such as Ti (O
CH ₃ ) ₂ Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Cl ₂ , Ti
(OiC ₃ H ₇ ) ₂ Cl ₂ , Ti (OC ₄ H ₉ ) ₂
Dialkoxytitanium dihalide such as Cl ₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ , Ti (OCH ₃ ) ₃ Cl, Ti
(OC ₂ H ₅ ) ₃ Cl, Ti (OiC ₃ H ₇ ) ₃ C
1, Ti (OC ₄ H ₉ ) ₂ Cl, Ti (OC ₂ H ₅ ) ₃
Monohalogenated trialkoxy titanium such as Br, Ti
(OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (O-i
Tetraalkoxytitanium such as —C ₃ H ₇ ) ₄ and Ti (OC ₄ H ₉ ) ₄ , and further Ti (OCOCH ₃ ) ₄ and T
i (OCOCH ₃ ) ₂ Cl _{2 and the} like.

In the present invention, among the highly active catalyst components that contain a transition metal and are soluble in an organic solvent, particularly those containing titanium as a transition metal are, as described above, higher fatty acids such as magnesium and manganese. It is obtained by reacting a salt, a higher alcohol salt or the above-mentioned phosphate with a titanium compound represented by the above general formula [I]. The reaction conditions at this time vary, but usually, these compounds may be mixed in a hydrocarbon solvent and reacted at a temperature in the range of 50 ° C. to the boiling point of the solvent for 10 minutes or more. In some cases, the above-mentioned higher fatty acid salt, higher alcohol salt or the above-mentioned phosphate and the filler (I) are mixed in a hydrocarbon solvent, and then the titanium compound represented by the above general formula [I] is mixed. And a reaction product of the catalyst component [A] containing titanium and the filler (I) may be prepared.

Further, in obtaining the titanium-containing catalyst component, together with the above-mentioned salt and titanium compound, V
Cl ₄ , VOCl ₃ , VO (OC ₂ H ₅ ) ₃ , VO (OC
_The use of a vanadium compound such as ₄ H ₉ ) ₃ is effective in expanding the molecular weight distribution of the obtained polymer and improving the copolymerizability.

In the present invention, the highly active catalyst component containing a transition metal and soluble in an organic solvent includes:
There are transition metal compounds, particularly those comprising a transition metal compound belonging to Group IVB of the periodic table (for example, titanium, zirconium, etc.) and aluminoxane. Among them, titanium-based compounds include, for example, a compound composed of a cyclopentadienyl titanium compound or a dicyclopentadienyl titanium compound, and aluminoxane.
Here, the aluminoxane can be obtained by a known method such as reacting trialkylaluminum such as trimethylaluminum and triethylaluminum, or dialkylaluminum monohalide such as dimethylaluminum chloride and diethylaluminum chloride with water. In addition, as a cyclopentadienyl titanium compound, dicyclopentadienyl titanium chloride, dimethyldicyclopentadienyl titanium, etc. are mentioned, for example.

The zirconium-based compound is prepared, for example, by mixing a cyclopentadienyl zirconium compound or this cyclopentadienyl compound with an aluminoxane obtained by the above-mentioned known method. Here, examples of cyclopentadienyl zirconium include dichlorodicyclopentadienyl zirconium, dimethyldicyclopentadienyl zirconium, and the like. In the case of mixing these cyclopentadienyl dititanium compounds or cyclopentadienyl zirconium compounds with aluminoxane, these compounds are mixed in an aromatic hydrocarbon solvent such as benzene, toluene, xylene and other alkylbenzenes. Is preferably mixed. In this case, it is not preferable to use an aliphatic hydrocarbon or an alicyclic hydrocarbon as the solvent because the above-mentioned zirconium compound or aluminoxane cannot be sufficiently dissolved. The mixing of these compounds is preferably performed before mixing with the filler (I) described later.
However, it is also possible to mix the filler (I) at the same time.

In the present invention, the highly active catalyst component containing a transition metal and soluble in an organic solvent includes:
A transition metal compound and a compound capable of forming an ionic complex by reacting with a transition metal in the transition metal compound, that is, a coordination complex comprising a transition metal compound, a cation and an anion in which a plurality of groups are bonded to an element. It can be used in combination with a compound. Here, the transition metal compound is a transition metal selected from the group IVB of the periodic table, specifically, titanium (Ti), zirconium (Zr) or hafnium (H
Any compound can be used as long as it is a compound containing f), in particular, a cyclopentadienyl compound containing these transition metals.

