JPH04335004A - Preparation of modified polyolefin particle - Google Patents

Abstract

PURPOSE:To obtain modified polyolefin particles which, when blended with other resin(s), can give shaped objects which are excellent in mechanical properties such as impact resistance, bondability and other properties. CONSTITUTION:A process for producing modified polyolefin particles which comprises heating polyolefin particles along with a free-radical initiator and a glycidyl ester of an unsaturated dicarboxylic acid in an inert gas atmosphere under such conditions that the individual particles can substantially retain their particulate shape, thereby to react the particles with the ester.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for producing modified polyolefin particles. More particularly, the present invention relates to a process for modifying polyolefins in the gas phase using unsaturated dicarboxylic acid glycidyl esters.

0002

[Technical Background of the Invention] Conventionally, various methods have been proposed for modifying polyolefins by reacting them with polar group-containing monomers in order to improve the compatibility and adhesion between polyolefins and other resins. There is. For example, after irradiating polyolefin with an energy beam such as an electron beam, the polyolefin is brought into contact with an ethylenically unsaturated group-containing monomer, or by dissolving the polyolefin and ethylenically unsaturated group-containing monomer in an organic solvent, and in this state, peroxide A method of reacting the two in the presence of a polyolefin, a method of reacting an ethylenically unsaturated group-containing monomer with a polyolefin that has been molten in a kneading device, etc. are known.

[0003] Apart from this method, there is also
No. 32722 and JP-A-2-140201 disclose that granular polyolefins are modified by reacting granular polyolefins with a specific glycidyl compound at a temperature that allows the polyolefin particles to maintain their shape. There is.

However, the polyolefin modification methods disclosed in these publications have problems in that the glycidyl compounds used not only cause significant skin irritation but also have low grafting efficiency.

[0005]

OBJECTS OF THE INVENTION The present invention aims to solve the above-mentioned problems, and aims to provide a novel method for modifying polyolefin particles with a glycidyl ester having a specific structure.

That is, the present invention is a method for producing highly uniform modified polyolefin particles by graft-modifying polyolefin particles with unsaturated dicarboxylic acid glycidyl ester.

[0007]

SUMMARY OF THE INVENTION The method for producing modified polyolefin particles according to the present invention includes a method for producing modified polyolefin particles in which polyolefin particles (A), a radical initiator (B), and an unsaturated dicarboxylic acid glycidyl ester are substantially It is characterized in that the polyolefin particles (A) and the unsaturated dicarboxylic acid glycidyl ester are reacted by heating under inert gas phase conditions that can maintain the particle shape.

[0008] By blending the modified polyolefin particles obtained in this manner with other resins, it is possible to prepare molded articles having excellent mechanical properties such as impact resistance or adhesive properties.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The method for producing modified polyolefin particles of the present invention will be specifically described below. In the method for producing modified polyolefin particles of the present invention, polyolefin particles (A), a radical initiator (B), and an unsaturated dicarboxylic acid glycidyl ester are reacted. A mixture of initiator (B) and unsaturated dicarboxylic acid glycidyl ester is used.

The polyolefin particles used in the present invention can be obtained, for example, by polymerizing or copolymerizing α-olefins having 2 to 20 carbon atoms. Examples of such α-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 1, ethylpentene-1, octene-1, methylpentene-1, dimethylhexene-1, trimethylpentene-1, ethylhexene-1, methylethylpentene-1, diethylbutene-1, propylpentene-1, decene-1 , methylnonene-1, dimethyloctene, trimethylheptene-1,
Mention may be made of α-olefins such as ethyl octene-1, methylethylheptene-1, diethylhexene-1, dodecene-1 and hexadodecene. Among these, α-olefins having 2 to 8 carbon atoms are preferably used alone or in combination, and it is particularly preferable to use ethylene and propylene in combination.

The polyolefin particles used in the present invention generally contain repeating units derived from the above α-olefin in an amount of 50 mol% or more, preferably 80 mol% or more, particularly preferably 100 mol%.

