CN1043144A - Modified polyolefin particles and preparation method thereof - Google Patents

Abstract

A method for preparing modified polyolefin particles, the method comprising:

(A) 100 parts by weight of polyolefin particles and

(B) 0.01-50 parts by weight of at least one olefin unsaturated compound selected from the following groups: carboxyl-containing olefin unsaturated compounds or their carboxylic anhydrides or their carboxylic acid derivatives, hydroxyl-containing olefin unsaturated compounds , olefinically unsaturated compounds containing amino groups, and olefinically unsaturated compounds containing glycidyl groups, present in

(C) from more than 10 parts to not more than 50 parts by weight of a medium that is liquid at normal temperature, the medium has a solubility in water of 0.5% by weight or less at 20°C and is capable of swelling the polyolefin, and

(D) 0.01-10 parts by weight of a free radical initiator is contacted and reacted.

Description

The invention relates to modified polyolefin particles and a preparation method thereof. More specifically, the present invention relates to the modification of polyolefin particles with monomers having certain polar groups, such as carboxyl groups, and to methods for their preparation.

Heretofore, a method of modifying polyolefin by imparting a polar group such as a carboxyl group is known.

For the modification of this polyolefin, various methods have been adopted, including, for example, compounding a modifier having a polar group and extruding the mixture in a molten state so that the polyolefin can be made A method of modifying an olefin (melt method), and a method comprising dissolving a polyolefin in a solvent and blending a modifying agent in the solvent to modify the polyolefin (solvent method).

On the other hand, Japanese Patent Laid-Open Publication No. 77493/1975 discloses a method which comprises making a finely divided polyolefin polymer in the presence of a free radical initiator in the substantial absence of a liquid medium below the melting temperature of the olefin. Contact with maleic anhydride to graft polymerize the maleic anhydride onto the fine particle olefin polymer.

This patent publication emphasizes that although when one of various polar monomers is graft-polymerized onto a fine-grained olefin polymer in the substantial absence of a liquid medium, a fine-grained olefin-containing polymer is formed on the inner wall of the polymerization vessel. A polymer-attached film, but this polymer-attached film is not only formed when maleic anhydride is used as the polar monomer.

This patent publication also points out that, regarding the conditions of the grafting reaction when substantially no liquid medium exists, a small amount of solvent that becomes gas at lower temperatures, such as acetone, methyl ethyl ketone, ether or trichloroethane, can be used to Prevent easily sublimated maleic anhydride from crystallization deposition in the low temperature part of the reactor.

Japanese Patent Laid-Open No. 32722/1980 discloses a method for preparing a modified polyolefin composition having improved adhesive properties by mixing polymer particles of a C ₂ -C ₁₀ α-olefin, a A polymerizable compound represented by the following structural formula:

(wherein R ¹ is a linear lower alkylene group, R ² is H or CH ₃ ), and an organic peroxide, and is used under the conditions of a temperature equal to or less than the sticky point of the polymer and an inert atmosphere They react. The patent publication also points out that the organic peroxide used above is preferably in a liquid state in order to obtain good dispersion in the mixing stage, and thus it is desirable that the solid peroxide is dissolved in an organic solvent before use. The text describes benzene, mineral spirit, toluene, chlorobenzene, dichlorobenzene, acetone, dimethyl phthalate, tert-butanol, anisole, decalin and xylene as organic solvents. The text further states that when 1-5 parts by weight of an inert solvent is used per 100 parts by weight of olefin polymer particles in the reaction, the modified polyolefin composition has more enhanced bonding properties.

In addition, Japanese Patent Laid-Open No. 174309/1982 discloses a method of gas-phase graft polymerization, which includes adding a radical polymerization initiator to a compound having methyl, methylene and methine (excluding polyphenylene) Oxygen) in the polymer, and at the graft polymerization temperature, when the pressure is equal to or less than the saturated vapor pressure, the monomer to be grafted is added, so that the monomer is graft-polymerized onto the polymer. The text gives examples with polyethylene, polypropylene etc. as polymers and maleic anhydride as monomer. In addition, although this document discloses that a solvent which does not inhibit radical polymerization can be added in an amount of 0 to 10 parts by weight per 100 parts by weight of the polymer, there is no specific example of such a solvent in the description or illustration.

The object of the present invention is to propose a process for the preparation of modified polyolefin particles by grafting ethylenically unsaturated compounds onto polyolefin particles.

Another object of the present invention is to propose an industrial and improved process for the preparation of modified polyolefin particles by grafting olefinically unsaturated compounds with good or high grafting efficiency.

Another object of the present invention is to propose a process by which a high grafting efficiency can be achieved by graft polymerizing olefinically unsaturated compounds onto polyolefin particles in essentially the gas phase.

Another object of the present invention is to propose a process for the preparation of modified polyolefins with good or high grafting efficiency by carrying out the grafting in the presence of a substantial amount of a liquid medium with specific properties polymerization.

Another object of the present invention is to propose modified polyolefin particles which can be prepared by the above-mentioned process of the invention and which have specific properties and are fully usable for various purposes.

Other objects and advantages of the invention are illustrated by the following description.

According to the present invention, these objects and advantages can be achieved by a method of preparing modified polyolefin particles, the method comprising:

(A) 100 parts by weight of polyolefin particles and

(B) 0.01-50 parts by weight of at least one olefinically unsaturated compound selected from the following groups: olefinically unsaturated compounds containing carboxyl groups or their carboxylic acid anhydrides or their carboxylic acid derivatives, olefinically unsaturated compounds containing hydroxyl groups , olefinically unsaturated compounds containing amino groups, and olefinically unsaturated compounds containing glycidyl groups, present in

(C) from more than 10 parts to not more than 50 parts by weight of an ordinary temperature liquid medium which has a solubility in water at 20°C of 0.5% by weight or less and which is capable of swelling the polyolefin, and

(D) 0.01-10 parts by weight of a radical initiator is contacted and reacted.

The method for preparing modified polyolefin of the present invention is now specifically described.

Unless otherwise noted, references to polymers in the present invention include polymers and copolymers.

The average particle size of the polyolefin particles (A) used in the present invention is preferably in the range of 10-5000 microns, more preferably 100-4000 microns, most preferably 300-3000 microns.

In addition, the polyolefin particles (A) used in the present invention are such polyolefin particles, which characterize the geometric standard deviation range of the particle size distribution is preferably 1.0-2.0, more preferably 1.0-1.5, most preferably 1.0-1.3 .

In addition, the polyolefin particles (A) used in the present invention are polyolefin particles whose natural fall apparent bulk density is preferably in the range of 0.2 g/ml or more, more preferably 0.3-0.7 g/ml, The optimum is 0.35-0.60 g/ml.

The polyolefin constituting the above-mentioned polyolefin particles can be obtained by polymerizing or copolymerizing preferably an ?-olefin having 2 to 20 carbon atoms.

Examples of the aforementioned α-olefins include: ethylene, propylene, butene-1, pentene-1, 2-methyl-butene-1, 3-methylbutene-1, hexene-1, 3-methyl Pentene-1, 4-methylpentene-1, 3,3-dimethylbutene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene ene-1, ethylpentene-1, octene-1, methylpentene-1, dimethylhexene-1, trimethylpentene-1, ethylhexene-1, methylethyl Pentene-1, diethylbutene-1, propylpentene-1, decene-1, methylnonene-1, dimethyloctene-1, trimethylheptene-1, ethyl Octene-1, methylethylheptene-1, diethylhexene-1, dodecene-1, hexadecene-1, and the like.

Among them, preferably used are ?-olefins having 2 to 8 carbon atoms individually or in combination.

The polymer particles used in the present invention, which contain repeating units derived from the above-mentioned α-olefin, are preferably in an amount of 50 mol% or more, more preferably 80 mol% or more, especially preferably 90 mol% or more, preferably 100 mol%.

Other copolymerizable unsaturated compounds usable in the present invention include chain polyene compounds, cyclic polyene compounds, cyclic monoene compounds, styrene and substituted styrenes, in addition to the above-mentioned α-olefins. Polyene compounds having two or more conjugated or non-conjugated olefinic double bonds can be preferably used as such polyene compounds, including, for example: chain polyene compounds such as 1,4-hexadiene, 1,5- Hexadiene, 1,7-octadiene, 1,9-decadiene, 2,4,6-octatriene, 1,3,7-octatriene, 1,5,9-decatriene and Divinylbenzene; cyclic polyene compounds such as 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cyclohexadiene ene, dicyclopentadiene, dicyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5 -isopropylidene-2-norbornene, methylhydroindene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene alkenes and 2-propenyl-2,5-norbornadiene; and the like. In addition, as such a polyene compound, one obtained by condensing a cyclopentadiene (for example, cyclopentadiene having an α-olefin such as ethylene, propylene, or butene-1) using a Diels-Alder reaction can also be used. polyene compounds.