Examples of such compounds include the following zirconium compounds and compounds in which zirconium of these compounds is replaced with titanium or hafnium.

That is, specific examples of the zirconium compound include (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (Cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trimethylzirconium,
(Methylcyclopentadienyl) tribenzylzirconium, (tetramethylcyclopentadienyl) trimethylzirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl ) Dimethyl (methoxy) zirconium, bis (cyclopentadienyl) dichloro zirconium, bis (cyclopentadienyl) dimethyl zirconium, bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclo (Pentadienyl) dibenzyl zirconium, bis (methylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dimethyl zircon , Bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) chloromethylzirconium, bis (pentamethylcyclopentadienyl) hydride Methyl zirconium, ethylene bis (indenyl) dimethyl zirconium, ethylene bis (tetrahydroindenyl) dimethyl zirconium, dimethylsilylenebis (cyclopentadienyl) dimethyl zirconium, isopropyl- (cyclopentadienyl)-(9
-Fluorenyl) -zirconium dichloride.

The compound capable of reacting with a transition metal in the transition metal compound to form an ionic complex is not particularly limited, but specifically, the following compounds are particularly preferably used. Can be. That is, triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, Triethylammonium hexafluoroarsenate, dimethylanilium tetra (pentafluorophenyl) borate, trimethylanilium tetra (pentafluorophenyl) borate, ferrocenium tetraphenylborate, decamethylferrocenium tetra (pentafluorophenyl) borate, tetra (pentane Fluorophenyl) acetylferrocenium borate, tetra (pentafluorophenyl)
Formylferrocenium borate, cyanoferrocenium tetra (pentafluorophenyl) borate, tetraphenylborate, silver tetra (pentafluorophenyl) borate, trityl tetraphenylborate, trityl tetra (pentafluorophenyl) borate, hexafluoroarsenate Silver, silver hexafluoroantimonate, silver tetrafluoroborate and the like can be mentioned.

The contact conditions of the above two are not particularly limited, but usually, the ratio of the former to the latter is 1: 0.01 to 1: 1.
00, particularly preferably 1: 1 to 1:10. The temperature can be in the range of -100 ° C to + 250 ° C, and the pressure and time can be arbitrarily set.

The thus obtained transition metal-containing catalyst component [A] is a component soluble in organic solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. In addition, this component has a high activity such that 10 kg or more of polyethylene can be produced per 1 atm of ethylene partial pressure and 1 g of transition metal atom in low-pressure polymerization of ethylene using the catalyst component and the organoaluminum compound [B]. It is. Here, when the activity of the component is low, the component must be added in a large amount to the reaction system, and as a result,
A decalcification step is required after the polymerization reaction, which makes post-treatment extremely complicated, which is not preferable.

In the present invention, the treated component obtained by previously contacting the catalyst component [A] containing a transition metal as described above with the filler (I), and the organoaluminum compound [B] are used to obtain α. -Preliminary polymerization of the olefin is carried out first.

Next, the filler (I) used in the method of the present invention
Examples of the material include, but are not particularly limited to, metals, metal oxides, metal carbonates, carbonaceous materials, conductive powders, ceramics, solid foaming agents, and organic pigments. First, metals include copper, aluminum, nickel, iron, tin, zinc and the like, and metal oxides include ferrite, mica,
Examples include alumina, titania, zirconia, silica, silica alumina, iron oxide, and zinc oxide. Further, examples of the metal carbonate include calcium carbonate and barium carbonate.
Examples of carbonaceous materials include carbon black such as furnace black and Ketjen black, graphite,
There are graphite and activated carbon. Further, as the conductive powder, there is zinc sulfide and the like in addition to the above. As ceramics, silicon carbide (SiC), chromium carbide (Cr
₃ C ₂ ), titanium carbide (TiC), zirconium carbide (ZrC), boron carbide (B ₄ C), diamond (C)
And silicon nitride (SiN, Si ₃ N, Si ₂ N
₃ , Si ₃ N ₄ ), boron nitride (BN), zirconium nitride (ZrN), niobium nitride (NbN), titanium nitride (T
iN), borides such as titanium boride (TiB), zirconium boride (ZrB), tantalum boride (TaB), vanadium boride (VB ₃ ), and lanthanum boride (LaB ₆ ); Silicides such as titanium silicide (TiSi), tantalum silicide (TaSi), molybdenum silicide (MoSi), and tungsten silicide (WSi ₂ ) can be given. Furthermore, when the composition is used as a foam, a solid foaming agent can also be used. The solid foaming agent may be any one which is insoluble in hydrocarbon solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. Specifically, azodicarbonamide, azobisisobutyro Examples include azo compounds such as nitriles, nitroso compounds such as dinitropentamethylenetetramine, and sulfonyl hydrazide compounds such as p-toluenesulfonyl hydridide and p, p'-oxybis (benzenesulfonyl hydrazide). Further, an organic pigment as a coloring material can also be used. The organic pigment is not particularly limited as long as it is insoluble in a hydrocarbon solvent, and is appropriately selected according to a desired coloring situation. Specific examples include insoluble azo, soluble azo, phthalocyanine, anthraquinone, thioindigoid, berylen, dioxazine, and quinacridone.

