JPS6411661B2 - - Google Patents

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 copolymer. More specifically, the purpose 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, electrical properties, etc. Due to these properties, it is used as an engineering plastic for electrical and electronic parts, aircraft parts, automobile parts, etc.
It is partially used in sanitary food equipment parts, etc. However, aromatic polysulfone is still an expensive material and does not necessarily have sufficient molding fluidity, so it has not yet been fully adopted for 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, Japanese Patent Publication No. 46-37896,
(Japanese Patent Publication No. 46-37905, Japanese Patent Publication No. 47-31095, Japanese Patent Application Publication No. 47-5581, Japanese Patent Application Publication No. 128048-1972, etc.). However, these blends of aromatic polysulfone and vinyl polymer are based on simple melt blending, and form a completely separated sea-island structure, with the vinyl polymer making up the sea component. In such compositions (compositions in which the vinyl polymer portion is quantitatively predominant), the excellent heat resistance properties of aromatic polysulfone are hardly utilized. For example, the BS method uses a composition obtained by simply melt blending aromatic polysulfone ("Udel P-1700" manufactured by UCC) and AS resin (styrene/acrylonitrile 76/24 weight ratio copolymer) using an extruder. Heat distortion temperature (British standard BS2782−
102C) is 108℃ with a 2080 weight mixing ratio, and only about 120℃ with a 4060 weight mixing ratio. This value is based on the additivity of the BS method heat distortion temperature of aromatic polysulfone (“Udel P-1700”), 185°C, and the BS method heat distortion temperature of AS (styrene/acrylonitrile 76/24 weight ratio copolymer) resin, 102°C. This is much lower than the value calculated from , 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 an aromatic polysulfone-vinyl chloride copolymer (Japanese Patent Publication No. 46-21216), a method for producing an aromatic polysulfone-vinyl monomer copolymer (Japanese Patent Publication No. 47-23665), etc. be.

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. In other words, the special public official 1977-
The method described in Publication No. 23665 had a too low grafting rate;
In addition, in the method described in Japanese Patent Publication No. 46-21216,
In particular, when graft polymerizing vinyl monomers other than vinyl chloride, it is difficult to carry out the graft reaction effectively.

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. The inventors have discovered that the above object can be achieved very effectively by introducing a specific grafting active site into the side chain of a vinyl polymer and performing a polymer grafting reaction using this, and have arrived at the present invention.

That is, the present invention provides an activated vinyl polymer 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. Alternatively, it provides a method for producing a graft copolymer, which comprises reacting copolymer A with aromatic polysulfone B having a phenolic hydroxyl group or an alkali phenolate group at the end in a polar organic solvent.

In the present invention, by introducing the above-mentioned specific active sites into the vinyl polymer or copolymer used in advance, the graft copolymer reaction can proceed efficiently and the desired properties can be achieved. A satisfactory 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. The graft copolymer has the desired properties. Therefore, for convenience, below,
The reaction of the present invention is called 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 an aprotic polar solvent. This type of polymer is a linear polymer that has three essential bond units: arylene bonds (aromatic bonds), ether bonds, and sulfone bonds. Specifically, (1) a method of condensation reaction between an alkali phenolate of bisphenols and an aromatic dihalide having a sulfone bond in the molecule, or (2) a method of condensation reaction of an alkali phenolate of bisphenols with an aromatic dihalide having a sulfone bond in the molecule, or (2) a method of condensation reaction of an alkali phenolate of bisphenols with an aromatic dihalide having a sulfone bond in the molecule, or (2) a method of condensation reaction of an alkali phenolate of bisphenols with an aromatic dihalide having a sulfone bond in the molecule. It is a polymer obtained by polymerizing an alkali phenolate by any of the methods of subjecting it to a self-condensation reaction.