In addition, examples of cyclic monomer compounds include monocyclic alkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methyl-cyclohexene, cycloheptene, cyclooctene, cyclodecene , cyclododecene, tetracyclodecene, octacyclodecene, cycloeicosene; bicyclic alkenes such as norbornene, 5-methyl-2-norbornene, 5-ethyl-2- Norbornene, 5-isobutyl-2-norbornene, 5-6-dimethyl-2-norbornene, 5,5,6-trimethyl-2-2-norbornene and 2-norbornene Bornene; tricyclic alkenes such as 2,3,3a,7a-tetrahydro-4,7-methylene-1hydro-indene and 3a,5,6,7a-tetrahydro-4,7-methylene -1 hydrogen-indene; tetracyclic alkenes such as 1,4,5,8-dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-methyl-1 , 4,5,8-dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethylene- 1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-propyl-1,4,5,8-dimethylene-1,2,3,4,4a,5, 8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-scleroyl -1,4,5,8-Dimethyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8- Dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethylene-1, 2,3,4,4a,5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethylene-1,2,3,4,4a,5,8, 8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene, 2-fluoro-1 , 4,5,8-dimethylene-1,2,3,4,4a,5,8,8a-octahydronaphthalene and 2,3-dichloro-1,4,5,8-diethylene Methyl-1,2,3,4,4a,5,8,8a-octahydronaphthalene; polycyclic alkenes such as hexacyclic [6,6,1,1 ^{3,6,1 10,13,0 2, 7} , 0 ^{9, 14} ] heptadecene-4, pentacyclic [8, ⁸ , 1 2, 9 1 4, 7, 1 ¹¹ , ¹⁸ , 0, 0 ^{3, 8} , 0 12, ¹⁷ ] twenty-one ^Carbene - ⁵ and octacyclo ^{[ 8,8,12,9,14,7,111,18,113,16,0,03,8,012,17 ]} dococene- ⁵ ; and the like.

Examples of the above-mentioned styrene and substituted styrene can be represented by the following structural formula:

In the formula, _R1 is a hydrogen atom, a lower alkyl group with 1-5 carbon atoms or a halogen atom, _R2 is a hydrogen atom, a lower alkyl group with 1-5 carbon atoms or a vinyl group, and n is an integer of 1-5 . Specific examples of styrene and substituted styrenes include styrene, α-methylstyrene, vinyltoluene, divinylbenzene, o-chlorostyrene, m-chlorostyrene and p-chlorostyrene.

The above-mentioned polyolefin particles (A) used in the present invention can be produced by the method described in detail below.

As the olefin unsaturated compound grafted onto the above-mentioned polyolefin particles, usable in the present invention are the above-mentioned olefin unsaturated compounds containing carboxyl groups or their carboxylic acid anhydrides or their carboxylic acid derivatives, containing hydroxy groups Olefinically unsaturated compounds, amino-containing olefinically unsaturated compounds and glycidyl-containing olefinically unsaturated compounds. These olefinically unsaturated compounds may be used alone or in combination of two or more.

As carboxyl-containing olefinically unsaturated compounds, their carboxylic anhydrides and their carboxylic acid derivatives, it is possible here, for example, to preferably use compounds from the following groups: acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrogenated Phthalic acid, itaconic acid, citraconic acid, crotonic acid and endo-cis-bicyclo[2,2,1]hept-5-ene-2,8-dicarboxylic acid, their carboxylic anhydrides, and Acid halides, amides, imides or esters of these carboxylic acids.

Anhydrides, halides, amides, imides and esters of the above carboxylic acids include maleic acid chloride, maleimide, maleic anhydride, citraconic anhydride, maleic acid-methyl ester, maleic acid dimethyl ester, etc. Among them, unsaturated dicarboxylic acids or their anhydrides, especially maleic acid or endo-cis-bicyclo[2,2,1]hept-5-ene-2,8-dicarboxylic acid or their anhydrides.

Examples of olefinically unsaturated compounds containing hydroxyl groups include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxy- 3-Phenoxypropyl ester, 3-Chloro-2-hydroxypropyl (meth)acrylate, -Glyceryl (meth)acrylate, -Pentaerythritol (meth)acrylate, -Trihydroxy (meth)acrylate Methyl propane ester, -tetramethylolethane (meth)acrylate, -butylene glycol (meth)acrylate, -polyethylene glycol (meth)acrylate, 2-(6-hydroxyhexyl acrylate Acyloxy) ethyl ester, 10-undecen-1-ol, 1-octen-3-ol, 2-hydroxymethyl norbornene, hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl Vinyl ether, N-methylolacrylamide, 2-(meth)acryloyloxyethyl phosphate, glycerol-allyl ether, allyl alcohol, allyloxyethanol, 2-butene-1, 4-diol, glycerol-alcohol, etc. Preference is given to using 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate as hydroxyl-containing olefinically unsaturated compound.

As the ethylenically unsaturated compound containing an amino group, for example, one having one ethylenically unsaturated double bond in the molecule and at least one compound represented by the chemical formula

The compound of the amino group represented, wherein R ¹ is a hydrogen atom, methyl or ethyl, R ² is a hydrogen atom, an alkyl group with 1-12 carbon atoms or a cycloalkyl group with 6-12 carbon atoms. Each of the above-mentioned alkyl group and cycloalkyl group may have a substituent. Examples of these amino group-containing olefinically unsaturated compounds include aminoethyl acrylate, alanaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl acrylate, phenaminoethyl methacrylate, cyclohexylamino methacrylate Ethyl ester, methacryloyloxyethyl phosphate, -methylene sesamerine half salt, N-vinyldiethylamine, N-acetylvinylamine, allylamine, methallyl Amine, N-methacrylamide, N,N-dimethylacrylamide, N,N-dimethylaminopropylacrylamide, acrylamide, N-methacrylamide, p-aminostyrene, 6-amino Hexylsuccinimide, 2-aminoethylsuccinimide, and the like. As the amino group-containing ethylenically unsaturated compound, acrylamide, aminoethyl methacrylate, aminopropyl methacrylate, aminostyrene, and the like can be used particularly preferably among the above-mentioned examples thereof.

As the glycidyl group-containing olefinically unsaturated compound, glycidyl ethers such as allyl glycidyl ether, 2-methallyl glycidyl ether and vinyl glycidyl ether can be preferably used. Among them, allyl glycidyl ether is particularly preferred. Since these glycidyl ethers have no carboxyl group in the molecule, they are highly resistant to hydrolysis, and there is no need to worry about removal of the glycidyl group by hydrolysis. Glycidyl esters of conjugated unsaturated dicarboxylic acids or other glycidyl compounds can also be used as long as they are used in small proportions together with the above-mentioned glycidyl ethers. Examples of the above-mentioned glycidyl esters of conjugated unsaturated dicarboxylic acids include diglycidyl maleate, methyl glycidyl maleate, isopropyl glycidyl maleate, t-butyl glycidyl maleate, Glyceryl Esters, Diglycidyl Fumarate, Methyl Glycidyl Fumarate, Isopropyl Glycidyl Fumarate, Diglycidyl Itaconate, Methyl Glycidyl Itaconate, Itaconic Acid Isopropyl glycidyl ester, diglycidyl 2-methylene glutarate, methyl glycidyl 2-methylene glutarate, monoglycidyl butenedicarboxylate, and the like. Examples of other glycidyl compounds mentioned above include 3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, monoxide of vinylcyclohexene, p-monoglycidyl Styrene, etc. These glycidyl esters or other glycidyl compounds are desirably used in a small proportion of 0.1 mole or less per mole of glycidyl ether.

The liquid medium (C) used in the present invention is a medium that is liquid at normal temperature, their solubility in water at 20°C is 0.5% by weight or less, preferably 0.4% by weight or less, and they can Swelling polyolefin. Examples of the above-mentioned liquid medium (C) include benzene (solubility 0.09% by weight), mineral spirits (mineral spirit) (solubility 0.00090% by weight), toluene (solubility 0.05% by weight), chlorobenzene (solubility 0.05% (weight)), o-dichlorobenzene (solubility at 25°C: 0.01% (weight)), xylene (solubility 0.02% (weight)), n-hexane (solubility 0.014% (weight)), n-heptane (solubility 0.005% (weight)), n-octane (solubility 0.002% (weight) at 25°C), carbon tetrachloride (solubility 0.44% (weight)), ClCH=C=CCl ₂ (solubility 0.11% (weight)), etc. These solvents may be used alone or in combination in the present invention.

