JPS63270739A - Production of graft copolymer - Google Patents

Abstract

PURPOSE:To produce a graft copolymer excellent in balance among heat resistance, mechanical properties and good flow, by reacting a specified active vinyl (co)polymer with a polyarylene ether sulfone in a polar organic solvent. CONSTITUTION:An alkali phenolate of a bisphenol [e.g., 2,2-bis(4-hydroxyphenyl) propane] is condensed with an aromatic dihalogen compound (e.g., 4,4'- dichlorodiphenyl sulfone) to obtain a polyarylene ether sulfone (B) terminated with a phenolic hydroxyl group or an alkali phenolate group. 1-99pts.wt. active vinyl (co)polymer (B) having 0.05-30wt.% at least one functional group in the side chain, selected from among acid halide, glycidyl, halomethyl and sulfonyl halide groups (e.g., P-chloromethylstyrene copolymer) is reacted with 99-1pt.wt. component B at room temperature to 200 deg.C in a polar organic solvent (e.g., dimethyl sulfoxide).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a graft copolymer comprising polyarylene ether sulfone (hereinafter abbreviated as aromatic polysulfone) and a vinyl polymer. More specifically, the purpose of the present invention is to provide a plastic material that is well-balanced in heat resistance, mechanical properties, and good fluidity.

Aromatic polysulfone is a thermoplastic material with excellent heat resistance, mechanical properties, and electrical properties.Because of these properties, it is used as an engineering plastic for electrical and electronic parts,
It is partially used in aircraft parts, automobile parts, sanitary food equipment parts, etc. However, aromatic polysulfone is still an expensive material and, moreover, does not necessarily have sufficient molding fluidity, so it has not been adopted on a full scale for single parts that require economic efficiency.

Therefore, various methods have been proposed for blending aromatic polysulfone with other general-purpose thermoplastic resins that are inexpensive and have good fluidity, such as vinyl polymers (for example,
Special Publication No. 46-37896, Special Publication No. 46-3790
Publication No. 5, Japanese Patent Publication No. 31095, Japanese Patent Publication No. 1973
However, these blends of aromatic polysulfone and vinyl polymer are based on the premise of simple melt blending; It forms an island-separated structure, and the excellent heat resistance properties of aromatic polysulfone are particularly important in compositions in which vinyl polymer constitutes the sea component (compounds in which the vinyl polymer portion is quantitatively predominant). For example, aromatic polysulfony/(tJc
"tJdel P-1,700" manufactured by c company) and ASvI
4 fat (styrene/acrylonitrile 76/24 weight ratio copolymer) BSS ripening temperature of the composition obtained by simple melt blending in an extruder British Standard B527
82-102C) i, t20/80fi quantity mixing ratio is 10
At 8°C and a 40/60 weight mixing ratio, the temperature is only about 120°C. This value is higher than aromatic polysulfone ("
BSS aging temperature of 185℃ and As (styrene/acrylonitrile 76/
24 weight ratio copolymer) BSS aging temperature of resin 102
This value is much lower than the value calculated from °C additivity and is unsatisfactory.

Furthermore, a method has been proposed in which a vinyl monomer is polymerized in the presence of a simple aromatic polysulfone for the purpose of graft copolymerizing a vinyl monomer onto an aromatic polysulfone. For example, a method for producing aromatic polysulfone-vinyl chloride copolymer (Japanese Patent Publication No. 46-21216),
Examples include a method for producing an aromatic polysulfone-vinyl monomer copolymer (Japanese Patent Publication No. 47-23665).

However, in these methods, it is difficult to carry out the graft reaction effectively because the vinyl monomer itself does not have a functional group that can react with a phenol group or an alkali phenolate group. That is, the method described in Japanese Patent Publication No. 47-23665 has a too low grafting rate, and the method described in Japanese Patent Publication No. 46-21216 is not effective, especially when graft polymerizing vinyl monomers other than vinyl chloride. It is difficult to carry out a graft reaction.

Therefore, the present inventors conducted intensive studies on a method for more effectively grafting aromatic polysulfone and vinyl polymer to obtain a graft copolymer with an excellent balance of heat resistance, mechanical properties, and good fluidity. , vinyl polymer ll1
The inventors have discovered that the above object can be achieved very effectively by introducing a specific grafting active site into the I chain and using this to perform a polymer grafting reaction, and have thus arrived at the present invention.

