KR910005580B1 - A manufacturing process of the graft resin composition - Google Patents

Abstract

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Description

Process for producing graft resin composition

TECHNICAL FIELD This invention relates to the manufacturing method of the graft resin composition with high graft efficiency useful as an adhesive agent, a coating agent, a modifier, a microdispersion aid, or a polymer-alloying agent, a functional molded material, a polymeric compatibilizer, etc.

Background Art Conventionally, ethylene-based (co) polymers are widely used because of their excellent properties, and their modifications and applications to new applications have also been made.

Conventionally, as an ethylene-based (co) polymer, for example, a low density ethylene polymer has been used as a molding material because of its good moldability and physical and chemical properties of the molded article.

In order to improve the rigidity, dimensional stability method, printability, etc. of the low density ethylene polymer as this molding material, the vinyl polymer, for example, polystyrene etc. is mixed with the low density ethylene polymer.

Moreover, it is well known that an epoxy group containing ethylene copolymer shows favorable adhesive force as an adhesive agent of a metal and a plastic material because of its polarity.

In addition, because of its elastic properties and reactivity, it is also reacted with a condensed polymer, in particular engineering plastics, and has been applied as an impact modifier.

Moreover, since ethylene- (meth) acrylic acid ester copolymer and the (alpha)-olefin-vinyl ester copolymer have the outstanding flexibility, weather resistance, and impact resistance, it is widely used as a molding material, and alpha-olefin-vinyl ester air Coalescing is also widely used for hot melt adhesives. In addition, both copolymers have also been used in recent years as impact modifiers for engineering plastics.

In addition, since ethylene-flopropylene copolymer copolymer rubber or ethylene-propylene-diene copolymer rubber has excellent rubber elasticity, flexibility, cold resistance, and weather resistance, it is mainly used as a rubber material and is also an impact modifier for engineering plastics in recent years. It is also tried to use.

However, the mixing of the ethylene (co) polymer and the vinyl polymer is generally poor in compatibility, so that 10% by weight or more of the vinyl polymer is not blended, and usually 0.2 to 5% by weight of the vinyl polymer is mixed. It was just too. Even in the case where such a small amount of vinyl polymer was mixed, the mixture had a low impact resistance due to the poor resin, and the appearance tended to deteriorate.

Moreover, when using an ethylene-based copolymer as an impact modifier for engineering plastics, there was a problem that the compatibility and dispersibility were low and sufficient impact resistance improvement effects were not obtained.

For example, in the case of an epoxy group containing ethylene copolymer, the application range is limited to the base material which reacts with an epoxy group, For example, with respect to the base material which does not react with an epoxy group, such as a vinyl polymer, sufficient adhesive force cannot be obtained or a base material The dispersing force against was not enough to obtain sufficient impact resistance.

Thus, attempts have been made to increase the usability with engineering plastics.

For example, attempts have been made to increase the usability with engineering plastics by increasing the proportion of (meth) acrylic acid esters and vinyl esters of ethylene- (meth) acrylic acid ester copolymers and α-olefin-vinyl ester copolymers. In addition, functional groups such as epoxy groups, carboxyl groups, and acid anhydride groups are introduced into the copolymer to react with the remaining functional groups of engineering plastics, particularly condensation-based engineering plastics, to improve compatibility and improve impact resistance improvement effects. It is trying.

On the other hand, in order to improve the usability to other resins, it is well-known that the graft copolymer which chemically combined the polymer which has high usability with other resins, and the function which has a function with other resins in one molecule is preferable.

In general, a method of graft bonding a vinyl polymer to an ethylene (co) polymer, wherein an ethylene (co) polymer is obtained by graft polymerizing a vinyl polymer such as a styrene polymer by irradiating ionizing radiation. It has been proposed and this method has shown a significant effect in uniformly dispersing the vinyl polymer in the ethylene (co) polymer.

As another known method, there is a solution graft polymerization method using a solvent such as xylene or toluene, and there is also an emulsion graft polymer.

In addition, impregnation of ethylene (co) polymer particles with a vinyl monomer to polymerize with an aqueous suspension system has also been proposed (JP-A-58-510101, JP-A-58-53003). According to this method, in the resin composition which completed superposition | polymerization, vinyl polymer is mixed uniformly, and it produces the preferable result compared with the method other than this.

However, the conventional method of graft bonding a vinyl polymer to an ethylene (co) polymer has the following problems.

That is, since the method of irradiating ionizing radiation is based on a special method called a radiation graft polymerization method, there is a problem in economy and it is difficult to put it into practical use.

Moreover, as this method, there is a limit to the amount of vinyl monomers to be introduced, which is not preferable.

Next, since the solution graft polymerization method is carried out in the state of dilution in a large amount of solvent in terms of the solubility of the ethylene (co) polymer, the contact between the vinyl monomer, the initiator and the ethylene (co) polymer It is disadvantageous because it has a disadvantage that the opportunity is small and generally the reaction efficiency of vinyl monomer is low, and the post-treatment process such as solvent recovery is complicated.

There is also an emulsion graft polymerization method, but in this case, since the reaction is limited only to the surface reaction of the ethylene (co) polymer particles, there is a drawback that the homogeneity of the product is poor.

Moreover, since the polymerization method in the aqueous suspension system has low graft efficiency of the resin composition obtained by this method, the vinyl polymer particles uniformly dispersed at the time of polymerization completion by heating by secondary processing or contact with a solvent. Secondary aggregation tends to occur, and there has been a problem when the obtained resin composition is used as a microdispersion aid, a polymer-allomer, and a polymer compatibilizer.

MEANS TO SOLVE THE PROBLEM The present inventors obtained the resin composition with the high graft efficiency of these conventional ethylene (co) polymers, and a vinyl polymer, and graft efficiency with respect to the polymer component which forms a dispersed phase in these resin compositions. As a result of the permanent procedure for the purpose of preventing the secondary aggregation of the dispersed phase by the secondary processing, a resin composition having a high graft effect can be obtained remarkably by mixing and kneading a specific graft precursor at a specific temperature. And the present invention was completed.

That is, in the present invention, the grafting reaction is carried out by melting and kneading a grafting precursor obtained by the following method or a mixture of 1 to 99% by weight of the grafting precursor and 99 to 1% by weight of the polymer below at 100 to 300 ° C. It relates to a method for producing a graft resin composition, characterized in that.

With the grafted precursor, 100 parts by weight of an ethylene-based (co) polymer is suspended in water, and about this, separately from the group consisting of a vinyl aromatic monomer, a (meth) acrylic acid ester monomer, a (meth) acrylonitrile and a vinyl ester monomer. One or two or more mixtures of the radical (co) polymerizable organic peroxides represented by the following general formula (I) or (II) are added to 5-400 parts by weight of the selected one or two or more vinyl monomers. A solution in which 0.01 to 5 parts by weight was dissolved with respect to 100 parts by weight of a total of 100 parts by weight of the monomer and the radical (co) polymerizable organic peroxide was added to parts by weight, and heated under conditions where decomposition of the radical polymerization initiator did not substantially occur. Monomers, radical (co) polymerizable organic peroxides and radical polymerization initiators are incorporated into ethylene-based (co) polymers and free vinyl monomers, radicals (co) When the content of the synthetic organic peroxide and the radical polymerization initiator is less than 50 wt% at the initial stage, the temperature of the aqueous suspension is raised, and the vinyl monomer and the radical (co) polymerizable organic monohydrate are added to the ethylene-based (co) polymer. It is a resin composition obtained by copolymerizing.

The radical (co) polymerizable organic peroxide represented by said general formula (I) is a formula

(Wherein 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 R ₄ are each an alkyl group having 1 to 4 carbon atoms, and R ₅ is 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 being 1 or 2.

Moreover, the radical (co) polymerizable organic peroxide represented by general formula (II) is a formula

(Wherein 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 R ₉ are each an alkyl group having 1 to 4 carbon atoms, and R ₁₀ is 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 being 0, 1 or 2.).

The polymer forming a mixture with the grafted precursor is (i) an ethylene-based (co) polymer, (ii) a vinyl aromatic monomer, (meth) acrylic acid ester monomer, (meth) acrylic acid ester monomer, (meth) acrylonitrile and vinyl It is a polymer which consists of either or both of the vinyl polymers obtained by superposing | polymerizing 1 or 2 or more types of vinyl monomers chosen from the group which consists of ester monomers.

As the ethylene-based (co) polymer used in the present invention, for example, an ethylene-based air composed of a low density ethylene polymer, an epoxy group-containing ethylene-based ethylene obtained by copolymerizing ethylene and glycidyl (meth) acrylate, and (meth) acrylic acid ester. Ethylene-propylene copolymer rubber and ethylene-propylene-diene-copolymer rubber composed of copolymer, ethylene and vinyl ester.

The low density ethylene polymer used in the present invention preferably has a density of 0.910 to 0.935 g / cm 3, and specifically, an ethylene homopolymer obtained by a high pressure polymerization method, ethylene and an α-olefin such as propylene for density adjustment. And copolymers with butene-1, pentene-1 and the like.

