JPH04356530A - Production of modified polyolefin particle - Google Patents

Abstract

PURPOSE:To produce modified polyolefin particles within a short modification reaction time at high productivity at low production cost by modifying polyolefin particles at a temperature lower than the melting point of the polyolefin particles without deteriorating them and changing their powder properties, etc. CONSTITUTION:The title process comprises bringing polyolefin particles into contact with at least one modifier selected from among an ethylenically unsaturated carboxylic acid, its anhydride or derivative, a hydroxylated ethylenically unsaturated compound and an ethylenically unsaturated epoxy compound and a radical polymerization initiator under conditions in which at least the polyolefin particles are irradiated with an actinic radiation.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for modifying polyolefin particles with carboxyl, hydroxyl or epoxy groups.

0002

TECHNICAL BACKGROUND OF THE INVENTION Conventionally, methods have been used to modify polyolefins by imparting polar groups such as carboxyl groups to them.

[0003] Modification of such polyolefins can be carried out by mixing a modifier with polyolefin, extruding the polyolefin in a molten state using an extruder, etc., and modifying it at high temperature and under high shear force (melt method); A method (solvent method) has been adopted in which the polyolefin is modified by dissolving it in a solvent and adding a modifier to the solution.

However, in these methods, even if particulate polyolefin is used as the raw material polyolefin, a modified polyolefin that retains its shape cannot be obtained. Apart from this method, Japanese Patent Application Laid-open No. 50-77493,
Special Publication No. 55-32722 and No. 57-174309
Each publication, such as No. 1, discloses a method of modifying a granular olefin polymer by heating the granular olefin polymer to a temperature below its melting point.

[0005] Furthermore, JP-A-50-77493 discloses the use of a solvent such as acetone, methyl ethyl ketone, ether, chloroform, etc. during modification. However, the modifiers used in the methods disclosed in these publications are maleic anhydride, epoxy compounds, etc., and compounds having hydroxyl groups are not disclosed. In addition, these methods have problems in terms of economic efficiency because the modification reaction time is relatively long and the productivity is low.

[0006]

OBJECTS OF THE INVENTION The present invention provides polyolefin particles modified with at least one of a carboxyl group, a group derived from an anhydride or a derivative of an ethylenically unsaturated carboxylic acid, a hydroxyl group, and an epoxy group. In addition, the present invention provides a method for producing modified polyolefin particles that can shorten the modification reaction time and reduce production costs.

[0007]

Summary of the Invention The method for producing modified polyolefin particles according to the present invention comprises at least irradiating the polyolefin particles (A) with an activation energy beam. At least one selected from the group consisting of carboxylic acid, its anhydride or its derivative, a hydroxyl group-containing ethylenically unsaturated compound, and an ethylenically unsaturated group-containing epoxy compound
It is characterized by bringing the seed modifier (B) into contact with the radical polymerization initiator (C).

[0008]

DETAILED DESCRIPTION OF THE INVENTION The method for producing modified polyolefin particles according to the present invention will be specifically described below.

[0009] In the present invention, when the term "polymer" is used, the term "polymer" is used in a concept that includes both polymers and copolymers. The average particle diameter of the above polyolefin particles (A) used in the present invention is usually 10 to 500.
0 μm, preferably within the range of 100 to 4000 μm.

The above polyolefin particles (A) can be obtained, for example, by polymerizing or copolymerizing α-olefins having 2 to 20 carbon atoms. α like this
- Examples of olefins include ethylene, propylene, butene-1, pentene-1, 2-methylbutene-1, 3-
Methylbutene-1, hexene-1, 3-methylpentene-1, 4-methylpentene-1, 3,3-dimethylbutene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene-1, Ethylpentene-1, octene-1, methylpentene-1, dimethylhexene-1, trimethylpentene-1, ethylhexene-1, methylethylpentene-1, diethylbutene-1
, propylpentene-1, decene-1, methylnonene-
1, dimethyloctene-1, trimethylheptene-1,
Mention may be made of α-olefins such as ethyl octene-1, methylethylheptene-1, diethylhexene-1, dodecene-1 and hexadodecene-1.

