JP3379793B2 - Method for producing modified olefin polymer particles - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to an olefin polymer,
Modified olefin polymer obtained by subjecting a vinyl monomer having at least one functional group selected from the group consisting of amino group, hydroxyl group, epoxy group and carboxyl group (including acid anhydride group) to a graft reaction condition. The present invention relates to a method for producing coalesced particles.

[0002]

2. Description of the Related Art Olefin polymers are inexpensive, have excellent processability in various molding processes, and are qualitatively superior in hardness, creep properties,
It is used in a wide range of applications because of its excellent mechanical properties such as abrasion resistance, water resistance, solvent resistance such as gasoline, and chemical resistance. However, on the other hand, there are drawbacks in rigidity, impact resistance, adhesiveness, printing characteristics and the like. on the other hand,
A polymer having a functional group such as an amino group, a hydroxyl group, an epoxy group, and a carboxyl group (including an acid anhydride group) is different from an olefin polymer in that it has a large polarity, and due to the ionic characteristics of the functional group, it has a surface chemical property. As the highly active material, for example, an ionic bond adhesive, a dispersant, a coagulant, a polymer electrolyte, an adsorbent, or the like can be widely applied. Therefore, if a polymer having the features of both polymers can be obtained, application to a wide range of fields can be expected. However, since the compatibility of these two polymers is poor, a homogeneous composition cannot be obtained by simply blending both polymers.

As a method of improving this, a method of copolymerizing an olefin and a vinyl monomer having the above functional group can be considered. However, since this method generally requires polymerization at high temperature or high pressure, it cannot be easily carried out with a simple apparatus, and the obtained copolymer has lost the characteristics of a homopolymer of each monomer. It is highly probable that a polymer having the expected properties cannot be obtained. Another improvement method is a graft reaction. As one of the methods, there is a method of graft-copolymerizing an olefin polymer and a vinyl monomer having a functional group under the influence of high-energy irradiation, which is a specific apparatus for carrying out irradiation graft polymerization reaction. It is hard to say that it is of practical value because it is necessary. It is also known to perform graft polymerization of an olefin polymer in a molten state in the presence of a radical polymerization initiator (JP-A-58-109505). However, this method does not always lead to the decomposition or crosslinking reaction of the olefin polymer in the molten state and the desired properties are obtained.

It is also known that the graft polymerization of the olefin polymer is carried out in a solution using an aromatic hydrocarbon solvent such as xylene, but since the solubility of the olefin polymer in the solvent is poor, the polymerization is carried out. Since the reaction must be carried out in a dilute solution, it is not easy to introduce a large amount of the monomer, and the vinyl monomer having a functional group does not have a high degree of polymerization. Furthermore, a method of graft-copolymerizing a vinyl monomer having a functional group in an aqueous dispersion medium is also known (JP-A-57-23614 and JP-A-52-32990).
Issue). That is, it is a method of dissolving an olefin polymer in a solvent or an aromatic vinyl monomer capable of swelling and graft-copolymerizing in an aqueous dispersion medium, but a vinyl monomer having a functional group is generally water-soluble, Due to the low solubility in the solvent or the aromatic vinyl monomer, there is a drawback that a large amount of vinyl monomer having a functional group cannot be introduced into the produced polymer.

[0005]

The present invention aims to solve the above-mentioned drawbacks, and completes the present invention by finding that this object can be achieved by using a specific manufacturing method. It came to. That is, the present invention
00 parts by weight, 5 to 100 parts by weight of olefin polymer particles,
0.05-50 parts by weight of vinyl monomer having at least one functional group obtained from the group consisting of amino group, hydroxyl group, epoxy group and carboxyl group (including acid anhydride) is obtained, and a half-life of 10 hours is obtained. For decomposition temperature is 40-1
0.0005 to 5 parts by weight of a radical polymerization initiator having a temperature of 30 ° C., and a dissolution inhibitor of the vinyl monomer in water of 0.1 to 0.1 parts by weight.
A method for producing modified olefin polymer particles, which comprises heating an aqueous suspension containing 10 parts by weight to complete the polymerization of the vinyl monomer.

In the method of the present invention, a vinyl monomer having a functional group such as an amino group, a hydroxyl group, an epoxy group or a carboxyl group (including an acid anhydride), which is generally water-soluble, is efficiently industrialized into an olefin polymer. The resulting modified polymer can have the advantages of both the olefin polymer and the polymer having the functional group, so that, for example, printability, adhesiveness, paintability, etc. It can be expected to develop into applications such as excellent films, sheets, and molded products.

