JPH0453883B2 - - Google Patents

Description

[Detailed description of the invention]

<Industrial Application Fields> The present invention is a highly efficient grafting agent useful as adhesives, coatings, modifiers, microdispersants, polymer alloying agents, functional molded body materials, polymer compatibilizers, etc. The present invention relates to a method for producing a graft resin composition. <Prior Art> Conventionally, in order to improve the rigidity, dimensional stability, printability, etc. of propylene polymer as a molding material, vinyl polymers such as polystyrene have been added to propylene polymer as a crosslinking agent or grafting agent. Attempts have been made to melt blend organic peroxides. In addition, a propylene polymer has been proposed in which styrene is grafted onto the propylene polymer by irradiation with ionizing radiation, and this method has shown considerable effectiveness in uniformly dispersing polystyrene into the propylene polymer. There is. On the other hand, other known methods include solution graft polymerization using a solvent such as xylene or toluene, and emulsion graft polymerization. Furthermore, it has also been proposed to produce a graft resin composition by impregnating propylene polymer particles with a vinyl monomer and polymerizing them in an aqueous suspension system (Japanese Patent Publication No. 58-53003). According to this method,
The resin composition that has undergone polymerization has a uniform blend of vinyl polymers, and provides more favorable results than other methods. <Problems to be Solved by the Invention> However, propylene polymers and styrene polymers are essentially incompatible, and even if an organic peroxide is added as a grafting agent, for example, the grafting effect will be low. Not at all. Therefore, 10% by weight or more of a styrene polymer has not been blended, and usually only 0.2 to 5% by weight of a styrene polymer has been blended. Even when such small amounts of styrenic polymers are blended, molded articles made from the blend tend to have reduced impact resistance and poor appearance due to poor compatibility between the two polymers. Next, the method of irradiating with ionizing radiation to improve this drawback is based on a special method called radiation graft polymerization, which has economical problems and is difficult to put into practical use. Furthermore, this method is not preferred because there is a limit to the amount of styrene that can be introduced. Thirdly, in the solution graft polymerization method, from the viewpoint of solubility of the propylene polymer, polymerization is performed while diluted in a large amount of solvent.
It is economically disadvantageous because there are few opportunities for contact between the polymerization initiator and the propylene polymer, and the reaction efficiency of the vinyl monomer is low, and the post-processing steps such as solvent recovery are complicated. be. moreover,
There is also an emulsion graft polymerization method, but this method has the disadvantage that the homogeneity of the product is poor because the reaction is limited to the surface reaction of the propylene polymer particles. Polymerization in an aqueous suspension system has low grafting efficiency of the resulting resin composition, so heating during secondary processing or contact with a solvent may result in the vinyl polymer being uniformly dispersed upon completion of polymerization. Secondary aggregation of particles is likely to occur, which poses a problem when the resulting resin composition is used as a functional molding material or a polymer compatibilizer. <Means for Solving the Problems> As a result of intensive research by the present inventors with the aim of obtaining a resin composition with high grafting efficiency of these conventional propylene polymers and vinyl polymers,
The present inventors have discovered that a resin composition with dramatically high grafting efficiency can be obtained by kneading a specific grafting precursor while melting at a specific temperature, leading to the completion of the present invention. That is, the present invention suspends water in a propylene polymer, and adds the propylene polymer to the suspension.
