JPH04335035A - Production of modified polyolefin particle - Google Patents

Abstract

PURPOSE:To produce polyolefin particles which give a molded article excellent in mechanical characteristics (e.g. impact resistance), adhesiveness, etc., when compounded into another resin. CONSTITUTION:Modified polyolefin particles are produced by reacting polyolefin particles preoxidized in a gas phase with at least one monomer selected from the group consisting of a hydroxylated, ethylenically unsatd. compd., an aminated, ethylenically unsatd. compd., and an epoxidized, ethylenically unsatd. compd. under heating in such an inert gas phase that the particles practically can maintain the state of particles.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD OF THE INVENTION The present invention relates to a new method for producing particulate modified polyolefins. For more details,
The present invention relates to a novel method for producing particulate modified polyolefins using polyolefin particles that have been oxidized in the gas phase.

0002

TECHNICAL BACKGROUND OF THE INVENTION Various methods have been proposed for modifying polyolefins using ethylenically unsaturated group-containing monomers such as styrene.

For example, a method in which a polyolefin is irradiated with an energy beam such as an electron beam and then brought into contact with an ethylenically unsaturated group-containing monomer, or a method in which a polyolefin and an ethylenically unsaturated group-containing monomer are dissolved in an organic solvent and then subjected to a reaction in this state. A method of reacting the two in the presence of an oxide, a method of reacting an ethylenically unsaturated group-containing monomer with a polyolefin that has been molten in a kneading device, etc. are known.

[0004] Based on this technical background, when producing a modified polyolefin by reacting a polyolefin with a monomer containing an ethylenically unsaturated group, a dispersion in which the polyolefin is dispersed in an aqueous solvent is prepared as the polyolefin, and this dispersion is prepared. It has been proposed to use an oxidized polyolefin prepared by oxidizing a polyolefin in a dispersion using an organic peroxide (see JP-A-58-93730). By oxidizing the polyolefin in advance in this manner, it becomes easier to introduce the ethylenically unsaturated group-containing monomer.

However, in this method, in order to carry out the oxidation reaction efficiently, it is necessary to increase the oxygen concentration in the aqueous medium considerably. Therefore, this method requires the use of a pressure-resistant reaction device such as an autoclave, which is disadvantageous in terms of equipment, and it is actually quite difficult to carry out continuous oxidation reactions using such a device. However, there are also problems in terms of workability.

[0006]

OBJECTS OF THE INVENTION The present invention aims to solve the above-mentioned problems, and provides a method for producing modified polyolefin particles that can efficiently and uniformly modify polyolefin particles with a specific modifying monomer. is intended to provide.

[0007]

Summary of the Invention The method for producing modified polyolefin particles according to the present invention comprises polyolefin particles (
A) and at least one modified monomer (B) selected from the group consisting of a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, and an epoxy group-containing ethylenically unsaturated compound, into the polyolefin. It is characterized in that the particles (A) are heated under inert gas phase conditions that can substantially maintain their particle state.

[0008] The present invention uses polyolefin particles (A) that have been oxidized in a gas phase when preparing modified polyolefin particles as described above. By oxidizing polyolefin particles in the gas phase in this way, the modification reaction of polyolefin particles can be carried out efficiently and uniformly without using a reaction device such as an autoclave that requires extremely high pressure resistance. . Moreover, in the present invention, since both the oxidation treatment step and the modification step following the oxidation treatment step are performed in the gas phase, both steps can be performed continuously.

Furthermore, by blending the modified polyolefin particles thus obtained with other resins, it is possible to prepare molded articles having excellent mechanical properties such as impact resistance.

0010

DETAILED DESCRIPTION OF THE INVENTION Next, the method for producing modified polyolefin particles of the present invention will be specifically explained. In the method for producing modified polyolefin particles of the present invention, polyolefin particles (A) that have been subjected to gas phase oxidation treatment are 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 above-mentioned repeating units derived from the α-olefin. 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.

[0015] 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[[8,8,12.9,1
4.7,111.18,0,03.8,012.17]
Examples include 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.