Furthermore, the polyolefin particles may have repeating units derived from other compounds polymerizable with this α-olefin, in addition to the repeating units derived from the α-olefin as described above. good.

Other compounds used here include, for example, linear polyene compounds, cyclic polyene compounds, and cyclic monoene compounds. These polyene compounds have two conjugated or non-conjugated olefinic double bonds.
Examples of such chain polyene compounds include 1,4-hexadiene, 1,5-
Mention may be made of hexadiene, 1,7-octadiene, 1,9-decadiene, 2,4,6-octatriene, 1,3,7-octatriene, 1,5,9-decatriene and divinylbenzene.

[0014] 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-vinyl-2-norbornene, 5-isopropylidene-2-norbornene, methylhydroindene, 2,3
-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-
Examples include ethylidene-3-isopropylidene-5-norbornene and 2-propenyl-2,5-norbornadiene.

Further examples of cyclic monoenes include monocycloalkenes such as cyclopropene, cyclobutene, cyclopentene, cyclohexene, 3-methylcyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclododecene, tetracyclodecene, octacyclodecene and cycloeicosene. Norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5,5,6-trimethyl-2-
Bicycloalkenes such as norbornene and 2-bornene; 2,3,3a,7a-tetrahydro-4,7-methano-1H-indene and 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene, etc. tricycloalkene; 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-dimethano-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 and 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,
Tetracycloalkenes such as 4a,5,8,8a-octahydronaphthalene; hexacyclo[6,6,1,13
．． 6,110.13,02.7,09.14]heptadecene-4,pentacyclo[8,8,12.9,14.7
, 111.18, 0, 03.8, 012.17] Heneikosene-5, Octacyclo [8, 8, 12.9, 14
．． 7,111.18,0,03.8,012.17] cyclic monoene compounds such as polycycloalkenes such as docosene-5.

Furthermore, when producing the above polyolefin particles, styrene or substituted styrene can also be used. The polyolefin particles used in the present invention can be obtained, for example, by polymerizing or copolymerizing the above α-olefins in the presence of a catalyst. This polymerization reaction can be carried out in the gas phase (gas phase method), or
It can also be carried out in a 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. Examples of the solvent used in this polymerization reaction or copolymerization reaction include inert hydrocarbons. Furthermore, the α-olefin as a raw material may be used as a reaction solvent.

[0018] In producing the polyolefin particles used in the present invention, the above polymerization or copolymerization may be carried out by a gas phase method, or by a gas phase method after reaction is carried out in a liquid phase using α-olefin as a solvent. It is preferable to adopt a method that combines the following.

[0019] In a method that combines a liquid phase method and a gas phase method,
Using an inert hydrocarbon or a raw material α-olefin as a reaction solvent, the α-olefin is prepolymerized in the presence of a specific catalyst, and then the α-olefin is further polymerized in the gas phase.

Examples of the inert hydrocarbons used as the solvent include propane, butane, n-pentane, i-pentane, i-hexane, n-hexane, n-octane, i-
Aliphatic hydrocarbons such as octane, n-decane, n-dodecane, and kerosene; Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane, and methylcyclohexane; Aromatic hydrocarbons such as benzene, toluene, and xylene; Methylene Mention may be made of halogenated hydrocarbon compounds such as chloride, ethylene chloride, and chlorobenzene.

[0021] Furthermore, the above catalyst preferably includes:
Periodic Table of Elements Groups IVA, VA, VIA, VIIA
Catalyst components containing transition metals of group and group VIII, such as titanium, zirconium, hafnium, vanadium [
A] and organoaluminum compounds having at least one Al-carbon bond in the molecule, such as those from Periodic Table I
Group, II and III organometallic compound catalyst components [
B].

The above catalyst component [A] can be prepared by further blending an electron donor [C] (inside donor) in addition to the above components. The catalyst component [A] is preferably a catalyst containing a transition metal atom of Group IVA or VA of the Periodic Table of the Elements, and among these, at least one selected from the group consisting of titanium, zirconium, hafnium, and vanadium. Catalyst components containing one type of atom are particularly preferred.