The shape of this low density ethylene polymer may be pellet form with a particle diameter of 1-5 mm, and may be powder form. It is preferable to use these according to the compounding ratio of the low density ethylene polymer in a grafting precursor. For example, when the low density ethylene polymer in a grafting precursor is 50 weight% or more, use of a pellet form is preferable, and if it is less than 50 weight%, a powder form is preferable.

The epoxy group containing ethylene copolymer used by this invention copolymerizes ethylene and glycidyl (meth) acrylic acid.

At this time, ethylene is preferably from 60 to 99.5% by weight.

The copolymerization ratio of (meth) acrylic acid glycidyl is 0.5 to 40% by weight, preferably 2 to 20% by weight. When the copolymerization amount is less than 0.5% by weight, the effect is not sufficient when used as an impact resistance improver. Moreover, when it exceeds 40 weight%, the fluidity | liquidity at the time of melting will fall and it is unpreferable.

Moreover, when the copolymerization ratio of (meth) acrylic acid glycidyl is less than 40 weight%, vinyl ester monomers, such as (meth) acrylic acid ester monomers, such as methyl (meth) acrylate and ethyl (meth) acrylate, vinyl acetate, and vinyl propionate It is also possible to copolymerize 1 or more types of a vinyl ether monomer, a (meth) acrylonitrile, a vinyl aromatic monomer, carbon monoxide, etc., These are contained in this invention.

The epoxy group-containing ethylene copolymer is specifically, for example, an ethylene / methacrylic acid glycidyl copolymer, an ethylene / vinyl acetate / methacrylic acid glycidyl copolymer, or an ethylene / ethyl acrylate / methacrylic acid glycidyl A copolymer, an ethylene / carbon oxide / glycidyl methacrylate copolymer, an ethylene / glycidyl copolymer, ethylene / vinyl acetate / glycidyl copolymer, etc. are mentioned. Among them, preferred is ethylene / methacrylate glycidyl copolymer.

These epoxy group containing ethylene copolymers can also be mixed and used.

Moreover, it is preferable that the shape of an epoxy group containing ethylene copolymer is a powder or pellet form with a particle diameter of about 0.1-5 m. It is preferable to use these separately according to the compounding ratio of the epoxy group containing ethylene copolymer in a grafting precursor.

When the particle size is excessively large, it is difficult to disperse during polymerization, and there is a drawback in that the time for the addition of vinyl monomers or the like becomes longer.

Specifically, the ethylene- (meth) acrylic acid ester copolymer used in the present invention is an ethylene- (meth) acrylic acid methyl copolymer, an ethylene- (meth) acrylic acid ethyl copolymer, and an ethylene- (meth) acrylic acid butyl aerial. Coalescence is mentioned. Preferably an ethylene-acrylic acid ethyl copolymer.

At this time, ethylene is preferably 50 to 99% by weight.

In the ethylene- (meth) acrylic acid ester copolymer, the (meth) acrylic acid ester copolymerization ratio is 1 to 50% by weight, preferably 2 to 40% by weight. When the copolymerization ratio is less than 1% by weight, the effect is not sufficient when used as an impact resistance improver.

Moreover, when it exceeds 50 weight%, moldability falls and it is not preferable.

Moreover, the shape and compounding ratio of an ethylene- (meth) acrylic acid ester copolymer are the same as that of the said epoxy group containing ethylene copolymer.

The ethylene-vinyl ester copolymer used in the present invention is ethylene and vinyl propionate; Vinyl acetate; Vinyl carboxylic acid; Vinyl caprylate; Vinyl laurate; Vinyl stearate; At least 1 type of vinyl ester monomers, such as a trifluoro vinyl acetate, was copolymerized in presence of a radical polymerization initiator, Preferably it is an ethylene-vinyl acetate copolymer.

The copolymerization ratio of a vinyl ester monomer in an ethylene-vinyl ester copolymer is the same as that of the (meth) acrylic acid ester copolymerization in the said ethylene- (meth) acrylic acid ester copolymer.

Moreover, the shape and compounding ratio of an ethylene-vinyl ester copolymer are the same as that of the said ethylene (meth) acrylic acid ester copolymer.

The ethylene-propylene copolymer rubber or the ethylene-propylene-diene copolymer rubber used in the present invention has an ethylene content of 40 to 80% by weight, 60 to 29% by weight of propylene, and an ethylene-flophylene having a viscosity of 15 to 90. Copolymer rubber and ethylene content are 40 to 80 weight%, propyrene is 60 to 20 weight%, ethylidedenol bolene; 1,4-hexidaene; As a rubber obtained by tertiary copolymerization of dicyclopentadiene and the like as a non-conjugated diene component, it is appropriate that the content of the diene is 4 to 30 by iodide, and the Ni-free viscosity is 15 to 120.

In addition, a viscosity-free viscosity is the value calculated | required by JISK6300 (100 degreeC). These ethylene-propylene copolymer rubber or ethylene-propylene-diene copolymer rubber can also be mixed and used.

In order to facilitate the impregnation of the vinyl monomer and to prevent agglomeration during suspension polymerization, the ethylene-propylene copolymer rubber or the ethylene-propylene-diene copolymer rubber particles have a narrow particle size distribution and pellets having an average particle diameter of about 2 to 8 mm. It is preferable.

If the particle size is excessively large, it is also difficult to disperse during polymerization, and there is a drawback in that the reaction time is long because the impregnation rate of the vinyl monomer is slowed.

Specifically, the vinyl monomer used in this invention is a vinyl aromatic monomer, for example, styrene; Hexyl substituted styrene such as methyl styrene dimethyl styrene; Ethyl styrene; Isopropylstyrene; Chlorstyrene; α-substituted styrenes such as α-methylstyrene; α-ethylstyrene; (Meth) acrylic acid ester monomers, for example, alkyl esters having 1 to 7 carbon atoms of (meth) acrylic acid; (Meth) acrylonitrile; Vinyl ester monomers such as vinyl propionate; Vinyl acetate vinyl acetate; Vinyl caprylate; Vinyl laurate; Vinyl stearate; Trifluoro vinyl acetate etc. are mentioned.

In addition, vinyl halide to vinylidene (in particular, vinyl chloride and vinylidene chloride), vinyl garbazole, acrylamide, methacrylamide, maleic anhydride, and the like can also be used, and can be used alone or in combination of two or more thereof. do.

Among these, preferred are vinyl aromatic monomers and (meth) acrylic acid ester monomers.

When these are especially used as impact resistance improvement products of engineering plastics, it is preferable that (co) polymerized the mixture containing 50 weight% or more of a vinylaromatic monomer or a (meth) acrylic acid ester monomer. This is because compatibility with engineering plastics is good.

Moreover, it is preferable to melt | dissolve and use a hydrophilic or solid vinyl monomer in a oil-soluble monomer especially.

The quantity of a vinyl monomer is 5-400 weight part with respect to 100 weight part of ethylene-type (co) polymers in manufacture of a grafting precursor, Preferably it is 10-200 weight part.

If the amount is less than 5 parts by weight, the grafting precursor after the grafting reaction is not preferable because the grafting precursor is only high in graft efficiency and hardly exhibits the performance as a grafting precursor.

Moreover, when this amount exceeds 400 weight part, the thing which was not impregnated with the ethylene-type (co) body among the radical (co) polymerizable organic peroxide and radical polymerization initiator represented by a vinyl monomer, general formula (I) or (II). It is not preferable because it is easy to be 50% by weight or more and the amount of the free vinyl homopolymer increases.

According to Japanese Unexamined Patent Application Publication No. 58-51010 or Japanese Unexamined Patent Application Publication No. 58-5300, in the aqueous suspension polymerization method, it is required that this free vinyl monomer is less than 20% by weight.

However, in the present invention, the resulting grafted precursor has a peroxy group in the group vinyl-based polymer molecule and has a grafting ability, and thus is represented as a free vinyl monomer, general formula (I) or (II). If the total amount of the radical (co) polymerizable organic peroxide and the radical polymerization initiator is 20% by weight or more but less than 50% by weight, it is possible to exhibit sufficiently good graftting ability.

The radical (co) polymerizable organic peroxide used in the present invention is a compound represented by the general formula (I) or (II).

