JPS6354009B2 - - 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 polymer. 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. 128048-1982, 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 BG 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 grafting rate was too low in the method described in Publication No. 26665;
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 graft active site into the side chain of a vinyl polymer and performing a graft copolymerization reaction using the site, and have thus arrived at the present invention.

That is, the present invention provides vinyl polymers 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 their side chains; The present invention provides a method for producing a graft copolymer, which comprises polymerizing an aromatic polysulfone-forming monomer in the presence of the copolymer.

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 in which the polymerization of aromatic polysulfone structural units and the graft reaction are simultaneously carried out in the presence of an activated vinyl (co)polymer, and the resulting graft copolymer is It has the characteristics of Therefore, hereinafter, for convenience, the reaction of the present invention will be referred to as a graft copolymerization reaction.

The aromatic polysulfone formed by the graft copolymerization reaction of the present invention is a condensation reaction of an alkali phenolate group and an aromatic halogen group activated with an electron-withdrawing sulfone group in an aprotic polar solvent. It is a linear polymer that has three essential bond units: an arylene bond (aromatic bond), an ether bond, and a sulfone bond. 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-
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-
di(hydroxyphenyl)ethers, such as bis-(4-hydroxyphenyl);
ether, 4,3'-, 4,2'-, 2,2'-, 2,
3'-dihydroxydiphenyl ether, 4,4'-
Dihydroxy-2,6-dimethyl diphenyl ether, bis-(4-hydroxynaphthyl) ether, etc.; di(hydroxyphenyl) sulfone, such as bis-(4-hydroxyphenyl) sulfone, bis(3-hydroxyphenyl) ) sulfone, 2,4'-dihydroxyphenyl sulfone, bis-(3-hydroxyphenyl) sulfone, 2,
Further examples thereof include analogs thereof having three or more phenyl nuclei, such as 4'-dihydroxydiphenyl sulfone. 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. where X represents halogen, i.e. fluorine, 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 aromatic halofenols having a sulfone bond in the molecule used in method (2) above include those shown in the following formula (where X is halogen, i.e., fluorine, chlorine, 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 may be used alone or in a mixture of two or more, or alternatively in a mixture 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 catalyst 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.

When aromatic polysulfone is polymerized in the presence of an activated vinyl (co)polymer by the above-mentioned graft copolymerization reaction, the polymerization method is not particularly limited. For example, methyl chloride, acetic anhydride, etc. may be added to block the terminals, or such operation may be omitted and the free terminals of the graft copolymer may remain as alkali phenolate groups or phenolic hydroxyl groups.

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
- It can be produced by (co)polymerizing one or more functional vinyl monomers such as bromomethylstyrene and p-chlorosulfonylstyrene. 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. 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, the amount of active sites (graft-reactive functional groups) should be 30% by weight or less as a functional group amount, and the copolymerization composition of functional vinyl monomer should be 50% by mole or less, preferably 20% by mole. % or less. Also,
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 functional groups and 0.1% by mole or more as the copolymerization composition of the functional vinyl monomer.

In other words, the active sites are 0.05 to 30% by weight as the amount of functional groups, and 0.1% as the copolymerization composition of the functional vinyl monomer.
mol% to 50 mol%. 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 _C1 to _C18 alkyl group components, _C1 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 a graft copolymerization reaction. In carrying out this method, 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. Therefore, in carrying out the graft copolymerization reaction, sulfoxide solvents such as dimethyl sulfoxide, which are commonly used as polymerization solvents for aromatic polysulfone, sulfone solvents such as dimethylsulfone and sulfolane, dimethylformamide, and dimethylacetamide are used. , N-methylpyrrolidone, etc.
It is desirable to select an activated vinyl (co)polymer that has the property of dissolving or swelling in aprotic polar solvents such as substituted amide solvents.

In the graft copolymerization reaction of the present invention, an active vinyl (co)polymer that is dissolved in the same solvent as the polymerization solvent of the aromatic polysulfone is added at the beginning of the polymerization of the aromatic polysulfone, and the graft reaction and the polymerization of the aromatic polysulfone are carried out in parallel. If you do this, it will proceed efficiently. In this case, the polymerization conditions for the aromatic polysulfone described above can be used as they are.

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.

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 tendency to delamination seen with simple blends is reduced. Also,
Compared to aromatic polysulfones themselves, the fluidity is much better 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. Also,
A foamed material can also be formed by incorporating a foaming agent.