Among these, α- having 2 to 8 carbon atoms
It is preferred to use olefins alone or in combination. In the present invention, polymer particles containing repeating units derived from the above-mentioned α-olefin are used, usually containing 50 mol% or more, preferably 80 mol%, particularly preferably 90 mol% or more, and even more preferably 100 mol%. used.

In the present invention, other compounds that can be used in addition to the above α-olefins include, for example, linear polyene compounds and cyclic polyene compounds. In the present invention, the polyene compound is a polyene having two or more conjugated or non-conjugated olefinic double bonds, and examples of such linear polyene compounds include 1,4-hexadiene and 1,5-hexadiene. ,1
, 7-octadiene, 1,9-decadiene, 2,4,6
-octatriene, 1,3,7-octatriene, 1,
Examples include 5,9-decatriene and divinylbenzene. Examples of cyclic polyene compounds include 1
,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3
-cycloheptadiene, 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, 2-propenyl-2,5-
Examples include norbornadiene.

Further, in the present invention, a polyene compound obtained by condensing cyclopentadiene such as cyclopentadiene and α-olefin such as ethylene, propylene, butene-1 using a Diels-Alder reaction is used. You can also do that.

Furthermore, in the present invention, cyclic monoene compounds can also be used, and examples of such cyclic monoene compounds include cyclopropene, cyclobutene,
Monocycloalkenes such as cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene, cycloeicosene;
Norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5,5
, 6-trimethyl-2-norbornene, 2-bornene and other bicycloalkenes; 2,3,3a,7a-tetrahydro-4,7-methano-1H-indene, 3a,5,6,
Tricycloalkenes such as 7a-tetrahydro-4,7-methano-1H-indene; 1,4,5,8-dimethano-
1,2,3,4,4a,5,8,8a-octahydronaphthalene, and in addition to these compounds, 2-methyl-
1,4,5,8-dimethano-1,2,3,4,4a,5
, 8,8a-octahydronaphthalene, 2-ethyl-1
,4,5,8-dimethano-1,2,3,4,4a,5,
8,8a-octahydronaphthalene, 2-propyl-1
,4,5,8-dimethano-1,2,3,4,4a,5,
8,8a-octahydronaphthalene, 2-hexyl-
1,4,5,8-dimethano-1,2,3,4,4a,5
,8,8a-octahydronaphthalene, 2-stearyl-1,4,5,8-dimethano-1,2,3,4,4a
, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,
4a,5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethanol-1,2
, 3,4,4a,5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,
3,4,4a,5,8,8a-octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-1,2,3
,4,4a,5,8,8a-octahydronaphthalene,
2-fluoro-1,4,5,8-dimethano-1,2,3
,4,4a,5,8,8a-octahydronaphthalene,
2,3-dichloro-1,4,5,8-dimethano-1,2
, 3,4,4a,5,8,8a-tetracycloalkenes such as octahydronaphthalene; hexacyclo[6,6,
1,13,6,110,13,0 2,7,0 9,1
4] heptadecene-4, pentacyclo[8,8.12,
9,14,7,111,18,0,0 3,8,0 1
2,17] Henikosene-5, Octacyclo[8,8,
12,9,14,7,111,18,113,16,0
,0 3,8,0 12,17] Cyclic monoene compounds such as polycycloalkenes such as docosene-5 can be mentioned.

Furthermore, in the present invention, styrene and substituted styrene can also be used. The polyolefin particles used in the present invention have at least the above α
- Obtained by polymerizing or copolymerizing olefins in the presence of a catalyst, but the above polymerization reaction or copolymerization reaction can be carried out in the gas phase (gas phase method) or in the liquid phase. (liquid phase method).

The polymerization reaction or copolymerization reaction by the liquid phase method is preferably carried out in a suspended state so that the resulting polyolefin particles can be obtained in a solid state. In the present invention, in producing polyolefin particles, a method of simultaneously producing a crystalline olefin polymer portion and an amorphous olefin polymer portion by supplying two or more types of monomers to a polymerization pot, or at least Examples include a method in which the synthesis of a crystalline olefin polymer portion and the synthesis of an amorphous olefin polymer portion can be performed separately and in series using two or more polymerization vessels. In this case, the latter method is preferred from the viewpoint that the molecular weight, composition, and amount of the amorphous olefin polymer portion can be freely changed.