[0019] In producing the polyolefin particles used in the present invention, the above polymerization or copolymerization can be carried out by a gas phase method, or after a reaction is carried out in a liquid phase using an α-olefin as a solvent, a gas phase method can be carried out. It is preferable to adopt a method that combines the following.

[0020] In the method that combines the liquid phase method and the 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.

[0022] 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 preferable catalyst components [A] include catalyst components containing halogen atoms and magnesium atoms in addition to the above-mentioned transition metal atoms, group A of the periodic table,
Examples include catalyst components containing a compound in which a group having conjugated electrons is coordinated to a group A transition metal atom.

The catalyst component [A] used in preparing the polyolefin particles of the present invention may be present in the reaction system in a solid state during the polymerization reaction or copolymerization reaction as described above; 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.

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.

[0028] Furthermore, 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.

[0030] 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.

[0032] 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.

[0033] 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.

[0034] In the polyolefin particles produced using 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.

In the present invention, the polyolefin particles as described above are oxidized in a gas phase and then reacted with a specific modifying monomer. This gas phase oxidation treatment is carried out by adding an organic peroxide to the polyolefin particles as described above, thoroughly mixing the mixture, and then heating the mixture to a temperature equal to or higher than the decomposition temperature of the organic peroxide in the presence of oxygen. In the present invention, such heat treatment is performed in a gas phase.

Examples of organic peroxides used here include 1,1-bis(t-butylperoxy)-3,5,
5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-
Peroxyketals such as butylperoxy)octane, n-butyl-4,4-bis(t-butylperoxy)valerate, 2,2-bis(t-butylperoxy)butane, di-t-butylperoxy oxide, 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-
Dialkyl peroxides such as bis(t-butylperoxy)hexyne-3, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl Peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diacyl peroxides such as m-trioyl peroxaoid, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxide Oxy-2-ethylhexanoate, t-butylperoxylaurylate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-dimethyl-2,5-di(benzoylperoxy) Hexane, t-butyl peroxymaleic acid, t-butyl peroxyisopropyl carbonate, peroxy esters such as cumyl peroxy octate, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2 ,5-dimethylhexane-2
, 5-dihydroperoxide, and 1,1,3,3-tetramethylbutylhydroperoxide.

[0037] Such organic peroxides can be used alone or in combination. Such an organic peroxide is usually used in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight, per 100 parts by weight of olefin particles to be oxidized.

[0038] Such an organic peroxide can be used as it is by mixing with polyolefin particles, but it can also be used by dissolving this organic peroxide in a small amount of an organic solvent. The organic solvent used here is not particularly limited as long as it can dissolve the organic peroxide. 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, and decahydronaphthalene. Alicyclic hydrocarbon solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, methylene chloride, chloroform, carbon tetrachloride, chlorinated hydrocarbons such as tetrachlormethylene, methanol, ethanol, n-propanol, isopropanol, n -butanol, sec-
Alcohol solvents such as butanol and tert-butanol, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ethyl ketone, ester solvents such as ethyl acetate and dimethyl phthalate, dimethyl ether, diethyl ether, di-n-amyl ether, and tetrahydride. Examples include ether solvents such as dorofuran 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, polyolefin particles (A
) The oxidation treatment of polyolefin 1 is preferably carried out so as not to damage the particle state of the polyolefin particles. Therefore, the organic solvent used to dissolve the peroxide should be
It is usually used in a proportion of 0.1 to 30 parts by weight, preferably 1 to 20 parts by weight.

[0040] Further, as the organic solvent, aromatic hydrocarbons,
If solvents with high affinity for polyolefins, such as aliphatic hydrocarbons, alicyclic hydrocarbons, or chlorinated hydrocarbons, are used, these solvents will penetrate into the polyolefin particles and swell the particles to some extent, causing organic peroxide It acts to expand things into particles.

Polyolefin particles (A) in the present invention
The oxidation treatment is carried out by heating the mixture with an organic peroxide to a temperature above the decomposition temperature of the organic peroxide used and below the temperature at which the polyolefin particles melt. Specifically, the heating temperature for this oxidation treatment is usually 50 to 140℃.
℃, preferably 60 to 120℃.

In the present invention, the above-mentioned oxidation treatment must be carried out in a gas phase, and is usually carried out in air. Therefore, in the present invention, no dispersion medium for polyolefin particles, such as an aqueous dispersion medium, is used.