Examples of bisphenols used in the above method (1) include hydroquinone, resorcinol, bis-(hydroxyphenyl)alkane, and
2,2-bis-(4-hydroxyphenyl)propane, 2,4'-dihydroxydiphenylmethane,
Bis-(4-hydroxyphenyl)methane, bis-(2-hydroxyphenyl)methane, bis-(4-hydroxyphenyl)methane,
-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)heptane, bis-(4-hydroxyphenyl)phenylmethane, para-α,α′- Bis(4-hydroxyphenyl)-para-diisopropylbenzene, etc.; di(hydroxyphenyl) ethers, such as bis-(4-hydroxyphenyl) ether, 4,3'-, 4,2'-, 2, 2′−,
2,3'-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′-dihydroxydiphenyl sulfone, etc.
Furthermore, analogs thereof having three or more phenyl nuclei may be mentioned. These bisphenols also have inert substituents introduced into the benzene nucleus, such as C ₁ to _{C 9} alkyl groups, C ₆ to _{C 18} aromatic or aralkyl groups, and C ₁ to _{C 12} ether groups. Can be used. These bisphenols may be used alone or in a mixture of two or more.

Further, the aromatic dihalides used in the above method (1) include, for example, 4,4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenylsulfone, 4,4'-dibromidiphenyl sulfone,
4,4'-diiododiphenyl sulfone, 2,4'-
Examples include dichlorodiphenyl sulfone, 2,4'-dibromidiphenyl sulfone, 2,4'-difluorodiphenylsulfone, 2,4'-diiododiphenyl sulfone, and those shown in the following formula. and X is halogen, i.e., fluorine,
(indicates chlorine, bromine or iodine).

C ₁ to C ₉ alkyl groups in these benzene nuclei,
_C6 - _C18 aromatic or aralkyl group, _C1 - _C12
It is also possible to use those into which an inert group such as an ether group or an electron-withdrawing activating group such as a halogen group, nitro group, alkylsulfone group, arylsulfone group, or nitroso group is introduced. These aromatic dihalides may be used alone or in a mixture of two or more.

On the other hand, examples of the 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, (indicates bromine or iodine).

C ₁ to C ₉ alkyl groups in these benzene nuclei,
_C6 - _C18 aromatic or aralkyl group, _C1 - _C12
Substituents such as ether groups can be introduced into the benzene nucleus to which halogen groups are bonded, and electron-withdrawing activities such as nitro groups, alkylsulfone groups, arylsulfone groups, nitroso groups, and halogen groups can also be used. It is also effective to introduce a chemical substituent. Although it is possible to use these halphenols that have been synthesized in advance, it is also possible to use an alkali halophenol prepared by reacting a dihalide and an alkali metal hydroxide in advance in the polymerization reaction system. It is also possible to use phenolates. These halophenols can be used alone, in combination of two or more, or in mixtures with the above-mentioned bisphenols/dihalides.

As the alkali phenolate of the bisphenols or aromatic halophenols, sodium phenolate and potassium phenolate 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, and alkali metal hydrides can be synthesized in advance in the polymerization reaction system. It can also be prepared by reacting with, etc.

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, aromatic polysulfone polymers may be obtained even by low-temperature interfacial polymerization. Examples of aprotic polar solvents suitable as polymerization solvents include dimethyl sulfoxide,
Sulfoxides such as diethyl sulfoxide and tetrahydrothiophene-1-monoxide, sulfones such as dimethylsulfone, diethylsulfone, diisopropylsulfone, and sulfolane, N-alkylamides such as dimethylformamide and dimethylacetamide, N-methylpyrrolidone,
Examples include N-substituted lactams such as N-methylcaprolactam, ketones such as acetophenone, and ethers such as diphenyl ether.

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

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

In addition, when these aromatic polysulfones are applied to the above-mentioned polymer graft reaction, it is necessary to have a phenolic hydroxyl group or an alkali phenolate group at the polymer end.
Aromatic polysulfones having such terminals can be obtained by not performing any operation for capping the terminals after the completion of the above-mentioned polymerization, or by simply adding an acid to neutralize the polysulfone 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 an α,β unsaturated carboxylic acid salt. compounds, their acid anhydrides, glycidyl esters, such as acrylic chloride, methacrylic chloride, crotonic chloride, p-vinylbenzoyl chloride, maleic anhydride, itaconic anhydride,
citraconic anhydride, glycidyl acrylate, glycidyl methacrylate or allyl chloride,
Allyl bromide, allyl iodide, allyl glycidyl ether, p-chloromethylstyrene, p
- One or two functional vinyl monomers such as bromomethylstyrene and p-chlorosulfostyrene
It can be produced by (co)polymerizing two or more species. Furthermore, the activated vinyl (co)polymer can also be produced by a method in which a desired graft active group is introduced into the side chain of an inactive vinyl (co)polymer prepared in advance by a 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. To reduce this tendency,
During the production of activated vinyl (co)polymers, it is effective to dilute and copolymerize vinyl monomers that are inactive with respect to phenolic hydroxyl groups or alkali phenolate groups, and in order to clearly avoid the gelation tendency. The amount of active sites (graft-reactive functional groups) is 30% by weight or less as the amount of active functional groups, and the copolymerization composition of the functional vinyl monomer is 50% by mole or less, preferably 20% by weight or less.
It is necessary to keep it below mol%. In addition, in order to exhibit the effects of the present invention, the active sites should be in a range of 0.05% by weight or more as the amount of active functional groups and 0.1% by mole or more as the copolymerization composition of the functional vinyl monomer.