Further, instead of using these fillers as they are, a metal plated or coated with a metal or metal oxide may be used. Examples of the treatment filler in this case include carbon fibers, carbon black, glass fibers, glass beads, glass balloons, mica, potassium titanate, and pulp coated with a metal or a metal oxide. . . The metal used for the treatment here is nickel,
Silver, copper, aluminum, iron, tin and the like can be mentioned, and as the metal oxide, titanium oxide, tin oxide, silica, alumina, ferrite, silica alumina and the like can be mentioned.

The filler may be in various shapes such as powder, granule, flake, foil, whisker and fiber.
Although any of them can be used, in each shape, those having a maximum length not exceeding 5 mm, particularly those having a maximum length of 2 mm or less are preferable. When a large filler having a size exceeding 5 mm is used, agglomeration occurs during the polymerization of ethylene to cause clogging of pipes and the like, and the obtained composition becomes inhomogeneous. Before use, the filler is preferably dried sufficiently by heating under reduced pressure, azeotropic drying using a solvent, or the like, or is treated with an organoaluminum compound such as trialkylaluminum or dialkylaluminum monohalide. . In particular, by using a material pre-treated with an organoaluminum compound, a decrease in the activity of the catalyst component due to moisture or a functional group in the filler is effectively prevented.

The contact-treated product containing a catalyst in the present invention is:
As described above, the treated product is obtained by previously contacting the highly active catalyst component [A] containing the transition metal and soluble in the organic solvent with the filler (I). There are no particular restrictions on the contact treatment between the two, and various types of solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons may be used, and may be determined in the range from room temperature to the boiling point of the solvent used. Also,
Usually, the aging time is about 1 hour or more at room temperature.

The mixing ratio of the two during the contact treatment is as follows:
It depends on various conditions, and it is difficult to determine uniquely. In short, when the polymerization or copolymerization of the α-olefin is carried out by the method of the present invention, it is appropriately determined depending on whether the polymerization or copolymerization proceeds efficiently and the amount of the filler in the target composition. do it. Usually, the content of the total filler with the filler (II) described later is 0.5
The filler (I) may be added in an amount of not less than 1% by weight, preferably about 1 to 99% by weight.

In the method of the present invention, a prepolymerization is carried out using the contact-treated product obtained as described above and an organoaluminum compound [B] to be described later. This contact-treated product may be introduced into the reaction system as a slurry, or may be introduced after the solvent is separated.

Next, as the component [B] used in the method of the present invention, an organoaluminum compound is used. Here, there are various kinds of organic aluminum compounds, and there is no particular limitation. Usually, the following general formula (II)

[0028]

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## EQU1 ## Note that R in the formula
² is an alkyl group having 1 to 10, preferably 1 to 6 carbon atoms,
It is a cycloalkyl group or an aryl group, and X ² is a halogen atom. In addition, m is a positive real number of 3 or less, specifically, m = 1, 1.5, 2, or 3.