According to the method of the present invention, wherein the modified polyolefin particles are prepared in the presence of the above-mentioned liquid medium (C), although the reason is not always clear, it is believed that the liquid medium swells the polyolefin particles, and as a result the olefinic unsaturated compounds and free radicals The initiators can easily penetrate into the polyolefin particles, with the result that even the interior of the polyolefin particles is uniformly modified with the olefinic unsaturated compound. Regardless of whether the above speculation is true or not, according to the present invention, modified polyolefin particles with excellent pellet performance can be obtained by performing graft polymerization in the presence of the liquid medium (C).

As the radical generator (D) used in the present invention, there can be used organic peroxides, azo compounds or the like known per se. Examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5- Dimethyl-2,5-bis(tert-butylperoxy)hexane-3,1,3-bis(tert-butylperoxyisopropyl)benzene, 1,1-bis(tert-butyl peroxy)-3,3,5-trimethylcyclohexane, n-butyl 4,4-bis(tert-butylperoxy)valerate, dibenzoyl peroxide, tert-butylperoxide Oxybenzoate, Acetyl Peroxide, Isobutyryl Peroxide, Caprylyl Peroxide, Capryl Peroxide, Lauroyl Peroxide, 3,5,5-Trimethylhexanoyl Peroxide , 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, etc. In addition, as the azo compound, azobisisobutyronitrile and the like can be used. The above radical initiators may be used alone or in combination. Among these radical initiators, dibenzoyl peroxide is particularly preferably used.

The method of implementing the present invention is by contacting and reacting the above-mentioned polyolefin particles (A), olefin unsaturated compound (B), liquid medium (C) and free radical initiator (D), using 0.01 per 100 parts by weight of polyolefin particles - 50 parts by weight, preferably 0.1-40 parts by weight, of an olefinically unsaturated compound, greater than 10 to not more than 50 parts by weight, preferably 12-40 parts by weight, of a liquid medium, and 0.01-10 parts by weight, preferably 0.05-8 parts by weight free radical initiator.

There are no particular restrictions on the contacting method and order of the above-mentioned components (A), (B), (C) and (D), and the following methods can be employed as examples:

The first method involves preparing a solution of an olefinically unsaturated compound and a radical initiator in a liquid medium, dispersing polyolefin particles therein, and reacting. The second method involves preparing a solution of a free radical initiator in a solution medium, dispersing polyolefin particles therein, bringing the polyolefin particles to a significantly active state by, for example, heating, and then adding an olefinically unsaturated compound to reaction. The third method involves bringing polyolefin particles into a substantially active state by, for example, heating, and dispersing the resulting polyolefin particles in a solution of an olefinically unsaturated compound and a radical initiator in a liquid medium to react. A fourth method involves dispersing polyolefin particles in a solution of a free radical initiator in a liquid medium, and contacting the dispersion with an olefinically unsaturated compound in a gaseous state under heating to effect a reaction.

Preferably, the contacting of the polyolefin particles with the olefinically unsaturated compound is carried out at a temperature at which the polyolefin particles can substantially retain their shape, ie below the temperature at which the polyolefin particles begin to dissolve into each other. Suitable contacting temperatures vary depending on the polyolefin particles and free radical initiator used, but are generally in the range of, for example, 0-150°C. In the case of polyolefin particles such as polyolefin particles mainly composed of polypropylene, the upper limit temperature is about 150°C, in the case of polyolefin particles mainly composed of high-density polyethylene, the upper limit temperature is about 120°C, and In the case of polyolefin particles mainly composed of low density polyethylene, the upper limit temperature is about 90°C.

The modification reaction time in the present invention can be appropriately determined in consideration of conditions such as reaction temperature, but is usually 1/60 to 20 hours, preferably 0.5 to 10 hours.

Any equipment can be used for the above reaction without particular limitation, as long as the equipment can mix and heat polyolefin particles, for example, any vertical or horizontal reactor can be used, specifically fluidized bed, moving bed, annular Reactor, horizontal reactor with stirring blades, drum, vertical reactor with stirring blades, etc.

Therefore, the modified polyolefin particles of the present invention can be prepared according to the method of the present invention, characterized in that:

(a) they have an average particle size in the range of 100-5000 microns,

(b) their geometric standard deviation is 1-2,

(c) 20% by weight or less of a particle component with a particle size of 100 microns or less, and

(d) they are modified by polar groups selected from the group consisting of carboxyl groups or their anhydrides or their derivatives, hydroxyl groups, amino groups, and glycidyl groups,

The modified polyolefin particles of the present invention preferably have an average particle size in the range of 200-4000 microns, especially 300-3000 microns.

In addition, the geometric standard deviation range of the modified polyolefin particles of the present invention is preferably 1.0-1.5, especially 1.0-1.3. In addition, the range of the fine particle component of 100 µm or less is preferably 0-10% by weight, more preferably 0-2% by weight.

In addition, the apparent specific gravity range of the modified polyolefin particles of the present invention is preferably 0.25-0.7, more preferably 0.30-0.60, and especially preferably 0.35-0.50. In addition, the average range of the ratio of the length of the major axis to the length of the minor axis of the particles composed of the above particles is preferably 1.0-3.0, more preferably 1.0-2.0, and especially preferably 1.0-1.5.

The modified polyolefin particles of the present invention have polarity and thus can be advantageously used as, for example, a raw material for fine particle coating.

Suitable preparation methods for the polyolefin particles used in the process of the invention are described hereinafter.

The polyolefin particles obtained by these methods generally contain only 100 ppm or less of transition metals in their ashes, preferably 10 ppm or less, especially preferably 5 ppm or less, and the amount of halogen is usually only 300ppm or less, preferably 100ppm or less, especially 50ppm or less.

The polyolefin particles used in the present invention can be obtained by polymerizing or copolymerizing at least the above-mentioned α-olefin in the presence of a catalyst. The above polymerization or copolymerization can be carried out in gas phase (gas phase method) or in liquid phase (liquid phase method).

The polymerization or copolymerization by the liquid phase method is preferably carried out in suspension so that the formed polyolefin particles are obtained in solid state.

In the production of polyolefin particles, it is desirable to employ a method wherein a crystalline olefin polymer portion is formed simultaneously with an amorphous olefin polymer portion by feeding two or more monomers into the reactor, or another method , wherein at least two or more polymerizing agents are used, the synthesis of the crystalline olefin polymer fraction and the synthesis of the amorphous olefin polymer fraction are performed separately and sequentially. The above-mentioned latter method is preferable from the viewpoint that the molecular weight, composition and amount of the amorphous olefin polymer portion can be freely changed.

The most desirable method involves the synthesis of a crystalline olefin polymer fraction by gas phase polymerization followed by the synthesis of an amorphous olefin polymer fraction by gas phase polymerization, or an alternative method which involves the synthesis of a crystalline olefin using monomers as solvents The polymer part is then synthesized into an amorphous olefin polymer part by gas phase polymerization.

As the solvent used in the polymerization or copolymerization reaction, an inert hydrocarbon can be used, or an α-olefin can be used as a raw material.

As the catalyst used in the above-mentioned polymerization or copolymerization reaction, generally, a catalyst comprising the following components can be used. The catalyst component (A) contains a transition metal of Group IVA, VA, VIA, VIIA or VIII of the Periodic Table of Elements. The catalyst component (B), which contains a metal of Group I, II, or III of the Periodic Table of Elements.

As the above-mentioned catalyst component (A), catalyst components each containing a transition metal atom of Group IVA or VA of the Periodic Table of the Elements are preferred, and among them, catalyst components each containing at least one atom selected from the group consisting of: titanium , zirconium, hafnium and vanadium.

In addition, other preferred catalyst components (A) also include catalyst components each containing a halogen atom and a magnesium atom in addition to each of the above-mentioned transition metal atoms, and catalyst components each containing A compound in which a group with conjugated π electrons is coordinated to a transition metal atom of Group IVA or VA of the Periodic Table.

As the catalyst component (A) of the present invention, it is preferable to use such a catalyst which can exist in the solid state in the reaction system of the above-mentioned polymerization or copolymerization reaction at the time of preparation, or by being supported on a carrier Exist in a solid state.

The above catalyst component (A) will be further described in detail, taking as an example the solid catalyst component (A) containing the above transition metal, halogen atom and magnesium atom.