That is, the present invention provides l! 0.05 to 30% by weight of a functional group selected from an acid halide group, an acid anhydride group, a glycidyl group, a halomethyl group, and a sulfonyl halide group in the I chain.
! Alternatively, a graft copolymer characterized by reacting an activated vinyl polymer or copolymer (A) having two or more types with an aromatic polysulfone (B) having a phenolic hydroxyl group or an alkali phenolate group at the terminal in a polar organic solvent. A method for producing a polymer is provided.

In the present invention, by introducing the above-mentioned specific active sites into the vinyl polymer or copolymer used in advance, the graft copolymerization reaction can proceed efficiently and the desired properties can be achieved. A graft copolymer can be obtained. Therefore, hereinafter, for convenience, the vinyl polymer or copolymer into which the above-mentioned active sites have been introduced will be referred to as an activated vinyl (co)polymer.

The graft copolymerization reaction of the present invention proceeds efficiently by a method of reacting the active group of the activated vinyl (co)polymer with the terminal end (phenolic hydroxyl group or alkali phenolate group) of the aromatic polysulfone, and the resulting graft copolymerization reaction The polymer has the desired properties. Therefore, hereinafter, for convenience, the reaction of the present invention will be referred to as a polymer graft reaction.

The aromatic polysulfone to be subjected to the polymer grafting reaction of the present invention is obtained by subjecting an alkali phenolate group and an aromatic halogen group activated with an electron-withdrawing sulfone group to a condensation reaction in a non-10-ton polar solvent. It is a linear polymer in which the essential bonding units are arylene bonds (aromatic bonds), ether bonds, and sulfone bonds. Specifically, (1) a method in which an alkali phenolate of bisphenols is subjected to a condensation reaction with an aromatic dihalide having a sulfone bond in the molecule, or (2) an alkali of an aromatic halophenol having a sulfone bond in the molecule. It is a polymer obtained by polymerizing phenolate by any of the methods of subjecting it to a self-condensation reaction.

Examples of bisphenols used in method (1) above include:
For example, hydroquinone, resorcinol, bis-(hydroxyphenyl) alkanes, e.g. 2,2-bis-(
4-hydroxyphenyl)propane, 214-monodihydroxydiphenylmethane, bis-(4-hydroxyphenyl)methane, bis-(2-hydroxyphenyl)methane, bis-(4-hydroxy-2,6-dimethyl-3-
methoxyphenyl)methane, 1.1-bis-(4-hydroxyphenyl)ethane, 1.2-bis-(4-hydroxyphenyl)ethane, 1.1=bis-(4-hydroxy-2-chlorophenyl) ) ethane, 2,2-bis-(4
-hydroxynaphthyl)propane, 2,2-bis-(4
-hydroxyphenyl)pentane, 3,3-bis-(4
-hydroxyphenyl)pentane, 2,2-bis-(4
-hydroxyphenyl)hebutane, bis-(4-hydroxyphenyl)phenylmethane, bara-α, α-bis(4-hydroxyphenyl)-bara-diisopropylbenzene, etc.; di(hydroxyphenyl)ethers, e.g. -(4-hydroxyphenyl)ether, 4
, 3--14.2--12.2--1213'-dihydroxydiphenyl ether, 4,4'-dihydroxy-
2,6-dimethyldiphenyl ether, bis-(4-hydroxynaphthyl) ether, etc. di(hydroxyphenyl) sulfone, e.g. bis-(4-hydroxyphenyl) sulfone, bis-(3-hydroxyphenyl)
sulfone, 2,4-dihydroxyphenyl sulfone,
Bis-(3-hydroxyphenyl)sulfone, 2.4-
Further examples thereof include analogs thereof having three or more phenyl nuclei, such as monodihydroxydiphenyl sulfone.

These bisphenols having inert substituents introduced into the benzene nucleus such as alkyl groups of 01 to C9, aromatic or aralkyl groups of 06 to CI8, and ether groups of 01 to CI2 can also be used. These bisphenols may be used alone or in a mixture of 2N or more.