[Detailed Description of the Invention] (1) Raw Material 1) Olefin Polymer Particles The olefin polymer used in the present invention is ethylene, propylene, butene-1, hexene-1, heptene-1, octene-. 1,4-Methylpentene-1-Pentene and other olefins having 2 to 12 carbon atoms, preferably about 2 to 8 carbon atoms, homopolymers or copolymers of two or more kinds, or these olefins and non-conjugated dienes, vinyl esters, unsaturated Examples thereof include a copolymer composed of an organic acid or its derivative, vinyl organic silane and the like. The copolymer may be in a random, block or graft type. These olefin polymers may be used as a mixture of two or more kinds.

Specific examples of the olefin polymer include:
High, medium and low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer (random and block), propylene-butene-1 random copolymer, propylene-ethylene-butene-1 random. Copolymer, propylene and carbon number 5-12
Α-olefin and optionally ethylene or butene
1), an ethylene-non-conjugated diene copolymer, a propylene-non-conjugated diene copolymer, an ethylene-propylene-non-conjugated diene copolymer, an ethylene-butene-
1-Non-conjugated diene copolymer (Specific examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene,
5-methyl-1,4-hexadiene, 7-methyl-1,
6-octadiene, 1,9-decadiene, etc.), ethylene-vinyl acetate copolymer, ethylene-vinyltrimethoxysilane copolymer, maleic anhydride grafted polyethylene, maleic anhydride grafted polypropylene, ethylene-methyl acrylate. Copolymer, ethylene-
Typical examples are ethyl acrylate copolymers, ethylene-methyl methacrylate copolymers, ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers and the like. Among them, polyethylene, polypropylene, ethylene-
Propylene copolymer, ethylene-methyl acrylate copolymer and the like are preferable.

The olefin polymer particles have a narrow particle size distribution and an average particle size of 50 to 500 μm from the viewpoint of affinity with the vinyl monomer, that is, from the viewpoint of adhering or impregnating the vinyl monomer into the olefin polymer. More preferably 100 to 25
It is preferably in the form of powder of 0 μm. If the particle size is excessively large, not only is it difficult to disperse during polymerization, but also the amount of vinyl monomer that is compatible is limited. On the other hand, if the particle size is excessively small, the olefin polymer particles are likely to aggregate, and the productivity of the modified olefin polymer particles is reduced. The amount of the olefin polymer particles used is 5 to 100 parts by weight, preferably 10 to 80 parts by weight, based on 100 parts by weight of water. Below this range, the affinity of the vinyl monomer with the olefin polymer is not efficiently achieved, and above this range, it becomes difficult to maintain a stable dispersed state.

2) Vinyl monomer having a functional group As the functional group-containing vinyl monomer used in the present invention,
Commercially available vinyl monomers can be used as long as they are vinyl monomers having an amino group, a hydroxyl group, an epoxy group or a carboxyl group (including an acid anhydride group). As the amino group-containing vinyl monomer, for example, vinyl monomers having a primary amino group such as aminomethyl acrylate, aminomethyl methacrylate, and aminoethyl methacrylate; N-methylaminoethyl acrylate, N-ethylaminoethyl Vinyl monomers having a secondary amino group such as methacrylate, N-ethylaminoisopropyl methacrylate, and N-ethylaminobutyl methacrylate; N, N-dimethylaminoethyl acrylate,
Third such as N, N-dimethylaminoethyl methacrylate and N, N-diethylaminoethyl methacrylate
Examples thereof include vinyl monomers having a primary amino group. Among them, N, N-dimethylaminoethyl methacrylate and N, N-diethylaminoethyl methacrylate are preferable from the viewpoint of exhibiting the functionality of the modified polymer, for example, coating property.

Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate and 3
-(Meth) acrylates such as hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, diethylene glycol monomethacrylate, polyethylene glycol monomethacrylate;
Unsaturated alcohols such as allyl alcohol, 9-decen-1-ol, 10-undecen-1-ol; vinyl ethers such as 2-hydroxy vinyl ether and diethylene glycol monovinyl ether; allyl ethers such as 2-hydroxyethyl allyl ether Can be mentioned. Among them, 2-hydroxyethyl methacrylate is preferable in terms of the functionality of the resulting modified polymer, for example, the expression of printability.

Examples of the epoxy group-containing vinyl monomer include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and the like. Of these, glycidyl methacrylate is preferred. Examples of the vinyl monomer containing a carboxyl group or an anhydride group thereof include acrylic acid, methacrylic acid, crotonic acid, butenoic acid, pentenoic acid, heptenoic acid, octenoic acid, nonenoic acid,
Unsaturated monocarboxylic acids such as decenoic acid and undecenoic acid; α, β-unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6-dicarboxylic acid; maleic acid Examples include α, β-unsaturated dicarboxylic acid anhydrides such as anhydrides, fumaric anhydride, itaconic anhydride, and citraconic anhydride. Of these, methacrylic acid or maleic anhydride is preferable from the viewpoint of the functionality of the resulting modified polymer, for example, the expression of adhesiveness.