5 to 400 parts by weight of vinyl monomer per 100 parts by weight (In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and
_R4 represents an alkyl group having 1 to 4 carbon atoms, and _R5 represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. m is 1 or 2. ) and formula (In the formula, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₇ is a hydrogen atom or a methyl group, R ₈ and
_R9 represents an alkyl group having 1 to 4 carbon atoms, and _R10 represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. n is 0, 1 or 2. ) per 100 parts by weight of vinyl monomer, one or more radical (co)polymerizable organic peroxides represented by
0.1 to 10% by weight of a radical polymerization initiator with a decomposition temperature of 40 to 90°C to obtain a half-life of 10 hours, in a total amount of 100% by weight of the above vinyl monomer and radical (co)polymerizable organic compound. After adding a liquid in which 0.01 to 5 parts by weight of the radical polymerization initiator is dissolved to form an aqueous suspension, the liquid is heated under conditions that do not substantially cause the decomposition of the radical polymerization initiator to dissolve the vinyl monomer. A propylene polymer is impregnated with a radical (co)polymerizable organic peroxide and a radical polymerization initiator, and further contains a free vinyl monomer, a radical (co)polymerizable organic peroxide, and a radical polymerization initiator. When the amount is less than the initial 50% by weight, the vinyl monomer and the radically (co)polymerizable organic peroxide are copolymerized in the propylene polymer by increasing the temperature of this aqueous suspension. The grafted precursor, which is the resulting resin composition, is heated at 100 to 300°C.
This invention relates to a method for producing a grafted resin composition, characterized in that a grafting reaction is carried out by kneading while melting. The propylene polymer used in the present invention is a propylene homopolymer and a copolymer mainly composed of propylene with other α-olefins or polar ethylenically unsaturated monomers (both of which contain 75% by weight propylene).
The above copolymers are preferred. )including. Specifically, for example, isotactic polypropylene, crystalline propylene-ethylene random copolymer, crystalline propylene-ethylene block copolymer, crystalline propylene-butene-1 random copolymer, maleic anhydride-modified polypropylene etc. are representative examples. These propylene polymers can also be used in combination. The shape of this propylene polymer has a particle size of 0.1 mm to
It is preferably in the form of powder or pellets of about 5 mm. It is preferable to use these appropriately depending on the blending ratio of the propylene polymer in the grafting precursor. If the particle size is too large, not only is dispersion difficult during polymerization, but also the time required for impregnation with vinyl monomer etc. is disadvantageous. In the present invention, the vinyl monomer used in producing the grafting precursor specifically refers to vinyl aromatic monomers such as styrene; substituted styrenes such as methylstyrene, dimethylstyrene,
Ethylstyrene, isopropylstyrene, chlorstyrene; α-substituted styrene such as α-methylstyrene, α-ethylstyrene; (meth)acrylic acid ester monomers, such as alkyl esters of (meth)acrylic acid having 1 to 7 carbon atoms ; (meth)acrylonitrile; Vinyl ester monomers, such as vinyl acetate, vinyl propionate, and the like. In addition, vinyl halides or vinylidene (especially vinyl chloride, vinylidene chloride), vinylnaphthalene, vinylcarbazole, acrylamide,
Methacrylamide, maleic anhydride, and other vinyl monomers can also be used, and these may be used alone or in combination of two or more. Among these, particularly preferred are vinyl aromatic monomers and (meth)acrylic acid ester monomers, and it is desirable that at least 50% by weight of either of them is present in the vinyl monomers. In particular, hydrophilic or solid vinyl monomers are preferably used dissolved in oil-soluble monomers. For the preparation of the grafted precursor, the amount of vinyl monomer is from 5 to 400 parts by weight, preferably from 10 to 200 parts by weight, based on 100 parts by weight of propylene polymer. If this amount is less than 5 parts by weight, the grafted product after the grafting reaction becomes difficult to exhibit its performance as a grafted product, although the grafting efficiency is high, which is not preferable. If this amount exceeds 400 parts by weight, some of the vinyl monomer, the radical (co)polymerizable organic peroxide represented by the general formula () or (), and the radical polymerization initiator may be impregnated into the propylene polymer. This is not preferable because the amount of free vinyl homopolymer is 50% by weight or more, which increases the amount of free vinyl homopolymer. According to Japanese Patent Publication No. 58-53003, in the aqueous suspension polymerization method, this free vinyl monomer is