Other preferred catalyst components [A] include catalyst components containing halogen atoms and magnesium atoms in addition to the transition metal atoms mentioned above, and catalyst components conjugated to transition metal atoms of Groups IVA and VA of the periodic table. Examples include catalyst components containing a compound coordinated with a group having electrons.

The above-mentioned catalyst component [A] used in preparing the polyolefin particles in the present invention may be present in the reaction system in a solid state during the above-mentioned polymerization reaction or copolymerization reaction, or Alternatively, it is preferable to use a catalyst prepared so that it can exist in a solid state by being supported on a carrier or the like.

[0025] Regarding such catalyst component [A], Japanese Patent Application Laid-open Nos. 55-135102, 55-135103,
Publication No. 56-67311 and patent application No. 1810/1983
No. 19, No. 61-21109.

The organometallic compound catalyst component [B] used together with the catalyst component [A] in the production of crystalline polyolefin polymer particles in the present invention is, for example, an organoaluminum compound, an organoaluminum compound and water, etc. An organoaluminumoxy compound obtained by the reaction of or an organoaluminumoxy compound obtained by the reaction of an aluminoxane solution with water or an active hydrogen-containing compound can be used.

[0027] Further, the catalyst component of the above-mentioned organometallic compound [
B] can also contain an electron donor [C] (outside donor) in addition to the above components. In preparing the polyolefin particles in the present invention, the above-mentioned catalyst is used to carry out preliminary polymerization prior to main polymerization.

The above polyolefin particles can be prepared by carrying out main polymerization in a gas phase after preliminary polymerization. The polymerization temperature during prepolymerization is usually -40 to 80
℃, and the polymerization temperature during main polymerization using the above catalyst is usually -50 to 200℃, and the pressure is normal pressure to
It is within the range of 100 kg/cm2.

[0029] In the method for producing such polyolefin particles, the technique described in Japanese Patent Application No. 63-294066 can be used. For example, the polyolefin particles produced as described above usually have a particulate form in which crystalline portions and amorphous portions are distributed in an island-like manner. Furthermore, by using polyolefin particles in which the crystal part is made of a crystalline polyolefin, particularly a polypropylene resin, and the amorphous part is made of ethylene-propylene random copolymer rubber, it is possible to obtain a composition with excellent impact resistance. can.

For example, according to ASTM D1238 of the polyolefin particles prepared as described above, 23
The melt flow rate measured at 0°C is usually 0.1 to 1.
00 g/10 minutes, preferably within the range of 1 to 50 g/10 minutes.

[0031] Furthermore, the average particle diameter is usually 10 to 5000
μm, preferably 100 to 4000 μm, particularly preferably 300 to 3000 μm. Furthermore, the geometric standard deviation indicating the particle size distribution of the polyolefin particles is usually 1.0 to 2.0, preferably 1.0 to 1.7.
, particularly preferably 1.0 to 1.5, more preferably 1
．． It is within the range of 0 to 1.3.

[0032] Furthermore, the apparent bulk density of the crystalline polyolefin particles due to natural fall is usually 0.20 g/cm.
3 or more, preferably in the range of 0.30 to 0.70, particularly preferably in the range of 0.35 to 0.60.

[0033] In the polyolefin particles produced by employing the above method, the transition metal component is usually 100%.
The halogen content is usually 300 ppm or less, preferably 10 ppm or less, particularly preferably 5 ppm or less.
It is contained in an amount of at most ppm, preferably at most 100 ppm, particularly preferably at most 50 ppm.

