JPH0229405A - Production of thermoplastic resin - Google Patents

Abstract

PURPOSE:To improve heat resistance and transparency by copolymerizing a specified (meth)acrylate with a specified N-substd. maleimide. CONSTITUTION:5-60wt.% N-substd. maleimide of formula I (wherein R is H or a 1-4C alkyl; n is 0 or 1) and a (meth)acrylate of formula II (wherein R1 is H or methyl; R2 is a 1-5C alkyl) are polymerized. To obtain a substance of formula I, an amine compd. of formula III (wherein R and n are the same as described above) is subjected to an addition reaction with maleic anhydride and the obtd. maleamic acid of formula IV (wherein R and n are the same as described above) is cyclized through dehydration.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a thermoplastic resin comprising a novel N-substituted maleimide as a monomer component.

[Conventional technology]

Traditionally, polymethyl methacrylate has been used as a general-purpose plastic due to its excellent light transmittance, weather resistance, impact resistance,
Although it is widely used in various applications due to its workability and light weight, it has the disadvantage that it cannot be used in fields subject to high heat because it does not have sufficient heat resistance.

Therefore, various types of N have been used to improve the heat resistance of vinyl thermoplastic resins such as polymethyl methacrylate.
A method of copolymerizing -substituted maleimides has been proposed. For example, a method of copolymerizing N-phenylmaleimide (Japanese Patent Publication No. 439753, Japanese Patent Publication No. 56-179034, Japanese Patent Publication No. 57-45692, Japanese Patent Publication No. 5B-162616, Japanese Patent Publication No. 58-206657, etc.), Method for copolymerizing xylmaleimide (JP-A-62-15611
Publication No. 5, etc.).

[Problem to be solved by the invention]

However, the above methods for improving the heat resistance of vinyl thermoplastic resins have various problems.The method of copolymerizing N-phenylmaleimide improves the heat resistance, but the N-phenylmaleimide itself Since it is yellow, there is a problem that not only is it impossible to obtain a colorless and transparent resin, but the resin is also significantly colored. In addition, with the method of copolymerizing N-cyclohexylmaleimide, a resin with excellent transparency and almost no coloring can be obtained, but the heat resistance is not sufficiently improved and it is difficult to obtain a satisfactory product. Can not.

Therefore, the present inventors have conducted extensive research with the objective of developing a vinyl thermoplastic resin with excellent heat resistance and transparency. As a result, the inventors discovered that the above-mentioned problems could be solved by copolymerizing a specific (meth)acrylic acid ester with a specific N-substituted maleimide, and completed the present invention.

[Means to solve the problem]

That is, the present invention provides (A) general formula [■]: [in the formula R
represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
n is O or 1] and (B) general formula [■]: R+ CHz=CCORz (II) [wherein R8 represents a hydrogen atom or a methyl group, and R2 represents the number of carbon atoms The present invention relates to a method for producing a thermoplastic resin characterized by polymerizing a (meth)acrylic acid ester represented by 1 to 5 alkyl groups.

The present invention will be explained in detail below.

The N-substituted maleimide represented by the general formula CI) used in the present invention is a novel compound, for example, an amine represented by the general formula [■]: [wherein R and n are as defined above] By adding the compound and maleic anhydride, - general formula [■]
: It can be obtained by obtaining a maleamic acid represented by [wherein R and n are as defined above] and then dehydrating and ring-closing this maleamic acid.

As mentioned above, the production of the N-substituted maleimide used in the present invention is a step of adding maleic anhydride to the amine compound represented by the general formula [111) to produce maleamic acid represented by the general formula (IV). (first step) and a step (second step) of dehydrating and ring-closing maleamic acid represented by general formula (IV) to form an N-substituted maleimide represented by general formula (I).

Although the first step and the second step can be performed separately or continuously, it is preferable to perform them continuously from the viewpoint of efficiency. Each step will be explained in more detail below.

In the first step, anhydrous male 4790.6 to 1.2
A mole, more preferably 1 mole, is reacted. this is,
This is to prevent unreacted raw materials from remaining in the reaction product.