Further, the aromatic dihalides used in the above method (1) include, for example, 4,4'-dichlorodiphenylsulfone, 4,4-difluorodiphenylsulfone, 4,4'-dichlorodiphenylsulfone,
'-Dibromidiphenylsulfone, 4.4''-short diphenylsulfone, 2.4''-dichlorodiphenylsulfone, 2.4-1 dibromidiphenylsulfone, 2.
Examples include 4-difluorodiphenylsulfone, 2,4°-short diphenylsulfone, and those shown in the following formula (where X represents halogen, that is, fluorine, chlorine, bromine or iodine).

C1-c9 alkyl group, 06-
Those into which an aromatic group or aralkyl group of C1δ, an inert group such as an ether group of 01 to CI2, or an electron-withdrawing activating group such as a halogen group, a nitro group, an alkylsulfone group, an arylsulfone group, or a nitroso group are introduced. can also be used.

These aromatic dihalides may be used alone or in a mixture of two or more.

On the other hand, examples of aromatic halophenols having a sulfone bond in the molecule used in the above method (2) include those shown in the following formula (where X is halogen,
i.e. fluorine, chlorine, bromine or iodine).

These benzene nuclei have 01-C9 alkyl groups, 06-
Substituents such as a C18 aromatic group or aralkyl group, or a 01 to CI2 ether group can also be used, and a nitro group or a nitro group to the benzene nucleus to which a halogen group is bonded
Those into which an electron-withdrawing active stationary vA group such as an alkylsulfone group, an arylsulfone group, a nitroso group, or a halogen group is introduced are also effective. Although it is possible to use these halophenols that have been synthesized in advance, alkaline phenols of halophenols prepared by reacting dihalides and alkali metal hydroxides in advance in the polymerization reaction system can be used. It is also possible to use rates. These herrophenols alone or in combination
A mixture of more than one species or the above bisphenols/
Used in mixtures with dihalides.

As the alkali phenolate of the bisphenol-containing or aromatic halophenol, sodium ferulate and potassium ferulate are preferred because they are economical and easy to handle, but other alkali phenolates can also be used. Alkali phenolates can be synthesized in advance, but aromatic hydroxyl groups and alkali metal hydroxides, alkali metal carbonates, alkali metals, alkali metal hydrides, etc. can be used in advance in the polymerization reaction system. It can also be prepared by reacting with.

Polymerization of the aromatic polysulfone consisting of the above components is generally carried out under anhydrous conditions during melting at a temperature of 100° C. or higher. In special cases, when a phase transfer solvent such as crown ether is used, an aromatic polynelphone polymer may be obtained even by low-temperature interfacial polymerization.0 An example of an aprotic polar solvent suitable as a polymerization solvent is dimethyl sulfoxide. , sulfoxides such as diethyl sulfoxide and tetrahydrothiophene-1-monooxide, sulfones such as dimethylsulfone, diethylsulfone, diisopropylsulfone, and sulfolane, N-alkylamides such as dimethylformamide and dimethylacetamide,
N-substituted lactams such as N-methylpyrrolidone and N-methylcaprolactam, ketones such as acetophenone,
Examples include ethers such as diphenyl ether.

Representative examples of aromatic polysulfones obtained in this manner include those having the following structural formula.

H3 The polymerization conditions for these aromatic polysulfones are, for example,
Further details are disclosed in Japanese Patent Publication No. 42-7799, Japanese Patent Publication No. 47-617, etc.

In addition, when these aromatic polysulfones are applied to the polymer grafting reaction mentioned above, it is necessary to have a phenolic hydroxyl group or an alkali phenolate group at the polymer end. Polysulfone can be obtained by a method such as not performing any terminal blocking operation after the completion of the above-mentioned polymerization, or by simply adding an acid to neutralize it after the completion of the polymerization.

The activated vinyl (co)polymer having a functional group selected from an acid halide group, an acid anhydride group, a glycidyl group, a halomethyl group, and a sulfonyl halide group in the side chain used in the present invention is
α, β unsaturated carboxylic acid chlorides, their acid anhydrides, glycidyl esters, such as acrylic acid chloride, methacrylic acid chloride, crotonic acid chloride, p-vinylbenzoyl chloride, maleic anhydride, phosphoric anhydride, Citracon dandan water, glycidyl acrylate, glycidyl methacrylate or allyl chloride, allyl promide, allyl iodide, allyl glycidyl ether,
It can be produced by (co)polymerizing one or more functional vinyl monomers such as p = chloromethylstyrene, p-bromomethylstyrene, and p-chlorosulfonylstyrene. In addition, activated vinyl (co)
The polymer can also be produced by a method in which a desired graft active group is introduced into the side chain of a previously prepared inactive vinyl (co)polymer by polymer reaction.