Specifically, as a compound represented by general formula (I), it is t-steel peroxy acryloxy hydroxy ethyl carbonate; t-amyl peroxy acryloxy oxyethyl carbonate; t-hexyl peroxy acryloxy oxy carbonate; 1,1,3,3-tetra methyl butyl peroxy acryloxyoxy ethyl carbonate; Kmil peroxy acrylooxy ethyl carbonate, p-isopropyl kmil peroxy acrylooxy ethyl carbonate; t-butyl peroxy methacrylo oxy ethyl carbonate; t-amyl peroxy methacrylo oxy ethyl carbonate; t-hexyl peroxy methacrylo oxyenyl carbonate; 1,1,3,3-petra methyl butyl peroxy methacrylooxyethyl carbonate; Kmil peroxy methacrylo oxy ethyl carbonate; p-isopropylchmil peroxy methacrylo oxy ethyl carbonate; t-butyl peroxy acryloxy ethoxy ethyl carbonate; t-yl peroxy acryloxy ethoxy ethyl carbonate; t-hexyl peroxyacrylooxy ethoxy ethyl carbonate; 1,1,3,3-tetra methyl butyl peroxy methacryloxy ethoxy ethyl carbonate; Kmil peroxy methacrylo oxy ethoxy ethyl carbonate; p-isopropyl kmil peroxy acryloxy ethoxy ethyl gaborate; t-butyl peroxy acryloxy isopropyl carbonate; t-amyl peroxy acryloxy isopropyl carbonate; t-hexyl peroxy acryloxy isopropyl carbonate; 1,1,3,3-tetra methyl butyl peroxy acryloxy isopropyl carbonate; Kmil peroxy acryloxyoxy isopropyl carbonate; p-isopropyl xyl peroxy acryloxy hydroxy isopropyl carbonate, etc. can be illustrated. Moreover, as a compound represented by general formula (II), t-butyl peroxy aryl carbonate; t-amyl peroxy aryl carbonate; t-hexyl peroxy aryl carbonate; 1,1,3,3-tetra methyl butyl peroxy aryl carbonate; p-mentane peroxy aryl carbonate; Kmil peroxy aryl carbonate; t-butyl peroxy metharyl carbonate; t-amyl peroxy metharyl carbonate; t-hexyl peroxy metharyl carbonate; 1,1,3,3-tetra methyl butyl peroxy metharyl carbonate; p-mentane peroxy metharyl carbonate; Kmil peroxy metharyl carbonate; t-butyl peroxy alioxy ethyl carbonate; t-amyl peroxy alioxy ethyl carbonate; t-hexyl peroxy alioxy ethyl carbonate; t-butyl peroxy methacryloxy ethyl carbonate; t-amyl peroxy methacryloxy ethyl carbonate; t-hexyl peroxy methacryloxy ethyl carbonate; t-butyl peroxy alioxy isopropyl carbonate; t-amyl peroxy alioxy isopropyl carbonate; t-hexyl peroxy alioxy isopropyl carbonate; t-butyl peroxy methacryloxy isopropyl carbonate; t-amyl peroxy methacryloxy isopropyl carbonate; t-hexyl peroxy methacryloxy isopropyl carbonate etc. can be illustrated.

Among them, t-butylperoxy acryloxy hydroxy ethyl carbonate; t-butyl peroxy methacrylo oxy ethyl carbonate; t-butyl peroxy aryl carbonate; t-butyl peroxy metharyl carbonate. The use amount of this radical (co) polymerizable organic peroxide is 0.1-10 weight part with respect to 100 weight part of vinyl monomers.

If the amount used is less than 0.1 part by weight, the amount of active oxygen contained in the grafted precursor used in the present invention to be produced is small, and it is difficult to exert sufficient grafting ability, which is not preferable.

When the amount exceeds 10 parts by weight, the radical (co) polymerizable organic peroxide undergoes induced decomposition during polymerization, and a large amount of gel is generated in the grafting precursor at the time of polymerization warming, or the grafting ability of the grafting precursor is increased. At the same time, the gel formation ability is also increased.

In the present invention, the radical polymerization initiator used to prepare the grafted precursor has a decomposition temperature (hereinafter referred to as a 10 hour half life temperature) of 40 to 90 ° C., preferably 50 to 75 ° C., for obtaining a half life of 10 hours. .

This is because the polymerization in the production of the grafted precursor in the present invention must be carried out under conditions in which the radical (co) polymerizable organic peroxide used does not decompose at all, while the radical (co) polymerizable organic peroxide itself It is because a 10-hour half life temperature is 90-110 degreeC, and it must be 110 degrees C or less as polymerization temperature.

When the 10-hour half-life temperature of the radical polymerization initiator exceeds 90 ° C., the polymerization temperature is high, and there is a possibility that the radical (co) polymerizable organic peroxide decomposes during the polymerization, which is not preferable.

Moreover, if it is less than 40 degreeC, superposition | polymerization will start in the process of impregnating an ethylene crab (co) polymer in a vinyl monomer, and since it will bring the uniformity of the grafted precursor produced | generated, it is unpreferable.

Here, the half-life temperature for 10 hours refers to the temperature at which the decomposition rate of the polymerization initiator becomes 50% when 0.1 mole of the polymerization initiator is added to 1 L of benzene and 10 hours elapses at a certain temperature.

As such a radical polymerization initiator, For example, Diisopropyl peroxy dicarbonate (40.5 degreeC); Di-n-propyl peroxy dicarbonate (40.5 ° C.); Dimyristyl peroxy dicarbonate (40.9 ° C.); Di (2-ethoxyethyl) peroxy dicarbonate (43.4 ° C.); Di (methoxy isopropyl) peroxy dicarbonate (43.5 ° C.); Di (2-ethylhexyl) peroxy dicarbonate (43.5 ° C.); t-hexyl peroxy neodecanoate (44.7 ° C.); Di (3-methyl-3-methoxy butyl) peroxy dicarbonate (46.5 ° C.); t-butyperoxy neodecanoate (46.5 ° C.); t-hexyl peroxy neohexaoate (51.3 ° C.); t-butyl peroxy neohexaoate (53 ° C.); 2,4-dichloro benzoyl peroxide (53 ° C.); t-hexyl peroxy pivalate (53.2 ° C.); Butyl peroxy pivalate (55 ° C.); 3,5,5-trimethyl hexanoyl peroxide (59.5 ° C.); Octanoyl peroxide (62 ° C.); Lauryl peroxide (62 ° C.); Kmil peroxyoctoate (65.1 ° C.); Acetyl peroxide (68 ° C.); t-butyl peroxy-2-ethylhexanoate (72.5 ° C.); m-toluoyl peroxide (73 ° C.); Benzoyl peroxide (74 ° C.); t-butyl peroxyisobutylate (78 ° C.); And 1,1-bis (t-butyl peroxy) -3,5,5-trimethyl cycloexoic acid (90 ° C) and the like (indicated by the brackets for 10 hours half-life temperature).

The usage-amount of a radical polymerization initiator is 0.01-5 weight part with respect to a total of 100 weight part of a vinyl monomer and a radical (co) polymerizable organic peroxide, Preferably it is 0.1-2.5 weight part.

If this amount is less than 0.01 part by weight, the polymerization of the vinyl monomer and the brittle (co) polymerizable organic peroxide is not completely performed and is not preferable. Moreover, when it exceeds 5 weight part, since the intermolecular crosslinking of an ethylene-type (co) polymer becomes easy to occur during superposition | polymerization, and radical (co) polymerizable organic peroxide will become easy to cause induced decomposition, it is unpreferable.

The polymerization for producing the grafted precursor in the present invention is performed by an aqueous suspension polymerization method which is generally performed.

Therefore, a suspending agent which can be used for aqueous suspension polymerization can be used for the aqueous suspension polymerization of an ethylene-based (co) polymer, a radical polymerization initiator and a radical (co) polymerizable organic peroxide previously adjusted separately from the vinyl monomer. For example, water-soluble polymers, such as polyvinyl alcohol, polyvinyl pyrrolidone, methyl cellulose and the like, or poorly water-soluble inorganic substances such as calcium phosphate, magnesium oxide and the like are stirred and dispersed in water.

Although the density | concentration of the aqueous suspension in this case is arbitrary, reactive content is generally performed in the ratio of 5-150 weight part with respect to 100 weight part of water.

In the present invention, the impregnation of the solution in the ethylene-based (co) polymer is preferably performed at a high temperature as much as possible.

However, if the radical polymerization initiator decomposes at the time of impregnation to start the polymerization, the composition of the resulting grafted precursor becomes very heterogeneous, and therefore is generally 5 ° C. or more lower than the 10 hour half-life temperature of the radical polymerization initiator used. It is preferable to carry out at temperature.

In addition, the total amount of the free vinyl monomer, the radical (co) polymerizable organic peroxide, and the radical polymerization initiator after impregnation should be less than 50% by weight, preferably less than 20% by weight based on the total amount of the initial use. If this amount is 54 weight% or more, since the grafting capability of the grafting precursor in this invention falls extremely, it is unpreferable.

The amount of free vinyl monomers, radical (co) polymerizable organic peroxides and radical polymerization initiators sampled arbitrary amounts of the aqueous suspension and quickly filtered them using a wire mesh of about 300 meshes to form an ethylene-based (co) polymer and It isolate | separates into a liquid phase and measures and computes the quantity of the vinyl monomer, radical (co) polymerizable organic peroxide, and radical polymerization initiator in a liquid phase.

Superposition | polymerization for manufacturing the grafting precursor in this invention is performed at the temperature of 30-110 degreeC normally. This is to prevent decomposition of the radical (co) polymerizable organic peroxide during polymerization as much as possible.

When this temperature exceeds 110 degreeC, when the polymerization time becomes 5 hours or more, the amount of decomposition of radical (co) polymerizable organic peroxide increases, which is not preferable.

Generally as polymerization time, 2 to 20 hours are suitable.

Moreover, the grafting precursor in this invention must contain 0.01-0.73 weight% of the vinyl polymer mixed in it as a small amount of active acid.

If the amount of active oxygen is less than 0.01% by weight, the grafting ability of the grafting precursor is extremely reduced, which is not preferable. Moreover, when it exceeds 0.73 weight%, the gel production capacity at the time of grafting becomes high and it is also unpreferably similar.