The most preferred method is to synthesize a crystalline olefin polymer portion by gas phase polymerization and then synthesize an amorphous olefin polymer portion by gas phase polymerization, or to synthesize a crystalline olefin polymer portion using a monomer as a solvent. This method involves synthesizing the amorphous olefin polymer portion by gas phase polymerization after synthesizing the amorphous olefin polymer portion.

[0018] As the solvent used in this polymerization reaction or copolymerization reaction, an inert hydrocarbon can be used. Furthermore, the α-olefin as a raw material may be used as a reaction solvent. Note that the above polymerization or copolymerization may be carried out by a combination of a liquid phase method and a gas phase method. In the production of the polyolefin particles used in the present invention, the above polymerization or copolymerization is carried out by a gas phase method or an α
- It is preferable to adopt a method in which a gas phase method is combined after the reaction is carried out using an olefin as a solvent. In the present invention, the catalyst used in the above-mentioned polymerization reaction or copolymerization reaction is usually selected from those listed in the Periodic Table of Elements IV.
Group A, Group V A, Group VI A, Group VII A and V
A catalyst consisting of a catalyst component [A] containing a transition metal of Group III and an organometallic compound catalyst component [B] of Groups I, II, and III of the Periodic Table of Elements is used.

Details of the method for producing polyolefin particles are described, for example, in publications such as JP-A-2-140205. In the present invention, the polyolefin particles obtained as described above are usually used as they are for the modification reaction without being subjected to a pulverization or granulation step.

In the present invention, the polyolefin constituting the above polyolefin particles is an ethylenically unsaturated group-containing carboxylic acid, an acid anhydride thereof, or a derivative thereof (in the present invention, an ethylenically unsaturated group-containing carboxylic acid, etc. ”
), at least one modifier (B) selected from the group consisting of hydroxyl group-containing ethylenically unsaturated compounds and ethylenically unsaturated group-containing epoxy compounds
It is denatured by

[0021] In the method for producing modified polyolefin particles according to the present invention, the polyolefin particles (A) and the modifier (B) are irradiated with an activation energy beam at least to the polyolefin particles (A) as described above.
and a radical polymerization initiator (C) to modify the polyolefin particles.

Examples of the ethylenically unsaturated group-containing carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid,
Citraconic acid, crotonic acid, nadic acid TM, (endocys-bicyclo[2,2,1]hept-5-ene-2,
Examples include unsaturated carboxylic acids such as 3-dicarboxylic acid.

Examples of the anhydrides and derivatives of ethylenically unsaturated group-containing carboxylic acids include acid halides, amides, imides, esters, etc.
Specific examples include maleyl chloride, malenylimide, maleic anhydride, citraconic anhydride, monomethyl maleate, and dimethyl maleate. Among these, unsaturated dicarboxylic acids or their acid anhydrides are preferred, and maleic acid, naldic acid TM, or their acid anhydrides are particularly preferred.

Examples of the above-mentioned hydroxyl group-containing ethylenically unsaturated compounds include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,
3-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerin mono(meth)acrylate, pentaerythritol mono(meth)acrylate, (meth)acrylate such as trimethylolpropane mono(meth)acrylate, tetramethylolethane mono(meth)acrylate, butanediol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, 2-(6-hydroxyhexanoyloxy)ethyl acrylate, etc. ) acrylic esters.

In addition to the above-mentioned (meth)acrylic acid ester, as the hydroxyl group-containing ethylenically unsaturated compound, 10
- undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene,
Hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, N-methylolacrylamide, 2-(
meta) acroyloxyethyl acid phosphate,
Glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene-1,4-diol,
Glycerin monoalcohol and the like can also be used.