Examples of such methods include, for example, reacting an acrylic acid (co)polymer with thionyl chloride to introduce acid chloride groups, and reacting a styrene (co)polymer with chloromethyl ether to introduce chloromethyl groups. Examples include a method of reacting a styrene (co)polymer with chlorosulfonic acid to introduce a sulfonyl chloride group.

In the present invention, the amount of active sites (graft-reactive functional groups) in the activated vinyl (co)polymer molecule influences the production effect of the graft copolymer.

If there are too many active sites with high grafting activity in the activated vinyl (co)polymer, a crosslinking reaction will occur as a side reaction during the grafting reaction with aromatic polysulfone, resulting in gelation and formation of insoluble and infusible polymers. The tendency to generate coalescence becomes stronger. In order to reduce this tendency, it is effective to dilute and copolymerize vinyl monomers that are inactive with respect to phenolic hydroxyl groups or alkali phenolate groups during the production of activated vinyl (co)polymers. In order to clearly avoid this tendency, it is necessary to set the amount of active sites (graft-reactive functional groups) to less than 3 salts as the amount of active functional groups. Further, in order to exhibit the effects of the present invention, the content of the active functional group should be 0.05% by weight or more, and the copolymerization composition of functional vinyl monomer water should be 0.1% by mole or more.

That is, the active site has an active functional group amount of 0°05 to 3
0% by weight, 0.0% as copolymer composition of functional vinyl monomer.
01 mol% to 50 mol%.

When introducing active groups in a polymer reaction, the preferable amount of active sites is similarly limited to #J.

Inert vinyl monomers that can be diluted and copolymerized for the purpose of controlling the amount of active sites mentioned above include, for example, styrene, α-methylstyrene, 2,6-dimethylstyrene, p-chlorostyrene, and vinyltoluene. α, β such as argenyl aromatic compounds such as acrylonitrile, acrylonitrile compounds such as methacrylonitrile, methacrylic acid alkyl esters consisting of alkyl group components of 01 to C18, acrylic acid alkyl esters consisting of alkyl group components of 01 to CI8, etc. Examples include unsaturated carboxylic acid esters, diene compounds such as butadiene, isogrene, and chlorogrene. These can be used alone or in a mixture of two or more.

As described above, the graft reaction of the present invention can be carried out by polymer graft reaction.

In carrying out a polymer graft reaction, it is necessary that both the active vinyl (co)polymer and the aromatic polysulfone (or its precursor during polymerization) be dissolved or swollen in the reaction system. Examples of such solvents include sulfoxide-based solvents such as dimethyl sulfoxide, which are commonly used as polymerization solvents for aromatic polysulfone, sulfonate-based solvents such as dimethylsulfone and sulfolane, and N ff fA such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. In addition to aprotic polar solvents such as amide solvents and polymerization solvents for aromatic polysulfone, methylene chloride, chloroform,
Aliphatic halogenated hydrocarbon solvents such as tetrachloroethane, aromatic halogenated hydrocarbon solvents such as chlorobenzene, ether solvents such as tetrahydrofuran, diphenyl ether, and dibutyl ether, and getone solvents such as acetonephenone, benzophenone, and cyclohexanone. You can choose from.

In the polymer grafting reaction of the present invention, an aromatic polysulfone having a phenolic hydroxyl group or an alkali phenolate group at the end and an activated vinyl polymer are mixed together in a solution state or in a swollen state in a solvent, and the mixture is stirred at room temperature to 200 ml. It is carried out by reacting at ℃ (preferably 50 to 1.60℃).

The ratio of the aromatic polysulfone moiety and the activated vinyl (co)polymer used in the graft reaction of the present invention can be carried out within any range, but in particular, the aromatic polysulfone moiety 1
~99 parts by weight, preferably 5 to 80 parts by weight, and 1 to 99 parts by weight, preferably 20 parts by weight of activated vinyl (co)polymer.
A proportion of ~95 parts by weight is practical.

The product obtained by the graft reaction of the present invention is rarely composed of 100% of the target graft copolymer, and may also contain the respective homopolymers of aromatic polysulfone and activated vinyl polymer that do not participate in the reaction. It is obtained as a graft copolymer composition containing.