In this case, the small amount of active acid can be calculated by extracting the vinyl polymer from the grafted precursor by solvent extraction, and obtaining the small amount of the active acid of the vinyl polymer by iodine titration.

In the graft resin composition of the present invention, a grafting reaction occurs by melting and kneading the grafting precursor alone or a mixture of the grafting precursor and the polymer below at a specific temperature to obtain a graft resin composition. .

In the present invention, the polymer forming the mixture with the grafted precursor is preferably the same as that used for the production of the grafted precursor, and a polymer composed of either or both of an ethylene-based (co) polymer or a vinyl polymer. to be.

For example, when the ethylene polymer in the grafting precursor is a low density ethylene polymer, the monomer composition or density is preferably the same.

If the monomer composition or density is different, the kneading is likely to be insufficient, and the mechanical strength and appearance of the obtained graft resin composition may deteriorate, which is not preferable.

In the case of other ethylene (co) polymers, the same monomer composition is preferable for the same reason.

In the present invention, the vinyl polymer forming a mixture with the grafted precursor is, among the vinyl monomers used for the production of the grafted precursor, specifically, a vinyl aromatic monomer such as styrene, nuclear substituted styrene, for example methyl. Styrene, dimethyl styrene, ethyl styrene, isopropyl styrene, chlor styrene, α-substituted styrene such as α-methyl styrene, α-ethyl styrene; (Meth) acrylic acid ester monomers, for example, alkyl esters having 1 to 7 carbon atoms of (meth) acrylic acid; (Meth) acrylonitrile; It is a polymer obtained by superposing | polymerizing 1 type, or 2 or more types, such as a vinyl ester monomer, for example, vinyl acetate, a vinyl propionate.

Preferably, the vinyl polymer in the graft precursor is the same as the monomer composition, and when the monomer composition is different, the kneading is likely to be insufficient as described above, and the mechanical strength and appearance of the obtained graft resin composition may be weakened. There is possibility, and it is not desirable.

When used as a mixture, the kraft resin composition of this invention consists of 1 to 99 weight% of grafting precursors, and 99 to 1 weight% of the polymer kneaded to it.

If the grafting precursor is less than 1% by weight, that is, the kneaded polymer is more than 99% by weight, the amount of the graft body in the graft resin composition is small, which is not preferable because it causes layered peeling.

In the manufacture of the graft resin composition of the present invention, the graft reaction is carried out by melting and kneading at 100 to 300 ° C.

If this temperature is less than 100 DEG C, melting is insufficient, kneading is difficult, and long time is required for decomposition of radical (co) polymerizable organic peroxide in the grafted precursor, which is not preferable.

Moreover, when it exceeds 300 degreeC, it is necessary for the maintenance of the uniformity of a graft resin composition, and the immersion fish of a dispersed phase.

In the present invention, the kneading is necessary for maintaining the uniformity of the graft resin composition and for entering the morphology of the dispersed phase.

In particular, when the temperature of the grafting reaction at the time of manufacture of the graft resin composition exceeds 200 ° C, aggregation of the dispersed phase easily occurs, but this aggregation can be prevented by kneading.

Although the time of the grafting reaction at the time of manufacture of a graft resin composition differs with the temperature of a grafting reaction, it is generally within 1 hour.

Heating melt and kneading | mixing for a grafting reaction are performed using an extruder, an injection molding machine, a mixer, etc., for example.

According to the present invention, the graft resin composition can be obtained in a short time easily and by using an existing kneader, and the change of the kneading ratio may be simply changed by the compounding ratio.

In addition, the graft resin composition obtained by the present invention has a higher content of the graft body than that of a conventional product, so that agglomeration of the vinyl polymer by secondary processing is small, and an adhesive, a coating agent, a modifier, a microdispersion aid, and a poly A graft resin composition useful as a maralloy agent, a functional molded material, a polymer compatibilizer, and the like is obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1

Into a 5 liter stainless steel autoclave, 2500 g of pure water was added, and 2.5 g of polyvinyl alcohol was dissolved as a suspending agent. Into this, 700 g of a low density ethylene polymer having a density of 0.925 g / cm 3 (trade name "Sumikasen G-401", manufactured by Sumidomo Chemical Co., Ltd., Japan, having a particle diameter of 3 to 4 mm) was added thereto, and stirred and dispersed. Separately, 1.5 g of a benzoyl peroxide (brand name "Nipa-B", a Japanese oil and fat company, 10-hour half-life temperature 74 degreeC) as a radical polymerization initiator, t- as a radical (co) polymerizable organic peroxide 6 g of butyl peroxy methacrylo oxyethyl carbonide was dissolved in 300 g of styrene as a vinyl monomer, and the solution was charged into the autoclave and stirred.

Subsequently, the autoclave was heated to 60 to 65 ° C. and stirred for 1 hour while the vinyl monomer containing the radical polymerization initiator and the radical (co) polymerizable organic peroxide was impregnated into the low density ethylene polymer. Subsequently, after confirming that the content of the free vinyl monomer, the radical (co) polymerizable organic peroxide and the radical polymerization initiator is less than 50% by weight in the initial stage, the temperature is raised to 80 to 85 ° C, and 7:00 is maintained at that temperature. The polymerization was completed, washed with water and dried to obtain a grafted precursor.

A small amount of active acid of the styrene polymer in the grafted precursor was measured by iodine titration and found to be 0.13% by weight. In addition, xylene insolubles were not present when the grafted precursor was extracted by xylene with a Soxhlet extractor.

Subsequently, this grafting precursor was kneaded for 10 minutes at a rotation speed of 50 RPM at 180 ° C. using a Labo Plasto and a B-75 type mixer (manufactured by DONGYANG ELECTRIC CORPORATION CO., LTD.) To perform a grafting reaction. . About this graft-forming reaction, the styrene-type polymer which is not grafted with ethyl acetate was extracted with the Soxhlet extractor, and it was 3.3 weight% with respect to the total amount. Therefore, the graft efficiency of the styrene polymer was calculated to be 89% by weight.

In the extraction with xylene, xylene insoluble content was 17.5 wt%, and the xylene insoluble content was analyzed by pyrolysis gas chromatography. As a result, the low density ethylene polymer styrene polymer was 79.0 wt%; It was 21.0 weight%.

Example 2-4

In Example 1, except that the kneading temperature of the grafting precursor is changed as shown in Table 1, the grafting reaction was carried out in accordance with Example 1, and the graft efficiency and the xylene insoluble content of the styrene polymer were measured.

TABLE 1

Example 5

In Example 1, the kneader was changed from a Labo Plastomil B-75 mixer to a Banbury mixer (manufactured by Toyo Electric Co., Ltd.), and others were grafted according to Example 1.

As a result, the graft efficiency of the styrene polymer was 86% by weight, and 15.6% by weight of xylene insoluble content.

Example 6

In Example 1, the kneader was changed to a single-screw extruder (manufactured by Toyo Electric Co., Ltd.), and others were grafted according to Example 1.

As a result, the graft efficiency of the styrene-based polymer was 80% by weight and xylene insoluble content was 20% by weight.

Example 7

In Example 1, 500 g of low-density ethylene polymers, 2.5 g of benzoyl peroxide, 2.5 g of t-butyl peroxy methacrylic, and 10 g of hydroxyethyl carbonate were changed to 500 g of styrene, and the rest were carried out. In accordance with Example 1, a grafting precursor was produced and a grafting reaction was performed. As a result, the graft efficiency of the styrene polymer was 82% by weight, and the xylene insoluble content was 23% by weight.

[Example 8]

In Example 1, 300 g of styrene was changed to 300 g of methyl methacrylate, and the rest of the grafted precursor was prepared in accordance with Example 1, and the graft reaction was performed.

As a result, the graft efficiency of the methyl methacrylate polymer was 64% by weight, and the xylene insoluble content was 22% by weight.

Example 9

In Example 1, 300 g of styrene was changed to a mixed monomer of 210 g of styrene and 90 g of acrylonitrile, and the rest was prepared in accordance with Example 1 to prepare a grafted precursor, and a grafting reaction was performed.

As a result, the graft efficiency of the styrene-acrylonitrile copolymer was 58% by weight, and xylene insoluble content was 28% by weight.

Example 10

In Example 1, 300 g of styrene was changed to a mixed monomer of 210 g of styrene and 90 g of acrylic acid-n-butyl, and the rest was prepared in accordance with Example 1 to prepare a grafted precursor, and a grafting reaction was performed.

As a result, the graft efficiency of the styrene-acrylic acid-n-butyl copolymer was 62% by weight, and xyl insoluble content was 23% by weight.

Example 11

In Example 1, 300 g of styrene was changed to 300 g of vinyl acetate, 6 g of t-butyl peroxy methacrylo oxyethyl carbonate to 6 g of t-butyl peroxy aryl carbonate, respectively, The grafting precursor was prepared accordingly, and the grafting reaction was performed. As a result, the graft efficiency of the vinyl acetate polymer was 69% by weight and xylene insoluble content was 29% by weight.