Radical initiator (B) used in the present invention
As the initiator, a radical initiator such as an organic peroxide or an azo compound is used. Specifically, the organic peroxides include 1,
1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, n- Butyl-4,4-bis(t-
peroxyketals such as butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane,
Di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-bis (t-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane,
-butyl peroxide) dialkyl peroxides such as hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3
, 5,5-trimethylhexanoyl peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-trioyl peroxide and other diacyl peroxides, t-butyl peroxyacetate, t-butyl peroxy Isobutyrate, t-
Butylperoxy-2-ethylhexanoate, t-butylperoxylaurylate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy) oxy)hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate,
Peroxy esters such as cumyl peroxyoctate, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1, Hydroperoxides such as 3,3-tetramethylbutyl hydroperoxide can be mentioned.

[0035] Examples of the azo compound include azoisobutyronitrile and the like. Such radical initiators can be used alone or in combination. Among such radical initiators, benzoyl peroxide, m-trioyl peroxide, t-butylperoxy-2-ethylhexanoate, and dicumyl peroxide are particularly preferred.

Such a radical initiator (B) is usually used in an amount of 0.001 to 10 parts by weight, preferably 0.001 to 10 parts by weight, based on 100 parts by weight of the polyolefin particles (A) in the above mixture.
．． It is used in a proportion of 0.01 to 5 parts by weight.

Such a radical initiator (B) can be used as it is by mixing with the polyolefin particles (A) and the unsaturated dicarboxylic acid glycidyl ester (C), but if a small amount of this radical initiator (B) is used, It can also be used by dissolving it in an organic solvent. The organic solvent used here is not particularly limited as long as it can dissolve the radical initiator. Examples of such organic solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, nonane, and decane, cyclohexane, methylcyclohexane, decahydronaphthalene, etc. alicyclic hydrocarbon solvent,
Halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene, methanol, ethanol, n-propanol, isopropanol,
Alcohol solvents such as n-butanol, sec-butanol, and tert-butanol; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ester solvents such as ethyl acetate and dimethyl phthalate; dimethyl ether, diethyl ether, di-n- Examples include ether solvents such as amyl ether, tetrahydrofuran, and dioxyanisole, among which toluene, xylene, and acetone are preferably used. Moreover, these solvents can be used alone or in combination.

In the present invention, as will be described later, the modification reaction of the polyolefin particles (A) is carried out in a state where the particle state of the polyolefin particles (A) is not impaired. Therefore, the organic solvent used to dissolve the radical initiator (B) is usually used in an amount of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the polyolefin particles (A). Ru. Even if such a small amount of organic solvent is used, the above-mentioned polyolefin particles (A) will not be dissolved and their particle state will not be impaired; rather, such an amount of organic solvent will not cause the polyolefin particles (A) to dissolve inside the polyolefin particles (A). It penetrates and swells the particles to some extent, acting to spread the radical initiator (B) into the particles.

The unsaturated dicarboxylic acid glycidyl ester (C) used in the present invention can be produced, for example, by reaction of maleic acid monoethyl ester potassium salt with epichlorohydride, and such unsaturated dicarboxylic acid glycidyl ester Specifically, for example, alkylglycidyl maleate, alkylglycidyl fumarate, alkylglycidyl itaconate, alkylglycidyl crotonate, alkylglycidyl tetrahydrophthalate, endocis-bicyclo[2,2,1] hept-5-ene-2
, 3-dicarboxylic acid alkylglycidyl ester, or diglycidyl ester derivatives thereof. Here, the alkyl group is usually preferably a group having 1 to 12 carbon atoms. Among these, unsaturated dicarboxylic acid alkylglycidyl esters are preferred, and unsaturated dicarboxylic acid monoalkylglycidyl esters are particularly preferred because they have a low possibility of side reactions. In particular, alkyl maleate glycidyl esters are preferable from the viewpoints of adhesion, compatibility, safety in handling, hygiene, grafting efficiency, ease of availability, and economy. Examples include glycidyl, ethylglycidyl maleate, propylglycidyl maleate, butylglycidyl maleate, and the like.

[0040] In addition, in the present invention, aromatic substances such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, etc. Group vinyl compounds can be used.