Under the above temperature conditions, the time required for the gas phase oxidation treatment is usually 0.5 to 15 hours. In the gas phase oxidation treatment of polyolefin particles, there is no need to carry out the reaction under pressure, so any reactor that can heat the mixture of polyolefin particles and organic peroxide to the above temperature can be used. There is no need to particularly limit the shape, etc., and various heating devices can be used. In particular, when performing continuous gas phase oxidation treatment,
Preferably, continuous heating devices are used, such as fluidized beds, moving beds, loop reactors, paddle dryers, etc.

[0044] As described above, the gas phase oxidation treatment of polyolefin particles not only has the advantage of being able to oxidize polyolefin particles continuously without using particularly complicated equipment, but also It can be done evenly. That is, by performing the oxidation treatment in the gas phase, the difference in the degree of treatment between the surface and deep portions of the polyolefin particles is reduced.

[0045] It is believed that by subjecting polyolefin particles having crystalline parts and amorphous parts to the vapor phase oxidation treatment as described above, the amorphous parts are oxidized more selectively than the crystalline parts.

By performing the gas phase oxidation treatment as described above, the melt flow rate of the oxidized polyolefin particles (A) measured at 230° C. according to ASTM D1238 is usually 0.1 to 500 g/10. minutes,
Preferably it is within the range of 1 to 100 g/10 minutes.

Further, the average particle diameter, geometric standard deviation, apparent bulk density, etc. of the polyolefin do not substantially change due to the gas phase oxidation treatment. In the present invention, a group consisting of the oxidized polyolefin particles (A) prepared as described above and an ethylenically unsaturated compound containing a hydroxyl group, an ethylenically unsaturated compound containing an amino group, and an ethylenically unsaturated compound containing an epoxy group is used. Modified polyolefin particles are produced by reacting the oxidized polyolefin particles (A) with at least one modification monomer (B) selected from the following under conditions in which the particle state of the oxidized polyolefin particles (A) is substantially maintained.

Specific examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 3-hydroxypropyl (meth)acrylate.
-Hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxy-propyl (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, and 2-(6-hydroxyhexanoyloxy)ethyl acrylate. ) 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, etc. can also be used.

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

The amino group-containing ethylenically unsaturated compound that can be used in the present invention is a compound having an ethylenic double bond and an amino group. Alternatively, vinyl monomers having at least one type of substituted amino group can be mentioned.

[0052]

[Chemical formula 1]

In the formula, R1 represents an atom or group selected from a hydrogen atom, a methyl group, and an ethyl group, and R2 is
It represents any atom or group of a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and a cycloalkyl group having 6 to 12 carbon atoms, preferably 6 to 8 carbon atoms. Note that the above alkyl group and cycloalkyl group may further have a substituent.

Specific examples of such amino group-containing ethylenically unsaturated compounds include aminoethyl (meth)acrylate, propylaminoethyl (meth)acrylate,
Alkyl ester derivatives of acrylic acid or methacrylic acid, such as dimethylaminoethyl methacrylate, aminopropyl (meth)acrylate, phenylaminoethyl methacrylate, cyclohexylaminoethyl methacrylate, and methacryloyloxyethyl acid phosphate monomethanol amino half sol , vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, allylamine derivatives such as allylamine, methacrylamine, N-methylacrylamine, N,N-dimethylacrylamide, and N,N-dimethylaminopropylacrylamide derivatives, acrylamide derivatives such as acrylamide and N-methylacrylamide, and aminostyrenes such as p-aminostyrene, 6-aminohexylsuccinimide,
2-aminoethylsuccinimide and the like are used. These compounds can be used alone or in combination. Among these, acrylamine, aminoethyl (meth)acrylate, aminopropyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, N,N-
Dimethylaminopropylacrylamide and aminostyrene are preferred.