Further, the graft copolymer (composition) obtained in the present invention can be further blended with vinyl polymers of the same or different kind and aromatic polysulfones for practical use. In this case as well, the graft copolymer obtained by the present invention acts as a compatibility imparting agent, and a composition exhibiting good uniform blendability can be obtained.

The graft copolymer obtained by the present invention not only has improved heat resistance compared to a simple blend of aromatic polysulfone and vinyl polymer, but also has improved compatibility between the constituent components of the composition, resulting in moldability. The surface smoothness of the product is also improved and the delamination tendency seen in the case of dream blends is also reduced. Furthermore, the fluidity is much better than that of aromatic polysulfones themselves, and the melt moldability is improved.

The graft copolymer obtained by the method of the present invention can be further mixed with other condensation polymers such as polycarbonate, nylon, polyester, etc., if necessary. Furthermore, various additives such as pigments, reinforcing agents, fillers, antioxidants, various stabilizers, plasticizers, lubricants, or mold release agents may be added as auxiliaries, if necessary.

Moreover, a foaming material can also be formed by blending a foaming agent.

Examples of the above-mentioned additives include pigments such as titanium oxide, carbon black, cadmium red, and cyanine blue HB manufactured by Sumitomo Chemical Co., Ltd., glass fibers, carbon fibers,
Reinforcing agents such as asbestos, fillers such as calcium carbonate, clay, talc, cellulose powder, silica, 3,5-di-tert-4-hydroxytoluene, 4,4-butylidene bis(6-tert-butyl-m-cresol) ), hindered phenolic antioxidants such as diphenyl monoisodecyl phosphite, lauryl-tert-
Phosphite stabilizers such as butylphenyl phosphite, organometallic salt stabilizers such as metal stearate, phthalic acid derivatives such as dioctyl phthalate and dimethyl phthalate, di(2-ethylhexyl azelate), diisooctyl Plasticizers such as azelaic acid derivatives such as azelate, oleic acid derivatives such as butyl oleate, sulfonic acid derivatives such as benzenesulfone butyramide, silicone mold release agents, ethylene bis stearyl amide, methylene bis stearyl amide, octyl Lubricants such as alcohol, cetyl alcohol, vegetable oil (for example, 13 WAX manufactured by Yoken Fine Chemical Co., Ltd.), mineral oil (for example, Sansen-250 manufactured by Nippon Sun Oil Co., Ltd.), sodium bicarbonate, N,N-dinitrosopenta. Foaming agents such as methylenetetramine, azodicarbonamide, and benzenesulfonyl hydrazide may be mentioned.

The graft polymer obtained by the present invention has excellent physical, mechanical, chemical, electrical, and thermal properties, and can be used for many purposes.

For example, it is useful for automobile parts, electric/electronic equipment parts, water supply and distribution equipment parts, office machine parts, air/aircraft parts, special machine parts, etc.

Hereinafter, the present invention will be further explained in detail by giving Examples.

Note that the values of % and parts shown in this example mean % by weight and parts by 1 fL, respectively, unless otherwise specified.

<Examples> Example 1 (1) Production of P-chloromethylstyrene copolymer In a flask with an internal volume of 500 m1 equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 48% of acrylonitrile was added.
ir (0,906 mol), styrene 144°8g (1,
392 mol), P-chloromethylstyrene 7.2 g (0
,047 mol), azobisisobutyronitrile 0.74
g, 400 g of water, 0.2 g of partially saponified methyl methacrylate/acrylamide (20/80) copolymer, 0.1 g of sodium dihydrogen phosphate, and 0.48 g of t-dodecylmercaptan were charged, stirred, and heated with nitrogen gas. Suspension polymerization was carried out at 70° C. for 2 hours and then at 90° C. for 1 hour while flowing.

After dehydrating the obtained granular polymer using a centrifuge,
After thoroughly washing with water and drying in a vacuum dryer at 70°C for 18 hours, a pale yellow acrylonitrile/styrene/
184g of P-chloromethylstyrene copolymer (yield: 9
2%) was obtained.

The chlorine content in this chloromethylstyrene copolymer is determined by JI
A quantitative determination according to SK-5580 revealed that the amount was 0.24 mmol/g-polymer, confirming that about 2 mol % of P-chloromethylstyrene units were copolymerized as initially charged.