It is said that it is necessary that the amount is less than % by weight. However, since the grafting precursor used in the present invention has a peroxy group in its vinyl polymer molecule and has grafting ability, free vinyl monomer, general formula () or () As long as the total amount of the radical (co)polymerizable organic peroxide and the radical polymerization initiator represented by is 20% by weight or more but less than 50% by weight, sufficiently excellent graftability can be demonstrated. . The radical (co)polymerizable organic peroxide used in the present invention is a compound represented by the above general formula () or (). Specifically, the compounds represented by the general formula () include t-butylperoxyacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethyl carbonate, t-hexylperoxyacryloyloxyethyl carbonate, 1,1,3 , 3-tetramethylbutylperoxyacryloyloxyethyl carbonate, cumylperoxyacryloyloxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t
-Amylperoxymethacryloyloxyethyl carbonate, t-hexylperoxymethacryloyloxyethyl carbonate, 1,1,3,3-
Tetramethylbutylperoxymethacryloyloxyethyl carbonate, cumylperoxymethacryloyloxyethyl carbonate, p-isopropylcumylperoxymethacryloyloxyethyl carbonate, t-butylperoxyacryloyloxyethoxyethyl carbonate, t-amylperoxyacryloyloxyethyl carbonate Ethyl carbonate, t-hexylperoxyacryloyloxyethoxyethyl carbonate, 1,1,3,
3-Tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate, p-isopropylcumylperoxyacryloyloxyethoxyethyl carbonate, t-butylperoxymethacryloyloxyethoxyethyl carbonate, t
- aluminum peroxymethacryloyloxyethoxyethyl carbonate, t-hexylperoxymethacryloyloxyethoxyethyl carbonate,
1,1,3,3-tetramethylbutylperoxymethacryloyloxyethoxyethyl carbonate, cumylperoxymethacryloyloxyethoxyethyl carbonate, p-isopropylcumylperoxymethacryloyloxyethoxyethyl carbonate, t-butylperoxyacryloyloxyisopropyl carbonate, t-amylperoxyacryloyloxyisopropyl carbonate, t-hexylperoxyacryloyloxyisopropyl carbonate, 1,1,3,3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate, cumylperoxyacryloyloxyisopropyl carbonate, p -isopropylcumylperoxyacryloyloxyisopropyl carbonate, t-butylperoxymethacryloyloxyisopropyl carbonate, t
-aluminum peroxymethacryloyloxyisopropyl carbonate, t-hexylperoxymethacryloyloxyisopropyl carbonate, 1,
Examples include 1,3,3-tetramethylbutylperoxymethacryloyloxyisopropyl carbonate, cumylperoxymethacryloyloxyisopropyl carbonate, and p-isopropylcumylperoxymethacryloyloxyisopropyl carbonate. Further, as compounds represented by the general formula (), t-butyl peroxyallyl carbonate, t-aluminum peroxyallyl carbonate,
t-hexyl peroxyallyl carbonate,
1,1,3,3-tetramethylbutylperoxyallyl carbonate, p-menthaneperoxyallyl carbonate, cumylperoxyallyl carbonate, t-butylperoxymethallyl carbonate, t-amylperoxymethallyl carbonate, t-hexylperoxyallyl carbonate carbonate, 1,1,3,3-tetramethylbutylperoxymethallyl carbonate, p-menthane peroxymethallyl carbonate, cumylperoxymethallyl carbonate, t-butylperoxyallyloxyethyl carbonate, t-amylperoxyallyloxyethyl carbonate , t-hexylperoxyallyloxyethyl carbonate, t
-Butylperoxymethallyloxyethyl carbonate, t-amylperoxymethallyloxyethyl carbonate, t-hexylperoxymethallyloxyethyl carbonate, t-butylperoxyallyloxyisopropyl carbonate, t-amylperoxyallyloxyisopropyl carbonate, t-hexylperoxyallyloxyisopropyl carbonate Roxyisopropyl carbonate, t-butylperoxymetallyloxyisopropyl carbonate, t-amylperoxymetallyloxyisopropyl carbonate,
Examples include t-hexylperoxymetallyloxyisopropyl carbonate. Among them, t-butylperoxyacryloyloxyethyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-butylperoxyallyl carbonate,
It is t-butylperoxymethallyl carbonate. The amount of the radical (co)polymerizable organic peroxide used is 0.1 to 10 parts by weight per 100 parts by weight of the vinyl monomer. If the amount used is less than 0.1 part by weight, the resulting grafting precursor of the present invention will have a small amount of active oxygen, making it difficult to exhibit sufficient grafting performance, which is not preferable. In addition, if the amount exceeds 10 parts by weight, it may undergo induced decomposition during polymerization, and a large amount of gel may be generated in the grafting precursor upon completion of polymerization.Although the grafting ability of the grafting precursor increases, at the same time gel This is not preferable because the production capacity may also increase. The radical polymerization initiator used in the present invention is 10
The decomposition temperature to obtain a half-life of 10 hours (hereinafter referred to as the 10-hour half-life temperature) is 40-90℃, preferably 50-90℃.