The epoxy group-containing ethylenically unsaturated compound is a monomer having at least one polymerizable unsaturated bond and epoxy group in one molecule, and such an epoxy group-containing ethylenically unsaturated compound includes: Specifically, mono- and diglycidyl esters of maleic acid, mono- and diglycidyl esters of fumaric acid, mono- and diglycidyl esters of crotonic acid, mono- and diglycidyl esters of tetrahydrophthalic acid, itacon, etc. Mono- and diglycidyl esters of acids, mono- and diglycidyl esters of butenetricarboxylic acid, mono- and diglycidyl esters of citraconic acid, endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-
Mono- and diglycidyl esters of dicarboxylic acids (nadic acid R), endo-cis-bicyclo[2.2.1]hept-5-ene-2-methyl-2,3-dicarboxylic acid (
dicarboxylic acid mono- and alkylglycidyl esters such as mono- and diglycidyl esters of methylnadic acid R), mono- and glycidyl esters of allylsuccinic acid (in the case of monoglycidyl esters, the alkyl group has 1 to 12 carbon atoms), p-styrene carboxylic acid alkyl glycidyl ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4
-Epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1
Examples include -pentene, 5,6-epoxy-1-hexene, and vinylcyclohexene monoxide. Among these, preferred are glycidyl acrylate, glycidyl methacrylate, methylglycidyl maleate, ethylglycidyl maleate, and propylglycidyl maleate.

In the present invention, when producing modified polyolefin particles, at least one compound selected from the group consisting of hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, and epoxy group-containing ethylenically unsaturated compounds is used. Styrene, nuclear substituted styrenes such as methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, with one modifying monomer
Chlorstyrene, alpha-substituted styrenes such as alpha-methylstyrene, alpha-ethylstyrene can be used.

[0057] The above hydroxyl group-containing ethylenically unsaturated compound,
At least one modified monomer selected from the group consisting of amino group-containing ethylenically unsaturated compounds and epoxy group-containing ethylenically unsaturated compounds is usually used in an amount of 1 part by weight per 100 parts by weight of the oxidized polyolefin particles. ~1
00 parts by weight, preferably 5 to 80 parts by weight.

Further, in the present invention, a reducing substance may be used when producing modified polyolefin particles. The reducing substance has the effect of increasing the amount of grafting in the obtained modified polyolefin particles.

[0059] As the reducing substance, iron (II) ion,
In addition to chromium ions, cobalt ions, nickel ions, palladium ions, sulfites, hydroxylamine, hydrazine, etc., -SH, SO3H, -NHNH2, -
Examples include compounds containing groups such as COCH(OH)-.

[0060] Specific examples of such reducing substances include ferrous chloride, potassium dichromate, cobalt chloride,
Cobalt naphthenate, palladium chloride, ethanolamine, diethanolamine, N,N-dimethylaniline,
Examples include hydrazine, ethyl mercaptan, benzenesulfonic acid, p-toluenesulfonic acid, and the like.

[0061] The above-mentioned reducing substance is usually used in an amount of 100 parts by weight of the oxidized polyolefin particles.
It is used in amounts of 0.001 to 5 parts by weight, preferably 0.1 to 3 parts by weight.

Further, in the present invention, a powdery filler may be used when producing modified polyolefin particles. When a powder filler is used, blocking of polyolefin particles during the reaction is prevented and workability is improved.

[0063] In the present invention, the powdery filler has an average particle diameter of usually 0.1 to 10 μm, preferably 0.5 to 5 μm.
It is used in micron powder form. Examples of such powder fillers include silica, diatomaceous earth, titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, and calcium sulfate. , potassium titanate, barium sulfate, calcium sulfite, talc, clay,
mica, asbestos, glass flakes, glass beads,
Calcium silicate, montmorillonite, bentonite,
Inorganic fillers such as graphite, aluminum powder and molybdenum sulfate, and organic fillers such as alpha-cellulose, silk, cotton, linen, polyamide resin, wood flour, poly-4-fluoroethylene, etc. are mentioned.

Among such powdery fillers, inorganic fillers are preferred, and talc, mica, and potassium titanate whiskers are particularly preferred. In the present invention, the powdery filler is usually contained in an amount of 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on the oxidized polyolefin particles.