These hydroxyl group-containing ethylenically unsaturated compounds can be used alone or in combination. Among such compounds, particularly in the present invention, it is preferable to use 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

The above ethylenically unsaturated group-containing epoxy compound has an unsaturated group consisting of an olefinic double bond and an epoxy group in the molecule. Specifically, aliphatic glycidyl esters or aliphatic glycidyl ethers such as glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate, and glycidyl maleate; 2
-Cyclohexene-1-glycidyl ether, cyclohexene-4,5-dicarboxylic acid digcidyl ester, cyclohexene-4-carboxylic acid glycidyl ester, 5
-norbornene-2-methyl-2-carboxylic acid glycidyl ester, endocis-bicyclo-[2,2,1]-
Examples include alicyclic glycidyl esters and alicyclic glycidyl ethers such as 5-heptene-2,3-dicarboxylic acid diglycidyl ester. Among them, glycidyl methacrylate is preferred.

In the present invention, the above-mentioned modifier (
B) is usually 0.1 to 50 parts by weight, preferably 0.3 to 30 parts by weight, based on 100 parts by weight of the polyolefin particles (A).
Used in parts by weight.

In the present invention, a radical polymerization initiator (C) is used. Examples of the radical polymerization initiator that can be used in the present invention include benzoin or benzoin ether type, benzyl ketal type,
α-hydroxyacetophenone type, chloroacetophenone type, α-aminoacetophenone type, acylphosphine oxide type, α-dicarbonyl type, α-acyloxime type, aromatic ketone type, thioxanthone type, anthraquinone type, amine type, organic peroxide type Examples include radical polymerization initiators such as molds.

Specific examples of such radical polymerization initiators include benzoin or its ether type,
Benzoin or its ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether; benzophenone, p, p belonging to the aromatic ketone type;
Benzophenone compounds such as '-diphenylbenzophenone, p,p'-tetramethyldiaminobenzophenone, p-chlorobenzophenone, p-methoxybenzophenone, anthraquinone, 1,2-benzoanthraquinone, benzoquinone, 1,2-naphthoquinone, 1,4 - Quinone compounds such as naphthoquinone, anthrone, 1,9-benzaanthrone, 6-phenyl-1,9-benzaanthrone, 3-phenyl-1,9-benzaanthrone, 2-
Anthrone compounds such as keto-3-aza-1,9-benzaanthrone and 3-methyl-1,3-diaza-1,9-benzaanthrone, and dibenzalacetone; benzyl and benzyl dimethyl belonging to the benzyl ketal type Benzyl compounds such as ketals; aromatic ketone type and α-
1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1 belonging to the hydroxyacetophenone type
- Hydroxyalkylphenyl ketone compounds such as propanone, 1-phenyl-2-hydroxy-2-methyl-1-propanone, 1-(4-tert-butylphenyl)-2-hydroxy-2-methyl-1-propanone, etc. can be mentioned. In addition, Nippon Ciba Geigy Co., Ltd.
Radical polymerization initiators sold under the trade name "Irgacure", such as 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-[4-(methylthio)phenyl]
-2-morpholino-1-propanone and the like are easily available and preferred.

The various types of radical polymerization initiators as described above may be used alone or in combination of two or more. When using a hydroxyl group-containing ethylenically unsaturated compound as a modifier, benzyl ketal type, α-
Hydroxyacetophenone type and organic peroxide type radical polymerization initiators are preferably used.

In the present invention, the above-mentioned radical polymerization initiator (C) is usually used in polyolefin particles (A
) is used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 8 parts by weight, per 100 parts by weight.

Furthermore, in the present invention, an activation energy beam sensitizer can also be used if necessary. Examples of such activation energy beam sensitizers include hydrocarbon compounds such as anthracene, naphthalene, chrysene, and phenanthrene; p-dinitrobenzene;
Nitro compounds such as p-nitroaniline, 1,3,5-trinitrobenzene, p-nitrodiphenyl; n-butylamine, di-n-butylamine, triethylamine, diethylaminoethyl methacrylate, p-nitroaniline, N-acetyl-4- Amino compounds such as nitro-1-naphthylamine; phenol, p-nitrophenol,
Phenol compounds such as 2,4-dinitrophenol and 2,4,6-trinitrophenol; benzaldehyde,
Ketones such as 9-anthraaldehyde and acetophenone are used.