Examples of such organoaluminum compounds include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diethylaluminum monobromide, and diethylaluminum monoiodide. Dialkylaluminum monohalides such as diide, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride and the like, and alkylaluminum sesquichlorides such as methylaluminum sesquichloride, ethylaluminum sesquichloride, ethylaluminum sesquibromide and butylaluminum sesquichloride are preferable. And Mixtures of these were also preferably used. In particular, a mixture of a trialkylaluminum and a dialkylaluminum halide, an alkylaluminum dihalide or an alkylaluminium sesquihalide is preferable when a component containing titanium is used as a component of the catalyst component (A). In addition, an organic lithium aluminum compound, an alkyl group-containing aluminoxane generated from trialkylaluminum and water, and the like can also be used. In particular, this aluminoxane is preferable when a component containing a cyclopentadienyl titanium or cyclopentadienyl zirconium compound is used as a component of the catalyst component of the component (A).

In the method of the present invention, using the above-mentioned contact-treated product and the above-mentioned organoaluminum compound [B],
First, preliminary polymerization of an α-olefin is performed. If the prepolymerization is not carried out in the method of the present invention, the object of the present invention cannot be achieved. Here, as the α-olefin, ethylene is usually used, and together with this ethylene, a small amount (usually, about 20% by weight) of α-olefin is used.
It can also be copolymerized with olefins such as propylene, butene-1, hexene-1, octene-1,4-methylpentene-1, decene, octadecene and the like. The prepolymerization amount is determined from the minimum amount required for the initiation of polymerization based on all the catalysts treated with the filler (I) to the filler (I)
Any amount may be used as long as a post-polymerized portion necessary for incorporating I) is left. Usually, it is about 0.1% to 90% by weight of the total polymerization amount. The polymerization method and conditions are not particularly limited, and either slurry polymerization or gas phase polymerization is possible, and both continuous polymerization and discontinuous polymerization are possible. The amount of the catalyst component [A] to be added may be determined in accordance with, for example, a relational expression described in Japanese Patent Publication No. 1-16403. That is,
The activity of the highly active catalyst component, which contains a transition metal and is soluble in an organic solvent, which is a component of the catalyst component of the component (A), produces polyethylene Wkg per gram of transition metal atoms in the catalyst component. The amount of the filler (I) used is N kg, and the amount of the filler (II) is P
kg, the ratio of the filler in the final composition is C%, and the amount of transition metal atoms required in this case is xg.

[0032]

(Equation 1)

The amount of the catalyst component [A] to be added may be determined according to the following formula. The ethylene pressure of the reaction system is from normal pressure to 50 kg / cm
² · G, the reaction temperature is 10 to 150 ° C., preferably 2
0 to 120 ° C. The molecular weight at the time of polymerization can be adjusted by known means, for example, hydrogen.

Next, in the method of the present invention, the filler (II)
To polymerize the α-olefin. Here filler (II), the compared filler and (I), polyolefins, der particular affinity for polyethylene than comparable
You. The filler (II) used here may be the same as the filler (I), but is usually a different one, and has the same or greater affinity for polyethylene than the filler (I). Things. In order to check the affinity of the filler, the desired two types of fillers are simultaneously present in the reaction system, polymerization of ethylene is performed, and which is separated from the produced polyethylene is observed. (I). As the shape and size of the filler (II), various ones can be used as in the case of the filler (I), but the particle size is preferably equal to or smaller than that of the filler (I). . As described above, these fillers are preferably dried before use or treated with organic aluminum.

In the method of the present invention, preferably, after the addition of the filler (II) having an affinity for polyethylene equal to or higher than that of the filler (I), the polymerization of the α-olefin Polymerization). The polymerization conditions and the like are the same as those for the preliminary polymerization. The pre-polymerization was carried out at 0.
Since about 1% to 90% by weight is carried out, the remaining amount is about 99.9 to 10% by weight in the main polymerization. According to the method of the present invention, after the polymerization or copolymerization reaction is performed, in the case of slurry polymerization, operations such as flashing and centrifugal separation are performed, and further drying is performed to remove the solvent and the like. The system composition can be obtained in the form of powder and granules.

[0036]

Next, the present invention will be described with reference to examples.