In other words, the active point is 0.05 as the amount of active functional group.
30% by weight, and 0.01 mol% to 50 mol% as a copolymerization composition of the functional vinyl monomer. When introducing active groups in a polymer reaction, the preferable amount of active sites is similarly limited.

Examples of inert vinyl monomers that can be diluted and copolymerized for the purpose of controlling the amount of active sites include styrene, α-methylstyrene,
Alkenyl aromatic compounds such as 2,6-dimethylstyrene, p-chlorostyrene, and vinyltoluene, acrylonitrile compounds such as acrylonitrile and methacrylonitrile, methacrylic acid alkyl esters consisting of C ₁ to C ₁₈ alkyl group components, C ₁ Examples thereof include α,β unsaturated carboxylic acid esters such as acrylic acid alkyl esters having a _C18 alkyl group component, and diene compounds such as butadiene, isoprene, and chloroprene. 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. When 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. Such solvents include sulfoxide solvents such as dimethyl sulfoxide, which are commonly used as polymerization solvents for aromatic polysulfone, sulfone solvents such as dimethylsulfone and sulfolane, and N-substituted amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. In addition to aprotic polar solvents such as aprotic polar solvents and polymerization solvents for aromatic polysulfone, aliphatic halogenated hydrocarbon solvents such as methylene chloride, chloroform, and tetrachloroethane, and aromatic halogenated hydrocarbons such as chlorobenzene. It can be selected from hydrogen-based solvents, ether-based solvents such as tetrahydrofuran, diphenyl ether, and dibutyl ether, and ketone-based solvents such as acetonephenone, penzophenone, and cyclohexanone.

The polymer grafting reaction of the present invention involves mixing both an aromatic polysulfone having a phenolic hydroxyl group or an alkali phenolate group at the end and an activated vinyl polymer in a solution state or in a swollen state in a solvent.
The reaction is carried out under stirring at room temperature to 200°C (preferably 50 to 160°C).

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 may be 1 to 99 parts by weight, preferably 5 parts by weight.
~80 parts by weight of activated vinyl (co)polymer 1
A proportion of ~99 parts by weight, preferably 20-95 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.

Furthermore, the graft copolymer (composition) obtained in the present invention can be further blended with the same or different types of vinyl polymers and aromatic polysulfones for practical use. In this case as well, the graft copolymer obtained in 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 tendency to delaminate, which is seen with simple blends, is reduced. Also,
Compared to aromatic polysulfones themselves, fluidity is greatly improved and 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. Also,
A foamed material can also be formed by incorporating a foaming agent.

Examples of the above additives include pigments such as titanium oxide, carbon black, cadmium red, cyanine blue HB manufactured by Sumitomo Chemical Co., Ltd., glass fibers, carbon fibers, reinforcing agents for asbestos, calcium carbonate, and clay. , talc, cellulose powder, fillers such as silica, 3,5-di-tert-4-hydroxytoluene, 4,4'-butylidene bis-(6
Hindered phenolic antioxidants such as -tert-butyl-m-cresol), phosphite stabilizers such as diphenyl monoisodecyl phosphite and lauryl-tert-butyl phenyl phosphite, and organic compounds such as stearic acid metal salts. Metal salt stabilizers, phthalic acid derivatives such as dioctyl phthalate and dimethyl phthalate, azelaic acid derivatives such as di-(2-ethylhexyl azelate) and diisooctyl azelate, oleic acid derivatives such as butyl oleate, benzenesulfone butyramide Plasticizers represented by sulfonic acid derivatives such as silicone mold release agents, ethylene bis stearyl amide, methylene bis stearyl amide, octyl alcohol, cetyl alcohol, vegetable oil,
(For example, K-
3WAX), mineral oil (for example, Sansen-250 manufactured by Nippon Sunoil Co., Ltd.), and blowing agents such as sodium bicarbonate, N,N'-dinitrosopentamethylenetetramine, azodicarbonamide, and benzenesulfonyl hydrazide. .