A vinyl monomer having such a functional group may be mixed with a copolymerizable vinyl monomer other than the above. Here, as the other vinyl monomer, for example, styrene, 2-methylstyrene, 3-methylstyrene,
Unsaturated aromatic monomers such as 4-methylstyrene, dimethylstyrene and chlorostyrene; vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate, ethyl acrylate, methyl methacrylate, dimethyl maleate, di maleate ( Unsaturated organic acid esters such as 2-ethylhexyl); unsaturated nitriles such as acrylonitrile and methacrylonitrile; unsaturated mono- or dihalides such as vinyl chloride and vinylidene chloride. Among these monomers, unsaturated aromatic vinyl monomers such as styrene have the function of increasing the affinity between the functional group-containing vinyl monomer and the olefin polymer, and are preferably used at the same time.

The amount of the functional group-containing vinyl monomer is 0.05 to 50 parts by weight, preferably 0.1 to 30 parts by weight, based on 100 parts by weight of water. If it exceeds 50 parts by weight,
The vinyl monomer that is not compatible with the olefin polymer particles increases, and a vinyl polymer independent of the olefin polymer particles is produced during the suspension polymerization, and the homogeneity of the modified polymer is hindered. Further, if the amount is less than 0.05 parts by weight, the properties of the modified polymer cannot be effectively exhibited. When the above-mentioned other monomer is used, it can be used usually in the range of 10 to 1000 parts by weight with respect to 100 parts by weight of the functional group-containing vinyl monomer.

3) Radical Polymerization Initiator As the radical polymerization initiator used in the production of the modified polymer, a general-purpose radical polymerization initiator can be used, but from the viewpoint of a preferable graft reaction efficiency described later. Those having a decomposition temperature of 40 to 130 ° C. and being oil-soluble are preferable. Here, the "decomposition temperature" is the temperature at which the decomposition rate of the radical generator becomes 50% when 0.1 mol of the radical generator is added to 1 liter of benzene and left standing for 10 hours. . So-called "10
"Decomposition temperature to obtain the half-life of time". If the decomposition temperature is lower than 40 ° C., the polymerization of vinyl monomer may progress abnormally, and there is a drawback that a homogeneous modified polymer cannot be obtained.
If it exceeds, the molecular cleavage reaction or molecular crosslinking reaction of the olefin polymer becomes remarkable, which is not preferable.

As such a radical polymerization initiator,
For example, 2,4-dichlorobenzoyl peroxide, t
-Butylperoxypivalate, o-methylbenzoyl peroxide, bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide,
Benzoyl peroxide, t-butylperoxy-2
-Ethyl hexanoate, cyclohexanone peroxide, 2,5-dimethyl-2,5-dibenzoylperoxyhexane, t-butylperoxybenzoate, di-t-butyl-diperoxyphthalate, methyl ethyl ketone peroxide , Dicumyl peroxide, di-
Examples thereof include organic peroxides such as t-butyl peroxide; azo compounds such as azobisisobutyronitrile and azobis (2,4-dimethylvaleronitrile).
These initiators can be used alone or in combination of two or more. When the initiator is used in combination, for example, by appropriately combining those having a high decomposition temperature and those having a low decomposition temperature, the decomposition can be carried out stepwise or continuously and the graft reaction can be efficiently carried out. The amount of radical polymerization initiator used is 0.0005 with respect to 100 parts by weight of water.
To 5 parts by weight, preferably 0.001 to 2 parts by weight, depending on the type of radical polymerization initiator and reaction conditions. If the amount used is less than this amount, the reaction will not proceed smoothly,
On the other hand, if this amount is exceeded, a gel is likely to be formed in the modified polymer, and the effect of the present invention is difficult to be exhibited.