Example 1 (1) Preparation of Titanium-Containing Soluble Catalyst Component In a 500-ml flask purged with argon, 150 ml of dehydrated n-heptane, 10.0 g (17 mmol) of magnesium stearate, and tetrachloride were placed at room temperature. 0.33 g (1.7 mmol) of titanium was charged. Then, the temperature was raised and the mixture was reacted under reflux of the solvent for 2 hours to obtain a viscous translucent titanium-containing soluble catalyst component. (2) Evaluation of the activity of the titanium-containing soluble catalyst component In an autoclave having an inner volume of 1 liter replaced with argon, 400 ml of dehydrated n-hexane, 1 mmol of triethylaluminum, and 1 mol of diethylaluminum monochloride were added.
0.005 mmol of the mmol and the titanium-containing soluble catalyst component obtained in the above (1) were collected as titanium atoms and supplied to the autoclave. Next, the temperature was raised to 80 ° C., and hydrogen was supplied to raise the pressure to 4 kg / cm ² · G.
g / cm ² · G, ethylene was continuously supplied to carry out polymerization for 1 hour. The obtained polyethylene was 58 g, and the polymerization activity was 242 kg / g · Ti · hr.
Met. (3) Contact treatment between the titanium-containing soluble catalyst component and the filler (I) In an autoclave having an inner volume of 1 liter replaced with argon, at room temperature, 450 ml of dehydrated hexane and average particles excluding those having a particle size of 44 μm or less were removed. 475 g of a ferrite powder having a diameter of 70 μm was added thereto, and 1 mmol of diethyl aluminum monochloride was added dropwise with stirring, followed by treatment at 40 ° C. for 1 hour. Next, 0.01 mmol of the titanium-containing soluble catalyst component obtained in the above (1) was added as titanium atoms,
The contact was carried out at 0 ° C. for 1 hour to obtain a treated product. (4) Polymerization of ethylene After the contact treatment of (3), the temperature was raised to 90 ° C. Thereafter, 1 mmol of triethylaluminum was added, hydrogen was supplied at 0.2 kg / cm ² · G, and then 2.3 g of ethylene was supplied for prepolymerization. Next, the temperature was lowered to 40 ° C., and 200 ml of a dehydrated hexane slurry solution containing 2.5 g of carbon black (Ketjen black) previously dried and having an average particle diameter of 30 nm was added thereto, and the temperature was raised to 90 ° C. again. Thereafter, hydrogen was supplied at 0.2kg / cm ² · G, followed to maintain the total pressure at 4kg / cm ² · G, ethylene was continuously fed, and polymerization of ethylene 20.2 g. The polymerization amount of all ethylene is 22.5 g,
The polymerization time was 20 minutes.

At this time, the target filler content is such that the filler (I) (ferrite) content in the total composition is 95.0% by weight,
The filler (II) (carbon black) content in the polyethylene is 10.0% by weight. The obtained polyethylene composition weighed 500 g. Classification was performed to confirm the homogeneity of the obtained polyethylene composition, and the filler content was determined. In classification, the particle size, which accounts for the majority of the composition, is 44.
１０５105 μm and the remaining particles were evaluated separately. As a result, the fraction of particles having a particle diameter of 44 to 105 μm was 96% by weight, and the ferrite content in the total composition and the carbon black content in the polyethylene were 9% each.
It was 5.0% by weight and 10.1% by weight. The contents of the remaining 4% by weight were 95.0% by weight and 7.6% by weight, respectively. The content of the filler was measured by the following method. A 20 g sample is heated in para-xylene to completely melt the polyethylene. This is filtered out using a 44 μm wire mesh in the molten state. Only the ferrite powder remains on the wire mesh. The ferrite powder is dried, and the weight is measured to calculate the ferrite content in the polyethylene composition. The filtrate is a mixture of polyethylene and carbon black by removing para-xylene by evaporation. TG /
The carbon black content is measured using DTA.

Comparative Example 1 (1) Preparation of Titanium-Containing Soluble Catalyst Component The preparation was carried out in the same manner as in Example 1 (1). (2) Evaluation of activity of titanium-containing soluble catalyst component The evaluation was performed in the same manner as in Example 1 (2). (3) Contact treatment between the titanium-containing soluble catalyst component and the filler (I) was carried out in the same manner as in Example 1 (3). (4) Polymerization of ethylene After the contact treatment of the above (3), the average particle diameter previously dried is 30 nm.
200 ml of a dehydrated hexane slurry solution containing 2.5 g of carbon black (Ketjen) was added, and the temperature was raised to 90 ° C. Then added triethylaluminum 1 mole, then after supplying of hydrogen 0.2kg / cm ² · G, the total pressure was continuously feeding ethylene to maintain the ^{4kg / cm 2 · G, 22} . 5 g of ethylene were polymerized. At this time, the polymerization time was 22 minutes. The obtained polyethylene composition weighed 500 g. The content of the filler was measured in the same manner as in Example 1. The results are shown in Table 1.