[0041] In the present invention, the unsaturated dicarboxylic acid glycidyl ester (C) as described above is usually used in an amount of 0.5 to 80 parts by weight based on 100 parts by weight of the polyolefin particles (A).
It is used in a proportion of 1 to 50 parts by weight, preferably 1 to 50 parts by weight.

In the method for producing modified polyolefin particles of the present invention, polyolefin particles (A), organic peroxide (B) and unsaturated dicarboxylic acid glycidyl ester (C
) can be mixed in any order.

For example, a method in which polyolefin particles (A), organic peroxide (B), and unsaturated dicarboxylic acid glycidyl ester (C) are mixed and then heated; A method of mixing and then heating the polyolefin particles (A) to a state where the reaction can substantially proceed, and then mixing the unsaturated dicarboxylic acid glycidyl ester (C), heating the polyolefin particles (A) A method of mixing the organic peroxide (B) and the unsaturated dicarboxylic acid glycidyl ester (C) simultaneously or separately after bringing the reaction to a state in which the reaction can substantially proceed; Examples include a method of mixing the peroxide (B) and bringing the mixture into contact with the unsaturated dicarboxylic acid glycidyl ester (C) while heating.

In the production method of the present invention, the above polyolefin particles (A) and a radical initiator (B)
and unsaturated dicarboxylic acid glycidyl ester (C),
Activation with a radical initiator is achieved by reacting the polyolefin particles (A) with the unsaturated dicarboxylic acid glycidyl ester by heating under inert gas phase conditions in which the polyolefin particles (A) can substantially maintain their particle shape. It is considered that the above unsaturated dicarboxylic acid glycidyl ester (C) is grafted onto the modified polyolefin particles (A) to obtain modified polyolefin particles.

[0045] Here, "inert gas phase conditions under which the polyolefin particles can substantially maintain their particle shape" means that the heating temperature is set to a temperature lower than the melting point of the polyolefin particles and the gas phase conditions are applied. This means that the reaction is carried out under gas phase conditions in which the polyolefin particles are not dissolved in a solvent or the like. Therefore, in the present invention, a dispersion medium for polyolefin particles such as an aqueous dispersion medium is not used.

Specifically, in the method of the present invention, predetermined amounts of polyolefin particles (A) and radical initiator (
B) and the unsaturated dicarboxylic acid glycidyl ester (C) are charged into a reaction vessel and mixed thoroughly, and then the above polyolefin is heated under inert gas phase conditions at a temperature equal to or higher than the decomposition temperature of the radical initiator (B). It is heated to a temperature below the temperature at which the particles (A) melt.

[0047] This heating temperature is usually 50 to 140°C,
Preferably it is 60-120°C. In addition, the heating time is
It is usually set within the range of 0.5 to 15 hours, preferably 1 to 10 hours.

In the present invention, polyolefin particles (A
) is carried out as described above, so there is no need to carry out the reaction under pressure. Therefore, as a reaction device, polyolefin particles (A) and a radical initiator (
B) and unsaturated dicarboxylic acid glycidyl ester (C), as long as it is an apparatus capable of heating it to the above temperature,
There are no particular limitations on its shape, and various heating devices can be used. Particularly in the case of continuous operation, it is desirable to use a continuous heating device such as a fluidized bed, moving bed, loop reactor, paddle dryer, or the like.

The above heating is usually carried out in an inert gas atmosphere such as nitrogen gas. The amount of grafting groups derived from the unsaturated dicarboxylic acid glycidyl ester (C) in the modified polyolefin particles thus prepared is usually 0.1 to 50% by weight, preferably 0.5 to 30% by weight. is within the range of

Although the average particle diameter, geometric standard deviation, and apparent bulk density of the polyolefin particles do not substantially change due to the introduction of the graft group as described above, the melt flow rate tends to change, and the ASTM D 1
The melt flow rate measured at 230°C according to 238 is usually 0.1 to 100 g/10 minutes, preferably 0.5
~80 g/10 minutes.