In the present invention, polyolefin particles (A) and at least one kind selected from the group consisting of hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds and epoxy group-containing ethylenically unsaturated compounds are used. The oxidized polyolefin particles (A) are reacted with the modified monomer (B) by heating under gas phase conditions in which the above-mentioned gas phase oxidation-treated polyolefin particles (A) can substantially maintain their particle size. By grafting the modifying monomer (B) onto A), particles can be produced from the modified polyolefin.

[0066] Here, "under gas phase conditions in which the polyolefin particles can substantially maintain their particle shape" means that the reaction is carried out under gas phase conditions with the heating temperature set to a temperature lower than the melting point of the polyolefin particles. , and means that the reaction is carried out under gas phase conditions in which the polyolefin particles are not dissolved in the solvent.

This graft polymerization reaction is carried out, for example, from polyolefin particles (A) subjected to gas phase oxidation treatment and an ethylenically unsaturated compound containing a hydroxyl group, an ethylenically unsaturated compound containing an amino group, and an ethylenically unsaturated compound containing an epoxy group. At least one modified monomer (B) selected from the group consisting of is 6
This is carried out by mixing while heating to a temperature of 0 to 120°C. Under the above temperature conditions, the grafting reaction time is usually 0.5 to 15 hours, preferably 1 to 15 hours.
It is set within a range of 10 hours.

Such a graft polymerization reaction is usually carried out in an inert gas atmosphere containing nitrogen gas. In the above reaction, when a radical initiator is used, examples of the radical initiator include the above-mentioned organic peroxides and azo compounds.

Such a radical initiator is generally used in an amount of 0.00 parts by weight based on 100 parts by weight of the crystalline polymer particles.
Preferably, it is used in an amount of 1 to 10 parts by weight. The amount of grafting groups derived from the modified monomer (B) in the polyolefin particles thus prepared is usually in the range of 0.1 to 50% by weight, preferably in the range of 0.3 to 30% by weight. It's within.

[0070] When the polyolefin particles consist of a crystalline part and an amorphous part, such graft groups tend to be preferentially introduced into the amorphous part rather than the crystalline part of the polyolefin particle. In modified polyolefin particles into which graft groups have been introduced in this way, mechanical strength such as impact strength is improved.

[0071] Although the average particle diameter, geometric standard deviation, apparent bulk density, etc. of the polyolefin do not substantially change due to the introduction of the graft group as described above, the melt flow rate tends to change. D
The melt flow rate measured at 230°C according to 1238 is usually 0.1 to 100 g/10 min, preferably 0.
It is within the range of 5 to 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, a polymer alloy with excellent mechanical properties such as impact resistance can be obtained.

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.

For example, as the inorganic filler, powdered fillers such as talc and titanium oxide are preferably used.

[0075]

Effects of the Invention In the present invention, when preparing a modified polyolefin as described above, polyolefin particles (A) which have been oxidized in a gas phase are used. By oxidizing the polyolefin particles in the gas phase in this manner, the oxidation treatment can be carried out without using a reaction device such as an autoclave which requires extremely high pressure resistance. Moreover, in the present invention, since the oxidation treatment step and the modification step following the oxidation treatment step are also performed in the gas phase, both steps can be performed continuously.

Furthermore, since the reaction is carried out in the gas phase, it is relatively easy to introduce water-soluble monomers. By blending the modified polyolefin particles thus obtained with other resins, it is possible to prepare molded articles having excellent mechanical properties such as impact resistance.

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. (1) Grafting amount Graft polymer particles are dissolved in p-xylene at 130°C, this solution is poured into a large amount of methyl ethyl ketone to precipitate the polymer, and the precipitated polymer is filtered and washed to obtain purified polymer. Prepare. Next, the absorbance was measured from the IR spectrum of the press film prepared from the purified polymer, and the amount of grafting was determined based on a calibration curve prepared in advance. (2) Initial flexural modulus (FM) Measured at 23° C. using a test piece with a thickness of 3.2 mm according to JIS K7203. (3) Bending yield point stress (FS) Measured according to JIS K7203 under the same conditions as FM. (4) IZ impact strength Measured according to JIS K7110 using a test piece with a thickness of 3.2 mm.