It is at 75℃. This is because the polymerization in the present invention must be carried out under conditions in which the radical (co)polymerizable organic peroxide used does not decompose at all; This is because the time half-life temperature is 90 to 110°C, so the polymerization temperature must be 110°C or lower. When the 10-hour half-life temperature of the radical polymerization initiator exceeds 90℃, the polymerization temperature becomes high and the radical (co-)
There is a possibility that the polymerizable organic peroxide will decompose during polymerization, which is not preferable. Furthermore, if the temperature is lower than 40°C, polymerization will be initiated during the process of impregnating the propylene polymer with the vinyl monomer, resulting in non-uniform composition of the resulting grafted precursor, which is not preferable. Here, the 10-hour half-life temperature is benzene 1
The temperature at which the decomposition rate of the polymerization initiator reaches 50% when 0.1 mole of the polymerization initiator is added to a liter and 10 hours have passed at a certain temperature. Specific examples of such radical polymerization initiators include diisopropyl peroxydicarbonate (40.5°C), di-n-propyl peroxydicarbonate (40.5°C), dimyristyl peroxydicarbonate (40.9°C), and (2-Ethoxyethyl)peroxydicarbonate (43.4
), di(methoxyisopropyl) peroxydicarbonate (43.5°C), di(2-ethylhexyl) peroxycarbonate (43.5°C), t-hexyl peroxyneodecanoate (44.7°C), di(3-methyl-3-methoxy) butyl) peroxydicarbonate (46.5℃), t-butylperoxyneodecanoate (46.5℃), t-hexylperoxyneohexanoate (51.3℃), t-butylperoxyneohexanoate (53℃)2,
4-dichlorobenzoyl peroxide (53°C),
t-hexyl peroxypivalate (53.2°C),
t-butyl peroxypivalate (55°C), 3,
5,5-trimethylhexanoyl peroxide (59.5°C), octanoyl peroxide (62°C),
lauroyl peroxide (62°C), cumyl peroxyoctoate (65.1°C), acetyl peroxide (68°C), t-butylperoxy-2-ethylhexanoate (72.5°C), m-trioyl peroxide (73°C), Berzoyl peroxide (74℃), t-butylperoxyisobutyrate (78℃), 1,1-bis(t-butylperoxy)
-3,5,5-trimethylcyclohexane (90
°C), etc. (The inside of the box represents the 10-hour half-life temperature.) The amount of radical polymerization initiator used is the total amount of vinyl monomer and radical (co)polymerizable organic peroxide.
0.01 to 5 parts by weight per 100 parts by weight, preferably
It is 0.1 to 2.5 parts by weight. If the amount used is less than 0.01 part by weight, the vinyl monomer and the radical (co)polymerizable organic peroxide will not be completely polymerized, which is not preferable. Moreover, if it exceeds 5 polymerization parts, molecular cleavage of the propylene polymer tends to occur during polymerization, and furthermore, the radical (co)polymerizable organic peroxide becomes susceptible to induced decomposition, which is preferable. Polymerization in the present invention is carried out by a commonly used aqueous suspension polymerization method. Therefore,
A propylene polymer, a separately prepared radical polymerization initiator, and a radical (co)polymerizable organic peroxide are dissolved in advance in a vinyl monomer solution, which can be used for aqueous suspension polymerization. It is stirred and dispersed in water in the presence of a clouding agent such as a water-soluble polymer such as pyrivinyl alcohol, polyvinylpyrrolidone, methylcellulose, etc., or a poorly water-soluble inorganic substance such as calcium phosphate, magnesium oxide, etc. The concentration of the aqueous suspension in this case is arbitrary, but
Generally, the reaction components are used in a proportion of 5 to 150 parts by weight per 100 parts by weight of water. In the present invention, the propylene polymer is preferably impregnated with the solution at as high a temperature as possible. However, when the radical polymerization initiator decomposes during impregnation and starts polymerization, the composition of the resulting grafted precursor becomes very heterogeneous.