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, aircraft parts, special machine parts, etc.

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

In addition, the values of % and parts shown in this example mean % by weight and parts by weight, respectively, unless otherwise specified.

<Example> Example 1 (1) Production of p-chloromethylstyrene copolymer 48 g (0.906 mol) of acrylonitrile was placed in a 500 ml flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas inlet tube. ), styrene 144.8
g (1.392 mol), p-chloromethylstyrene 7.2
g (0.047 mol), azobisisobutyronitrile
0.74g, water 400g, partially saponified methyl methacrylate/acrylamide (20/80) copolymer 0.2
g, 0.1 g of sodium dihydrogen phosphate and 0.48 g of t-dodecylmercaptan were charged, stirred, and heated at 70°C for 2 hours while flowing nitrogen gas, then at 90°C.
Suspension polymerization was carried out by holding for 1 hour.

The resulting granular polymer was dehydrated using a centrifuge, thoroughly washed with water, and dried at 70°C in a vacuum dryer.
When dried for 18 hours, 184 g (yield 92%) of a pale yellow acrylonitrile/styrene/p-chloromethylstyrene copolymer was obtained.

The chlorine content in this chloromethylstyrene copolymer was determined according to JISK-5580 and was 0.24.
mmol/g-polymer, and p-chloromethylstyrene units are approximately 2 mol% as initially charged.
It was confirmed that they were copolymerized.

(2) Production of aromatic polysulfone having a sodium phenolate group at the end In a 300 ml flask equipped with a stirrer, thermometer, gas inlet tube and distillation tube, 50 g of dimethyl sulfoxide,
Chlorbenzene 133g, Bisphenol A 22.8g
(0.10 mol) and 28.7 g (0.10 mol) of 4,4'-cyclodiphenylsulfone were charged, and the atmosphere was immediately replaced with nitrogen. Thereafter, a small amount of nitrogen was continued to flow during the reaction operation. After heating this reaction solution to 75℃,
16.0 g (0.20 mol) of a % strength aqueous sodium hydroxide solution 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 temperature gradually rose, and when it reached 140°C, water in the system was almost completely removed and bisphenol di-sodium salt precipitated. Next, the temperature was gradually raised to about 170° C. over about 20 minutes, 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 to carry out the polymerization reaction. Thereafter, the reaction mixture was diluted with 200 g of chlorobenzene and filtered through a Buchner funnel equipped with paper to remove by-product sodium chloride and a small amount of gel. The polymer was separated by pouring the liquid into 5 times the amount of methanol and solidifying it, and then heated at 70℃.
After vacuum drying for 16 hours, the aromatic polysulfone with sodium phenolate group at the end was 42.0
g (yield 95%) was obtained.

(3) Production of graft polymer 15 g of the aromatic polysulfone having a sodium phenolate group at the end obtained in (2) above and 100 c.c. of chlorobenzene were charged into a flask equipped with a stirrer, thermometer, and cooling tube until complete. Dissolved. Next, 200 g of a chlorobenzene solution containing 35 g of the acrylonitrile/styrene/p-chloromethylstyrene copolymer (hereinafter abbreviated as p-chloromethylstyrene copolymer) obtained in (1) above was added with stirring, 120℃
The mixture was allowed to react for 2 hours.

Thereafter, the reaction mixture was poured into methanol in Step 2 and coagulated to separate the polymer, washed thoroughly with methanol, and vacuum dried at 70°C for 16 hours.
An aromatic polysulfone (=70/30 charging ratio) graft copolymer composition was quantitatively obtained.