The modified polyolefin particles prepared as described above can be used alone or together with other resins. Here, as the other resin, a thermoplastic resin is used, and examples of such thermoplastic resin include polyester, polyamide, polycarbonate, polystyrene, high impact polystyrene, ABS, AES, MBS, PMMA, styrene-maleic anhydride. Examples include acid copolymers, polyphenylene ethers, vinyl chloride, and the like. By using it together with such a thermoplastic resin, it is possible to obtain a polymer alloy having extremely excellent mechanical properties such as impact resistance, adhesive properties, and the like.

The modified polyolefin particles obtained by the method of the present invention may further contain an inorganic filler, an organic filler, a heat stabilizer, a weathering stabilizer, an antistatic agent, an anti-slip agent, an anti-blocking agent, Additives such as antifogging agents, lubricants, pigments, dyes, natural oils, synthetic oils, and waxes may also be blended.

[0053]

Effects of the Invention In the present invention, when preparing a modified polyolefin as described above, polyolefin particles (A)
A radical initiator (B) and an unsaturated dicarboxylic acid glycidyl ester (C) are reacted under inert gas phase conditions.

It is thought that the groups derived from the unsaturated dicarboxylic acid glycidyl ester are uniformly distributed in the modified polyolefin particles obtained in this way, and such modified polyolefin particles can be blended with other resins. By doing so, a molded article having excellent mechanical properties such as impact resistance can be prepared.

Next, the present invention will be explained by showing examples. However, the present invention will be described by showing these embodiments. However, the present invention is not limited to these Examples. (Evaluation method) In the present invention, the characteristics of modified polyolefin particles were measured as follows. Amount of Grafting Grafted polymer particles are dissolved in p-xylene at 130°C, this solution is poured into a large amount of acetone to precipitate the polymer, and the precipitated polymer is filtered and washed to prepare a purified polymer. Next, from the IR spectrum of the press film prepared from the purified polymer, 1730 cm-
The absorbance of No. 1 was measured, and the amount of grafting was determined based on a previously prepared and used calibration curve.

[0056]

[Example 1] (Preparation of crystalline propylene homopolymer particles) After thoroughly purging a high-speed stirring device (manufactured by Tokushu Kika Kogyo) with an internal volume of 2 liters with nitrogen, 700 ml of refined kerosene and 210 g of commercially available MgCl were added.
, 24.2 g of ethanol and brand name Emazol 320
(Sorbitane distearate, manufactured by Kao Atlas Co., Ltd.)
3g was added, and the system was heated to 800℃ at 120℃ while stirring.
Stir for 30 minutes at rpm. Under high-speed rotation, using a Teflon tube with an inner diameter of 5 mm, the liquid was transferred to a 2-liter glass flask (equipped with a stirrer) filled with 1 liter of refined kerosene cooled in advance to -10°C. The produced solid was collected by filtration and sufficiently replaced with hexane to obtain a carrier.
After suspending 7.5 g of the carrier 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 part was collected by filtration and heated again at 150°C.
The suspension was suspended in 1 ml of titanium tetrachloride, and stirred and mixed again at 130° C. for 2 hours. Further, a reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to obtain a solid catalyst component [A]. The components were 2.2% by weight of titanium, 63% by weight of chlorine, 20% by weight of magnesium, and 5.5% by weight of isobutyl phthalate in terms of atoms. A truly spherical catalyst having an average particle size of 64 μm and a geometric standard deviation (δg) of particle size distribution of 1.5 was obtained.

The catalyst component [A] was subjected to the following prepolymerization. After charging 200 ml of purified hexane into a 400 ml glass reactor purged with nitrogen, 20 mmol of triethylaluminum, 4 mmol of diphenyldimethoxysilane, and 2 mmol of the titanium catalyst component [A] in terms of titanium atoms were charged. Propylene was then fed over 1 hour at a rate of 5.9 Nl/hour, and the titanium catalyst component [A
] 2.8 g of propylene was polymerized per 1 g. After the preliminary polymerization, the liquid portion was removed by filtration, and the separated solid portion was suspended again in decane.