[0017] 4) an inorganic salt for dissolution inhibiting used for dissolution inhibiting an inorganic salt present invention, namely as an inorganic salt for dissolution inhibiting in water of the vinyl monomer having a functional group, ion concentration per unit weight It is possible to use an inorganic salt, which has a high activity, reduces the activity of water as a solvent, and has a large action of decreasing the solubility of the vinyl monomer in water. These inorganic salts are alkali metal salts or alkaline earth metal salts of inorganic acids that are readily soluble in water, and include, for example, sodium chloride, calcium chloride, sodium sulfate, sodium phosphate, sodium carbonate, sodium nitrate, potassium chloride,
Examples thereof include potassium phosphate, potassium nitrate, potassium carbonate, calcium nitrate, potassium bromide, calcium bromide, lithium chloride, lithium nitrate and lithium sulfate. Among them, sodium chloride, sodium phosphate and sodium carbonate are preferable, and sodium chloride is particularly preferable from the viewpoint of the dissolution inhibiting effect. In addition, it is necessary to consider the solubility of the inorganic salt for suppressing dissolution in water because of the use of the aqueous medium. From this viewpoint, sodium phosphate is preferable among the above inorganic salts. Therefore, considering the dissolution inhibiting effect of the vinyl monomer in water and the solubility of the inorganic salt itself for inhibiting dissolution in water, for example, a combination of sodium chloride and sodium phosphate is used for inhibiting dissolution. It is preferable to use the inorganic salt of . The amount of the dissolution inhibiting inorganic salt used is selected in the range of 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of water. If the amount used is less than this amount, the effect of suppressing the dissolution of the vinyl monomer in water cannot be sufficiently expressed, while if it exceeds this amount, the suspension system becomes unstable and particles are aggregated or agglomerated during polymerization. Cause

(2) Production of Modified Polymer The modified polymer of the present invention can be produced by the aqueous suspension grafting method described below for each raw material component. That is, an olefin polymer particle, a vinyl monomer having a functional group, a radical polymerization initiator, an aqueous suspension containing a dissolution inhibitor of the vinyl monomer in water, the decomposition of the initiator is substantially After the temperature is raised to a temperature at which it does not occur, the monomer is made to be compatible with the olefin polymer particles, and then the temperature of this aqueous suspension is raised to the decomposition temperature of the initiator or higher to polymerize the vinyl monomer. Is preferable, and this method will be described in detail below.

1) Preparation of Aqueous Suspension Olefin polymer particles, preferably a vinyl monomer in which a radical polymerization initiator is previously dissolved, are dispersed in an aqueous medium in which a dissolution inhibitor is dissolved. Such an aqueous dispersion,
A stable dispersion state can be maintained by simply performing sufficient stirring, but it is preferable to use an appropriate suspension stabilizer in order to prepare an easier and more stable suspension dispersion liquid. In this case, examples of the suspension stabilizer include water-soluble polymers such as polyvinyl alcohol, methyl cellulose, and hydroxy cellulose; anionic surfactants such as alkylbenzene sulfonate; nonionic surfactants such as polyoxyethylene alkyl ether. Agents; or water-insoluble inorganic salts such as magnesium oxide, calcium phosphate, etc., alone or in a mixture, with respect to water of 0.01 to 1
It is used in an amount of about 0% by weight.

2) Affinity of olefin polymer particles with vinyl monomer having functional group The aqueous suspension prepared as described above is heated to a temperature at which the radical polymerization initiator is not substantially decomposed. , Make the vinyl monomer having a functional group compatible with the olefin polymer particles. Affinity is the majority weight of vinyl monomer, preferably 8
The aqueous suspension is preferably left under agitation until 0% by weight or more is deposited or impregnated on the olefin polymer particles. At that time, the temperature of the aqueous suspension is preferably higher from the viewpoint of promoting affinity, but this is prevented because the vinyl monomer having no affinity is polymerized by the premature decomposition of the radical polymerization initiator. From the point, the lower the better. Generally, it is preferable to operate from room temperature to 100 ° C, especially 50 to 90 ° C. The time is usually about 1 to 8 hours. The content of the olefin polymer and the functional group-containing vinyl monomer in the aqueous suspension is usually about 5 to 100 parts by weight with respect to 100 parts by weight of water. When the vinyl monomer (and radical polymerization initiator etc.) is made to be compatible with the olefin polymer particles,
Auxiliary materials such as a plasticizer, a lubricant, and an antioxidant can be impregnated at the same time (these auxiliary materials may be already added to the olefin polymer or may be added after the graft polymerization reaction).

3) Polymerization If the temperature of the aqueous suspension thus prepared is raised to a temperature above the temperature at which the radical polymerization initiator used is decomposed at an appropriate rate, the vinyl group containing the functionalized vinyl group having affinity is polymerized. The polymer is graft-polymerized to produce modified polymer particles. It is preferable to appropriately stir the aqueous suspension during the graft polymerization. The polymerization temperature should generally be appropriately selected within the range of 50 to 150 ° C., but need not be constant throughout the graft polymerization process. The polymerization time is usually about 2 to 10 hours. The polymerization pressure is usually atmospheric pressure to about 10 kg / cm ² . In addition, n-butyl mercaptan, n-butylmercaptan, or n-butyl mercaptan may be used to control the molecular weight of the polymer resulting from the polymerization of the vinyl monomer.
A chain transfer agent such as -dodecyl mercaptan or t-dodecyl mercaptan may be added. After the polymerization, if the same post-treatment as the usual post-treatment of aqueous suspension polymerization of vinyl monomer (eg styrene) is carried out, the shape of the olefin polymer used is almost retained and it can be used immediately as a molding material. Modified polymer particles that can be obtained are obtained.