It is preferable to carry out the reaction at a temperature lower than the time half-life temperature by at least 5°C. In addition, impregnation is carried out until the free vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator become less than 50% of the initial addition amount.
It should preferably be carried out to less than 20% by weight. If this amount is 50% by weight or more, the grafting ability of the grafting precursor of the present invention will be extremely reduced, which is not preferable. free vinyl monomer,
To determine the total amount of the radical (co)polymerizable organic peroxide and radical polymerization initiator, sample an arbitrary amount of the aqueous suspension, quickly pass it through a wire mesh of about 300 mesh, and combine it with the propylene polymer. It is calculated by separating into a liquid phase and measuring the amounts of vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator in the liquid phase. The polymerization of the present invention is usually carried out at a temperature of 30 to 110°C. This is because the amount of decomposition of the radical (co)polymerizable organic peroxide during polymerization increases, which is not preferable. If this temperature exceeds 110°C and the polymerization time exceeds 5 hours, the amount of radical (co)polymerizable organic peroxide decomposed increases, which is not preferable. Generally, a suitable polymerization time is 2 to 20 hours. In the present invention, the grafting reaction is carried out at a temperature of 100 to 300°C.
This is done by kneading while melting. If this temperature is less than 100°C, the melting will be insufficient and kneading will be difficult, and it will take a long time to decompose the radical (co)polymerizable organic peroxide, which is not preferable. Also. If the temperature exceeds 300°C, molecular cleavage (decomposition) of the grafting precursor occurs, which is not preferable. In the present invention, kneading is necessary to maintain the uniformity of the graft resin composition and to control the particle size of the dispersed phase. In particular, when the temperature of the grafting reaction exceeds 200°C, aggregation of the dispersed phase tends to occur, but this aggregation can be prevented by kneading. The time for the grafting reaction varies depending on the temperature of the grafting reaction, but is generally within 1 hour. <Effects of the Invention> According to the present invention, a grafted resin composition with high grafting efficiency can be obtained easily in a short time and by using an existing kneader. Therefore, compared to those obtained by conventional aqueous suspension polymerization methods, there is less agglomeration of vinyl polymers during secondary processing, making them suitable for adhesives, coatings, modifiers, microdispersion aids, and polymer alloys. Resin compositions useful as agents, functional molded body materials, polymer compatibilizers, etc. are obtained. <Examples> The present invention will be described in more detail below with reference to Examples and Comparative Examples. Example 1 In a stainless steel autoclave with an internal volume of 5,
2500 g of pure water was added, and 2.5 g of polyvinyl alcohol was further dissolved therein as a suspending agent. This contains propylene polymer (product name: ``Sumitomo Noblen'').
W-101”, produced by Sumitomo Chemical Co., Ltd., pellet form) 700
g and stirred to disperse. Separately, 1.5 g of benzoyl peroxide (trade name "Niver B", manufactured by NOF Corporation, 10 hour half-life temperature 74°C) as a radical polymerization initiator, and t-butyl peroxide as a radical (co)polymerizable organic peroxide. 6 g of methacryloyloxyethyl carbonate as a vinyl monomer was dissolved in 300 g of styrene, and this solution was charged into the autoclave and stirred. Next, by heating the autoclave to 60 to 65°C and stirring for 2 hours, the vinyl monomer containing the radical polymerization initiator and the radical (co)polymerizable organic peroxide is impregnated into the propylene polymer. I let it happen. Next, the content of free vinyl monomer, radical (co)polymerizable organic peroxide, and radical polymerization initiator is reduced to 50%.