[0078]

[Example 1] (Preparation of catalyst component [A]) After sufficiently 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, 210 g of commercially available MgCl, and 24 ml of ethanol were added.
．． 2g and brand name Emazol 320 (Kao Atlas (
3 g of sorbitan distearate (manufactured by Co., Ltd.) was added thereto, and the temperature of the system was raised while stirring, and the mixture was stirred at 120° C. and 800 rpm for 30 minutes. A 2-liter glass flask (with a stirrer) is filled with 1 liter of refined kerosene pre-cooled to -10°C using a Teflon tube with an inner diameter of 5 mm under high-speed rotation.
The liquid was transferred to 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, 1.5 g of diisobutyl phthalate was added.
3 ml was added and the system was heated to 120°C. 120℃
After stirring and mixing for 2 hours, the solid part was collected by filtration.
Suspend again in 150 ml of titanium tetrachloride and resuspend at 130 ml.
Stirring and mixing were performed at ℃ 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. (Prepolymerization) 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. did. Next, propylene was supplied at a rate of 5.9 Nl/hour over 1 hour, and 2.8 g of propylene was polymerized per 1 g of titanium catalyst component [A]. After the preliminary polymerization, the liquid portion was removed by filtration, and the separated solid portion was suspended again in decane. (Preparation of crystalline propylene homopolymer particles (A)) 17
Add 5 liters of propylene to a liter polymerization vessel at room temperature, add 1.5 liters of hydrogen, raise the temperature to 50℃, and add 8 mmol of triethylaluminum and 8 mmol of diphenyldimethoxysilane.
Millimoles and 0.08 millimoles of the prepolymerized product of 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.

[0082] 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. (Production of modified polyolefin particles) To 100 parts by weight of the crystalline propylene homopolymer particles produced as described above, 5 ml of a solution prepared by dissolving 0.05 parts by weight of benzoyl peroxide in toluene was added, After thorough mixing, oxidation treatment was performed by heating in a gear oven set at a temperature of 90° C. for 3 hours.

[0083] The MFR after the oxidation treatment was 36 g/10 minutes. Next, 100 parts by weight of the above oxidized propylene homopolymer was charged into a stainless steel autoclave equipped with a stirring blade having a double helical ribbon, and the air in the system was completely replaced with nitrogen gas.

While stirring the oxidized propylene homopolymer at room temperature, a mixed solution consisting of 5 parts by weight of styrene and 10 parts by weight of 2-hydroxypropyl acrylate was gradually added dropwise. After dropping, the temperature in the system was lowered to 10% over 30 minutes.
The temperature was raised to 0° C., and the reaction was completed by further stirring at this temperature for 2 hours to obtain graft polymer particles. As mentioned above, the maximum temperature of the reaction system was 100° C., and since this temperature was lower than the melting point of the propylene homopolymer, the graft reaction could be carried out without damaging the morphology of the propylene homopolymer particles.

In the graft polymer particles A, the amount of styrene grafted was 3% by weight, and the amount of 2-hydroxypropyacrylate grafted was 5% by weight. The graft polymer particles obtained as described above were molded into an injection molding machine (Toshiba Corporation).
IS-55EPN-1), cylinder temperature 2
A test piece was obtained by injection molding under the conditions of 10°C and a mold temperature of 60°C.

Table 1 shows the physical properties of this test piece.

[0087]

[Example 2] (Preparation of ethylene propylene copolymer (B)) 2.5 kg of propylene and 20 kg of hydrogen were placed in a 17 liter polymerization vessel at room temperature.
15 mmol of triethylaluminum and 1.5 mmol of diphenyldimethoxysilane were added at 50°C.
5 mmol and the prepolymerized product of catalyst component [A] produced in Example 1 were added in an amount of 0.05 mmol in terms of titanium atoms. Next, the inside of this polymerization vessel was maintained at 70°C. Open the vent valve 14 minutes after reaching 70°C. Propylene was purged until the inside of the polymerization vessel reached normal pressure. Copolymerization was carried out after purging, ie ethylene was fed into the polymerizer at a rate of 480 Nl/h, propylene at 720 Nl/h and hydrogen at a rate of 12 Nl/h. The pressure of the polymerization vessel is 10kg/cm2・G
The vent opening of the polymerization reactor was adjusted so that The temperature during copolymerization was kept at 70°C. After 60 minutes of copolymerization time had elapsed, the pressure was removed and the resulting polymer weighed 3.2 kg.