Example 2 In Example 1, the amount of prepolymerized ethylene in Example 1 (4) was set to 2.0 g, the amount of post-polymerization was set to 18.0 g (total amount of polymerization: 20.0 g), and carbon black was used. Instead of conductive zinc sulfide (TYP) having an average particle size of 0.2 μm
E-III: Mitsui Kinzoku) except that 5.0 g was used.
Polymerization was carried out in the same manner as in Example 1 to obtain 500 g of a polyethylene composition. The content of the filler was measured in the same manner as in Example 1. First result
It is shown in the table.

COMPARATIVE EXAMPLE 2 In Comparative Example 1, the amount of ethylene polymerization in Comparative Example 1 (4) was 20.0 g, and conductive zinc sulfide (TYPE-
III: made by Mitsui Kinzoku Co., Ltd.) Polymerization was carried out in the same manner as in Comparative Example 1 except that the amount was 5.0 g.
00 g were obtained. The content of the filler was measured in the same manner as in Example 1. The results are shown in Table 1.

Example 3 (1) Preparation of Soluble Titanium-Containing Catalyst Component In a 200-ml flask purged with argon, 50 ml of dehydrated n-heptane, 5.64 g (10 mmol) of magnesium stearyl alcohol salt and 0.19 g (1 mmol) of titanium tetrachloride was added. Then, the temperature was raised, and the mixture was reacted for 3 hours under reflux of the solvent to obtain a viscous translucent titanium-containing soluble catalyst component. (2) Evaluation of the activity of the titanium-containing soluble catalyst component In a 1-liter autoclave purged with argon, 400 ml of dehydrated n-hexane, 2 mmol of triethylaluminum, and 2 mmol of diethylaluminum monochloride were added.
The mmol and the titanium-containing soluble catalyst component obtained in the above (1) were collected in 0.01 mmol as titanium atoms and supplied to the autoclave. Next, the temperature was raised to 80 ° C., hydrogen was supplied, and the pressure was raised to 4 kg / cm ² · G.
/ Cm ² · G, ethylene was continuously supplied and polymerization was carried out for 1 hour. The obtained polyethylene is 60 g and the polymerization activity is 126 kg / g · Ti · h
r. (3) Contact treatment between titanium-containing soluble catalyst component and filler (I) The procedure was the same as in Example 1 (3) except that the titanium-containing soluble catalyst component prepared in (1) above was used. Was. (4) Ethylene polymerization In Example 1 (4), the ethylene prepolymerization amount was 2.0
g, the post-polymerization amount was 18.0 g (total polymerization amount: 20.0 g), and the average particle size was 30 in place of carbon black.
Polymerization was carried out in the same manner as in Example 1 (4) except that 5.0 g of SiC powder having a thickness of 500 nm was used, to obtain 500 g of a polyethylene composition. In the same manner as in Example 1, the content of the filler was measured. First result
It is shown in the table.

COMPARATIVE EXAMPLE 3 Comparative Example 1 (3) uses the titanium-containing soluble catalyst obtained in Example 3 (1).
In (4), the polymerization amount of ethylene is 20.0 g,
SiC with average particle size of 30nm instead of carbon black
Polymerization was carried out in the same manner as in Comparative Example 1 except that the powder was changed to 5.0 g, to obtain 500 g of a polyethylene composition. The content of the filler was measured in the same manner as in Example 1. The results are shown in Table 1.

Example 4 In Example 1 (3), 44 μm was used instead of ferrite.
475 g of aluminum powder having an average particle size of 74 μm, excluding those having a particle size of not more than m. In Example 1 (4), the ethylene prepolymerization amount was 2.0 g, the post-polymerization amount was 1 g.
Polymerization was carried out in the same manner as in Example 1 except that 8.0 g (total polymerization amount: 20.0 g) and 5.0 g of SiC powder having an average particle diameter of 30 nm were used instead of carbon black. 500 g of the composition were obtained. The content of the filler was measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4 In Comparative Example 1 (3), 44 μm was used instead of ferrite.
475 g of aluminum powder having an average particle diameter of 74 μm excluding those having a particle diameter of not more than m. In Comparative Example 1 (4), the polymerization amount of ethylene was 20.0 g, and the average particle diameter was replaced with carbon black. Polymerization was carried out in the same manner as in Comparative Example 1 except that 5.0 g of 30 nm SiC powder was used to obtain 500 g of a polyethylene-based composition. The content of the filler was measured in the same manner as in Example 1. The results are shown in Table 1.