Example 12

In Example 1, the low-density ethylene polymer was changed to a powdered low-density ethylene polymer (trade name "Pro-Sen G-401", manufactured by Nippon Steel Co., Ltd., density 0.925 gcm 3), and the rest was changed to Example 1 The grafting precursor was prepared accordingly, and the grafting reaction was performed. As a result, the graft efficiency of the styrene-based polymer was 85% by weight and 13% by weight of xylene insoluble content.

Comparative Example 1

When the grafting precursor prepared according to Example 1 was grafted at a rotational speed of 50 RPM using a Labo Plastomil B-75 mixer at 90 ° C. for 1 hour, the system did not melt. Without kneading.

In addition, the graft efficiency of the styrene polymer was measured in accordance with Example 1 at that time, and the graft efficiency was insufficient at 8% by weight.

Comparative Example 2

In Example 1, the graft reaction was performed according to Example 1 except having graft-ized temperature in 320 degreeC.

As a result, decomposition of the grafted precursor occurred and coloring of the resin occurred.

Comparative Example 3

In Example 1, the grafted precursor was produced according to Example 1 without using oxyethyl carbonate as t-butyl peroxy methacrylic, and the grafting reaction was performed.

As a result, the graft efficiency of the styrene polymer was 7% by weight, 3% by weight of xylene insoluble content, and the effect of t-butyl peroxy methacrylo hydroxyethyl carbonate was clearly confirmed.

Example 13

50 g of the granulated precursor prepared in Example 1 and 50 g of a granular low density ethylene polymer having a density of 0.925 g / cm 3 were added and mixed well at room temperature, and kneaded in accordance with Example 1 except that this mixture was used. The graft reaction was carried out to obtain a graft resin composition. About the graft resin composition, it was 72 weight% as a result of calculating | requiring the graft-to-efficiency of a styrene polymer according to Example 1.

Moreover, xylene insoluble content was 9.7 weight%.

Subsequently, this graft resin composition was press-molded at 200 ° C. to prepare a plate having a thickness of 2 mm. Its appearance was uniform white and no phase separation was recognized. Moreover, when the board was broken, the filling peeling was also not certified.

Example 14-17

In Example 13, the graft resin composition was prepared according to Example 13 except that the blending ratio of the grafted precursor and the low density ethylene polymer was changed as shown in Table 2.

Table 2 shows the graft efficiency of the styrene polymer of the graft resin composition, the xylene insoluble content, and the appearance of the plate press-molded at 200 ° C.

TABLE 2

Example 18-20

In Example 13, the kneading temperature was changed as shown in Table 3, and the rest was prepared in accordance with Example 13 to prepare a graft resin composition. Table 3 shows the graft efficiency of the styrene polymer of the graft resin seed, the xylene insoluble content and the appearance of the plate press-molded at 200 ° C.

TABLE 3

Example 21

In Example 13, the kneader was changed from the Labo Plastomil B-75 mixer to the Banbury mixer used in Example 5, and the rest of the graft resin composition was prepared according to Example 13. No phase separation or delamination was observed on the plate press-formed at 78 ° C and graft efficiency 78% by weight of the styrene-based polymer of the graft resin composition, 9.2% by weight of xylene insoluble content.

Example 22

In Example 13, the graft resin composition was prepared in accordance with Example 13 except that the kneader was changed to the single screw extruder used in Example 6. No phase separation or delamination was observed on the plate press-molded at 68 ° C, 13.1% by weight of xylene insoluble content, and styrene-based polymer of the graft resin composition.

Example 23

In Example 13, except that low-density ethylene was used as the kneaded material, 50% of a styrene polymer (trade name "Dialex HF-55", manufactured by Mitsubishi Monsanto Chemical Co., Ltd.) as a vinyl polymer was used in Example 13 The graft resin composition was prepared accordingly.

Since the graft resin composition is considered to be a matrix of styrene-based polymers, it is considered that it is preferable to obtain the graft efficiency of the low density ethylene polymer, but unfortunately, there is no suitable measuring means. Therefore, the graft efficiency of the styrene polymer with respect to the low density ethylene polymer was calculated | required according to Example 1. As a result, the graft efficiency of the styrene polymer was 20% by weight and the xylene insoluble content was 2.8% by weight. In addition, no phase separation or delamination was observed on the plate formed by molding the graft resin composition according to Example 13.

Example 24-27

In Example 23, the mixing amount of the grafted precursor and the styrene polymer was changed as shown in Table 4, and the rest of the raft resin composition was prepared in accordance with Example 13. Table 4 shows the graft efficiency of the styrene polymer of the graft resin composition, the xylene insoluble content, and the appearance of the plate press-molded at 200 ° C.

In addition, as shown in Examples 26 and 27, when the styrene-based polymer is matrixed, the graft efficiency of the styrene-based polymer to the low-density ethylene polymer is low in calculation, but the low-density ethylene polymer in the dispersed phase is applied to the styrene-based polymer. It seems to be grafted with considerably high efficiency.

TABLE 4

[Examples 28-31]

In Example 13, 700 g of low density ethylene polymer used for preparing the grafted precursor was 500 g, 300 g of styrene, 500 g, 1.5 g of benzoyl peroxide, 2.5 g, t-butyl peroxy methacrylo oxyethyl 6 g of carbonate was changed to 1 g, and the rest was prepared in accordance with Example 13 to prepare a graft and a precursor. Subsequently, the amount of the grafted precursor mixed with the low density ethylene polymer and the styrene polymer was changed as shown in Table 5, and the rest of the graft resin composition was prepared according to Example 13. Table 5 shows the graft efficiency of the styrene polymer of the graft resin composition in terms of xylene insoluble content and a plate press-molded at 200 ° C.

TABLE 5

Example 32-36

In Example 13, the grafting precursor was produced according to Example 13 except that 300 g of styrene was changed to methacrylic acid and 300 g of methyl, and 0.6 g of n-dodecyl mercaptan was further used as the molecular weight regulator. The amount of the grafted precursor-density ethylene polymer and methyl methacrylate polymer (trade name "Derfat 50", manufactured by Asahi Kasei Kogyo Co., Ltd.) was changed as shown in Table 6, and the rest was grafted according to Example 13. Resin composition was prepared. The test results are shown in Table 6.

TABLE 6

[Examples 31 to 41]

In Example 13, a grafting precursor was prepared according to Example 13 except that instead of 300 g of styrene, a mixed monomer of 210 g of styrene, 90 g of acrylonitrile, and 0.6 g of m-dodecyl mercaptan as a molecular weight regulator was used. . Separately, a mixed solution of 70 g of styrene, 30 g of acrylonitrile, 0.2 g of n-dodecyl mercaptan and 0.5 g of benzoyl peroxide was added to 500 g of a 1% polyvinyl alcohol aqueous solution, and maintained at a temperature of 80 to 85 ° C for 7 hours. The polymerization was completed and acrylonitrile-styrene copolymer was obtained. The mixing amount of the copolymer, the grafting precursor and the low density ethylene polymer prepared earlier was changed as shown in Table 7, and the rest of the graft resin composition was prepared according to Example 13. The test results are shown in Table 7.

TABLE 7

Example 42

In Example 13, a grafting precursor was produced in accordance with Example 13 except that 300 g of styrene was changed to a mixed monomer of 210 g of methyl methacrylate and 90 g of acrylate-n butyl. Next, using the graft-formation precursor 50g and the low-density ethylene polymer 50g, the graft resin composition was prepared in accordance with Example 13. As a result, the graft efficiency of the metamethyl-acrylic acid-n-butyl copolymer was 8.9 wt% for the 62 wt% xylene insoluble content. Moreover, according to Example 13, phase separation and filling peeling were not recognized by the press-molded board.

Example 43

In Example 13, except that 300 g of styrene was changed to 300 g of vinyl acetate, and 6 g of t-butyl peroxy methacrylo oxyethyl carbonide was changed to 6 g of t-butyl peroxy aryl carbonate. The grafted precursor was prepared accordingly. Next, using the graft-formation precursor 50g and the low-density polymer 50g, the graft resin composition was prepared in accordance with Example 13.

In addition, graft efficiency was measured by changing the extraction solvent from ethyl acetate to methanol in Example 13. As a result, the graft efficiency of the vinyl acetate polymer was 73% by weight and the xylene insoluble content was 16.3% by weight. Moreover, phase separation and layer peeling were not recognized by the plate press-formed according to Example 13.

Example 44

In Example 13, a grafted precursor was prepared. Subsequently, as a low density ethylene polymer kneaded and kneaded, 50 g of a trade name "Sumikasen G-201" (density 0.919 g / cm 3, manufactured by Sumidomo Chemical Co., Ltd.) was mixed with 50 g of a grafted precursor, A graft resin composition was prepared in accordance with Example 13. At this time, the graft efficiency of the styrene polymer was 74% by weight, and the xylene insoluble content was 9.8% by weight. In addition, in the plate press-formed according to Example 13, phase separation was not observed, but a slight layer peeling phenomenon was observed on the fracture surface.