Examples of the additives include pigments such as titanium oxide, carbon black, cadmium red, and cyanine blue HB manufactured by Sumitomo Chemical Co., Ltd., reinforcing agents such as glass fiber, carbon fiber, and asbestos;
Fillers such as calcium carbonate, clay, talc, cellulose powder, silica, 3,5-di-tert-4
-hydroxytoluene, hindered phenolic antioxidants such as 4,4'-butylidene bis-(6-tert-butyl-m-cresol), 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 aze Plasticizers such as azelaic acid derivatives such as ester, 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 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 described in further detail with reference to Examples.

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

Examples Example 1 (1) Production of p-chloromethylstyrene copolymer In a flask with an internal volume of 500 ml equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube,
Acrylonitrile 48g (0.906mol), styrene
144.8g (1.392mol), p-chloromethylstyrene 7.2g (0.047mol), azobisisobutyronitrile 0.74g, water 400g, partially saponified methyl methacrylate/acrylamide (20/80) copolymer 0.2g , sodium dihydrogen phosphate 0.1g
and 0.48 g of t-dodecyl mercaptan, stirred, and heated to 70℃ for 2 hours while flowing nitrogen gas.
Suspension polymerization was carried out by holding at 90° C. for 1 hour.

Next, the obtained granular polymer was dehydrated using a centrifuge, thoroughly washed with water, and then dried using a vacuum dryer.
After drying at 70° C. 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.
0.24 mmol/g of polymer, with approximately 2 p-chloromethylstyrene units according to the initial charging ratio.
It was confirmed that mol% copolymerization was carried out.

(2) Production of graft copolymer Add 50% dimethyl sulfoxide to one flask equipped with a stirrer, thermometer, gas inlet tube, and distillation tube.
g, chlorobenzene 133g, bisphenol
23.3 g (0.102 mol) of A 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. After heating this reaction solution to 75°C, 16.32 g (0.204 mol) of a 50% concentration sodium hydroxide aqueous solution was added, and then heated to 75°C.
When the mixture was heated to 100%, 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 partially proceeded. At this point, the temperature of the reaction system was quickly lowered to about 150-160°C, and after 30 minutes, 500 g of a dimethyl sulfoxide solution containing 103.1 g of the acrylonitrile/styrene/p-chlorostyrene copolymer produced in (1) above was added. Addition (Preparation ratio of aromatic polysulfone chloromethyl styrene copolymer = 3070), 150~
The mixture was stirred at a temperature of 160° C. for about 1 hour to carry out a graft reaction and a polysulfone polymerization reaction.
Thereafter, the reaction mixture was diluted with 300 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 coagulating, and vacuum-dried at 70°C for 16 hours. As a result, 138.5g of the polysulfone/p-chloromethylstyrene copolymer-based graft copolymer was obtained ( yield 94%)
Obtained.

Graft copolymer thus obtained
When 1.0g was added to 100ml of acetone and extracted for 3 hours under reflux temperature conditions, the extraction residue was
It was 0.41g. This residue corresponds to polysulfone and grafted p-chloromethylstyrene copolymer. From this, the grafting ratio of p-chloromethylstyrene copolymer to the polysulfone backbone [=(grafted chloromethylstyrene copolymer weight/polysulfone backbone polymer weight)×100
] was calculated to be 36.7%.

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 133°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 102°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 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 In the graft polymerization of aromatic polysulfone in Example 1 (2), styrene/acrylonitrile (76/24) copolymer was used instead of 103.1 g of acrylonitrile/styrene/p-chloromethylstyrene copolymer.
A polymer composition was obtained by performing the same polymerization operation and post-treatment except that 103.1 g was used. Subsequently, the grafting rate of this polymer composition was determined according to Example 1.
When measured using the same method as above, it was a small value of 2.8%. 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.

Further, when the softening point of this polymer composition was measured by the BS method, it was 112°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, and a 20 mmφ glass product was prepared. Enclosed in an ampoule.
Place this ampoule in an oil bath and heat at 70℃ for 3 minutes.
When polymerization was carried out by holding the mixture at 90° C. for 2 hours, a colorless methyl methacrylate/methacrylic acid chloride (97/3 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 copolymer Add dimethyl sulfoxide to a 300 ml flask equipped with a stirrer, thermometer, gas inlet tube, and distillation tube.
50g, chlorobenzene 133g, bisphenol
22.8 g (0.10 mol) of A 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°C, 16.0 g (0.20 mol) of a 50% concentration sodium hydroxide aqueous solution was added, and then heated to 75°C.
When the mixture was heated to 100%, 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 after 10 minutes, 150 g of a dimethyl sulfoxide solution containing 29.4 g of the methacrylic acid chloride copolymer produced in (1) above was added (polysulfone methacrylic acid chloride Copolymer = 6040 preparation ratio),
The mixture was stirred at a temperature of 150 to 160°C for about 1 hour to carry out graft and polysulfone polymerization reactions.
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 coagulating, and vacuum-dried at 70°C for 16 hours. 66 g (yield: 90%) of polysulfone/methacrylic acid chloride graft copolymer was obtained. It was done.