5 kg of propylene was added to a 17 liter polymerization vessel at room temperature, 1.5 liters of hydrogen was added, and the temperature was raised.
At 50°C, 8 mmol of triethylaluminum, 8 mmol of diphenyldimethoxysilane, and 0.08 mmol of prepolymerized catalyst component [A] were added in terms of titanium atoms. Next, the inside of the polymerization vessel was maintained at 70°C for 1 hour and 20 minutes. Thereafter, residual propylene was purged and the polymer was recovered. The yield of the obtained polymer was 3.3 kg.

The average particle diameter of the crystalline propylene homopolymer particles obtained as described above is 520 μm, the geometric standard deviation of the particles is 1.3, and the apparent bulk density is 0.
46 g/cm3, MFR was 0.3 g/10 min, and the temperature of the main peak of crystalline phase melting measured by differential scanning calorimetry was 160°C.

[0060] The differential scanning calorimetry method was measured under the following conditions. The sample was heated from room temperature to 200° C. at a rate of 10 K/min in a nitrogen atmosphere, kept at 200° C. for 10 minutes, and then cooled down to 0° C. at a rate of 10 K/min. 1 more
The rate of change in heat amount over time was measured when the temperature was raised from 0°C to 200°C at a rate of 0K/min.

Crystalline propylene homopolymer particles 1 produced as described above in a stainless steel autoclave equipped with a stirring blade having a spiral double helical ribbon.
0.08 parts by weight of benzoyl peroxide, 2 parts by weight of butylglycidyl maleate, and 2 parts by weight of toluene, and the inside of the system was completely replaced with nitrogen gas.

After stirring at room temperature for 30 minutes, the temperature in the system was raised to 100°C over 30 minutes, and at this temperature the mixture was further stirred for 4 minutes.
Grafted heavy particles were obtained by stirring for a period of time to complete the reaction. The grafted amount of butylglycidyl maleate in the graft polymer particles was 1.8% by weight.

The thus obtained modified propylene homopolymer and ethylene-propylene copolymer rubber (ethylene content 75% by weight, MFR at 230°C 0.7g/
10 minutes) at a weight ratio of 70/30 to prepare a composition, and a 0.5 mm thick press sheet of this composition was prepared. This sheet was pressed against aluminum foil having a thickness of 0.1 mm at 200° C. for 5 minutes to form a laminated sheet, and this laminated sheet was cut into strips with a width of 15 mm. The interlayer peel strength was measured using a tensile tester at a speed of 10 mm/min.

The results are shown in Table 1.

[0065]

[Example 2] In place of butylglycidyl maleate in Example 1, 1.5 parts by weight of methylglycidyl maleate,
t-butylperoxy-2 instead of benzoyl peroxide
Modified polypropylene particles were prepared in the same manner as in Example 1, except that 0.10 parts by weight of -ethylhexanoate was used. The grafting amount of methylglycidyl maleate is
It was 1.2% by weight.

A composition was prepared in the same manner as in Example 1, and its peel strength was measured. The results are shown in Table 1.

[0067]

Comparative Example 1 Glycidyl methacrylate-modified polypropylene particles were prepared in the same manner as in Example 1, except that glycidyl methacrylate was used in place of butylglycidyl maleate. The amount of glycidyl methacrylate grafted was 0.8% by weight.

A composition was prepared in the same manner as in Example 1, and its peel strength was measured. The results are shown in Table 1.

[0069]

[Table 1]

Claims (1)

[Claims] 1. Polyolefin particles (A), a radical initiator (B), and an unsaturated dicarboxylic acid glycidyl ester (C) are combined into an inert compound that allows the polyolefin particles (A) to substantially maintain their particle shape. Heating under gas phase conditions,
A method for producing modified polyolefin particles, which comprises reacting polyolefin particles (A) with unsaturated dicarboxylic acid glycidyl ester.