[Comparative Example 4]

A grafted precursor was prepared in accordance with Example 13. Subsequently, 0.5 g of this grafting precursor, 50 g of low-density ethylenic polymer, and 49.5 g of "Diarex HF-55" used in Example 23 were mixed to prepare a graft resin composition according to Example 13. At this time, the graft efficiency of the styrene polymer was 0.3% by weight, and the xylene insoluble content was 0.1% by weight. Moreover, the phase-separated shape was seen in the board press-formed according to Example 13, and the large layer peeling phenomenon also occurred in the fracture surface.

[Comparative Example 5]

In Example 13, the grafting reaction was attempted according to Example 13 except that the kneading temperature of the grafting precursor and the polymer was set at 90 ° C. However, melt training was impossible because of the low kneading temperature.

Comparative Example 6

In Example 13, the grafting reaction was performed in accordance with Example 13 except that the kneading temperature of the grafting precursor and the polymer was 320 ° C. As a result, the graft resin composition obtained by decomposition of the resin during the grafting reaction was colored brown.

Comparative Example 7

In Example 13, the grafting reaction was performed in accordance with Example 13 except that the grafting precursor was prepared without using hydroxyethyl carbonate with t-butyl peroxy methacrylic. As a result, the graft efficiency of the styrene polymer was 7% by weight and the xylene insoluble content was 2.8% by weight. However, in the plate press-formed according to Example 13, some phase separation was seen, and large layer peeling phenomenon appeared at the fracture surface. That is, the effect of t-butyl peroxy methacrylo oxy ethyl carbonide which is a radical (co) polymerizable organic peroxide was confirmed clearly.

[Examples 45-49]

Instead of the ethylene (co) polymer for kraft-ized precursor in Example 1, various ethylene-based (co) polymers shown in Table 8 were used, respectively, and the time for impregnation was changed from 1 hour to 2 hours, respectively. Each grafting precursor was obtained in the same manner as in Example 1 except that the polymerization temperature at the time of preparation of the grafting precursor was also changed to the temperature shown in Table 8.

For these grafted precursors, extraction was performed for 7 days at room temperature with ethyl acetate to obtain a styrene polymer solution, and the mixture was charged with methane to obtain a white powdery styrene polymer.

The amount of active oxygen of this styrene polymer is measured according to Example 1, and the results are shown in Table 8.

Next, xylene insolubles are measured and the results are shown in Table 8.

In addition, the grafting reaction was performed in accordance with Example 1 using these grafting precursors.

For each of the obtained graft resin compositions, the graft efficiency and the xylene insoluble content of the styrene polymer were measured in accordance with Example 1, and the results are shown in Table 8.

In addition, graft efficiency shows the ratio of the grafted polystyrene with respect to total polymerization polystyrene.

TABLE 8

Note 1: Ethylene group-containing ethylene copolymer (ethylene-methacrylate glycidyl copolymer, glycidyl methacrylic content 15% by weight, pellet form)

Note 2: Ethylene-acrylic acid ethyl copolymer (trade name "Niseki Rexlon EEAA-4200" manufactured by Nippon Petrochemical Co., Ltd., 20% by weight ethyl acrylate, pellet form)

Note 3: Ethylene-vinyl acetate copolymer (trade name "Niseki Rexlon Ever V-270" manufactured by Nippon Petrochemical Co., Ltd., vinyl acetate content 15% by weight, pellet form)

Note 4: Ethylene-propylene-diene copolymer rubber (trade name "Mitsui Elastoma K-9720", Mitsui Petrochemical Co., Ltd., Ni-free viscosity (ML 1 + 4,100 ° C) 40 Iodide 22, pellet shape)

Note 5: Ethylene-propylene copolymer rubber (trade name "Mitsui EDP # 0045", Mitsui Petrochemical Co., Ltd., Ni-free viscosity (ML 1 + 4,100 ℃) 40

[Examples 50-53]

In each of the grafting precursors obtained in the middle of Examples 45-48, except that the kneading temperature was changed at 180 ° C. as shown in Table 9, the grafting reaction was carried out according to Example 1, and each of the styrene polymers was used. The graft efficiency of and xylene insolubles were measured. The results are shown in Table 9.

TABLE 9

Note 6: Grafting Precursor (Used Ethylene Copolymer)

Example 45 Epoxy Group-Containing Ethylene Copolymers

Example 46 Use of Ethylene-Ethyl Acrylate Copolymer

Example 47 Use of Ethylene-Vinyl Acetate Copolymer

Example 48 Use of Ethylene-Propylene-Diene Rubber

[Examples 54 to 57]

The grafting reaction was carried out in accordance with Example 1 except that each of the grafting precursors obtained in the middle of Examples 45-48 was used, and the kneading machine was changed to a kneader shown in Table 10 in a Labo Plastomil B-75 mixer. Each graft resin composition was obtained.

About each, the graft efficiency and xylene insoluble content of a styrene polymer are measured, and the result is shown in Table 10. FIG.

TABLE 10

Note 6: see table 9

Note 7: Kinds of kneader

① Banbury type mixer

② → Single Screw Extruder

[Examples 58-61]

In Example 1, the respective compounding amounts of benzoyl peroxide, t-butylperoxy oxymethylooxy ethyl carbonate, and respective ethylene-based (co) polymers of styrene used to prepare the grafted precursor The grafting precursors were prepared in the same manner as in Table 11, with the remainders prepared in Example 1 respectively.

The graft resin composition was obtained in accordance with Example 1 using grafting precursors, respectively.

About each of these graft resin compositions, the graft efficiency microstyrene insoluble content of a styrene polymer was measured according to Example 1, and the result is shown in Table 11.

TABLE 11

Note 1 ~ 4: Refer to the table

[Examples 62-73]

In Example 1, a grafting precursor was prepared according to Example 1 except that styrene was changed as shown in Table 12 as an ethylene-based (co) polymer using the grafting precursor, and then each grafting precursor was prepared. In accordance with Example 1, a graft resin composition was obtained.

For each of the obtained graft resin compositions, the graft efficiency and the xylene insoluble content of the styrene polymer were measured in accordance with Example 1, and the results are shown in Table 12.

TABLE 12

Note 8: Specifically shown in Table 8.

① low density ethylene polymer

② Ethylene Group-Containing Ethylene Copolymer

③ Ethylene-ethyl acrylate copolymer

④ ethylene-vinyl acetate copolymer

⑤ Ethylene-propylene-diene copolymer

Note: Styrene-based (MMA) (co) polymer is a styrene-based polymer methacrylate-based polymer

Styrene-acrylonitrile copolymer or styrene-acrylic acid nbutyl copolymer

EXAMPLE 74-77

In Example 1, except for changing the ethylene (co) polymer of styrene and t-butyl peroxy methacryloxyethyl carbonate used to manufacture the grafted precursor as shown in Table 13, The grafted precursor was prepared accordingly.

The graft resin composition was obtained in accordance with Example 1 using each of the grafted precursors.

About each of these graft resin compositions, the graft efficiency and xylene insoluble content of a vinyl acetate polymer are measured by the method according to Example 1, and the result is shown in Table 13.

TABLE 13

EXAMPLES 78-80

In Example 1, the low-density ethylene polymer as the ethylene-based (co) polymer using the grafted precursor in the preparation was used in the epoxy group-containing ethylene copolymer in Example 78, the ethylene-acrylic acid ester copolymer in Example 79, and In Example 80, the grafting reaction was carried out in accordance with Example 1 except that the ethylene-vinyl acetate copolymer was freeze-pulverized and powdered to obtain each graft resin composition.

As a result, the graft efficiency and the xylene insoluble content of the styrene polymer were as shown in Table 14.

TABLE 14

Example 81

A grafted precursor was prepared in accordance with Example 45 except that the epoxy group-containing ethylene copolymer of Example 45 was changed to 82 wt% of ethylene, 12 wt% of glycidyl methacrylate, and 6 wt% of vinyl acetate to prepare a grafted precursor. The reaction was performed.

As a result, the graft efficiency of the styrene polymer was 19.5% by weight of 79.5 xylene insoluble content.

Example 82

In Example 46, the ethylene-acrylic acid copolymer was replaced with a copolymer composed of 95% by weight of ethylene and 5% by weight of ethyl acrylate (trade name "Nisse selex Rexlon EEA A-3050", manufactured by Nippon Shoyu Chemical Co., Ltd.). Prepared a grafting precursor in accordance with Example 46, and performed a grafting reaction.

As a result, the graft efficiency of the styrene polymer was 76.7% by weight and 18.8% by weight of xylene insoluble content.

Example 83

In Example 47, it carried out except having changed the ethylene-acrylic-acid copolymer into the copolymer which consists of 72 weight% of ethylene, and 28 weight% of vinyl acrylate (brand name "Everfrax 260", Japan Mitsui Polychemical Co., Ltd. product). In accordance with Example 47, a grafting precursor was produced and a grafting reaction was performed.

As a result, the graft efficiency of the styrene polymer was 84.8 wt% and the xylene insoluble content was 27.4 wt%.

[Comparative Examples 8-11]

When the grafting precursor prepared according to Examples 45 to 49 was attempted at a rotational speed of 50 RPM using a Labo Plasto Mill B-75 mixer at 90 ° C. for 1 hour, the system did not melt. Not trained

In addition, when the graft efficiency of the styrene polymer was measured according to Example 1, the graft efficiency was 6.2% by weight in Comparative Example 8, 3.1% by weight in Comparative Example 9 and 2.7% by weight in Comparative Example 10. Insufficient reaction.