The average particle size of the solid catalyst component (A) is preferably in the range of 1-200 microns, more preferably 5-100 microns, especially 10-80 microns. In addition, the geometric standard deviation (δg) of the solid catalyst (A), which is a measure of the particle size distribution of the solid catalyst (A), is preferably in the range of 1.0-3.0, more preferably 1.0-2.1, and most preferably 1.0-1.7.

The average particle size and particle size distribution of the catalyst component (A) can be measured by the following light transmission method: first add the catalyst component (A) to the solvent that does not dissolve the catalyst component (A), so that the concentration (content) Up to 0.1 to about 0.5% by weight, preferably 0.1% by weight, make a dispersion, fill it into a measuring cell to measure the particle size distribution, apply light in the state where the particles are settled and continuously measure the transmission light intensity through the liquid. The standard deviation (δg) is determined from the lognormal distribution function based on this particle size. _More specifically, the standard deviation (δg) was determined as the ratio (θ ₅₀ /θ 16 ) of the mean particle size (θ ₅₀ ) to the particle size (θ ₁₆ ), 16% by weight of all particles contained in θ ₁₆ Between and minimum particle size, the average particle size of the catalyst in this context is the weight average particle size.

In addition, the catalyst component (A) has a certain shape, such as an ideal spherical shape, ellipsoidal granular shape, and the aspect ratio of the particles is preferably 3 or less, more preferably 2 or less, especially Preferably 1.5 or less.

In addition, when the catalyst component (A) contains magnesium atoms, titanium atoms, halogen atoms or electron donors, the ratio of magnesium to titanium (atomic ratio) is preferably greater than 1, usually in the range of 2-50, preferably for 6-30. In addition, the ratio (atomic ratio) of halogen to titanium is usually in the range of 4-100, preferably 6-40, and the ratio of electron donor to titanium (atomic ratio) is usually in the range of 0.1-10, preferably 0.2 -6. Furthermore, the unit surface area of this catalyst component (A) is usually in the range of 3 ^m2 /g or more, preferably 40 ^m2 /g or more, most preferably 100-800 ^m2 /g.

The titanium compound in this catalyst component (A) is generally not removed by simple steps such as washing with hexane at ordinary temperature.

Furthermore, the catalyst component (A) may contain other atoms or metals in addition to the above-mentioned components, or may be diluted with an organic or inorganic diluent. In addition, functional groups or the like may also be introduced into this catalyst component (A).

The above-mentioned catalyst component (A) can be prepared by employing, for example, a method comprising forming a magnesium compound whose average particle size and particle size distribution fall within the above-mentioned range and whose shape is the above-mentioned shape, and then preparing catalyst, or alternatively, which involves contacting a liquid magnesium compound with a liquid titanium compound and then forming a solid catalyst so as to have the particle characteristics described above.

The above catalyst component (A) can be used as such. In addition, as the catalyst component (A), a catalyst component obtained by supporting a magnesium compound, a titanium compound, and, if necessary, an electron donor on a carrier of a uniform shape can also be used. It is also possible to prepare a finely powdered catalyst in advance and then granulate it into the above-mentioned preferred shape.

The above catalyst component (A) has been disclosed in Japanese Patent Laid-Open Nos. 135102/1980, 135103/1980, 811/1981 and 67311/1981, and Japanese Patent Application Nos. 181019/1981 and 21109/1986.

Some examples of the process for preparing the catalyst component (A) are described below:

(1) A solid complex of a magnesium compound and an electron donor having an average particle size of 1-100 microns and a geometric standard deviation (δg) of particle size distribution of 3.0 or less is mixed with a liquid titanium halide (preferably tetrachloro titanium oxide) under the reaction conditions, before the reaction, or the complex is pretreated with reaction aids such as electron donors and/or organic aluminum compounds or halogen-containing silicon compounds, or without any be dealt with.

(2) The liquid magnesium compound that does not have reducing power is preferably reacted with the liquid titanium compound in the presence of an electron donor, resulting in the deposition of a solid component with an average particle size of 1-200 microns and a geometric standard deviation (δg) 3.0 or less. If desired, the solid component is further reacted with a liquid titanium compound, preferably titanium tetrachloride, or with a liquid titanium compound and an electron donor.

(3) The reactive liquid magnesium compound is contacted with a reaction aid (such as polysiloxane or a halogen-containing silicon compound) that can cause the magnesium compound to lose its reducing ability in advance, and as a result, a solid component is deposited, and its average The particle size is 1-200 microns, and the geometric standard deviation (δg) of the particle size distribution is 3.0 or less. The solid component is then reacted with a liquid titanium compound, preferably titanium tetrachloride, or with a titanium compound and an electron donor.

(4) Make the magnesium compound with reducing ability contact with an inorganic carrier such as silicon dioxide or an organic carrier, and after the obtained carrier is contacted with a halogen-containing compound (or not carry out this contact), it is then contacted with a liquid titanium compound (preferably four titanium chloride), or a titanium compound and an electron donor, whereby the magnesium compound supported on the carrier reacts with the titanium compound or the like.

This catalyst component (A) has the ability to produce polymers having high stereoregularity with high catalyst efficiency. For example, when the homopolymerization of propylene is carried out under the same conditions, the solid catalyst has the ability to produce polypropylene having an isotacticity index of 92% or more, preferably 96% or more (substances insoluble in boiling n-heptane), the amount thereof is usually 3000 g or more, preferably 5000 g or more, especially 10000 g or more per millimole of titanium.

Examples of magnesium compounds, halogen-containing silicon compounds, titanium compounds and electron donors usable for the preparation of the above catalyst component (A) are described below. Furthermore, in the case of the organometallic compound catalyst components (B) described later, the aluminum complexing agents used in the preparation of these catalyst components (A) are exemplified as compounds.

Examples of magnesium compounds include inorganic magnesium compounds such as magnesium oxide, magnesium hydroxide, and hydrotalcite; organic magnesium compounds such as magnesium carboxylate, alkoxymagnesium, allyloxymagnesium, halides of alkoxymagnesium, allyloxymagnesium Magnesium halides and magnesium dihalides, as well as dialkylmagnesiums and diarylmagnesiums.

Examples of titanium compounds include halides of titanium such as titanium tetrachloride, halides of alkoxytitanium, halides of allyloxytitanium, alkoxytitanium, allyloxytitanium and the like. Of these, tetrahalides of titanium are preferred, and titanium tetrachloride is particularly preferred.

Examples of electron donors include oxygen-containing electron donors, such as alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic or inorganic acids, ethers, amides, acid anhydrides, and alkoxysilanes; nitrogen-containing electron donors, Such as ammonia, amines, nitriles and isocyanates.

Specific examples of compounds that can be used as the above-mentioned electron donors include alcohols having 1 to 18 carbon atoms, such as methanol, ethanol, propanol, pentanol, hexanol, heptanol, dodecanol, stearyl alcohol, oleyl alcohol, Benzyl alcohol, phenylethyl alcohol, isopropanol, cumyl alcohol and cumyl alcohol; phenols having 6-20 carbon atoms (these phenols may have lower alkyl groups as substituents), such as phenol, cresol, xylenol Phenol, ethylphenol, propylphenol, nonylphenol, cumylphenol or naphthol; ketones having 3 to 15 carbon atoms, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, Benzophenones and benzoquinones; aldehydes with 2-15 carbon atoms, such as acetaldehyde, propionaldehyde, octanal, benzaldehyde, tolualdehyde, naphthalene formaldehyde; organic acid esters with 2-30 carbon atoms, such as methyl formate , methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionate, methyl butyrate, ethyl valerate, methyl chloroacetate, dichloroacetate Ethyl acetate, methyl methacrylate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonate, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate , Butyl Benzoate, Octyl Benzoate, Cyclohexyl Benzoate, Phenyl Benzoate, Benzyl Benzoate, Methyl Toluate, Ethyl Toluate, Amyl Toluate, Ethyl Benzoate, Anise methyl ester, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl-1,2 cyclohexane dicarboxylate, endo-cis-bicyclo[2,2 , 1) Hept-5-ene-2,8-dicarboxylate diethyl ester, diisopropyl tetrahydrophthalate, diethyl phthalate, diisobutyl phthalate, phthalate Di-n-butyl dicarboxylate, di-2-ethylhexyl phthalate, gamma-butyrolactone, delta-valerolactone, coumarin, 2-benzo[c]furanone and ethylene carbonate ;acyl halides with 2-15 carbon atoms, such as acetyl chloride, benzoyl chloride, toluoyl chloride and anisoyl chloride; ethers with 2-20 carbon atoms, such as methyl ether, diethyl ether, isopropyl ether, butyl ether, pentyl ether , tetrahydrofuran and anisole and diphenyl ether; amides such as acetamide, benzamide and toluamide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine , picoline, and tetramethylenediamine; nitriles such as acetonitrile, benzonitrile, and tolylonitrile; organophosphorus compounds with P-O-P bonds, such as trimethyl phosphite and triethyl phosphite; alkoxysilanes such as silicon Acetate ethyl ester and diphenyldimethoxysilane, etc.