It is preferable to use a solvent during the reaction, and known solvents for maleimide acid synthesis can be used. However, in order to perform the first and second steps continuously, dehydration Solvents that can azeotropically remove water produced in the ring-closing reaction, are inert, and do not participate in the reaction are preferred, such as paraffinic solvents such as octane, nonane, decane, dodecane, trimethylhexane, tetrachloroethane, and ethylcyclohexane; benzene, toluene,
xylene, ethylbenzene, cumene, mesitylene, L-
Butylbenzene, pseudocumene, chlorobenzene, 0
- Aromatic systems such as dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, butylbenzene, P-cymene, n-butylbenzene, 5ec-butylbenzene, tetrahydronaphthalene, decahydronaphthalene, naphthalene, cyclohexylbenzene, etc. Solvents can be used. Tetrahydronaphthalene and p-cymene are preferred. The amount of solvent used is 1 to 2 per amine compound as the raw material.
It is preferably 0 times the amount (weight), and 4 to 10 times the amount (by weight).
weight) is more preferable.

During the reaction, the entire amount of the amine compound and maleic anhydride may be charged from the beginning, but since the reaction is exothermic, it is more preferable to add one of the two later, and more preferably, the maleic anhydride is completely dissolved in the solvent. under stirring, taking care to maintain the temperature below 120°C, preferably between 30 and 100°C, in a flask
The amine compound is added dropwise over 20 minutes, and maleic anhydride is mainly added to the amine compound to obtain maleamic acid represented by the general formula [IV]. At this time, the amine compound to be added may be dissolved in the same solvent as in the flask.

In the second step, all the solvents that can be used in the first step can be used, but in order to perform the first and second steps continuously, the solvent used in the first step must be used as is. is preferred. Since the amount used is the same as that in the first step, there is no need to add a new solvent when performing the reaction continuously.

In the second step, Lewis acids such as boron trifluoride, mineral acids such as sulfuric acid, sulfuric anhydride, orthophosphoric acid, metaphosphoric acid, and pyrophosphoric acid, paratoluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, etc. are used as acid catalysts. It is preferable to use organic acids, heteropolyacids such as phosphotungstic acid, silicotungstic acid, and the like. The amount used is preferably 5 to 150% by weight based on the raw material amine compound. More preferably, it is 20 to 100% by weight. The entire amount of the catalyst may be added at once, but it may also be added in several portions. If the amount of catalyst is too small, the reaction will not progress easily, and if it is too large, there is no particular advantage. The reaction is
It is preferable to carry out dehydration condensation (dehydration ring closure) by raising the temperature to 140 to 270°C.

It is more preferable to carry out dehydration condensation by raising the temperature to 170 to 250'C. This time can be selected as appropriate depending on the batch size, catalyst and reaction conditions employed.

In the reaction, the metal-containing compound is an oxide, acetate, maleate, succinate, or nitrate of at least one metal selected from the group consisting of zinc, chromium, palladium, cobalt, nickel, iron, and aluminum. It is preferable to add phosphates, chlorides, sulfates, etc.
Among these, zinc acetate is particularly effective. The amount of these used is O,OO5 to 1 mole of maleamic acid.
0.5 mol% is preferred. More preferably 0.01 to 0.3 mol%.

Furthermore, as a stabilizer, a polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, 2,4-dimethyl-6-monobutylphenol, p-benzoquinone, 25-diphenyl-p-benzoquinone, phenothiazine, n-nitrosodiphenylamine, &Ii salt, etc. ~2000p
It is preferable to add pm.

After the completion of the dehydration ring-closing reaction, if an acid catalyst is used, remove the catalyst by washing the reaction solution in water or an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, etc., or neutralizing with water. Method: add alkali powder such as sodium carbonate, sodium bicarbonate, magnesium oxide, etc., stir, and then pass through neutralized salt to remove the catalyst; or add amine such as triethylamine, triethanolamine, morpholine, etc. The acid catalyst can be treated by methods such as neutralizing the catalyst.

After the dehydration ring-closing reaction (if an acid catalyst is used, carry out the above treatment), the reaction solution is purified by vacuum distillation or sublimation after removing the reaction solvent under pressure in the heating range.
The N-substituted maleimide represented by the formula [a] can be obtained with high purity.

The N-substituted maleimide thus obtainable is a white crystal.

In addition, the general formula (1) can also be obtained by the manufacturing method described below.
An N-substituted maleimide represented by can be produced.