[0022]

EXAMPLES Next, the present invention will be described more specifically by way of examples. The content of the vinyl monomer having a functional group in the modified olefin polymer particles was measured by using an infrared spectrophotometer (Infrared spectrophotometer IR-810 type manufactured by JASCO Corporation) and KBr.
It was determined from the infrared absorption spectrum by the method.

[Example 1] 20 kg of water and a suspension of tricalcium phosphate 8 in a 50 liter autoclave
0 g, polyvinyl alcohol (polymerization degree 1700, saponification degree 86%) 8 g, and sodium chloride as a dissolution inhibitor 0.4
Mix kg to make an aqueous medium, and add polyethylene powder (Polylett 250
(0.2, average particle size: 150 to 200 μ), 7.2 kg was stirred and suspended. Separately, 80 g of t-butyl peroxypivalate,
80 g of benzoyl peroxide was dissolved in 0.8 kg of N, N-dimethylaminoethyl methacrylate, and this was added to the above suspension system to prepare an aqueous suspension. Next, the inside of the autoclave was heated to 50 ° C., and the mixture was left for 1 hour while stirring at this temperature to make all vinyl monomers containing a radical polymerization initiator compatible with the polyethylene powder. Next, the temperature of this suspension was raised to 75 ° C., the mixture was left standing for 4 hours while stirring at this temperature to carry out polymerization, and the temperature was further raised to 85 ° C. and maintained for 2 hours to complete the polymerization. After cooling, the solid contents were taken out and washed with water to obtain 7.8 kg of modified polyethylene particles. The content of the dimethylaminoethyl methacrylate polymer in the obtained modified polymer particles was determined by infrared absorption spectrum, and was 8% by weight.

[Example 2] Polypropylene powder (SPX86 manufactured by Mitsubishi Petrochemical Co., Ltd.) was used instead of polyethylene in Example 1.
00Q, average particle size: 450 μ), and 7.9 kg of modified polypropylene particles were obtained in the same manner except that N, N-diethylaminoethyl methacrylate was used instead of N, N-dimethylaminoethyl methacrylate. The content of the diethylaminoethyl methacrylate polymer in the obtained modified polymer particles was determined from the infrared absorption spectrum.
% By weight.

Example 3 In an autoclave having a volume of 50 liters, 20 kg of water and a suspending agent of tricalcium phosphate 8
0 g, polyvinyl alcohol (polymerization degree 1700, saponification degree 86%) 8 g, dissolution inhibitor sodium chloride 0.2 kg
And 0.2 kg of disodium phosphate are mixed to make an aqueous medium, and polyethylene powder (Polyletts 2500 made by Chusei Wax Polymer, average particle size: 100 to 1)
50 μ) 4 kg was suspended by stirring. Separately, 80 g of t-butyl peroxypivalate and 40 g of azobisisobutyronitrile were added to N, N-dimethylaminoethyl methacrylate.
Dissolved in 0.4 kg of styrene and 3.6 kg of styrene, and this was added to the above suspension system to prepare an aqueous suspension. Next, the temperature inside the autoclave was raised to 50 ° C., and the mixture was left standing for 1 hour while stirring at this temperature to make all the vinyl monomer containing the polymerization initiator compatible with the polyethylene powder. Next, the temperature of this suspension was raised to 75 ° C., the mixture was left standing for 4 hours while stirring at this temperature to carry out polymerization, and the temperature was further raised to 85 ° C. and maintained for 2 hours to complete the polymerization. After cooling, the solid contents were taken out and washed with water to obtain 8 kg of modified polyethylene particles. When the content of the dimethylaminoethyl methacrylate polymer in the obtained modified polymer particles was determined from the infrared absorption spectrum,
It was 5% by weight.

Example 4 In an autoclave having a volume of 50 liters, 20 kg of water and a suspending agent of tricalcium phosphate 8 were added.
0 g, polyvinyl alcohol (polymerization degree 1700, saponification degree 86%) 8 g and disodium phosphate 0.4 kg as a dissolution inhibitor were mixed to prepare an aqueous medium, and polypropylene powder (Mitsubishi Petrochemical SPX8600Q, average particle size: 450 μ) 4.8 kg was suspended by stirring. Separately t
-Butyl peroxypivalate 120 g and benzoyl peroxide 120 g were dissolved in N, N-dimethylaminoethyl methacrylate 1.6 kg and styrene 1.6 kg, and this was added to the above suspension system to prepare an aqueous suspension. . Next, the inside of the autoclave was heated to 50 ° C., and left for 1 hour while stirring at this temperature to make all vinyl monomers containing a polymerization initiator compatible with the polypropylene powder.
Next, the temperature of this suspension was raised to 70 ° C., the mixture was left standing for 4 hours while stirring at this temperature to carry out polymerization, and the temperature was further raised to 85 ° C. and maintained for 2 hours to complete the polymerization. After cooling, the solid contents are taken out and washed with water to give modified polypropylene particles of 7.5 kg.
Got The content of the dimethylaminoethyl methacrylate polymer in the obtained modified polymer particles was determined by infrared absorption spectrum and found to be 15% by weight.