In the present invention, the polyolefin particles (A), the modifier (B), and the radical polymerization initiator (C) are brought into contact with each other under the condition that at least the polyolefin particles (A) are irradiated with an activation energy beam. However, at that time, a solvent that swells the polyolefin particles (hereinafter referred to as
It is preferable to use a solvent (sometimes referred to as a "swelling solvent").

In the present invention, when an ethylenically unsaturated group-containing carboxylic acid or the like and an ethylenically unsaturated group-containing epoxy compound are used as the modifier, the swelling solvent (D) is 2
A solvent having a solubility in water at 0° C. of 0.5% by weight or less, preferably 0.4% by weight or less is used. When modified polyolefin particles are produced in the presence of such a swelling solvent, modified polyolefin particles with excellent granule properties can be obtained, although the reason is unknown. Moreover, such solvents
When it comes into contact with polyolefin particles, it swells the polyolefin particles, especially the amorphous olefin polymer part of the polyolefin particles, and serves to facilitate the penetration of the above-mentioned modifier and radical polymerization initiator into the polyolefin particles. , even the inside of polyolefin particles can be uniformly modified.

20 that can be used in the present invention
Examples of solvents with solubility in water at 0.5% by weight or less include benzene (solubility: 0.09% by weight), mineral spirit (solubility: 0.00090% by weight), and toluene (solubility: 0.05% by weight). %), chlorobenzene (solubility: 0.05% by weight), o-dichlorobenzene (25
Solubility at °C: 0.01% by weight), xylene (25% by weight)
Solubility at °C: 0.02% by weight), n-hexane (
Solubility at 25°C: 0.014% by weight), n-heptane (Solubility at 25°C: 0.005% by weight), n
-Octane (solubility at 25°C: 0.002% by weight)
), carbon tetrachloride (solubility at 25°C: 0.44% by weight), and ClCH=C=CCl2 (solubility at 25°C: 0.11% by weight).

In the present invention, these swelling solvents can be used alone or in combination. Furthermore, if used with the above swelling solvents, acetone, tert-butyl alcohol, methyl ethyl ketone,
It is also possible to use other solvents such as chloroform, diethyl ether, etc. However, when using a mixed solvent, the content of the solvent having a water solubility of 0.5% by weight or less at 20° C. is usually 5% by weight or more, preferably 10% by weight or more.

[0038] As described above, by using a solvent whose solubility in water at 20°C is 0.5% by weight or less,
The reaction can proceed smoothly. The swelling solvent as described above is based on 100 parts by weight of the polyolefin particles.
It is usually used in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight.

When a hydroxyl group-containing ethylenically unsaturated compound is used as a modifier, the swelling solvent (D) that can be used in the present invention includes aromatic hydrocarbon solvents such as benzene, toluene, and xylene; , aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane, decane; cyclohexane, methylcyclohexane,
Alicyclic hydrocarbon solvents such as decahydronaphthalene; chlorobenzene, dichlorobenzene, trichlorobenzene,
Examples include chlorinated hydrocarbon solvents such as methylene chloride, chloroform, carbon tetrachloride, and tetrachloroethylene. It is also possible to use a suitable amount of a phagocytic solvent mixed with the above-mentioned solvents. As the phagocytic solvent, methanol,
Alcohol solvents such as ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone;
Ester solvents such as ethyl acetate and dimethyl phthalate;
Examples include ether solvents such as dimethyl ether, diethyl ether, di-n-amyl ether, tetrahydrofuran, and dioxyanisole.

When the above-mentioned solvent comes into contact with the polyolefin particles used in the present invention, it swells the polyolefin particles, especially the amorphous olefin polymer portion of the polymer particles, and causes the above-mentioned modifier and radical polymerization to occur. It plays a role in making it easier for the initiator to penetrate into the particles.

When the above-mentioned swelling solvent is used, the swelling solvent is usually used in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the polyolefin particles.

[0042] Specifically, the activation energy beam used in the present invention includes ultraviolet rays, electron beams, radiation, and γ beams.
Examples include lines. In the present invention, ultraviolet light is preferably used.

As the light source for the ultraviolet rays, conventionally known light sources can be used, and specific examples include high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, and halogen lamps.