For example, i) an amine compound and maleic anhydride are reacted, and the resulting maleamic acid is heated and dehydrated and ring-closed with a solvent such as toluene, xylene, or chlorobenzene, and an acid catalyst such as sulfur trisulfide, sulfuric acid, orthophosphoric acid; A production method in which the produced water is distilled out of the yarn by azeotropy with a solvent,
ii) An amine compound and maleic anhydride are reacted in an organic solvent, and the generated maleamic acid is dehydrated and ring-closed in the coexistence of an aprotic polar solvent such as dimethylformamide or dimethyl sulfoxide and an acid catalyst without isolation. Production method, yama) A production method in which maleamic acid is dehydrated and ring-closed using a tertiary amine as a catalyst in the presence of a dehydrating carboxylic anhydride, iv) Maleamic acid is prepared in an organic solvent capable of azeotroping with water, using an acid catalyst, zinc, etc. Examples include a production method in which dehydration and ring closure are carried out at a reaction temperature in the range of 170 to 250°C in the coexistence of a metal-containing compound and a stabilizer. The production method iv) is preferred.

(Meta) represented by general formula (n) used in the present invention
Examples of acrylic esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-pentyl acrylate, methyl methacrylate, ethyl methacrylate, Mn-propyl methacrylate, Examples include isopropyl methacrylate, n-butyl methacrylate, and n-pentyl methacrylate. Among these, methyl methacrylate is preferred from the viewpoint of transparency, heat resistance, moldability, strength, etc.

When copolymerizing the above-mentioned N-substituted maleimide and (meth)acrylic acid ester to obtain a thermoplastic resin, other polymerizable monomers that can be polymerized with these may be blended as necessary. Can be copolymerized.

In the present invention, other polymerizable monomers include general formula (
[There are unsaturated fatty acid esters, aromatic vinyl compounds, vinyl cyanide compounds, N-substituted maleimides not included in general formula (1), etc. that are not included in II.

-a Unsaturated fatty acid esters not included in formula (II) include acrylic acid alkyl esters such as hexyl acrylate and 2-ethylhexyl acrylate, cyclohexyl acrylate, and tricyclo(5,2,1,0
"°6] Acrylic acid cycloalkyl esters such as decar-8-yl, isobornyl acrylate, norbornyl acrylate, acrylic acid aromatic esters such as phenyl acrylate and benzyl acrylate, acrylic acid esters such as glycidyl acrylate, methacrylic acid methacrylic acid alkyl esters such as hexyl, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, cycloalkyl methacrylate such as tricyclo(5,2,1,0''°b]decar-8yl methacrylate, isobornyl methacrylate, norbornyl methacrylate) Examples include esters, aromatic methacrylic esters such as phenyl methacrylate and benzyl methacrylate, and methacrylic esters such as glycidyl methacrylate.

Examples of aromatic vinyl compounds include α-methylstyrene, α
There are α-substituted styrenes such as -ethylstyrene, nuclear substituted styrenes such as chlorostyrene, vinyltoluene, and t-7'tylstyrene.

Furthermore, examples of vinyl cyanide compounds include acrylonitrile and methacrylonitrile.

Examples of N-substituted maleimides not included in general formula (1) include N-methylmaleimide, N-ethylmaleimide, N-
-isopropylmaleimide, N-butylmaleimide, N-
Aliphatic N-substituted maleimides such as lauryl maleimide, N
Examples include alicyclic N-substituted maleimides such as -cyclohexylmaleimide, aromatic N-substituted maleimides such as N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide, and N-methoxyphenylmaleimide.

In order to obtain a thermoplastic resin with excellent heat resistance and transparency and good moldability, it is necessary that the polymerization solution contains 5 to 60% by weight of the N-substituted maleimide of the -C formula (1). Preferable. If the amount of N-substituted maleimide is too small, it will be difficult to fully achieve the above effects, and if it is too large, moldability will tend to deteriorate. Also, if the solution to be polymerized has the general formula ( It is preferable that the content of (meth)acrylic acid ester represented by IN is 95% by weight or less. If it is too large, the heat resistance tends to be poor.

Moreover, it is preferable that the other polymerizable monomers are contained in the polymerization solution in an amount of 40% by weight or less. If it is too large, moldability and heat resistance tend to deteriorate.