Comparative Example 1 Modified polyethylene particles were obtained in the same manner as in Example 1 except that the dissolution inhibitor sodium chloride was not used. The content of dimethylaminoethyl methacrylate polymer in the obtained modified polymer particles was determined by infrared absorption spectrum to be 2% by weight.
Met.

[Comparative Example 2] Polymerization was carried out in the same manner as in Example 1 except that 3 kg of sodium chloride as a dissolution inhibitor was used in Example 1. As a result, coagulation of particles occurred during the polymerization and the polymer was converted into particles. It could not be obtained in shape.

Comparative Example 3 Modified polypropylene particles were obtained in the same manner as in Example 1 except that 0.4 kg of sodium lauryl sulfate was used in place of sodium chloride as the dissolution inhibitor in Example 2. When the content of the diethylaminoethyl methacrylate polymer in the obtained modified polymer particles was determined from the infrared absorption spectrum, the polymer was not measured.

[Embodiment 5] In an autoclave having a volume of 50 liters, 20 kg of water and 8 parts of tricalcium phosphate as a suspending agent.
0 g, polyvinyl alcohol (polymerization degree 1700, saponification degree 86%) 8 g and dissolution inhibitor sodium chloride 0.2
kg and 0.2 kg of disodium phosphate were mixed to make an aqueous medium, and polyethylene powder (Polyletts 2500 made by Chusei Wax Polymer, average particle size: 10
0-150 μ) 4.8 kg was stirred and suspended. Separately t-
80 g of butyl peroxypivalate and 80 g of benzoyl peroxide were dissolved in 3.2 kg of 2-hydroxyethyl methacrylate, and this was added to the above suspension system to prepare an aqueous suspension. Next, the inside of the autoclave was heated to 50 ° C., and the mixture was left for 1 hour while stirring at this temperature to make all vinyl monomers containing a radical polymerization initiator compatible with the polyethylene powder. Then the suspension is heated to 75 ° C.,
Polymerization was carried out by standing at this temperature for 4 hours while stirring, and the temperature was further raised to 85 ° C. and maintained for 2 hours to complete the polymerization. After cooling, the solid contents were taken out and washed with water to obtain 7.65 kg of modified polyethylene particles. The content of the 2-hydroxyethyl methacrylate polymer in the obtained modified polymer particles was determined from the infrared absorption spectrum, and it was 37.2% by weight.

Example 6 In an autoclave having a volume of 50 liters, 20 kg of water and a suspending agent of tricalcium phosphate 8 were added.
0 g, polyvinyl alcohol (polymerization degree 1700, saponification degree 86%) 8 g, and sodium chloride as a dissolution inhibitor 0.4
Mix kg to make an aqueous medium, and add polyethylene powder (Polylett 250
0, average particle size: 100-150μ) 3 kg was suspended by stirring. Separately, 160 g of benzoyl peroxide was added to 4 kg of 2-hydroxyethyl methacrylate and 1 k of styrene.
g, and this was added to the above suspension system to prepare an aqueous suspension. Next, the inside of the autoclave was heated to 60 ° C., and the mixture was left at this temperature for 1 hour with stirring to allow all vinyl monomers containing a radical polymerization initiator to be compatible with the polyethylene powder. Next, the suspension was heated to 75 ° C., polymerization was carried out by allowing the suspension to stir at this temperature for 4 hours to carry out polymerization at 85 ° C.
The temperature was raised to and maintained for 2 hours to complete the polymerization. After cooling, the solid content was taken out and washed with water to obtain 6.9 kg of modified polyethylene particles. The content of the 2-hydroxyethyl methacrylate polymer in the obtained modified polymer particles was 42% by weight as determined by infrared absorption spectrum.

[Example 7] Polypropylene powder (SPX86 manufactured by Mitsubishi Petrochemical Co., Ltd.) was used instead of the polyethylene of Example 5.
Modified polypropylene polymer particles (7.5 kg) were obtained in the same manner except that (00Q, average particle size: 450 μ) was used. The content of the 2-hydroxyethyl methacrylate polymer in the obtained modified polymer particles was determined by infrared absorption spectrum, and it was 36% by weight.