(2) Production of aromatic polysulfone having a sodium ferulate group at the end
In a 0ml flask, 50g of dimethyl sulfoxide, 133g of chlorobenzene, 22.8g of bisphenol A (0,
10 mol) and 28.7 g (0.10 mol) of 4,4'-dichlorodiphenylsulfone were charged, the atmosphere was immediately replaced with nitrogen, and a small amount of nitrogen was continued to flow during the reaction operation. After heating this reaction solution to 75°C, a 50% sodium hydroxide aqueous solution was prepared. r! 16, Og (0.20 mol)
was added and then heated to 120° C., and a water/chlorobenzene azeotrope began to distill from the system. As the distillation of the azeotrope continued, the internal hot water gradually rose, and when it reached 140°C, the water in the system was almost completely removed, and the di-sodium salt of bisphenol precipitated.9 Then, the temperature was gradually lowered over about 20 minutes. C':l The temperature was raised to about 170°C, and excess chlorobenzene was distilled off. At this point, the di-sodium salt of bisphenol A was dissolved, the reaction system became homogeneous, and the polymerization reaction progressed considerably. The temperature of the reactant was quickly lowered to 150-160°C, and the mixture was stirred at this temperature for 1 hour and 1 hour to carry out the polymerization reaction. Thereafter, the reaction mixture was diluted with 200 g of chlorobenzene and suction filtered using a Buchner funnel equipped with r paper to remove by-product sodium chloride and a small amount of gel. The polymer was separated by pouring the P solution into 5 times the amount of methanol and coagulating it, and vacuum-drying it at 70°C for 16 hours. As a result, an aromatic polysulfone having a sodium ferulate group at the terminal was obtained. Or (yield 95%) was obtained.

(3) Production of graft polymer 15 g of the aromatic polysulfone having a sodium ferulate group at the end obtained in (2) above, 1 chlorobenzene
00CC was charged into a flask equipped with a stirrer, a thermometer, and a cooling tube and completely dissolved. Next, the acrylonitrile/styrene/p-chloromethylstyrene copolymer obtained in (1) above (hereinafter referred to as P-chloromethylstyrene) 200 g of a solution of 35 g of chlorobenzene (abbreviated as copolymer) was added with stirring, and the mixture was reacted at 120° C. for 2 hours.

Thereafter, the reaction mixture was poured into 21 methanol and coagulated to separate the polymer, thoroughly washed with methanol, and then vacuum dried at 70°C for 16 hours. Group polysulfone (=
A graft copolymer composition (70/30 charging ratio) was quantitatively obtained.

1.0 g of the graft copolymer thus obtained was
00 [+11] in acetone under reflux temperature conditions.
When time extraction was performed, the amount of extraction residue was 39 g. This residue corresponds to polysulfone and grafted p-chloromethylstyrene copolymer. From this, the grafting ratio of the P-chloromethylstilcin copolymer to the polysulfone backbone was calculated to be 30%.

In addition, this graft copolymer was prepared at a temperature of 250°C and a pressure of 40°C.
Compression molding under hg/- conditions and measurement of BS method softening point (British standard B52782-102C) 1
The temperature was 29°C. The BS method softening point of the aromatic polysulfone made from the same polymerization recipe as above is 185°C, and the acrylonitrile/styrene/p-
The BS method softening point of chloromethylstyrene copolymer is 102
℃, B of the graft polymer produced in this example
The measured value of the S method softening point is 1ifi (185 .3+10
2×0.7=126.9° C.), and it is clear that the graft copolymer of this example has excellent heat resistance.

Comparative Reference Example 1 In the production of the graft polymer of Example 1 (3), styrene/acrylonitrile (7 g) was used instead of 35 g of acrylonitrile/styrene/p-chloromethylstyrene copolymer.
6/24) A polymer composition was obtained by performing the same reaction operation and post-treatment except that 35 g of the copolymer was used.

Subsequently, when the grafting rate of this polymer composition was measured in the same manner as in Example 1, it was found to be a small value of 0.6%. This result shows that it is important for the vinyl polymer to have an active group such as a chloromethyl group in order to obtain a polymer with a high grafting rate.