[Comparative Examples 12-15]

In Example 1, except the temperature of the grafting reaction was changed to 320 ° C, the grafting precursor was decomposed according to Comparative Example 8-11, and coloring of the resin occurred.

[Comparative Examples 16 ~ 19]

In Examples 45-48, without using oxyethyl carbonate with t-butylperoxy oxymethacryl, the remainder was prepared according to Examples 45-48, respectively, and the grafting reaction is performed. It was.

As a result, in the epoxy group-containing ethylene copolymerization system of Comparative Example 16, the graft efficiency of the styrene-based polymer was 3.2% by weight and xylene insoluble content 0% by weight. In Comparative Example 17 using the ethylene-acrylic acid ethyl copolymer, the styrene-based polymer It is 1.2 weight% of grapto efficiency, 0 weight% of xylene insolubles, and in the comparative example 18 of an ethylene-vinyl acetate copolymer system, it is 1.9 weight% of graft efficiency of a styrene polymer, 0 weight% of xylene insolubles, and ethylene-propylene In Comparative Example 19 using a diene copolymer rubber system, the grafting efficiency of the styrene polymer was 1.9% by weight xylene insoluble content of 0% by weight, and the effect of t-butyl peroxymethaclear clearoxy ethyl carbonate was clearly observed.

[Examples 84-88]

Except for adding 50 g of the ethylene copolymer shown in Table 15 to the granular material 50 g of the various grafting precursors obtained in Examples 45 to 49, the grafting reaction was carried out in accordance with Example 13 to obtain each graft. The resin composition was obtained.

About each of these graft resin compositions, the graft efficiency and the xylene insoluble content were measured by the method according to Example 1, and the result is shown in Table 15.

Subsequently, the boards of thickness 2mm similar to Example 13 were created using these graft resin compositions, respectively. As a result, all of them were uniform white and phase separation was not recognized.

In addition, the delamination was not recognized as the plate was broken.

TABLE 15

Note 9: Refer to note 1 to 5 in table 8.

[Examples 89-92]

In Examples 84 to 87, the amounts of the grafting precursor for producing the graft resin composition and the ethylene-based (co) polymer were changed as shown in Tables 16 to 19, respectively. The graft resin composition was prepared.

About the obtained graft resin composition, the graft efficiency and xylene insoluble content of a styrene polymer were measured according to Example 1, and the external appearance of the press-formed board at 200 degreeC is shown to 16-19, respectively. .

TABLE 16

TABLE 17

TABLE 18

TABLE 19

[Examples 93 to 96]

In Examples 84 to 87, a graft resin composition was prepared according to Examples 84-87 except that the kneading temperature was changed at 180 ° C as shown in Table 20, respectively. The graft efficiency and insoluble content of each styrene polymer are measured, and the external appearance of the board | substrate press-formed at 200 degreeC is shown in Table 20. FIG.

TABLE 20

[Examples 97-100]

In Examples 84 to 87, except that the kneader was changed to a kneader shown in Table 21 from the Labo Plastomil B-75 mixer, the graft reaction was carried out according to Examples 84-87, and the respective graft resin compositions were Got it.

The characteristics of each graft resin composition and the appearance of the press-formed plate are shown in Table 21.

TABLE 21

Note 7: Kinds of kneader

① Banbury type mixer

② Single Screw Extruder

[Examples 101 to 104]

In Examples 84 to 87, except that a styrene polymer (trade name "Dynaprex HF-55" Japan Mitsubishi Simon Tokasei Co., Ltd. product) was used as the vinyl polymer instead of the grafted precursor and the ethylene-based (co) polymer. According to 84-87, the graft resin compositions were obtained, respectively.

The characteristics of each of the graft resin compositions and the outer appearance of the press-formed plate are shown in Table 22.

Table 22

Note 10: Since each graft resin composition is considered to be a matrix of styrene-based copolymers, it is considered that it is preferable to obtain the graft efficiency of the ethylene-based copolymer, but since there is no measuring means, an ethylene-based copolymer of styrene-based polymer The graft efficiency for was obtained.

Examples 105 to 108

In Examples 101 to 104, the graft resin compositions were prepared according to Examples 101 to 104 except that the amounts of the grafted precursor and the styrene polymers were changed as shown in Tables 23 to 26, respectively.

About each obtained graft resin composition, the graft efficiency and xylene insoluble content of a styrene polymer were measured according to Example 1, and the outer space of the board formed by press molding at 200 degreeC is shown in Tables 23-26, respectively. .

TABLE 23

TABLE 24

TABLE 25

TABLE 26

In addition, as can be seen in the grafted precursor 1 styrene polymer = 25/75 and 5/95 shown in Tables 23 to 26, the grafting efficiency of the styrene polymer with respect to the ethylene copolymer when the styrene polymer is used as a matrix Although it is calculated as a low thing, it is thought that the ethylene-type copolymer which is a dispersion layer is grafted to the styrene-type polymer at a very high rate.

[Examples 109-112]

In Examples 84 to 87, 700 g of ethylene-based copolymer used for preparing the grafted precursor was 50 g, 300 g of styrene, 500 g, 1.5 g of benzoyl peroxide, 2.5 g, and t-butylperoxy metachlorooxy Except having changed 6 g of ethyl carbonates into 9 g, each graft-formation precursor was produced according to Example 84-87.

Subsequently, the mixing amount of the grafted precursor, the ethylene copolymer and styrene was changed as shown in Tables 27 to 30, and the rest was obtained in accordance with the polymerization 84 to 87 to obtain a graft resin composition.

About each of these graft resin compositions, graft efficiency and xylene insoluble content were measured by the method according to Example 1, and the external appearance of the board press-formed at 200 degreeC is shown in Table 27-30.

TABLE 27

Note 1: The ethylene copolymer used for grafting precursor manufacture is the same as that of the epoxy group containing ethylene copolymer used for a mixture, and is the same as the note 1 of Table 8.

TABLE 28

Note 2: The ethylene-based copolymer used for producing the grafted precursor is the same as the ethylene-ethyl acrylate copolymer used for the mixture, and is the same as Note 2 in Table 8.

TABLE 29

Note 3: The ethylene-based copolymer used for producing the grafted precursor is the same as the ethylene-vinyl acetate copolymer used for the mixture, and is the same as Note 3 in Table 8.

TABLE 30

Note 4: The ethylene-based copolymer used for producing the grafted precursor is the same as the ethylene propylene-diene copolymer rubber used for the mixture, and is the same as Note 4 in Table 8.

Examples 113 to 116

In Examples 84 to 87, grafting was performed in accordance with Examples 84 to 87 except that styrene used for grafting precursor production was changed to metal methacrylate and 0.6 g of n-dodecyl mercaptan was further used as a molecular weight regulator. Each precursor precursor was prepared, respectively.

Examples 84-87 except having changed the mixing amount with each graft-formation precursor ethylenic body and the methyl methacrylate polymer (brand name "derfat 50N" Japan Asahi Kasei Co., Ltd. product) were changed as Table 31-34. According to the graft resin composition was prepared.

The results are shown in Tables 31 to 34.

Table 31

Note 1: Refer to Table 27

Table 32

Note 2: Refer to Table 28

Table 33

Note 3: Refer to Table 29

Table 34

Note 4: Refer to Table 30

Examples 117 to 120

In Examples 84 to 87, except that 300 g of styrene was changed to a mixed monomer of 210 g of styrene and 90 g of acrylonitrile, and 0.6 g of n-dodecyl mercaptan was further used as a molecular weight regulator. Each precursor precursor was prepared, respectively.

Separately, a mixed solution of 70 g of styrene, 30% of acrylonitrile, 0.2 g of n-dodecyl mercaptan and 0.5 g of benzoyl peroxide was added to 500 g of a 1% polyvinyl alcohol aqueous solution, and maintained at a temperature of 80 to 85 for 7 hours. The polymerization was completed and acrylonitrile-styrene copolymers were obtained respectively.

A graft resin composition was obtained in accordance with Examples 84-87, except that the amount of the copolymer blended with the previously produced grafted residue and ethylene copolymer was changed as in Tables 35 to 38.

The results of the obtained graft resin compositions are shown in Tables 35 to 38, respectively.

Table 35

Note 1: Refer to Table 27

TABLE 36

Note 2: Refer to Table 28

Table 37

Note 3: Refer to Table 39

TABLE 38

Note 4: Refer to Table 30

[Examples 121-124]

In Examples 84 to 87, graft precursors were prepared in accordance with Examples 84 to 87, except that 300 g of styrene was mixed with a mixed monomer of 210 g of ethyl methacrylate and 90 g of n-butyl acrylate.

Subsequently, graft resin compositions were obtained in accordance with Examples 84-87 using 50 g of these graft precursors and 50 g of the ethylene copolymers shown in the following table, respectively.

Table 39 shows the results of each obtained graft resin composition.

TABLE 39

Note 1 ~ 4: Refer to Table 8

[Examples 125-128]

Examples 84 to 87 except that 300 g of styrene was changed to 300 g of vinyl acetate, and 6 g of t-butyl peroxy methacryloxyethyl carbonate was changed to 6 g of t-butylperoxyaryl carbonate, respectively. According to ˜87, the grafted precursors were prepared, respectively.