[Example 8] In the same manner as in Example 5 except that glycidyl methacrylate was used instead of 2-hydroxyethyl methacrylate, 7.4 kg of modified polyethylene polymer particles were obtained. The content of the glycidyl methacrylate polymer in the obtained modified polymer particles was determined by infrared absorption spectrum, and it was 35% by weight.

Example 9 In an autoclave having a volume of 50 liters, 20 kg of water and a suspending agent of tricalcium phosphate 8 were added.
0 g, polyvinyl alcohol (polymerization degree 1700, saponification degree 86%) 8 g, and sodium chloride as a dissolution inhibitor 0.4
An aqueous medium was prepared by mixing kg with polypropylene powder (Mitsubishi Yuka SPX8600Q, average particle size: 450).
μ) 4.8 kg was stirred and suspended. Separately, 12.8 g of t-butyl peroxypivalate and 9.6 g of azobisisobutyronitrile were added to 0.8 k of glycidyl methacrylate.
g and styrene (2.4 kg), and this was added to the above suspension system to prepare an aqueous suspension. Next, the inside of the autoclave was heated to 60 ° C., and the mixture was allowed to stand for 1 hour with stirring at this temperature to make all vinyl monomers containing a radical polymerization initiator compatible with the polypropylene powder. Next, the temperature of this suspension was raised to 75 ° C., the mixture was left standing for 4 hours while stirring at this temperature to carry out polymerization, and the temperature was further raised to 85 ° C. and maintained for 2 hours to complete the polymerization. After cooling, the solid content was taken out and washed with water to obtain 7.95 kg of modified polypropylene particles. When the content of the glycidyl methacrylate polymer in the obtained modified polymer particles was determined from the infrared absorption spectrum,
It was 9.5% by weight.

[Example 10] 7.9 kg of modified polypropylene polymer particles were obtained in the same manner as in Example 9 except that methacrylic acid was used instead of glycidyl methacrylate. The content of the methacrylic acid polymer in the obtained modified polymer particles was determined from the infrared absorption spectrum and found to be 8.8.
% By weight.

[Example 11] 7.3 kg of modified polypropylene polymer particles were obtained in the same manner as in Example 9 except that maleic anhydride was used instead of glycidyl methacrylate. The content of the maleic anhydride polymer in the obtained modified polymer particles was determined from the infrared absorption spectrum, and it was 3% by weight.

Comparative Example 4 Modified polyethylene particles were obtained in the same manner as in Example 5, except that the dissolution inhibitors sodium chloride and disodium phosphate were not used. The content of the 2-hydroxyethyl methacrylate polymer in the obtained modified polymer particles was determined by infrared absorption spectrum, and it was 9% by weight.

[Comparative Example 5] Polymerization was carried out in the same manner as in Example 5 except that 3 kg of sodium chloride alone was used as the dissolution inhibitor in Example 5, and particles were condensed during the polymerization to form the polymer particles. Could not be obtained in the shape of.

Comparative Example 6 Modified polyethylene particles were obtained in the same manner as in Example 8 except that the dissolution inhibitors sodium chloride and disodium phosphate were not used. The content of the glycidyl methacrylate polymer in the obtained modified polymer particles was determined by infrared absorption spectrum and found to be 5% by weight.

[Comparative Example 7] Modified polypropylene particles were obtained in the same manner as in Example 10 except that the dissolution inhibitor sodium chloride was not used. When the content of the methacrylic acid polymer in the obtained modified polymer particles was determined from the infrared absorption spectrum, the polymer was not observed.

[Comparative Example 8] Modified polypropylene particles were obtained in the same manner as in Example 11 except that the dissolution inhibitor sodium chloride was not used. When the content of the maleic anhydride polymer in the obtained modified polymer particles was determined from the infrared absorption spectrum, the polymer was not observed.

Comparative Example 9 Modified polyethylene particles were obtained in the same manner as in Example 6 except that 0.4 kg of sodium lauryl sulfate was used in place of sodium chloride as the dissolution inhibitor. 2 in the obtained modified polymer particles
When the content of the -hydroxyethyl methacrylate polymer was determined from the infrared absorption spectrum, the polymer was not observed.