After confirming that it was less than % by weight, the temperature was raised to 80-85°C and maintained at that temperature for 7 hours to complete polymerization, followed by washing with water and drying to obtain a grafted precursor. This grafted precursor was extracted with ethyl acetate at room temperature for 7 days to obtain a styrenic polymer solution, which was poured into methanol to obtain a white powdery styrene polymer. The amount of active oxygen in this styrene polymer was measured by iodometry and was found to be 0.13% by weight. Furthermore, when this grafted precursor was extracted with xylene using a Soxhlet extractor, no xylene-insoluble matter was present. Next, this grafted precursor was mixed with Labo Plastomill B-75 type mixer (manufactured by Toyo Seiki Seisakusho Co., Ltd.).
The grafting reaction was carried out by kneading at 180° C. for 10 minutes at a rotational speed of 50 RPM. The non-grafted styrene polymer was extracted with ethyl acetate using a Soxhlet extractor using a Soxhlet extractor, and the amount was found to be 9.8% by weight based on the total amount. Therefore, the grafting efficiency of the styrene polymer was calculated to be 67.3% by weight. Furthermore, when extracted with xylene, the xylene insoluble content was 10.3% by weight. (Grafting efficiency refers to the ratio of the grafted styrene polymer to the total polymerized styrene polymer.) Examples 2 to 4 In Example 1, except that the kneading temperature of the grafted precursor was changed as shown in Table 1. carried out a grafting reaction according to Example 1, and measured the grafting efficiency and xylene insoluble content of the styrene polymer.
The results are shown in Table 1.

[Table] Example 5 In Example 1, the kneading machine was changed from Labo Plastomill B-75 type mixer to Banbury type mixer (Co., Ltd.).
(manufactured by Toyo Seiki Seisakusho), and the grafting reaction was carried out in the same manner as in Example 1 except for the following. As a result, the grafting efficiency of the styrene polymer was 70.1% by weight, and the xylene insoluble content was 8.5% by weight. Example 6 In Example 1, the kneader was changed to a single-screw extruder, and the grafting reaction was carried out in the same manner as in Example 1 except for the above. As a result, the grafting efficiency of styrenic polymers
The content was 62.4% by weight, and the xylene insoluble content was 12.5% by weight. Example 7 In Example 1, the respective blending amounts were 500 g of propylene polymer, 2.5 g of benzoyl peroxide, 10 g of t-butylperoxymethacryloyloxyethyl carbonate, and styrene.
A grafting precursor was produced in the same manner as in Example 1, except that the amount was changed to 500 g, and a grafting reaction was performed. As a result, the grafting efficiency of the styrene polymer was 65.3 parts by weight, and the xylene insoluble content was 19.1% by weight. Example 8 A grafting precursor was prepared in the same manner as in Example 1 except that 300 g of styrene was replaced with 300 g of methyl methacrylate, and a grafting reaction was carried out. As a result, the grafting efficiency of the methyl methacrylate polymer was 59.2% by weight, and the xylene insoluble content was 5.7% by weight. Example 9 In Example 1, 300g of styrene was
A grafting precursor was prepared in the same manner as in Example 1, except that a mixed monomer of 210 g and 90 g of acrylonitrile was used, and a grafting reaction was carried out. the result,
The grafting efficiency of the styrene-acrylonitrile copolymer was 51.0% by weight, and the xylene insoluble content was 12.6% by weight. Example 10 In Example 1, 300g of styrene was
A grafting precursor was prepared in the same manner as in Example 1, except that a mixed monomer of 210 g and 90 g of n-butyl acrylate was used, and a grafting reaction was carried out. As a result, the grafting efficiency of styrene-n-butyl acrylate copolymer was 57.7% by weight, and the xylene-insoluble content was
It was 15.0% by weight. Example 11 In Example 1, 300 g of styrene was replaced with 300 g of vinyl acetate, and 6 g of t-butyl peroxymethacryloyloxyethyl carbonate was replaced with 6 g of t-butyl peroxyethyl allyl carbonate, except that the grafting precursor was prepared according to Example 1. A grafting reaction was performed. the result,
The vinyl acetate polymer grafting efficiency was 62.3% by weight, and the xylene insoluble content was 23.1% by weight. Example 12 In Example 1, the propylene polymer was replaced with a powdered propylene polymer (trade name: Flowblen B-
200'' (manufactured by Seitetsu Kagaku Kogyo Co., Ltd.), and the others were as in Example 1.