In the present invention, when irradiating ultraviolet rays, the amount of ultraviolet irradiation is usually in the range of 1 to 500 J/cm 2 , preferably 5 to 300 J/cm 2 . Irradiation with an activation energy beam such as ultraviolet rays is carried out in air or in an inert gas such as nitrogen gas or argon gas, preferably in an inert gas.

In the method for producing modified polyolefin particles according to the present invention, there are no particular restrictions on the method or order of contact between the polyolefin particles as described above, the modifier, and the radical polymerization initiator. , various methods can be adopted.

In the present invention, when using an ethylenically unsaturated group-containing carboxylic acid or the like or an ethylenically unsaturated group-containing epoxy compound as a modifier, an example of the method or order of contacting the above-mentioned components is as follows. The following methods can be mentioned. (1) A method in which polyolefin particles are dispersed in a solution prepared by dissolving a modifier and a radical polymerization initiator in a swelling solvent, and then this solution is irradiated with an activation energy beam. (2) A method in which polyolefin particles are dispersed in a solution prepared by dissolving a radical polymerization initiator in a swelling solvent, and then this solution is irradiated with an activation energy beam, and then a modifier is added. (3) A method of irradiating polyolefin particles with an activation energy beam in advance and then blending a solution in which a modifier and a radical polymerization initiator are dissolved in a swelling solvent.

In the above methods (1) to (3), the reaction temperature must be a temperature at which the polyolefin particles can maintain their original shape, that is, a temperature below the melting point of the polyolefin particles.

[0048] To give an example of the upper limit of the modification temperature of polyolefin particles constituting polyolefin particles, the upper limit of the modification temperature of polyolefin particles containing polypropylene as the main component is around 150°C; The upper limit of the modification temperature of polyolefin particles containing low-density polyethylene as a main component is approximately 90°C.

Further, in the present invention, when a hydroxyl group-containing ethylenically unsaturated compound is used as a modifier, the following methods may be mentioned as examples of the method and order of contacting the components as described above. (1) A method of mixing polyolefin particles, a modifier, and a radical polymerization initiator, and then irradiating this mixture with an activation energy beam. (2) A method in which polyolefin particles and a radical polymerization initiator are mixed, and then this mixture is irradiated with an activation energy beam to bring the mixture into contact with a modifier in a gas or liquid state. (3) A method of bringing polyolefin particles, a modifier, and a radical polymerization initiator into contact while irradiating an activation energy beam.

[0050] In these methods as well, the reaction temperature needs to be a temperature at which the polyolefin particles can maintain their original shape, that is, a temperature below the melting point of the polyolefin particles.

The modified polyolefin particles obtained in the above manner can be effectively used as raw materials for powder coatings and resin modifiers, for example, since polar groups have been added to the particles.

[0052]

[Effects of the Invention] According to the method for producing modified polyolefin particles according to the present invention, since the modification reaction time is short,
The productivity of modified polyolefin particles is high, and modified polyolefin particles can be obtained at low manufacturing cost.

Furthermore, according to the present invention, since the polyolefin particles are modified at a temperature below the melting point of the polyolefin particles, there is little deterioration that occurs during modification of the polyolefin.
Polyolefin particles can be modified without changing the powder characteristics of the polyolefin particles used.

[0054] Furthermore, if the polyolefin particles are modified using a swelling solvent for the polyolefin particles, the modifier and the radical polymerization initiator can be well transported to the inside of the polyolefin particles, and the polyolefin particles can be uniformly modified. .

[0055] The present invention will be explained below with reference to Examples.
The present invention is not limited to these examples in any way.

[0056]

Examples 1 to 4 100 parts by weight of the polypropylene particles shown in Table 1 were charged into a stainless steel autoclave equipped with a stirring blade having a helical double ribbon, and the inside of the system was completely purged with nitrogen. Next, while stirring the polypropylene particles at room temperature, maleic anhydride and a radical polymerization initiator [trade name IRGACURE-9] were added in the proportions shown in Table 1.
07, manufactured by Nippon Ciba Geigy Co., Ltd.], ultraviolet sensitizer [trade name KAYACURE CTX, manufactured by Nippon Kayaku Co., Ltd.],
A solution consisting of a solvent was added dropwise over a period of 10 minutes, and after the addition, stirring was further performed at room temperature for 30 minutes, and ultraviolet rays were irradiated. The amount of ultraviolet irradiation is shown in Table 1.