These electron donors can be used alone or in combination.

A preferred class of these electron donors are compounds without active hydrogen, such as esters of organic or inorganic acids, alkoxy(aryloxy)silane compounds, ethers, ketones, tertiary amines, acid halides or anhydrides; A further preferred class is organic acid esters and alkoxy (aryloxy) silane compounds; and a particularly preferred class is esters of aromatic monocarboxylic acids having 1 to 8 carbon atoms, dicarboxylic acids such as propanediene esters of acid, substituted malonic acid, substituted succinic acid, maleic acid, substituted maleic acid, 1,2-cyclohexanedicarboxylic acid or phthalic acid with alcohols having 2 or more carbon atoms, etc. wait. It is of course possible to add an electron donor of this type directly in the preparation of the catalyst. In addition, when preparing the catalyst component (A), the electron donor may not be added as a raw material, but, for example, a compound that can be converted into such an electron donor is synthesized in the reaction system, and the compound is used in the preparation of the catalyst is converted to this electron donor in the step.

The catalyst component (A) thus prepared can be purified by suitable washing with liquid inert hydrocarbons. Examples of hydrocarbons that can be used for scrubbing include: aliphatic hydrocarbon compounds such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, kerosene and liquid paraffin; alicyclic hydrocarbon compounds such as cyclopentane, methylcyclopentane, cyclohexane and methylcyclohexane; aromatic hydrocarbon compounds such as benzene, toluene xylene and methyl, cumene; and Halogenated hydrocarbon compounds such as chlorobenzene and dichloroethane.

These compounds can be used alone or in combination.

As the catalyst component (B) of the organometallic compound, an organoaluminum compound having at least one aluminum-carbon bond in the molecule can be used.

Examples of such organoaluminum compounds include, for example

(i) An organoaluminum compound represented by the following general formula

(In the formula, R ^{and R} are generally 1-15, preferably hydrocarbon groups with 1-4 carbon atoms, they can be the same or different from each other, X is a halogen atom, m, n, p and q are numbers, respectively 0≤m≤3, 0≤n<3, 0≤p<3, 0≤q<3, and m+n+p+q=3), and

(ii) An alkylated compound of a metal and aluminum complex from Group I of the Periodic Table, which is represented by the general formula:

(wherein M ¹ is Li, Na or k, R ¹ is as defined above).

The following compounds may especially be included among the organoaluminum compounds of the above formula (i):

Compounds represented by the following general formula

(where ^R1 and ^R2 are as defined above, preferably the value of m is 1.5≤m≤3);

Compounds represented by the following general formula

(In the formula, ^R1 is as defined above, X is a halogen atom, and the preferred value of m is 0<m<3);

Compounds represented by the following general formula

(In the formula ^{, R1} is as defined above, and the preferred value of m is 2≤m<3);

Compounds represented by the following general formula

(In the formula, ^R1 and ^R2 are as defined above, X is a halogen atom, m, n and q are numbers, respectively 0<m≤3, 0≤n<3 and 0≤q<3, and m+n+ q=3).

Specific examples of the organoaluminum compound represented by the above general formula (i) include trialkylaluminum such as triethylaluminum, tributylaluminum and triisopropylaluminum; trialkenylaluminum such as triisoprenyl Aluminum; dialkylaluminum alkoxides such as diethylaluminum ethoxide and dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquioxide ; partially alkoxylated aluminum alkyls, such as those having the average composition represented by the general formula R ¹ 2.5Al(OR ² ) _0.5 ; dialkylaluminum halides, such as diethylaluminum chloride, dibutyl Aluminum chloride and diethylaluminum bromide; Alkyl aluminum sesquihalides, such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide; partially halogenated aluminum alkyls , such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride and butylaluminum dibromide; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; parts of Hydrogenated alkylaluminums, for example alkylaluminum dihydrides, such as ethylaluminum dihydride and propylaluminum dihydride; and partially alkoxylated and halogenated alkylaluminums, such as ethylethoxyaluminum chloride, Butylbutoxyaluminum chloride and ethylethoxyaluminum bromide.

In addition, the organoaluminum compound may be a compound similar to those represented by the general formula (i), for example, an organoaluminum compound in which two or more aluminum atoms are linked by oxygen or nitrogen atoms. Specific examples of these compounds include:

(C ₂ H ₅ ) ₂ AlOAl(C ₂ H ₅ ) ₂ ,

(C ₄ H ₉ ) ₂ AlOAl(C ₄ H ₉ ) ₂ ,

Further, examples of the organoaluminum compound represented by the above general formula (ii) include LiAl(C ₂ H ₅ ) ₄ , LiAl(C ₇ H ₁₅ ) ₄ , and the like.

Among the various organoaluminum compounds mentioned above, trialkylaluminum, a mixture of a trialkylaluminum and an alkylaluminum halide or a mixture of a trialkylaluminum and an aluminum halide is particularly preferably used.

In addition, it is preferable to use the electron donor (C) together with the catalyst component (A) and the organometallic compound catalyst component (B).

Examples of electron donors (C) that can be used include amines, amides, ethers, ketones, nitriles, phosphines, , arsine, phosphoramide, ester, thioether, thioester, acid anhydride, acid halide, aldehyde, alcoholate, alkoxy (aryloxy) silane, organic acid, metal of Group I, II, III or IV of the Periodic Table of Elements Amides, and acceptable salts of the aforementioned compounds. These salts can also be formed by reacting an organic acid with an organometallic compound as the catalyst component (B) in a reaction system.

Specific examples of compounds which may be mentioned as electron donors have been described previously as examples in catalyst component (A). Particularly preferred electron donors among these electron donors are organic acid esters, alkoxy(aryloxy)silane compounds, ethers, ketones, acid anhydrides, amides and the like. Alkyl aromatic carboxylates are particularly preferred electron donors when the electron donor in catalyst component (A) is a monocarboxylic acid ester. In addition, when the electron donor in the catalyst component (A) is an ester of a dicarboxylic acid and an alcohol having 2 or more carbon atoms, preferred as the electron donor (C) is the general formula:

Represented alkoxy (aryloxy) silane compounds (where R and R ¹ are hydrocarbon groups, n is a number of 0≤n<4) or amines with large steric hindrance.

Specific examples of preferred alkoxy(aryloxy)silane compounds include: trimethylmethoxysilane, trimethoxyethoxysilane, dimethyldimethoxysilane, dimethylethoxysilane, Diisopropyldimethoxysilane, tert-butylmethyldimethoxysilane, tert-butylmethyldiethoxysilane, tert-amylmethyldiethoxysilane, diphenyldimethoxysilane, phenyl Methyldimethoxysilane, diphenyldiethoxysilane, bis-o-tolyldimethoxysilane, bis-m-tolyldimethoxysilane, bis-p-tolyldimethoxy Silane, bis-p-tolyldiethoxysilane, bis(ethylphenyl)dimethoxysilane, dicyclohexyldimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyl Diethoxysilane, Ethyltrimethoxysilane, Ethyltriethoxysilane, Vinyltrimethoxysilane, n-Propyltriethoxysilane, Decyltrimethoxysilane, Decyltriethoxy ylsilane, phenyltrimethoxysilane, γ-chloropropyltrimethoxysilane, methyltriethoxysilane, vinyltriethoxysilane, tert-butyltriethoxysilane, n-butyltriethylsilane Oxysilane, Isobutyltriethoxysilane, Phenyltriethoxysilane, γ-Aminopropyltriethoxysilane, Chlorotriethoxysilane, Ethyltriisopropoxysilane, Vinyl Tributoxysilane, Cyclohexyltrimethoxysilane, Cyclohexyltriethoxysilane, 2-Norbornanetrimethoxysilane, 2-Norbornanetriethoxysilane, 2-Norbornanemethyldi Methoxysilane, ethyl silicate, butyl silicate, trimethylphenoxysilane, methyltriallyloxysilane, vinyltris(β-methoxyethoxy)silane, dimethyl Tetraethoxydisiloxane and the like. Particularly preferred among them are ethyltriethoxysilane, n-propyltriethoxysilane, tert-butyltriethoxysilane, vinyltriethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, Butoxysilane, diphenyldimethoxysilane, phenylmethyldimethoxysilane, p-p-tolyldimethoxysilane, p-tolylmethyldimethoxysilane, bicyclic Hexyldimethoxysilane, Cyclohexylmethyldimethoxysilane, 2-Norbornanetriethoxysilane, 2-Norbornanemethyldimethoxysilane, Diphenyldiethoxysilane, Ethyl silicate, etc.