Example 5 In Example 1 (3), instead of ferrite, 44
475 g of aluminum powder having an average particle size of 74 μm, excluding those having a particle size of μm or less, and
In (4), ethylene prepolymerized amount 2.0 g, and post-polymerization amount 18.0 g (total polymerization amount 20.0 g), and the car
Phthalocyan with average particle size of 30nm instead of Bon Black
Except for using the Nin green 5.0 g, subjected to the polymerization in the same manner as in Example 1, a polyethylene-based composition 500
g was obtained. About this thing, similarly to Example 1,
The content of the filler was measured. The results are shown in Table 1.

Comparative Example 5 In Comparative Example 1 (3), instead of ferrite, 44
475 g of aluminum powder having an average particle size of 74 μm, excluding those having a particle size of μm or less, and Comparative Example 1
Polymerization was carried out in the same manner as in Comparative Example 1 except that the polymerization amount of ethylene was 20.0 g in (4) and 5.0 g of phthalocyanine green having an average particle size of 30 nm was used instead of carbon black. 500 g of the system composition was obtained. The content of the filler was measured in the same manner as in Example 1. The results are shown in Table 1.

Example 6 (1) Preparation of Aluminoxane In a 500-ml flask purged with argon, 100 ml of dehydrated toluene and 71 mmol of commercially available copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) were placed at room temperature. A toluene solution (2 mol / l) of 246 mmol of trimethylaluminum was added dropwise at 20 ° C. for 30 minutes. The reaction was allowed to proceed at room temperature for 24 hours. After filtration, toluene was removed from the filtrate under reduced pressure to obtain 4.2 g of a colorless solid component (molecular weight 763 according to benzene freezing point depression method). Next, toluene was added to this solid again to prepare a 2 mol / liter solution at an aluminum equivalent. (2) Evaluation of activity of zirconium-containing catalyst component In a 1-liter autoclave purged with argon, 400 ml of dehydrated toluene, 6 mmol of aluminum aluminoxane obtained in the above (1) in terms of aluminum equivalent (hereinafter the same), and dicyclopentadiene were added. After feeding 0.003 mmol of enyl zirconium dichloride and heating the mixture to 50 ° C., ethylene was continuously supplied so that the total pressure was maintained at 8 kg / cm ² · G, and polymerization was carried out for 5 minutes. 0.4 g of polyethylene was obtained. Its catalytic activity is 719 kg
/ G · Zr · hr. (3) Contact between the zirconium-containing soluble catalyst component and the filler (I) In a 1-liter autoclave purged with argon, at room temperature, 450 ml of dehydrated toluene and the average particle size excluding those having a particle size of 44 μm or less were removed. 475 g of 74 μm aluminum powder was added, 1 mmol of diethyl aluminum monochloride was added dropwise with stirring, and the mixture was treated at 40 ° C. for 1 hour. Next, the zirconium-containing soluble catalyst component obtained in the above (1) was added in an amount of 0.005 mmol as zirconium atoms, and contacted at 20 ° C. for 1 hour to obtain a contact-treated product. (4) Polymerization of ethylene In Example 1 (4), the polymerization temperature was set to 50 ° C.
10 mmol of the aluminoxane prepared in the above (1) was used in place of triethylaluminum, the ethylene prepolymerization amount was 2.0 g, and the post-polymerization amount was 18.0 g.
Polymerization was carried out in the same manner as in Example 1 (4) except that 5.0 g of azodicarbonamide having an average particle size of 30 nm was used instead of carbon black, and 500 g of a polyethylene-based composition was obtained. The content of the filler was measured in the same manner as in Example 1. First result
It is shown in the table.

The content of the filler was measured by the following method. A 20 g sample is heated in para-xylene to completely melt the polyethylene. This is filtered out using a 44 μm wire mesh in the molten state. Only the aluminum powder remains on the wire mesh. The aluminum powder is dried and weighed to calculate the aluminum content in the polyethylene composition. The filtrate is removed by evaporating para-xylene to form a mixture of polyethylene and azodicarbonamide. The mixture is heated on a hot press at 250 ° C. to decompose the azodicarbonamide. The content of the filler is measured from the difference in weight of the mixture before and after azodicarbonamide decomposition.