In order to produce the thermoplastic resin of the present invention, the general formula (1
The N-substituted maleimide of ), the vinyl monomer of general formula [11), and other polymerizable monomers as necessary can be copolymerized by a known method such as radical polymerization or ionic polymerization. For example, it can be produced by methods such as bulk polymerization, solution polymerization, and suspension polymerization in the presence of a polymerization initiator.

Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, di-butylperoxyhexahydrophthalate, t-butylperoxy-2-ethylhexanoate, 1,1-di-butylperoxy-3.3. 5
-) Organic peroxides such as limethylcyclohexane, azobisisobutyronitrile, azobis-4-methoxy-24
-Ab compounds such as dimethylvaleronitrile 7-1-carbonitrile and abdibenzoyl, water-soluble catalysts represented by potassium persulfate and ammonium persulfate, and redox catalysts using a combination of peroxides or persulfates and reducing agents, etc. Anything that can be used in normal radical polymerization can be used.

The polymerization catalyst is preferably used in an amount of 0.01 to 10% by weight based on the total amount of monomers. Mercaptan compounds, thioglycol, carbon tetrabromide as polymerization regulators,
α-methylstyrene dimer or the like may be added as necessary to adjust the molecular weight.

The polymerization temperature is preferably selected appropriately within the range of 0 to 200°C, particularly preferably 50 to 150°C.

Solvents for solution polymerization include benzene, toluene,
Xylene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, dichloroethylene, etc. can be used. Suspension polymerization is carried out in an aqueous medium, with the addition of suspending agents and, if necessary, suspension aids. Suspending agents include polyvinyl alcohol, methylcellulose,
Examples include water-soluble polymeric substances such as polyacrylamide, and sparingly soluble inorganic substances such as calcium phosphate and magnesium pyrophosphate. The water-soluble polymer substance is 0% based on the total amount of monomers.
．． It is preferable to use the slightly soluble inorganic substance in an amount of 0.05 to 0.5% by weight based on the total amount of monomers.

Suspending aids include anionic surfactants such as sodium dodecylbenzenesulfonate, and when a sparingly soluble inorganic substance is used as a suspending agent, it is preferable to use a suspending aid in combination.

The suspension aid is 0.001 to 0.0 based on the total amount of monomers.
Preferably, 2% is used.

Further, the thermoplastic resin of the present invention can also be used by graft polymerizing other rubbery polymers.

The thermoplastic resin of the present invention contains antioxidants such as phenol-based, thioether-based, and phosphite-based antioxidants, lubricants, antistatic agents, ultraviolet absorbers, etc. from the viewpoint of preventing deterioration of the thermoplastic resin and improving moldability. It may be added if necessary.

The thermoplastic resin of the present invention can be used as a raw material for optical elements as an optical resin, and can also be used as a general molding material, coating material, etc.

The above-mentioned optical elements include optical members such as plastic lenses and prisms, information recording media such as audio discs, video discs, and information discs, or optical equipment elements such as substrates therefor, and automobile hendroid and taillight 1. Translucent materials (covers) such as -, covers for meter displays in automobiles, etc., transparent materials (covers) for closed lighting fixtures for bathrooms, etc.
There are parts for lighting equipment such as covers).

[Example] The present invention will be specifically explained with reference to Examples below, but the present invention is not limited thereto.

Synthesis Example 1 [Synthesis of N-norbornylmethylmaleimide] Stirrer,
49.98 g (0.51 mol) of maleic anhydride and 49.98 g of p-cymene were placed in a 1,000 ml glass funnel flask equipped with a thermometer, a dropping funnel, and a reflux condenser with an oil-water separator. After raising the temperature with stirring to completely dissolve maleic anhydride in p-cymene at about 60°C, add norbornylmethyl while being careful to maintain the temperature in the flask below 100°C. 63.75 g (0.51 mol) of amine was mixed with 382.7 g (0.51 mol) of p-cymene.
5g? The dissolved solution was added dropwise over 1 hour while stirring to synthesize a slurry of p-cymene in N-norbornylmethylmaleimide acid.

Next, 45.5 g of orthophosphoric acid was added to the slurry liquid.

Zinc acetate 0.3774g, hydroquinone 0.0569g
After adding 0.0569 g of cupric chloride, the temperature was raised, and when the temperature inside the flask reached about 150°C, water began to distill out together with p-cymene.