The ethylene content of the ethylene-propylene copolymer particles (B) obtained as described above was 25 mol%.
, 23°C n-decane soluble content is 25% by weight, ethylene content in the soluble component is 50 mol%, average particle size is 150%.
0 μm, the geometric standard deviation of the particles is 1.5, the apparent bulk density is 0.42 g/cm3, and the MFR is 10
g/10 minutes, and the temperature of the main peak of crystal phase melting measured by differential scanning calorimetry was 163°C. (Production of modified polyolefin particles) A solution prepared by dissolving 0.05 parts by weight of benzoyl peroxide in toluene was added to 100 parts by weight of the ethylene-propylene copolymer particles produced as described above, and sufficient After mixing with
Oxidation treatment was carried out by heating for 3 hours in a gear oven set at a temperature of 90°C.

The MFR after the oxidation treatment was 42 g/10 minutes. Next, 100 parts by weight of the above oxidized propylene homopolymer was charged into a stainless steel autoclave equipped with a stirring blade having a double helical ribbon, and the air in the system was completely replaced with nitrogen gas.

While stirring the oxidized propylene homopolymer at room temperature, a mixed solution consisting of 5 parts by weight of styrene and 10 parts by weight of 2-dimethylaminoethyl methacrylate was gradually added dropwise. After the dropwise addition, the temperature in the system was raised to 100° C. over 30 minutes, and stirring was continued at this temperature for an additional 2 hours to complete the reaction and obtain graft polymer particles.

The graft polymer particles had a styrene grafting amount of 3% by weight and a grafting amount of 2-dimethylaminoethyl methacrylate of 7% by weight. Table 1 shows the physical properties of the test piece prepared in the same manner as in Example 1.

[0092]

[Example 3] 0 parts of benzoyl peroxide was added to 100 parts by weight of the crystalline propylene homopolymer particles produced in Example 1.
．． 5ml of a solution prepared by dissolving 05 parts by weight in toluene
was added and thoroughly mixed, and then heated for 1.5 hours in a gear oven set at a temperature of 90°C to perform oxidation treatment.

[0093] The MFR after the oxidation treatment was 22 g/10 minutes. Next, 100 parts by weight of the above oxidized propylene homopolymer,
10 parts by weight of styrene, 10 parts by weight of 2-hydroxypropyl acrylate, and 20 parts by weight of talc were charged, and the air in 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 stirring was continued at this temperature for another 4 hours to complete the reaction and remove the graft polymer. Coalced particles were obtained.

The graft polymer particles A had a styrene grafting amount of 6% by weight and a grafting amount of 2-hydroxypropyacrylate of 8% by weight. Table 1 shows the physical properties of the test piece prepared in the same manner as in Example 1.

[0096]

[Example 4] 0 parts of benzoyl peroxide was added to 100 parts by weight of the crystalline propylene homopolymer particles produced in Example 1.
．． 8 ml of a solution prepared by dissolving 05 parts by weight in toluene
was added and thoroughly mixed, and then heated for 1.5 hours in a gear oven set at a temperature of 90°C to perform oxidation treatment.

[0097] The MFR after the oxidation treatment was 22 g/10 minutes. Next, 100 parts by weight of the above oxidized propylene homopolymer,
10 parts by weight of styrene, 15 parts by weight of glycidyl methacrylate, and 0.1 part by weight of N,N-dimethylaniline were charged, and the air in 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 stirring was continued at this temperature for another 4 hours to complete the reaction and remove the graft polymer. Coalced particles were obtained.

The graft polymer particles had a styrene grafting amount of 7% by weight and a glycidyl methacrylate grafting amount of 10% by weight. Table 1 shows the physical properties of the test piece prepared in the same manner as in Example 1.

[0100]

[Example 5] 0 parts of benzoyl peroxide was added to 100 parts by weight of the ethylene-propylene copolymer particles produced in Example.
．． A solution prepared by dissolving 0.5 parts by weight in toluene was added thereto, thoroughly mixed, and then heated for 3 hours in a gear oven set at a temperature of 90° C. for oxidation treatment.