COMPARATIVE EXAMPLE 6 Comparative Example 1 was carried out in the same manner as in Example 6 except that the types and amounts of the catalyst component, the solvent and the filler were the same.
Polymerization was carried out in the same manner as in Comparative Example 1 except that the polymerization amount of ethylene in (4) was changed to 20.0 g to obtain 500 g of a polyethylene composition. This was measured for the content of the filler in the same manner as in Example 6. The results are shown in Table 1.

Example 7 In Example 1 (3), 44 μm was used instead of ferrite.
m, and a silver-coated glass having an average particle diameter of 74 μm, excluding those having a particle diameter of not more than m, and in Example 1 (4), 2.0 g of ethylene prepolymerization and 18.0 g of postpolymerization (total polymerization of 20 g) 0.0g), and polymerization was carried out in the same manner as in Example 1 except that 5.0 g of phthalocyanine green having an average particle diameter of 30 nm was used instead of carbon black, to obtain 500 g of a polyethylene-based composition. The content of the filler was measured in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 7 In Comparative Example 1 (3), 44 μm was used instead of ferrite.
m and a silver-coated glass having an average particle size of 74 μm excluding those having a particle size of not more than m, and in Comparative Example 1 (4), the polymerization amount of ethylene was 20.0 g, and the average Polymerization was carried out in the same manner as in Comparative Example 1, except that 5.0 g of phthalocyanine green having a particle size of 30 nm was used, to obtain 500 g of a polyethylene-based composition.
The content of the filler was measured in the same manner as in Example 1. The results are shown in Table 1.

[0053]

[Table 1]

[0054]

[Table 2]

* 1: Particle size 44-105 μm * 2: Remaining

[0056]

According to the method of the present invention, by performing prepolymerization, when the filler (II) is added, only a part of the catalyst supporting the filler (I) is filled with the filler (II). Can be prevented. Moreover, the filler (I
Since the formation of a composition of (I) and polyethylene can be prevented, the content accuracy of the filler (I) and the filler (II) can be improved. For this reason, it is possible to stabilize the properties and physical properties of the composition caused by the filler (I) and the filler (II). In particular, according to the method of the present invention, since the content of the filler (II) is controlled, it is effective for stabilizing the properties and physical properties of the composition caused by the filler (II). For example, when a conductive material such as carbon black is used as the filler (II), the conductive properties such as electric resistance of the composition can be stabilized. Further, according to the method of the present invention, the product yield can be improved, and the adhesion between the polymer and the filler is good, and a strong multilayer structure coating can be obtained. In particular, even in special cases where the filler content is 90% by weight or more,
Powder / granules having a uniform composition can be obtained.

[Brief description of the drawings]

FIG. 1 is a drawing showing a process for preparing a catalyst used in the method of the present invention.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-60-106809 (JP, A) JP-A-50-92337 (JP, A) JP-A-60-106808 (JP, A) JP-A-60-106808 238307 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70 C08F 2/00-2/60

Claims (3)

(57) [Claims] 1. A catalyst containing a transition metal, soluble in an organic solvent, and an organic aluminum compound.
In low-pressure polymerization of ethylene with
Pressure 1 atmosphere, 1g of transition metal atom, polyethylene 10
Preliminary polymerization of α-olefin is carried out using a treated product obtained by previously contacting a highly active catalyst component [A] capable of producing at least kg and a filler (I), and an organoaluminum compound [B]. After filling, compared to the filler (I)
Fillers affinity for re-olefin is equal to or more (I
A process for producing a polyolefin-based composition, comprising adding I) to polymerize an α-olefin. Wherein α- olefins The process according to claim 1, wherein ethylene or ethylene and other α- olefins. 3. A highly active catalyst component soluble in an organic solvent,
Magnesium or manganese and high-grade fats with 10 or more carbon atoms
Salt with fatty acid, magnesium or manganese and carbon number 10
Salt or magnesium or magnesium with higher alcohol
Has long-chain aliphatic hydrocarbon groups with carbon atoms of 6 or more
To the salt with phosphoric acid,It is obtained by adding and reacting a titanium compound.
Reaction products, Transition metal compound and aluminoxane,
Or Transition metal compound and transition in the transition metal compound
Compounds that can react with metals to form ionic complexes
Claim1 or 2The manufacturing method as described.