Thereafter, the temperature was further raised to about 180°C, and the reaction was carried out for 7 hours while distilling water produced by the reaction out of the system together with p-cymene. After the reaction was completed, the acid catalyst layer precipitated in the lower layer was separated and removed.

Subsequently, 200 ml of ion-exchanged water was added to the reaction solution, and the mixture was stirred and washed with water at about 60° C. for 30 minutes, and the aqueous layer was separated and removed.

After repeating this operation once more, the reaction solution was transferred to a 21 separatory funnel and washed repeatedly with ion-exchanged water to completely remove the catalyst. Thereafter, in order to remove a trace amount of water remaining, anhydrous sodium sulfate was added to the reaction solution after washing with water, and after sufficient stirring, the sodium sulfate was removed by filtration.

After water washing and dehydration, 0.0569 g of hydroquinone and 0.0569 g of cupric chloride were newly added to the reaction solution, which was then subjected to an evaporator to completely remove the solvent p-cymene to obtain light brown crystals. .

Next, the light brown crystals obtained as described above were
Purified by sublimation at 10°C with 10.1 Hg to give white crystals 62.
7 g was obtained.

The analysis results of the obtained white crystals are shown below.

First, elemental analysis was performed and the results were as follows.

Element CHO Theoretical value (%) 70.22 7.37 6.8
2 Actual measurement value (%)? 0.15 7.45 6.
76 Furthermore, when we analyzed the 'H-NMR spectrum using deuterated chloroform as a solvent, the signal of the norbornyl group was around 1.0 to 2.4 ppra, and the signal of methylene based on norbornylmethylamine was around 3.1 to 3.5 ppra. 6
ppm, a signal of an olefinic double bond based on maleic anhydride was present at around 6.65 ppm, and when the integrated intensity ratio of this proton was measured, it was 11:2:2.
Met. This 'H-NMR spectrum is shown in FIG.

From the above analysis results, it was confirmed that the obtained white crystals were N-norbornylmethylmaleimide.

Synthesis Example 2 [Synthesis of N-norbornylmaleimide] Into the same flask as in Synthesis Example 1, 49.98 g of maleic anhydride (0.51
mol) and 49.98 g of P-cymene were charged, the temperature was raised without stirring, and the maleic anhydride was completely dissolved in p-cymene at about 60°C, and then the temperature inside the flask was raised to 100°C.
56.61 g (0.51 mol) of 2-aminonorbornane was added to 33 g of p-cymene, taking care to maintain a
A solution in which 9.7 g of N-norbornyl maleamic acid was dissolved in p-cymene was added dropwise over 1 hour while stirring to prepare a slurry of N-norbornyl maleamic acid in p-cymene.

Next, after adding 42.6 g of orthophosphoric acid, 0.3519 g of zinc acetate, 0.0533 g of hydroquinone, and 0.0533 g of cupric chloride to the slurry liquid, the temperature was raised, and the same reaction as in Synthesis Example 1 was carried out. After post-treatment and purification, 58.6 g of white crystals were obtained.

When 'H-NMR spectrum was analyzed using deuterated chloroform as a solvent, the signal of norbornyl group was 1.0~
The signal of the proton at the position substituted with maleimide of the norbornyl group is present at around 2.4 ppm, the signal of the proton at the position substituted with maleimide of the norbornyl group is present at around 3.9 ppm, and the signal of the olefinic double bond based on maleic anhydride is present at around 5.6 ppm. When the integrated intensity ratio was measured, it was 10:1:2. This 'H-NMR spectrum is shown in FIG.

From the above analysis results, it was confirmed that the obtained white crystals were N-norbornylmaleimide.

Example 1 10 g of N-norbornylmethylmaleimide obtained in Synthesis Example 1, 90 g of methyl methacrylate, 084 g of lauroyl peroxide, and 0.2 g of lauroyl mercaptan were charged into a 500-piece Erlenmeyer flask equipped with a three-way stopcock, and mixed. After dissolving and purging the inside of the flask with nitrogen gas, it was immersed in a constant temperature water bath at 60°C with stirring and shaking, and heated for 30 minutes under a nitrogen stream.
Polymerization was carried out for a minute to obtain a partially polymerized product. Subsequently, this partially polymerized product was injected into a glass cell and polymerized at 65°C for 5 hours, and then at 100°C for 2 hours to obtain a transparent sheet-like resin [A]. When the obtained resin (A) was analyzed by infrared absorption spectrum (hereinafter abbreviated as IR spectrum), absorption of imide group at around 1710 cm-' was detected.
Absorption of carbonyl group based on methyl methacrylate was observed around 40 cm-'. The IR spectrum of resin (A) is shown in FIG.