Example 1 about the obtained graft copolymer
When the grafting rate was measured in the same manner as above, it was 23%. Furthermore, when the BS method softening point of this polymer was measured, it was found to have excellent heat resistance of 148°C.

Comparative Reference Example 2 In the graft polymerization of aromatic polysulfone in Example 2 (2), 29.4 g of methyl methacrylate homopolymer was used instead of 29.4 g of methyl methacrylate/methacrylic acid chloride (97/30 molar ratio) copolymer. A polymer composition was obtained by performing all the same polymerization operations and post-treatments except for the use. When the grafting rate of this polymer composition was measured, it was a small value of 1% or less, and the softening point according to the BS method was 132°C, indicating that the polymer composition had inferior heat resistance compared to Example 2.

Example 3 (1) Production of maleic anhydride copolymer 1 equipped with a stirrer, thermometer and reflux condenser
5 g (0.05 mol) of maleic anhydride, 95 g (0.95 mol) of methyl methacrylate, 0.5 g of azobisisobutyronitrile, and 1 mol of methyl ethyl ketone were placed in a flask, and the mixture was heated to 70° 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 graft copolymer Add dimethyl sulfoxide to a 300 ml flask equipped with a stirrer, thermometer, gas inlet tube, and distillation tube.
50g, chlorobenzene 133g, bisphenol
22.8 g (0.10 mol) of A 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°C, 16.0 g (0.20 mol) of a 50% aqueous sodium solution was added, and then heated to 75°C.
When the mixture was heated to 100%, 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 to 160°C, and after 10 minutes, 250 g of a dimethyl sulfoxide solution of 66.2 g of the methyl methacrylate/maleic anhydride (95/5 molar ratio) copolymer prepared in 1 above was added. (polysulfone maleic anhydride copolymer = 4060 charging ratio) and stirred at a temperature of 150 to 160°C for about 1 hour to carry out grafting and polysulfone polymerization reactions. Thereafter, the reaction mixture was diluted with 400 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 filtrate into 5 times the amount of methanol and coagulating it, and the polymer was incubated at 70°C for 16
After vacuum drying for an hour, 97 g of polysulfone/maleic anhydride graft copolymer was obtained (yield 88
%) obtained.

Example 1 about the obtained graft copolymer
When the grafting rate was measured in the same manner as above, it was 59%.

Example 4 (1) Production of allyl glycidyl ether copolymer 23 g (0.221 mol) of styrene, 6 g (0.113 mol) of acrylonitrile, 1 g (0.009 mol) of allyl glycidyl ether, 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 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 dimethyl sulfoxide to a 300 ml flask equipped with a stirrer, thermometer, gas inlet tube, and distillation tube.
50g, chlorobenzene 133g, bisphenol
22.8 g (0.10 mol) of A 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°C, 16.0 g (0.20 mol) of a 50% concentration sodium hydroxide aqueous solution was added, and then heated to 75°C.
When the mixture was heated to 100%, a water/chlorobenzene azeotrope began to distill from the system. As the azeotrope continued to be distilled off, 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 partially proceeded. The temperature of the reactant was quickly lowered to 150-160°C, and after 10 minutes, the styrene/produced in (1) above was added.
Dimethyl sulfoxide solution of 18.9 g of acrylonitrile/allyl glycidyl ether copolymer
Add 120g (polysulfone allyl glycidyl ether copolymer = 7030 preparation ratio),
The mixture was stirred at a temperature of 150 to 160°C for about 1 hour to carry out the graft reaction and the polysulfone polymerization reaction. Then, convert the reaction mixture to 200% of chlorobenzene.
After diluting the solution with 1.5 g of water, the mixture was filtered by suction 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 57.5 g of polysulfone/allyl glycidyl ether copolymer-based graft copolymer (yield
91.1%) obtained.

Example 1 about the obtained graft copolymer
In the same manner as above, the grafting ratio of styrene/acrylonitrile/allyl glycidyl ether copolymer to the main polysulfone was measured.
It was 17.1%.

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. 1. A method for producing a graft copolymer, which comprises polymerizing a polyarylene ether sulfone-forming monomer in the presence of.