[0101] The MFR after the oxidation treatment was 42 g/10 minutes. Next, 100 parts by weight of the above oxidized propylene homopolymer,
10 parts by weight of styrene, 10 parts by weight of 2-hydroxyethyl acrylate, 0.4 parts by weight of cobalt naphthenate, and 20 parts by weight of talc were charged, and the air in the system was completely replaced with nitrogen gas.

[0102] 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 it was further stirred for 2 minutes.
The reaction was completed by stirring for a period of time to obtain graft polymer particles.

The graft polymer particles had a styrene grafting amount of 6% by weight and a 2-hydroxyethyl acrylate grafting amount of 7% by weight. Table 1 shows the physical properties of the test piece prepared in the same manner as in Example 1.

[0104]

[Example 6] 0 parts by weight of benzoyl peroxide was added to 100 parts by weight of the crystalline propylene homopolymer particles produced in Example 1.
．． 8 ml of a solution prepared by dissolving 05 parts by weight in toluene
was added and thoroughly mixed, and then heated for 1.5 hours in a gear oven set at a temperature of 90°C to perform oxidation treatment.

[0105] The MFR after the oxidation treatment was 22 g/10 minutes. Next, 100 parts by weight of the above oxidized propylene homopolymer,
8 parts by weight of glycidyl methacrylate and 0.1 parts by weight of N,N-dimethylaniline were charged, and the air in the system was completely replaced with nitrogen gas.

[0106] After stirring at room temperature for 30 minutes, the temperature in the system was raised to 100°C over 30 minutes, and stirring was continued at this temperature for another 4 hours to complete the reaction and remove the graft polymer. Coalced particles were obtained.

The grafting amount of glycidyl methacrylate in this graft polymer was 5% by weight. 40 parts by weight of the graft polymer particles obtained in Examples 1 to 6 as described above and 60 parts by weight of nylon 6 (manufactured by Unitika Co., Ltd., Unitika Nylon, A1020BRL) were mixed into a 44 mm diameter two-layer tube set at a temperature of 230°C. A polyolefin resin composition was obtained by supplying the mixture to a screw extruder (L/D=30) and kneading it.

Next, the obtained polyolefin resin composition was molded into an injection molding machine (manufactured by Toshiba Corporation, IS-55EPN-1).
), cylinder temperature 240℃, mold temperature 60℃
A test piece was obtained by injection molding under the following conditions.

Table 1 shows the physical properties of this test piece.

[0110]

[Comparative Example 1] 100 parts by weight of the crystalline propylene homopolymer particles produced in Example 1, 0.05 parts by weight of benzoyl peroxide, and glycidyl methacrylate were placed in a stainless steel autoclave equipped with a stirring blade having a spiral double helical ribbon. 8 parts by weight was charged, and the system was completely replaced with nitrogen gas.

[0111] After stirring at room temperature for 30 minutes, the temperature in the system was raised to 100°C over 30 minutes, and stirring was continued at this temperature for another 4 hours to complete the reaction and remove the graft polymer. Coalced particles were obtained.

The grafting amount of glycidyl methacrylate in this graft polymer was 0.2% by weight. 40 parts by weight of the graft polymer particles obtained as described above and nylon 6 (manufactured by Unitika Co., Ltd., Unitika Nylon, A1
A polyolefin resin composition was obtained by feeding and kneading 60 parts by weight of 020BRL) into a 44 mmφ twin-screw extruder (L/D=30) set at a temperature of 230°C.

[0113] Then, the obtained polyolefin resin composition was molded into an injection molding machine (manufactured by Toshiba Corporation, IS-55EPN-1).
) and injection molded at a cylinder temperature of 240°C and a mold temperature of 60°C to obtain a test piece.

Table 1 shows the physical properties of this test piece.

[0115]

[Table 1]

Claims (1)

[Claims] Claim 1: Polyolefin particles (A) subjected to gas phase oxidation treatment and selected from the group consisting of hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, and epoxy group-containing ethylenically unsaturated compounds. Production of modified polyolefin particles by heating and reacting at least one modified monomer (B) under inert gas phase conditions in which the polyolefin particles (A) can substantially maintain their particle state. Method.