[0057] The polymer after the reaction was purified by dissolving it in p-xylene at 130°C, allowing it to cool, and precipitating it with acetone to remove unreacted substances. The results are shown in Table 1.

[0058]

[Table 1]

(*1): MFR (230°C, 2160g
) 0.43g/10min [η] 4.46dl/g (*2): MFR (230°C, 2160g) 10.
9g/10min Ethylene content 24mol%

[0060]

Examples 5 to 8 100 parts by weight of the polypropylene particles shown in Table 2 were charged into a stainless steel autoclave equipped with a stirring blade having a helical double ribbon, and the system was completely purged with nitrogen. Next, while stirring the polypropylene particles at room temperature, a hydroxyl group-containing ethylenically unsaturated compound (2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate) and a radical polymerization initiator [trade name IRGACURE-907] were added in the proportions shown in Table 2. , manufactured by Nippon Ciba Geigy Co., Ltd.], ultraviolet sensitizer [trade name KA
A solution consisting of YACURE CTX (manufactured by Nippon Kayaku Co., Ltd.) and a solvent was added dropwise over 10 minutes, and after the addition, the mixture was further stirred at room temperature for 30 minutes and irradiated with ultraviolet light. The amount of ultraviolet irradiation is as shown in Table 2.

[0061] The polymer after the reaction was purified by dissolving it in p-xylene at 130°C, allowing it to cool, and precipitating it with acetone to remove unreacted substances. The results are shown in Table 2.

[0062]

[Table 2]

(*1): MFR (230°C, 2160g
) 0.43g/10min [η] 4.46dl/g (*2): MFR (230°C, 2160g) 10.
9g/10min Ethylene content 24mol%

[0064]

Examples 9 to 12 100 parts by weight of the polypropylene particles shown in Table 3 were charged into a stainless steel autoclave equipped with a stirring blade having a helical double ribbon, and the system was completely purged with nitrogen. Next, while stirring the polypropylene particles at room temperature, glycidyl methacrylate and a radical polymerization initiator [trade name IRGA
CURE-907, manufactured by Nippon Ciba Geigy Co., Ltd.], a UV sensitizer [trade name KAYACURE CTX, manufactured by Nippon Kayaku Co., Ltd.], and a solvent were added dropwise over a period of 10 minutes, and after the dropwise addition, the solution was further left at room temperature for 30 minutes. Stirring was performed and ultraviolet rays were irradiated. The amount of ultraviolet irradiation is as shown in Table 3.

[0065] The polymer after the reaction was purified by dissolving it in p-xylene at 130°C, allowing it to cool, and precipitating it with acetone to remove unreacted substances. The results are shown in Table 3.

[0066]

[Table 3]

(*1): MFR (230°C, 2160g
) 0.43g/10min [η] 4.46dl/g (*2): MFR (230°C, 2160g) 10.
9g/10min Ethylene content 24mol%

Claims (2)

[Claims] Claim 1: At least polyolefin particles (A)
The polyolefin particles (A), an ethylenically unsaturated group-containing carboxylic acid, its anhydride or its derivative, a hydroxyl group-containing ethylenically unsaturated compound, and an ethylenically unsaturated group are irradiated with an activation energy beam. At least one modifier (B) selected from the group consisting of containing epoxy compounds and a radical polymerization initiator (C)
A method for producing modified polyolefin particles, the method comprising contacting with. Claim 2: At least polyolefin particles (A)
The polyolefin particles (A), an ethylenically unsaturated group-containing carboxylic acid, its anhydride or its derivative, a hydroxyl group-containing ethylenically unsaturated compound, and an ethylenically unsaturated group are irradiated with an activation energy beam. At least one modifier (B) selected from the group consisting of containing epoxy compounds and a radical polymerization initiator (C)
2. The method for producing modified polyolefin particles according to claim 1, wherein the polyolefin particles are brought into contact with a swelling solvent (D) for the polyolefin particles.