A grafting precursor was prepared and a grafting reaction was carried out according to the method described in . As a result, the grafting efficiency of the styrene polymer was 71.5% by weight, and the xylene insoluble fraction was 8.9% by weight. Comparative Example 1 A grafted precursor prepared according to Example 1 was heated at 90°C for 1 hour in a Laboplastomill B-
When a grafting reaction was attempted using a Model 75 mixer at a rotational speed of 50 RPM, the system did not melt and could not be kneaded. Further, at that time, the grafting efficiency of the styrene polymer was measured according to Example 1, and as a result, the grafting efficiency was 4.2% by weight, indicating that the reaction was insufficient. Comparative example
2 The grafting reaction was carried out in the same manner as in Example 1, except that the grafting temperature was 320°C. As a result, decomposition of the grafted precursor occurred and coloration of the resin occurred. Comparative Example 3 A grafting precursor was produced according to Example 1 except for excluding t-butylperoxymethacryloyloxyethyl carbonate,
A grafting reaction was performed. As a result, the grafting efficiency of the styrene polymer was 1.9% by weight, and the xylene insoluble content was 0% by weight, clearly confirming the effect of t-butylperoxymethacryloyloxyethyl carbonate.

Claims (1)

[Claims] 1. Suspend water in a propylene polymer, and add 5 to 400 parts by weight of vinyl monomer per 100 parts by weight of the propylene polymer to the suspension. (In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, R ₂ is a hydrogen atom or a methyl group, R ₃ and
_R4 represents an alkyl group having 1 to 4 carbon atoms, and _R5 represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. m is 1 or 2. ) and formula (In the formula, R ₆ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ₇ is a hydrogen atom or a methyl group, R ₈ and
_R9 represents an alkyl group having 1 to 4 carbon atoms, and _R10 represents an alkyl group having 1 to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group, or a cycloalkyl group having 3 to 12 carbon atoms. n is 0, 1 or 2. ) per 100 parts by weight of vinyl monomer, one or more radical (co)polymerizable organic peroxides represented by
Add 0.1 to 10 parts by weight of a radical polymerization initiator whose decomposition temperature is 40 to 90°C to obtain a half-life of 10 hours, and add 100 parts by weight of the above vinyl monomer and radical (co)polymerizable organic compound. After forming an aqueous suspension by adding a liquid in which 0.01 to 5 parts by weight of the radical polymerization initiator is dissolved, the liquid is heated under conditions that do not substantially cause decomposition of the radical polymerization initiator to dissolve the vinyl monomer. A propylene polymer is impregnated with a radical (co)polymerizable organic peroxide and a radical polymerization initiator, and further contains a free vinyl monomer, a radical (co)polymerizable organic peroxide, and a radical polymerization initiator. The amount is the first 50
% by weight, by raising the temperature of this aqueous suspension, a resin obtained by copolymerizing a vinyl monomer and a radical (co)polymerizable organic peroxide in a propylene polymer. 1. A method for producing a graft resin composition, which comprises kneading a grafting precursor composition under melting conditions at 100 to 300°C to cause a grafting reaction. 2 Vinyl monomer is vinyl aromatic monomer, (meth)
The method for producing a graft resin composition according to claim 1, which is one or more selected from the group consisting of acrylic acid ester monomers, (meth)acrylonitrile, and vinyl ester monomers. 3. The method for producing a graft resin composition according to claim 1, wherein at least 50% by weight of the vinyl monomer is a vinyl aromatic monomer. 4. The method for producing a graft resin composition according to claim 1, wherein at least 50% by weight of the vinyl monomer is composed of (meth)acrylic acid ester monomer.