In addition, 2,2,6,6-tetramethylpyridine and 2,2,5,5-tetramethylpyrrolidine are particularly preferable as the above-mentioned amines with large steric hindrance, derivatives of these amines, tetramethylpyrrolidine Methyldiamine, etc.

Particularly preferred electron donors for the various catalyst components mentioned above are alkoxy(aryloxy)silane compounds.

In addition, preferable catalysts in the above method include catalyst component (A) (a compound containing a transition metal atom in Group IVA or Group VA of the Periodic Table of Elements having a conjugated π electron as a ligand group) and an organometallic compound catalyst Component (B).

Examples of transition metals of Groups IVA and V _A of the Periodic Table of the Elements include zirconium, titanium, hafnium, chromium, vanadium and the like.

In addition, examples of ligands having conjugated π-electron groups include unsubstituted or alkyl-substituted cyclopentadienyl groups such as cyclopentadienyl, methylcyclopentadienyl, ethylcyclopentadiene Alkenyl, tert-butylcyclopentadienyl, dimethylcyclopentadienyl and pentamethylcyclopentadienyl groups; indenyl groups; fluorene groups, etc.

In addition, examples of the preferred ligands mentioned here, wherein at least two of the above-mentioned ligands, which have a cycloalkadienyl skeleton and are composed of a lower alkyl group or a group containing silicon, phosphorus, oxygen or nitrogen connect. Examples of these groups include ethylenebisindenyl and isopropyl(cyclopentadienyl-1-fluorenyl) groups and the like.

One or more or preferably two ligands having a cycloalkadienyl skeleton are coordinated to the transition metal.

Other ligands other than those having a cycloalkadienyl skeleton include hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups, aryloxy groups, halogens and hydrogen.

As examples of the hydrocarbon group having 1 to 12 carbon atoms, there are alkyl group, cycloalkyl group, aryl group, aralkyl group and the like. Specifically, examples of alkyl groups include methyl, ethyl, propyl, isopropyl, and butyl, etc.; examples of cycloalkyl groups include cyclophenyl, cyclohexyl, etc.; examples of aryl groups include phenyl and tolyl, etc.; examples of aralkyl groups include benzyl, neophyl, and the like.

Examples of alkoxy include methoxy, ethoxy, butoxy and the like; examples of aryloxy include phenoxy and the like; and halogen include fluorine, chlorine, bromine and iodine.

The transition metal compound containing the ligand having a cycloalkadienyl skeleton used in the present invention is more clearly represented, for example, in the case where the valence of the transition metal is 4, by the general formula

Table formula (in the formula, M is zirconium, titanium, hafnium, vanadium, etc., R ² is a group with a cycloalkadienyl skeleton, R ³ , R ⁴ and R ⁵ are groups with a cycloalkadienyl skeleton, Alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, aryloxy group, halogen atom or hydrogen, K is an integer greater than 1, and K, l, m and n is the number of k+l+m+n=4). Particularly preferred compounds among the compounds of the general formula above are those wherein R ^{and R} are groups having a cycloalkadienyl backbone and groups having a ring chain connected by groups containing silicon, phosphorus, oxygen or nitrogen. Two groups of the dienyl skeleton.

A specific example of a transition metal compound wherein M is zirconium and contains a ligand having a cycloalkadienyl skeleton is shown below:

Monochlorobis(cyclopentadienyl)zirconium hydride,

Monobromobis(cyclopentadienyl)zirconium hydride,

Methylbis(cyclopentadienyl)zirconium hydride,

Ethylbis(cyclopentadienyl)zirconium hydride,

Phenylbis(cyclopentadienyl)zirconium hydride,

Benzylbis(cyclopentadienyl)zirconium hydride,

Neopentylbis(cyclopentadienyl)zirconium hydride,

Monochlorobis(methylcyclopentadienyl)zirconium hydride,

Chlorobis(indenyl)zirconium hydride,

Bis(cyclopentadienyl)zirconium dichloride,

Bis(cyclopentadienyl)zirconium dibromide,

Methylbis(cyclopentadienyl)zirconium chloride,

Ethylbis(cyclopentadienyl)zirconium chloride,

Cyclohexylbis(cyclopentadienyl)zirconia,

Phenylbis(cyclopentadienyl)zirconium chloride,

Benzylbis(cyclopentadienyl)zirconium chloride,

Bis(methylcyclopentadienyl)zirconium dichloride,

bis(tert-butylcyclopentadienyl)zirconium dichloride,

Bis(indenyl)zirconium dichloride,

Bis(indenyl)zirconium dibromide,

bis(cyclopentadienyl)zirconium dimethyl,

Bis(cyclopentadienyl)diphenylzirconium,

Bis(cyclopentadienyl)dibenzyl zirconium,

Bis(cyclopentadienyl)methoxyzirconium chloride,

Bis(cyclopentadienyl)ethoxyzirconium chloride,

Bis(methylcyclopentadienyl)ethoxyzirconium chloride,

Bis(cyclopentadienyl)phenoxyzirconium chloride,

bis(fluorenyl)zirconium dichloride,

Diethylethylenebis(indenyl)zirconium,

Diphenylethylenebis(indenyl)zirconium,

Dimethylethylenebis(indenyl)zirconium,

Ethylethylenebis(indenyl)zirconium chloride,

Ethylenebis(indenyl)zirconium dichloride,

Isopropylidene bis(indenyl)zirconium dichloride,

Isopropylidene(cyclopentadienyl)-1-fluorenylzirconium chloride,

Ethylenebis(indenyl)zirconium dibromide,

Ethylenebis(indenyl)methoxyzirconium chloride,

Ethylenebis(indenyl)ethoxyzirconium chloride,

Ethylenebis(indenyl)phenoxyzirconium chloride,

Ethylenebis(cyclopentadienyl)zirconium dichloride,

Propylenebis(cyclopentadienyl)zirconium dichloride,

Ethylenebis(tert-butylcyclopentadienyl)zirconium dichloride,

Dimethylethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium,

Methylethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium chloride,

Ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dichloride,

Ethylenebis(4,5,6,7-tetrahydro-1-indenyl)zirconium dibromide,

Ethylenebis(4-methyl-1-indenyl)zirconium dichloride,

Ethylenebis(5-methyl-1-indenyl)zirconium dichloride,

Ethylenebis(6-methyl-1-indenyl)zirconium dichloride,

Ethylenebis(7-methyl-1-indenyl)zirconium dichloride,

Ethylenebis(5-methoxy-1-indenyl)zirconium dichloride,

Ethylenebis(2,3-dimethyl-1-indenyl)zirconium dichloride,

Ethylenebis(4,7-dimethyl-1-indenyl)zirconium dichloride,

Ethylenebis(4,7-dimethoxy-1-indenyl)zirconium dichloride.

Transition metal compounds in which zirconium is replaced by metal titanium, metal hafnium, metal chromium, metal vanadium, etc. among the above zirconium compounds can also be used.

In this case, preferably used as organometallic compound catalyst component (B) is an organoaluminum compound obtained by reacting an organoaluminum compound with water, or by reacting an organoaluminum compound with water, or by Aluminoxane solutions are obtained by reacting with water or hydrogen-containing reactive compounds.

These organoaluminum compounds are insoluble or slightly soluble in benzene at 60°C.

The amount of the catalyst used varies depending on the type of catalyst used and the like. For example, when the above catalyst component (A), organometallic compound catalyst component (B) and electron donor (C) are used, the amount of catalyst component (A) used is usually 0.001 -0.5 mmol range, preferably 0.005-0.5 mmol. In addition, the amount of the organometallic compound catalyst (B) used is generally, per mole of the transition metal atom in the catalyst component (A) in the polymerization system, the amount of the metal atom of the organometallic compound catalyst (B) is 1 to 10,000 moles , preferably 5 to 500 moles. In addition, when an electron donor is used, the amount of the electron donor is 100 moles or less, preferably 1 to 50 moles, most preferably 3 to 20 moles.

Preliminary polymerization is preferably carried out before main polymerization using the above-mentioned catalyst. This preliminary polymerization is carried out using a catalyst prepared by combining at least the catalyst component (A) and the organometallic compound catalyst component (B).