Furthermore, when the softening point of this polymer composition was measured by the BS method, it was 110°C, which was considerably inferior to Example 1 in heat resistance.

Example 2 (1) Production of methacrylic acid chloride copolymer Methyl methacrylate 24.4 g (0,244 mol), methacrylic acid chloride 0.94 g (0,009 mol) and azobisisobutyronitrile 0.09 g Uniformly dissolve 20
It was sealed in a +mφ glass ampoule. Place this ampoule in an oil bath at 70°C for 3 hours, then at 90°C.
When polymerization was carried out by holding the mixture for 2 hours, a colorless methyl methacrylate/methacrylic acid chloride (97 parts, 3 molar ratio) copolymer was obtained. After pulverizing this polymer, it was dried in a vacuum dryer at 70°C for 14 hours.

(2) Production of graft polymer 15g5 of aromatic polysulfone having a sodium ferrate group at the terminal obtained by polymerization similar to Example 1 (2)
Charge 70.CC of chlorobenzene into a 200cc flask equipped with a stirrer, thermometer, and condenser and dissolve completely.

Next, 100 g of a chlorobenzene solution of 15 g of the methyl methacrylate/methacrylic acid chloride (97 parts, 3 molar ratio) copolymer obtained in (1) above was added with stirring,
The reaction was carried out at ~70°C for 1 hour.

Thereafter, the reaction mixture was poured into 11 methanol and coagulated to separate the polymer, washed thoroughly with warm water, and vacuum dried at 70'C for 16 hours. A polysulfone-based graft copolymer composition was quantitatively obtained.

Next, the graft ratio of the graft copolymer thus obtained was measured in the same manner as in Example 1, and was found to be 25%. Furthermore, when the softening point of this polymer was measured by the BS method, it was found to have excellent heat resistance of 141°C.

Comparative Reference Example 2 At the end of polymerization, 6 g of acetic anhydride (0.05 g
A terminal-capped powdery aromatic polysulfone was produced by performing the same polymerization and post-treatment operations as in Example 1 (2), except that 8 mol) was added.

Next, 50 parts of this end-blocked aromatic polysulfone and 50 parts of a separately prepared granular methyl methacrylate polymer (Mitsubishi Rayon (A) 'Acrypet') were tri-blended and placed in a Brabender Plastograph extruder for 30 minutes. Melt blending was performed by circulating the mixture (processing temperature: 260-280°C.
1, screw rotation speed 25 rpn). When the BS method softening point of the thus obtained melt blend pellet was measured, it was 107°C, which was significantly inferior in heat resistance compared to Example 2. .

Comparing the results of Example 2 and Comparative Reference Example 2, it can be seen that the graft polymer composition is far superior in heat resistance to a simple melt blend.

Example 3 (1) Preparation of maleic anhydride copolymer In a 11 flask equipped with a stirrer, a thermometer and a reflux condenser, 5 g (0,051 mol) of maleic anhydride and 95+r methyl methacrylate (0°95 mol) were added. ), 1 g of azobisisobutyronitrile, and methyl ethyl ketone Ift were charged, and the mixture was heated to 75° C. with stirring and polymerization was continued for 5 hours.

Next, this reaction mixture was poured into a large amount of petroleum ether that was being stirred vigorously, and the polymer was coagulated to separate the polymer. After vacuum drying at 70°C for 16 hours, a maleic anhydride/methyl methacrylate copolymer was obtained. 85g (yield 85%
) was obtained.

(2) Production of aromatic polysulfone with terminal alkali phenolate In a flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, 4.4-1 dichlorodiphenyl sulfone 14.3
6 g (0.05 mol), 50% potassium hydroxide aqueous solution 1
1.2 g < 0.10 mol) and 100 ml of sulfolane
and stirred and heated at 140°C under nitrogen gas for 3 minutes.
After reacting for an hour, 1/15 xylene was added, the reflux condenser was replaced with a distillation pipe, and the reaction was continued for an additional 3 hours to azeotropically remove water in the system. Next, xylene was distilled off, the temperature of the reactor was set at 240°C, and a polymerization reaction was carried out for 7 hours. After the product was allowed to cool to 100°C, the reaction mixture was poured into vigorously stirring water through a glass filter, and the polymer was separated by dispersion and coagulation.Then, the polymer was separated by washing with water and centrifugation. The polymer was collected and dried with hot air at 110°C for 2 hours, and then dried at 120°C for 16 hours.
After vacuum drying for hours, 11 g of aromatic polysulfone with potassium ferulate groups at the end (yield 95%) was obtained.
Obtained.