Graft copolymer 1.0 thus obtained
When the extract was placed in 100 ml of acetone and extracted for 3 hours under reflux temperature conditions, the amount of extracted residue was 39 g. This residue corresponds to polysulfone and grafted p-chloromethylstyrene copolymer. From this, the grafting ratio of the p-chloromethylstyrene copolymer to the polysulfone backbone [=(grafted chloromethylstyrene copolymer weight/polysulfone backbone polymer weight)×100] was calculated to be 30%.

Further, this graft copolymer was compression molded at a temperature of 250°C and a pressure of 40 kg/cm ² and its softening point by BS method (British Standard BS2782-102C) was measured to be 129°C. The BS method softening point of aromatic polysulfone using the same polymerization recipe as above is 185.
℃, and the acrylonitrile produced in (1) above/
Styrene/p-chloromethylstyrene copolymer
Since the BS method softening point is 120°C, the actual BS method softening point value of the graft polymer produced in this example is the BS method softening point of the trunk polysulfone and the branched acrylonitrile/styrene/p-chloromethylstyrene copolymer. The value calculated theoretically from the point value using the principle of additivity (185 x 0.3 + 102 x 0.7 =
126.9°C), and it is clear that the graft copolymer of this example has excellent heat resistance.

Comparative reference example 1 Except for using 35 g of styrene/acrylonitrile (76/24) copolymer instead of 35 g of acrylonitrile/styrene/p-chloromethylstyrene copolymer in the production of the graft polymer in Example 1 (3). A polymer composition was obtained by performing all the same reaction operations and post-treatments. Subsequently, the grafting rate of this polymer composition was measured in the same manner as in Example 1, and was found to be a small value of 0.6%. This result shows that the presence of an active group such as a chloromethyl group in a vinyl polymer is important in order to obtain a polymer with a high grafting rate.

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

Example 2 (1) Production of methacrylic acid chloride copolymer 24.4 g (0.244 mol) of methyl methacrylate, 0.94 g (0.009 mol) of methacrylic acid chloride, and 0.09 g of azobisisobutyronitrile were uniformly dissolved.
It was sealed in a 20 mmφ glass ampoule. This ampoule was placed in an oil bath and held at 70°C for 3 hours and then at 90°C for 2 hours to polymerize, resulting in a colorless methyl methacrylate/methacrylic acid chloride (97/3 molar ratio) copolymer. was gotten. After pulverizing this polymer, it was dried in a vacuum dryer at 70°C for 14 hours.

(2) Production of graft polymer 15 g of aromatic polysulfone having a sodium phenolate group at the terminal obtained by polymerization similar to Example 1 (2) and 70 c.c. of chlorobenzene were mixed with a stirrer, a thermometer,
The mixture was placed in a 200 c.c. flask equipped with a cooling tube and completely dissolved.

Next, methyl methacrylate/methacrylic acid chloride (97/3 molar ratio) copolymer 15 obtained in (1) above
100 g of chlorobenzene solution was added with stirring, and the mixture was reacted at 50 to 70° C. for 1 hour.

Thereafter, the reaction mixture was poured into methanol (1) 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 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 BS method softening point of this polymer was measured, it was found to have excellent heat resistance of 141°C.

Comparison reference row 2 6 g of acetic anhydride as a terminal stopper at the end of polymerization
All Example 1(2) except for adding (0.058 mol)
Polymerization and post-treatment operations similar to those described above were carried out to produce end-capped powdery aromatic polysulfone.

Next, 50 parts of this end-blocked aromatic polysulfone and 50 parts of a separately prepared granular methyl methacrylate polymer ("Acripet" manufactured by Mitsubishi Rayon Co., Ltd.) were dry blended and passed through a Brabender Plus graph extruder three times. Melt blending was performed (processing temperature 260-280°C, screw rotation speed 25 rpm). The softening point of the molten blend pellets thus obtained was measured using the BS method and was found to be 107°C.
The heat resistance was significantly inferior to that of 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) Production of maleic anhydride copolymer 1 equipped with a stirrer, thermometer and reflux condenser
5 g (0.051 mol) of maleic anhydride in the flask;
95 g (0.95 mol) of methyl methacrylate, 1 g of azobisisobutyronitrile, and 1 portion of methyl ethyl ketone 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 coagulated to separate the polymer, which was vacuum dried at 70°C for 16 hours, resulting in a maleic anhydride/methyl methacrylate copolymer. 85g (85% yield) 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, 14.36 g (0.05 mol) of 4,4'-dichlorodiphenyl sulfone and 50% water were added. Potassium oxide aqueous solution 11.2g (0.10mol) and sulfolane 100ml
After reacting at 140℃ for 3 hours while stirring and flowing nitrogen gas, 15ml of xylene was added,
The reflux condenser was replaced with a distillation tube, 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. product 100
After being allowed to cool to ℃, the reaction mixture was poured into vigorously stirred water via a glass filter, and the polymer was separated by dispersing and coagulating it. Next, the polymer is recovered by washing with water and centrifugation.
After drying with hot air at 110°C for 2 hours and then vacuum drying at 120°C for 16 hours, 11g of aromatic polysulfone having a potassium phenolate group at the end (yield 95%) was obtained.
%) obtained.