When titanium is used as the transition metal, the initial polymerization amount is usually 1 to 2000 grams, preferably 3 to 1000 grams, most preferably 10 to 500 grams per gram of the titanium catalyst component.

It is preferable to use an inert hydrocarbon solvent when carrying out the initial polymerization. Examples of the inert hydrocarbon solvent include aliphatic hydrocarbons such as propane, butane, n-pentane, isopentane, n-hexane, isohexane, n-heptane, n-octane, Isooctane, n-decane, n-dodecane, and kerosene; alicyclic hydrocarbons, such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbons, such as benzene, toluene, xylene and halogenated hydrocarbons such as dichloromethane, ethyl chloride, ethylene chloride and chlorobenzene. Aliphatic hydrocarbons are preferred among these inert hydrocarbon solvents, particularly preferred are aliphatic hydrocarbons having 4 to 10 carbon atoms. In addition, it is also possible to use monomers as solvents in the reaction.

Suitable examples of α-olefins used in the initial polymerization include α-olefins having 10 carbon atoms or less such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1 -pentene, 3-methyl-1-pentene, 1-heptene, 1-octene and 1-decene, further preferably α-olefins having 3 to 6 carbon atoms, particularly preferably propylene. These α-olefins may be used alone or in combination of two or more as long as a crystalline polymer is produced.

The polymerization temperature of the initial polymerization is variable, depending on the α-olefin and inert solvent used, and cannot be determined unconditionally, but the temperature range is generally -40 to 80°C, preferably -20 to 40°C, most preferably -10 to 30°C ℃. For example, in the case of using propylene as the α-olefin, the temperature range is -40 to 70°C, in the case of 1-butene, -40 to 40°C, and in the case of 3-methyl-1-pentene, -40°C. to 70°C. It is also possible to make hydrogen coexist in this initial polymerization reaction system.

After the initial polymerization is carried out according to the above method or without initial polymerization, the above monomers are introduced into the reaction system to carry out polymerization reaction (main polymerization) to prepare polyolefin particles.

The monomer used in the main polymerization may be the same as or different from the monomer used in the preliminary polymerization.

The polymerization temperature in the main polymerization of olefin is usually in the range of -50 to 200°C, preferably 0 to 150°C. The polymerization pressure is usually in the range of atmospheric pressure to 100 kg/ ^cm2 , preferably atmospheric pressure to 50 kg/ ^cm2 . Polymerization can be carried out in batch, semi-continuous and continuous processes.

The molecular weight of the olefin polymer obtained can be adjusted by hydrogen and/or polymerization temperature.

In the present invention, the polyolefin particles thus obtained are generally not subjected to the step of particle pulverization or pulverization, but are used for the modification reaction.

The present invention is further described by the following examples without limiting the invention.

Examples 1 to 10

(a) Preparation of Catalyst Component (A)

After purging a high-speed stirrer (manufactured by Tpkushu Kika kogyo Co.) with a 2-liter inner chamber with nitrogen, 700 ml of purified kerosene, 10 g of commercially available MgCl ₂ , 24.2 g of ethanol and 3 g of Emozol 320 (Kao-Atlas Co., Ltd. (commercial name of sorbitan distearate), the system was heated while stirring, and stirred at 120° C. for 30 minutes at 800 rpm. Using a Teflon tube with an internal diameter of 5 mm, with high-speed stirring, the mixture was transferred to a 2-liter glass flask (with a stirrer) containing 1 liter of purified kerosene precooled to -10°C. The resulting solid was collected by filtration and washed thoroughly with hexane, whereby a carrier was obtained.

7.5 g of the support was suspended in 150 ml of titanium tetrachloride at room temperature, 1.3 ml of diisobutyl phthalate was added, and the system was heated to 120°C. After stirring and mixing at 120°C for 2 hours, the solid portion was collected by filtration and resuspended in 150 ml of titanium tetrachloride, and stirred and mixed at 130°C for another 2 hours. The reaction solid was collected from the reaction mixture by filtration and washed with an appropriate amount of purified hexane, whereby a solid catalyst component (A) was obtained. The composition was (atomically) 2.2% by weight titanium, 63% by weight chlorine and 20% by weight magnesium, and 5.5% by weight diisobutyl phthalate. The obtained ideal spherical catalyst has an average particle size of 64 microns and a geometric standard deviation (δg) of particle size distribution of 1.5.

(b) initial gathering

The following primary polymerizations were carried out on the catalyst component (A).

Add 200 milliliters of purified hexane to a 400 milliliter glass reactor purged with nitrogen, and then add 20 millimoles of triethylaluminum, 4 millimoles of diphenyldimethoxysilane and 2 millimoles (as titanium atomic basis) the above-mentioned titanium catalyst component (A). Then propylene was fed at a rate of 5.9 Nl/hour for 1 hour, whereby 2.8 g of propylene was polymerized per gram of the titanium catalyst component (A). After the initial polymerization the liquid portion was filtered off and the separated solid portion was resuspended in decane.

(c) Aggregation

(I) Homopolymerization (1)

Add 5 kg of propylene to a 17-liter polymerizer at room temperature and heat it, then add 8 mmoles of triethylaluminum, 8 mmoles of diphenyldimethoxysilane and 0.08 mmoles (calculated as titanium atoms) at 50 ° C The initial polymerization treatment of the catalyst component (A). The temperature in the polymerizer was maintained at 70°C for 2 hours, and then the remaining propylene was removed to isolate the polymer. The obtained polymer had [η] of 6.97 dl/g, an apparent bulk density of 0.45 g/ml, and a yield of 3.1 kg.

In addition, the average particle size of the polymer was 1.8 mm, the geometric standard deviation thereof was 1.3, and the content of fine particles having a particle size of 100 µm or less contained in the polymer was 0.1% by weight.

Homopolymer (2)

Selected from the same procedure as homopolymerization (1) except that 1.5 Nl of hydrogen was added 20 minutes after the 5 kg of propylene. 3.3 kg of a polymer having a [?] of 3.5 dl/g and an apparent bulk density of 0.46 g/ml was obtained.

In addition, the average particle size of the polymer was 1.7 mm, the geometric standard deviation thereof was 1.3, and the content of fine particles of 100 µm or less contained in the polymer was 0.2% by weight.

(II) Copolymer

At room temperature, 2.5 kg of propylene and 20 Nl hydrogen were added to a 17-liter polymerizer and heated, and at 50 ° C, 15 mmoles of triethylaluminum, 1.5 mmoles of diphenyldimethoxysilane and 0.05 mmoles (calculated as titanium atoms) were added ) The catalyst component (A) treated with initial polymerization, the temperature in the polymerizer is kept at 70°C. Fourteen minutes after the temperature reached 70°C, the outlet valve was opened and propylene was purged until the pressure in the polymerizer became atmospheric. After the propylene is removed, the copolymerization is carried out. That is, ethylene, propylene and hydrogen were fed into the polymerizer at rates of 480 Nl/hour, 720 Nl/hour and 12 Nl/hour, respectively. The outlet hole was adjusted so that the pressure in the polymerizer was 10 kg/cm ² ·G. The temperature was kept at 70°C during the copolymerization. After 60 minutes of polymerization, the inside of the polymerizer was depressurized to obtain 3.2 kg of polymer. At 230°C and a pressure of 2 kg, the polymer has an MI of 10 g/10 min, an ethylene content of 25 mol%, and an apparent bulk density of 0.42 g/ml. Also, at 23°C, the n-decane-soluble component content of the polymer was 25% by weight, and the ethylene content of the soluble component was 50 mol%.

In addition, the average particle size of the obtained polymer was 1.9 mm, the geometric standard deviation thereof was 1.3, and the content of fine particles of 100 m or less contained in the polymer was 0.0% by weight.

(d) 100 parts by weight of polypropylene (PP)

100 parts by weight of polypropylene listed in Table 1 were added into a stainless steel high-pressure tank equipped with a spiral double strip stirring blade, and the inside of the high-pressure tank was thoroughly blown with nitrogen. A solution containing maleic anhydride (MAH), benzoyl peroxide (BPO) and solvent in the mutual ratios listed in Table 1 was dropped into the polypropylene within 10 minutes while stirring the polypropylene at room temperature, thereafter, at room temperature The mixture was further stirred for 30 minutes.

Then, the temperature of the system was raised to 100°C, and the reaction was carried out for 4 hours.

The reacted polymer was dissolved in p-xylene at 130°C, the solution was cooled, and the polymer was precipitated with acetone, whereby the polymer was free of unreacted substances and thus purified.