(3) Production of graft polymer 10 g of the aromatic polysulfone having terminal potassium ferrate groups obtained in (2) above and 50 ml of chlorobenzene were placed in a flask equipped with a stirrer, a thermometer, and a cooling tube, and completely dissolved. Ta. Next, 60 r of a chlorobenzene solution containing 10 g of the maleic anhydride/methyl methacrylate copolymer obtained in (1) above was added with stirring, and 70
The reaction was carried out at ~100°C for 1 hour.

Thereafter, the reaction mixture was poured into methanol (No. 11) and coagulated to separate the polymer, washed thoroughly with warm water, and vacuum dried at 70°C for 16 hours. A graft copolymer composition was obtained quantitatively.

Next, the grafting ratio of the obtained graft copolymer was determined in Example 1.
When measured in the same manner as above, it was 42%.

Example 4 (1) Production of allyl glycidyl ether copolymer Styrene 23g < 0.221 mol), acrylonitrile 6ir
(0,113 mol), allyl glycidyl ether Ig (
0,009 mol) and azobisisobutyronitrile 0
．． 09 g was uniformly dissolved and sealed in a 20 mm diameter glass ampoule. This ampoule was placed in an oil bath and polymerized by holding it at 70°C for 3 hours and then at 90°C for 2 hours to obtain a colorless styrene/acrylonitrile/allyl glycidyl epi-tyl copolymer. . After pulverizing this polymer, it was dried in a vacuum dryer at 70°C for 14 hours. (2) Production of graft copolymer
50 tons of dimethyl sulfoxide, 133 g of chlorobenzene, and 22.8 g of bisphenol A (0,
10 mol) and 28.7 g (0.10 mol) of 4.4"-dichlorodiphenylsulfone were charged, and the atmosphere was immediately replaced with nitrogen. From then on, a small amount of nitrogen was continued to flow during the reaction operation. The reaction solution was heated to 75°C. After heating, 16.0 g (0.20 mol) of a 50% strength aqueous sodium hydroxide solution was added and then heated to 120°C, and a water/chlorobenzene azeotrope began to distill out of the system.Azeotrope As the distillation continued, the internal temperature gradually rose, and when it reached 140°C, the water in the system was almost completely removed, and the di-sodium salt of bisphenol precipitated. The temperature was raised to 170°C, and excess chlorobenzene was distilled off. At this point, the di-sodium salt of bisphenol A was dissolved and the reaction system became homogeneous, and the temperature of the reactant, in which the polymerization reaction had progressed considerably, was lowered. After the polymerization was completed, the temperature of the reaction mixture was lowered to 120°C, and the styrene/acrylonitrile produced in (1) above was heated. /Allyl glycidyl ether copolymer 18.9g dimethyl sulfoxide solution 120
g (polysulfone 2 allyl glycidyl ether copolymer = 70/30 charging ratio), 150-160°C
The graft reaction was carried out by stirring at a temperature of about 1 hour.

Thereafter, the reaction mixture was diluted with 200 g of chlorobenzene and suction filtered using a Buchner funnel equipped with a filter paper to remove by-product sodium chloride and a small amount of gel. The polymer was separated by pouring the furnace solution into 5 times the amount of methanol and coagulating it, and vacuum-dried it at 70°C for 16 hours. As a result, 56.8 g of the polysulfone/allyl glycidyl ether copolymer-based graft copolymer was obtained ( yield 90.0%)
Obtained.

Regarding the obtained graft copolymer, the grafting ratio of the styrene/acrylonitrile/allyl glycidyl ether copolymer to the main polysulfone was measured in the same manner as in Example 1, and it was found to be 15.6%.

Claims (1)

[Claims] An activated vinyl polymer or copolymer having 0.05 to 30% by weight of one or more functional groups selected from acid halide groups, acid anhydride groups, glycidyl groups, halomethyl groups, and sulfonyl halide groups in the side chain. A method for producing a graft copolymer, which comprises reacting a polymer (A) with a polyarylene ether sulfone (B) having a phenolic hydroxyl group or an alkali phenolate group at its terminal in a polar organic solvent.