(3) Production of graft polymer 10 g of the aromatic polysulfone having terminal potassium phenolate 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. Then above
60 g of a chlorobenzene solution of 10 g of the maleic anhydride/methyl methacrylate copolymer obtained in (1) was added with stirring, and the mixture was reacted at 70 to 100° C. for 1 hour.

After that, the reaction mixture was poured into methanol (1) and coagulated to separate the polymer, washed thoroughly at temperature, and vacuum dried at 70°C for 16 hours. A graft copolymer composition was obtained quantitatively.

Next, the graft ratio of the obtained graft copolymer was measured in the same manner as in Example 1, and was found to be 42%.

Example 4 (1) Production of acrylic glycidyl ether copolymer Styrene 23 g (0.221 mol), acrylonitrile 6 g (0.113 mol), allyl glycidyl ether 1
(0.009 mol) and 0.09 g of azobisisobutyronitrile were uniformly dissolved and sealed in a 20 mmφ 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 ether copolymer. After pulverizing this polymer, it was dried in a vacuum dryer at 70°C for 14 hours.

(2) Production of graft copolymer Add 50 g of dimethyl sulfoxide to a 500 ml flask equipped with a stirrer, thermometer, gas inlet tube, and distillation tube.
Chlorbenzene 133g, Bisphenol A 22.8g
(0.10 mol) and 28.7 g (0.10 mol) of 4,4'-cyclodiphenylsulfone 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. After heating this reaction solution to 75℃, 50%
When 16.0 g (0.20 mol) of a concentrated aqueous sodium hydroxide solution was added and then heated to 120° C., a water/chlorobenzene azeotrope began to distill out from the system. As the distillation of the azeotrope continued, the internal temperature gradually rose, and when it reached 140°C, water in the system was almost completely removed and bisphenol di-sodium salt precipitated. Next, the temperature was gradually raised to about 170° C. over about 20 minutes, and excess chlorobenzene was distilled off. 2 of bisphenol A at this point.
The sodium salt was dissolved and the reaction system became homogeneous, and the polymerization reaction proceeded considerably. The temperature of the reactant was quickly lowered to 150-160°C, and the mixture was stirred at this temperature for 1 hour to carry out the polymerization reaction. After the polymerization was completed, the temperature of the reaction mixture was lowered to 120°C and the above
Add 120 g of a dimethyl sulfoxide solution containing 18.9 g of the styrene/acrylonitrile/allyl glycidyl ether copolymer prepared in (1) (polysulfone allyl glycidyl ether copolymer = 7030
The grafting reaction was carried out by stirring at a temperature of 150 to 160° C. for about 1 hour. Thereafter, the reaction mixture was diluted with 200 g of chlorobenzene and filtered through a Buchner funnel equipped with paper to remove by-product sodium chloride and a small amount of gel.
The polymer was separated by pouring the liquid into 5 times the volume of methanol and coagulating, and vacuum-dried at 70°C for 16 hours, resulting in 56.8 g of polysulfone/allyl glycidyl ether copolymer-based graft copolymer.
(yield 90.0%).

The obtained graft copolymer was treated in the same manner as in Example 1, and the styrene/polysulfone base was
The grafting rate of the acrylonitrile/allyl glycidyl ether copolymer was measured and found to be 15.6%.

Claims (1)

[Claims] 1. 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 with a polyarylene ether sulfone B having a phenolic hydroxyl group or an alkali phenolate group at the end in a polar organic solvent.