The results are listed in Table 1.

Comparative example 1

100 parts by weight of polypropylene [homopolymer (2)], 2.27 parts by weight of MAH and 0.17 parts by weight of 2,5-di-methyl-2,5-bis(tert-butylperoxy)hexyne-3 (Nippon Yushi Co. Ltd.) were mixed in a Henschel mixer, fed to a twin-screw extruder (Plastic Kagaku Co. Ltd.), PLABOR 40L/D-40 set to 200°C, melted and kneaded. The modified product thus obtained had a grafted amount of 0.18% by weight and an MFR of 30.

Examples 11 to 13

(a) Aggregation

(I) Homopolymer

5 kg of propylene was fed to a 17 liter polymerizer at room temperature, followed by 1.5 liters of hydrogen. The mixture was heated, and 8 mmoles of triethylaluminum, 8 mmoles of diphenyldimethoxysilane and 0.08 mmoles (calculated as titanium atoms) of the initial polymerization treatment obtained in Example 1 (b) were added at 50° C. catalyst component (A). The inside of the polymerizer was maintained at a temperature of 70° C. for 1 hour and 20 minutes. The remaining propylene is then removed and the polymer collected. [η] of the polymer was 3.5 dl/g, the apparent bulk density was 0.46 g/ml, and its yield was 3.3 kg.

(b) Add 100 parts by weight of polypropylene (PP) shown in Table 2 into a stainless steel high-pressure tank equipped with a spiral double-barrel stirring blade, and thoroughly blow the inside of the system with nitrogen. Within 10 minutes, the solution containing allyl glycidyl ether, benzoyl peroxide (BPO) and toluene in the mutual ratio shown in Table 2 was dropped into polypropylene, while the polypropylene was stirred at room temperature. The mixture was further stirred at room temperature for 30 minutes.

Thereafter, the internal temperature of the system was raised to 100°C, and the reaction was carried out for 4 hours.

The reacted polymer was dissolved in p-xylene at 130° C., and the mixture was naturally cooled, followed by precipitation with acetone, whereby unreacted substances were removed to purify the polymer.

Table 2

Examples 14 to 16

The respective amounts of monomers, benzoyl peroxide (BPO) and toluene shown in Table 3 were added to 100 parts by weight of the copolymer obtained in Example 1(c), followed by mixing at normal temperature. 10 g of this mixture was weighed into a 25 mm diameter test tube and cooled with liquid nitrogen to freeze. Then, the inside of the system was purged with nitrogen, the temperature of the system was returned to room temperature, and the test tube was placed in an oil bath at 100° C., and the reaction was carried out for 4 hours.

The reacted polyolefin particles were dissolved in p-xylene at 130°C, and after the mixture was cooled, it was precipitated with methanol for purification. The amount of grafting was determined by IR using a pre-made calibration curve.

table 3

1) HEMA: Di-hydroxyethyl methacrylate

2) HEA: 2-hydroxyethyl acrylate

3) HPA: 2-hydroxypropyl acrylate

Example 17

300 grams of the homopolymer (2) obtained in Example 1 (c) were added to a 1-liter glass reactor equipped with a helical double-barrel stirring blade and a drop funnel, and the inside of the system was thoroughly purged with nitrogen , and then a solution containing 52 grams of toluene, 9.1 grams of N,N-dimethylaminomethacrylate and 0.51 grams of BPO was placed in the dropping funnel. This solution was dropped into PP over 10 minutes at room temperature while stirring the latter, after which the mixture was further stirred at room temperature for 30 minutes. Then the temperature inside the system was raised to 100°C, and the reaction was carried out for 4 hours.

After the reaction, the polyolefin particles were dissolved in xylene at 130°C, and after the solution was cooled, it was precipitated with acetone to purify it. Measurement of the amount of grafting of the particles showed that 0.25% by weight of N,N-dimethylurethane methacrylate was grafted. The MFR of the grafted polymer was 1.1 g/10 min.

These modified polyolefin particles had an average particle size of 1.7 mm and a geometric standard deviation of 1.3, and the polymer contained 0.2% by weight of fine particles of 100 µm or less.

Claims (13)

1. A method for preparing modified polyolefin particles, the method comprising (A) 100 parts by weight of polyolefin particles and (B) 0.01-50 parts by weight of at least one olefin unsaturated compound selected from the following groups: carboxyl-containing olefin unsaturated compounds or their carboxylic anhydrides or their carboxylic acid derivatives, hydroxyl-containing olefin unsaturated compounds , olefinically unsaturated compounds containing amino groups, and olefinically unsaturated compounds containing glycidyl groups, present in (C) from more than 10 parts to not more than 50 parts by weight of a medium that is liquid at normal temperature, the medium has a solubility in water of 0.5% by weight or less at 20°C and is capable of swelling the polyolefin, and (D) 0.01-10 parts by weight of a radical initiator is contacted and reacted. 2. The method of claim 1, wherein the average particle size of the polyolefin particles is in the range of 10 to 5000 microns. 3. The method of claim 1, wherein the polyolefin particles consist of homopolymers or copolymers of alpha-olefins having 2 to 20 carbon atoms. 4. The method of claim 1, wherein the olefin unsaturated compound is a carboxyl-containing olefin unsaturated compound or their carboxylic acid anhydrides or their derivatives, which are selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetra Hydrogenated phthalic acid, itaconic acid, citraconic acid, crotonic acid and endo-cis-bicyclo[2,2,1]hept-5-ene-2,8-dicarboxylic acid, their carboxylic anhydrides, and acid halides, amides, imides or esters of these carboxylic acids. 5. The method of claim 1, wherein the olefinically unsaturated compound is a hydroxyl-containing olefinically unsaturated compound selected from the group consisting of hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid 3-hydroxypropyl ester, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, -glyceryl (meth)acrylate, -( Pentaerythritol methacrylate, -trimethylolpropane (meth)acrylate, -tetramethylolethane (meth)acrylate, -butylene glycol (meth)acrylate, -(meth)acrylate Polyethylene glycol acrylate, 2-(6-hydroxyhexanoyloxy)ethyl acrylate, 10-undecen-1-ol, 1-octen-3-ol, 2-hydroxymethylnorbornene , hydroxystyrene, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylolacrylamide, 2-(meth)acryloyloxyethyl phosphate, glycerol-allyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol, and monoglycerol. 6. The method of claim 1, wherein the olefinically unsaturated compound is an amino-containing olefinically unsaturated compound having an ethylenically unsaturated double bond and at least one of the formula The compound of the amino represented by wherein R ¹ is a hydrogen atom, a methyl group or an ethyl group, and R ² is a hydrogen atom, an alkyl group with 1-12 carbon atoms or a cycloalkyl group with 6-12 carbon atoms. 7. The method of claim 1, wherein the amino group-containing olefinically unsaturated compound is selected from the group consisting of aminoethyl acrylate, alanaminoethyl acrylate, dimethylaminoethyl methacrylate, aminopropyl acrylate, and phenaminoethyl methacrylate , cyclohexylaminoethyl methacrylate, methacryloyloxyethyl phosphate, -methylene sesamepine half salt, N-vinyldiethylamine, N-acetylvinylamine, allyl Amine, methallylamine, N-methacrylamide, N,N-dimethylacrylamide, N,N-dimethylaminopropylacrylamide, acrylamide, N-methacrylamide, p- Aminostyrene, 6-aminohexylsuccinimide, and 2-aminoethylsuccinimide. 8. The method of claim 1, wherein the olefinically unsaturated compound is selected from the group consisting of allyl glycidyl ether, 2-methallyl glycidyl ether and vinyl glycidyl ether. 9. The method of claim 1, wherein the liquid medium at normal temperature is selected from the group consisting of benzene, mineral spirits, toluene, chlorobenzene, o-dichlorobenzene, xylene, n-hexane, n-heptane, n-octane alkanes, carbon tetrachloride and 1,3,3-trichloropropadiene. 10. The method of claim 1, wherein the contacting and reacting are carried out at a temperature at which the polyolefin particles are immiscible and the radical initiator used does not decompose. 11. The method of claim 10, wherein the contacting and reaction are carried out at a temperature of 0 to 150°C. 12. Modified polyolefin particles prepared by the process of claim 1. 13. The modified polyolefin particles are characterized by: (a) having an average particle size in the range 100-5000 microns, (b) Its geometric standard deviation is between 1 and 2, (c) 20% by weight or less of particles having a particle size of 100 microns or less, and (d) They are modified by a polar group selected from carboxyl or its anhydride or derivatives thereof, hydroxyl, amino and glycidyl.