Example 2 N obtained in Synthesis Example 1 was placed in the same Erlenmeyer flask as in Example 1.
-Norbornylmethylmaleimi t” 20g.

Methyl methacrylate 80g, lauroyl peroxide 0.4g
and 0.2 g of lauro il mercaptan were added to obtain resin CB in the same manner as in Example 1. resin CB
) [R spectrum is shown in FIG.

Example 3 N obtained in Synthesis Example 2 was placed in an Erlenmeyer flask similar to Example 1.
- 10 g of norbornylmaleimide, 90 g of methyl methacrylate, 0.4 g of lauroyl peroxide and 0.2 g of tau and 1 coil mercaptan were charged, and the same procedure as in Example 1 was carried out to obtain a resin (C).

The IR spectrum of resin [C] is shown in FIG.

Example 4 N obtained in Synthesis Example 2 was placed in an Erlenmeyer flask similar to Example 1.
- 20 g of norbornylmaleimide, 80 g of methyl methacrylate, 0.4 g of lauroyl peroxide and 0.2 g of lauroyl mercaptan were charged, and the same procedure as in Example 1 was carried out to obtain resin CD).

Comparative Examples 1 to 5 N-phenylmaleimide (manufactured by Nippon Shokubai Chemical Co., Ltd., trade name Imilex-P) was placed in the same Erlenmeyer flask as in Example 1.
N-cyclohexylmaleimide (manufactured by PFALTZ & BAtlER), methyl methacrylate, lauroyl peroxide and lauroyl mercaptan were prepared in the proportions shown in Table 1, and the mixture was exactly the same as in Example 1. Resins (E) to (1) were obtained.

After dissolving the resin (A) obtained as above (1,350 g in 250 g of tetrahydrofuran), the obtained solution was stirred and poured into 2,500 g of methanol to precipitate and precipitate the resin. A white powdery resin was obtained. The weight average molecular l (Mw), number average molecular weight (M, n), glass transition temperature and thermal decomposition temperature of this resin were measured by the following methods, and the results are shown in Table 2.

Weight average molecular weight (Mw) and number average molecular weight (Mn) were obtained by obtaining a chromatogram using gel permeation chromatography (GPC) and converting it into polystyrene.

Glass transition temperature (Tg) It was measured with a differential scanning calorimeter (DSC).

Thermal decomposition temperature (Td) Measured by thermogravimetric analysis under the following conditions, and the temperature measured in %M was read.

Atmosphere: Air 20mR 1 minute Temperature rising rate: 5°C/min 5 times (blank below) As is clear from the above results, Examples 1 to 4 of the present invention
The resin obtained is N-phenylmaleimide or N
-It has better heat resistance than a copolymer resin of cyclohexylmaleimide and methyl methacrylate.

[Effects of the Invention] The thermoplastic resin obtained by the present invention has excellent heat resistance and transparency.

[Brief explanation of the drawing]

Figure 1 shows the 'H-NMR spectrum of N-7/rubornylmethylmaleimide obtained in Synthesis Example 1, and Figure 2 shows the 'H-N MR spectrum of N-norbornylmaleimide obtained in Synthesis Example 2.
H-NMR spectrum, Figure 3 is the IR spectrum of resin (A) obtained in Example I, Figure 4 is the IR spectrum of resin CB) obtained in Example 2, and Figure 5 is the example. This is an IR spectrum 1 of resin [C] obtained in Step 3. Agent Patent Attorney Kunihiko Wakabayashi

Claims (1)

[Claims] 1. (A) General formula [I]: ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] [In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, n is 0 or 1] and (B) general formula [II]: ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [II] [In the formula, R_1 represents a hydrogen atom or a methyl group , R_2 represents an alkyl group having 1 to 5 carbon atoms] (
A method for producing a thermoplastic resin, characterized by polymerizing a meth)acrylic acid ester. 2. The method for producing a thermoplastic resin according to claim 1, wherein 5 to 60% by weight of the N-substituted maleimide represented by the general formula [I] is used.