Example 12 An autoclave having a volume of 50 liters was mixed with 20 kg of water, 200 g of tricalcium phosphate as a suspending agent and 0.25 kg of sodium chloride as a dissolution inhibitor to prepare an aqueous medium. Wax polymer Polyletts 2500,
5.6 kg (average particle size: 150-200μ) were stirred and suspended. Separately, 24 g of t-butylperoxypivalate and 18 g of azobisisobutyronitrile were dissolved in 2.4 kg of N, N-dimethylaminoethyl methacrylate, and this was added to the above suspension system to prepare an aqueous suspension. . Next, the inside of the autoclave was heated to 65 ° C., and the mixture was allowed to stand for 1 hour with stirring at this temperature to make all vinyl monomers containing a radical polymerization initiator compatible with the polyethylene powder. Next, the temperature of this suspension was raised to 75 ° C., the mixture was left standing for 4 hours while stirring at this temperature to carry out polymerization, and the temperature was further raised to 85 ° C. and maintained for 2 hours to complete the polymerization. After cooling, the solid contents were taken out and washed with water to obtain 6.4 kg of modified polyethylene particles. The content of the dimethylaminoethyl methacrylate polymer in the obtained modified polymer particles was determined by infrared absorption spectrum and found to be 13% by weight.

[Example 13] 20 kg of water, 200 g of tricalcium phosphate as a suspending agent and 0.25 kg of sodium chloride as a dissolution inhibitor were mixed in an autoclave having a volume of 50 liters to prepare an aqueous medium, and polyethylene small particle pellets were added thereto. (Mitsubishi Yuka Mitsubishi Polyethylene ZC30 (average particle size 3m
m) was reduced to an average particle size of 1 mm, and 6.1 kg was suspended by stirring. Separately, 24 g of t-butyl peroxypivalate and 18 g of azobisisobutyronitrile were added to N,
Dissolved in 2.4 kg of N-dimethylaminoethyl methacrylate, this was added to the above suspension system to prepare an aqueous suspension. Next, the inside of the autoclave was heated to 65 ° C., and the mixture was allowed to stand for 1 hour with stirring at this temperature to make all vinyl monomers containing a radical polymerization initiator compatible with the polyethylene powder. Next, the temperature of this suspension was raised to 75 ° C., the mixture was left standing for 4 hours while stirring at this temperature to carry out polymerization, and the temperature was further raised to 85 ° C. and maintained for 2 hours to complete the polymerization. After cooling, the solid contents are taken out and washed with water to obtain modified polyethylene particles 6.1
I got kg. The content of the dimethylaminoethyl methacrylate polymer in the obtained modified polymer particles was determined by infrared absorption spectrum, and was 8% by weight.

Example 14 In an autoclave having a volume of 50 liters, 20 kg of water, 200 g of tricalcium phosphate as a suspending agent, and 0.25 kg of sodium chloride as a dissolution inhibitor were mixed to prepare an aqueous medium. Mitsubishi Polyethylene ZC30, average particle size: 3 mm)
5.6 kg were stirred and suspended. Separately, 24 g of t-butylperoxypivalate and 18 g of azobisisobutyronitrile were dissolved in 2.4 kg of N, N-dimethylaminoethyl methacrylate, and this was added to the above suspension system to prepare an aqueous suspension. . Next, the inside of the autoclave was heated to 65 ° C., and the mixture was allowed to stand for 1 hour with stirring at this temperature to make all vinyl monomers containing a radical polymerization initiator compatible with the polyethylene powder. Then the suspension is heated to 75 ° C.,
Polymerization was carried out by standing at this temperature for 4 hours while stirring, and the temperature was further raised to 85 ° C. and maintained for 2 hours to complete the polymerization. After cooling, the solid content was taken out and washed with water to obtain 5.8 kg of modified polyethylene particles. The content of the dimethylaminoethyl methacrylate polymer in the obtained modified polymer particles was determined by infrared absorption spectrum and found to be 3% by weight.

The results of the above Examples and Comparative Examples are summarized in Table 1.

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[Table 1]

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[Table 2]

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According to the method of the present invention, a vinyl monomer having a functional group such as an amino group, a hydroxyl group, an epoxy group or a carboxyl group (including an acid anhydride group), which is generally water-soluble, has In an aqueous medium, which was difficult, it became possible to introduce the olefin polymer under industrially satisfactory conditions, as a result, there is no defect of those grafted by the above-mentioned melt graft method, solution graft method, And,
A highly practical modified olefin polymer is obtained that is not a heterogeneous product such as a blend.

Claims (2)

(57) [Claims] 1. At least one functional group selected from the group consisting of 100 parts by weight of water, 5 to 100 parts by weight of olefin polymer particles, amino group, hydroxyl group, epoxy group and carboxyl group (including acid anhydride group). 0.05 to 50 parts by weight of a vinyl monomer having a radical polymerization initiator having a decomposition temperature of 40 to 130 ° C. for obtaining a half-life of 10 hours, and the vinyl monomer. A modified olefin polymer, characterized in that the temperature of an aqueous suspension containing 0.1 to 10 parts by weight of an inorganic salt for suppressing the dissolution of water in water is completed to complete the polymerization of the vinyl monomer. Particle manufacturing method. 2. The olefin polymer particles are 50 to 500 μm.
The method of claim 1 having an average particle size of m.