Subsequently, the graft resin composition was obtained according to Examples 84-87 using 500 g of these grafting precursors and 50 g of ethylene copolymers, respectively, similar to those used for the grafting precursors.

The graft extraction solvent was measured by changing from ethyl acetate to methanol, and the results are shown in Table 40.

TABLE 40

Example 129

A grafted precursor was prepared in accordance with Example 84. Subsequently, as the epoxy group-containing ethylene copolymer kneaded with the grafted precursor, 50 g of a copolymer made of 82% by weight of ethylene, 12% by weight of glycidyl methacrylate and 6% by weight of vinyl acetate was used, and 50g of a grafted precursor was used. By mixing, a graft resin composition was prepared in accordance with Example 84.

At this time, the graft efficiency of the styrene polymer was 55.5 wt% and 14.5 wt% of xylene insoluble content. In addition, although phase separation was not recognized in the press-formed plate according to Example 84, some lamellar peeling was recognized in the single-layered surface.

Example 130

In Example 85, a copolymer of ethylene-acrylic acid ethyl copolymer with 95% by weight of ethylene and 5% by weight of ethyl acrylate (trade name "Niseki Rexlon EEA A-3050", manufactured by Nippon Shoku Chemical Co., Ltd. A graft resin composition was prepared in accordance with Example 85 except for replacing with. As a result, it was 49.5 weight% of graft efficiency and 9.7 weight% of xylene insoluble content.

Example 131

In Example 86, except that the ethylene-vinyl acetate copolymer was replaced with a copolymer of 72% by weight of ethylene and 28% by weight of vinyl acetate (trade name "Ever Frex 260", manufactured by Mitsui Polyca., Ltd.) A graft resin composition was prepared in accordance with Example 86. As a result, it was 53.5 weight% of graft efficiency and 10.5 weight% of xylene insoluble content.

[Comparative Example 20 ~ 23]

A grafted precursor was prepared in accordance with Examples 84 to 87. Subsequently, 0.5 g of each of the grafted precursors and 50 g of the same ethylene-based copolymer as used in the preparation of the respective grafted precursors and 49.5 g of the styrene polymers similar to those used in Example 101 were mixed, and Example 84. A grafted resin composition was prepared in accordance with -87. At this time, the graft efficiency of the styrene-based polymer is 0.3% by weight, 0.4% by weight, 0.9% by weight, 0.7% by weight sequentially from Comparative Example 20, the xylene insoluble content, respectively, 0.1% by weight, 0.4% by weight, 0.3 wt% and 0.2 wt%. All of the plates formed by press molding showed phase separation, and large delamination occurred on the fracture surface.

[Comparative Examples 24 ~ 27]

In Examples 84-87, the grafting reaction was attempted according to Examples 84-87 except that the kneading temperature of the grafting precursor and the ethylene-based copolymer was 90 deg. However, melt kneading was impossible because the kneading temperature was low.

[Comparative Examples 28-31]

In Examples 84 to 87, the grafting reaction was carried out in accordance with Examples 84 to 87, except that the kneading temperature of the grafting precursor and the ethylene-based copolymer was 320 ° C. As a result, any of the resins decomposed during the grafting reaction, and the obtained resin composition was colored brown.

[Comparative Examples 32-35]

In Examples 84 to 87, the graft reaction was carried out in accordance with Examples 84 to 87, except that graft precursors were prepared without using t-butyl peroxy methacrylo oxyethyl carbonide, respectively. It was done. As a result, the graft efficiency of the styrene polymer was 0.1% by weight, 0% by weight, 0.2% by weight and 0% by weight, respectively, sequentially from Comparative Example 32, and all of the xylene insolubles were 0% by weight. In addition, in the press-formed plate, all of the phase separation was observed, and in the fracture surface, all of the large layer peeling phenomena appeared.

From this day, the effect of t-butyl peroxy methacrylooxyethyl carbonate, which is a radical (co) polymerizable organic peroxide, was clearly observed.

Claims (16)

The grafting reaction obtained by the following method or a mixture of 1 to 99% by weight of the grafting precursor and 99 to 1% by weight of the polymer described below is grafted by kneading at 100 to 300 ° C while kneading and kneading. Method for producing a graft resin composition. The grafted precursor is 100 parts by weight of an ethylene-based (co) polymer is suspended in water, and, in contrast, selected from the group consisting of vinyl aromatic monomers, (meth) acrylic acid ester monomers, (meth) acrylonitrile, and vinyl ester monomers. 100 parts by weight of one or two or more kinds of a mixture of one or two or more of the radical (co) polymerizable organic peroxides represented by the following general formula (I) or (II) is used in 5 to 400 parts by weight of one or two or more vinyl monomers. 0.01 to 10 parts by weight, and a radical polymerization initiator having a decomposition temperature of 40 to 90 ° C. to obtain a half-life of 10 hours, 0.01 to 100 parts by weight of the total of the vinyl monomer and the radical (co) polymerizable organic peroxide. A solution obtained by dissolving ˜15 parts by weight is added and heated under conditions where decomposition of the radical polymerization initiator does not substantially occur, and a vinyl monomer, a radical (co) polymerizable organic peroxide and When the decal polymerization initiator is impregnated into the ethylene-based (co) polymer, and the total amount of the free vinyl monomer, the radical (co) polymerizable organic peroxide and the radical polymerization initiator is less than 50% by weight of the first, the temperature of the aqueous suspension It is a resin composition obtained by raising and copolymerizing a vinyl monomer and a radical (co) polymerizable organic peroxide in ethylene-type (co) polymerization. The radical (co) polymerizable organic peroxide represented by said general formula (I) is a formula

(Wherein 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 R ₄ are each an alkyl group having 1 to 4 carbon atoms, R ₅ is an alkyl group having 1 to 12 carbon atoms, a phenyl group, An alkyl substituted phenyl group or a C3-C12 cycloalkyl group is shown, m is 1 or 2. It is a compound represented by these. Moreover, the radical (co) polymerizable organic peroxide represented by said general formula (II) is a formula

(Wherein 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 R ₄ are each an alkyl group having 1 to 4 carbon atoms, R ₅ is an alkyl group having 1 to 12 carbon atoms, a phenyl group, An alkyl substituted phenyl group or a C3-C12 cycloalkyl group is shown, m is 1 or 2. It is a compound represented by these. Moreover, the radical (co) polymerizable organic peroxide represented by said general formula (II) is a formula

(Wherein 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 R ₉ are each an alkyl group having 1 to 4 carbon atoms, R ₁₀ is an alkyl group having 1 to 12 carbon atoms, a phenyl group, An alkyl substituted phenyl group or a C3-C12 cycloalkyl group is represented, m is 0.1 or 2. It is a compound represented by these. The polymer forming a mixture with the grafted precursor is 1 selected from the group consisting of (1) an ethylenic (co) polymer, (2) vinyl aromatic monomers, (meth) acrylic acid ester monomers, (meth) acrylonitrile and vinyl ester monomers. Either of the vinyl polymers obtained by superposing | polymerizing a species or 2 or more types of vinyl monomers is a polymer of both. The method of claim 1, wherein the ethylene polymer is a low density ethylene polymer having a density of 0.910 0.935 g / cm 3. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer is an epoxy group-containing ethylene copolymer obtained by copolymerizing ethylene and glycidyl (meth) acrylate. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer is an epoxy group-containing ethylene copolymer obtained by copolymerizing 60 to 99.5% by weight of ethylene and 0.5 to 40% by weight of glycidyl (meth) acrylate. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer is made of ethylene and (meth) acrylic acid ester. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer comprises 50 to 99% by weight of ethylene and 50 to 1% by weight of (meth) acrylic acid ester. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer is made of ethylene and vinyl ester. 8. The process according to claim 7, wherein the vinyl ester vinyl acetate is a graft resin composition. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer comprises 50 to 99% by weight of ethylene and 50 to 1% by weight of vinyl ester. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer is an ethylene-propylene copolymer rubber. The method for producing a graft resin composition according to claim 1, wherein the ethylene copolymer is an ethylene-propylene-diene copolymer rubber. The method for producing a graft resin composition according to claim 1, wherein the monomer composition of the ethylene-based (co) polymer kneaded into the grafting precursor is the same as that of the monomer composition of ethylene and (co) polymer in the grafting precursor. The method for producing a graft resin composition according to claim 1, wherein the density of the low density ethylene polymer kneaded into the grafting precursor is the same as that of the low density ethylene polymer in the grafting precursor. The manufacturing method of the graft resin composition of Claim 1 in which 50 weight% or more of the vinyl monomers used for manufacture of a grafting precursor consist of vinyl aromatic monomers. The manufacturing method of the graft resin composition of Claim 1 in which 50 weight% or more of the vinyl monomer used for manufacture of a grafting precursor consists of a (meth) acrylic acid ester monomer. The method for producing a graft resin composition according to claim 1, wherein the monomer composition of the vinyl polymer kneaded into the grafting precursor is the same as the monomer composition of the vinyl polymer in the grafting precursor.