JPS62250007A - Production of n-(hydroxyphenyl)maleimide copolymer - Google Patents

Abstract

PURPOSE:To readily produce the titled copolymer in high yield while holding hydroxyl groups without passing through ester interchange reaction, by reacting maleic anhydride-unsaturated hydrocarbon compound copolymer with an aminophenol and primary amine. CONSTITUTION:A copolymer of maleic anhydride and an unsaturated hydrocarbon compound, e.g. styrene, etc., is reacted with an aminophenol and a primary amine, e.g. o-aminotoluene, etc., having no group capable of imparting solubility in aqueous alkali solutions in an organic solvent to afford the aimed copolymer having constituent units expressed by formulas I-IV [R1 and R2 are aryl or 1-16C (cyclo)alkyl; l, m, n and p satisfy formulas V-VII]. USE:Useful as a thin film coating resin because of solubility in organic solvents and base polymer for photosensitive resins, etc., since the copolymer has phenolic hydroxyl groups and is soluble in aqueous alkali solutions as well as heat- resistant resins.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing an N-(hydroxyphenyl)maleimide copolymer, specifically, a method for producing an N-(hydroxyphenyl)maleimide copolymer, specifically a method for producing an N-(hydroxyphenyl)maleimide copolymer by copolymerizing maleic anhydride and an unsaturated hydrocarbon compound. The resulting copolymer is reacted with aminophenol and a general amine that does not have a group imparting solubility in an aqueous alkaline solution in an organic solvent to modify the copolymer. The present invention relates to a method for producing a hydroxyphenyl)maleimide copolymer.

The N-(hydroxyphenyl)maleimide copolymer obtained by the production method of the present invention is useful as a thin film coating resin because it is soluble in organic solvents such as dimethylformamide, cyclohexanone, tetrahydrofuran, and ethyl cellosolve. Because it has a hydroxyl group, it is soluble in aqueous alkaline solutions, so it is useful as a base polymer for photosensitive resins and the like, and can also be used in a wide range of applications as heat-resistant resins.

[Conventional technology]

A method for producing a copolymer as an N-(hydroxyphenyl)maleimide mo component is described in Kobunshi Kagaku, Vol. 26, 598.
(1969), N-(p-
A method of copolymerizing hydroxyphenyl)maleimide monomer and styrene to synthesize an N-(p-hydroxyphenyl)maleimide-styrene copolymer having a slightly larger number of constituent units based on N-(p-hydroxyphenyl)maleimide is described. and the 7th Photopolymer Conference (sponsored by SPE, Ellenville).

N, Y,) Proceedings, p. 35 (1985), describes the copolymerization of N-(p-acetoxyphenyl)maleimide monomer in which the hydroxyl group at the rose position is esterified with styrene, followed by a transesterification reaction. -(p-hydroxyphenyl)maleimide-styrene copolymer (composition ratio 1:1
) is shown.

In the above-mentioned conventionally known method for producing N-(p-hydroxyphenyl)maleimide-styrene copolymer, a step of converting the esterified hydroxyl group at the monomer or polymer stage back to hydroxyl group by transesterification reaction is necessary. This is because an imide compound having a hydroxyl group, such as the above-mentioned N-(p-hydroxyphenyl)maleimide monomer, cannot be produced only by the usual method for producing an imide compound.

In general, the method for producing imide compounds involves using a base such as pyridine, triethylamine, or sodium acetate as a catalyst.
A well-known method is to react an amino compound with an acid anhydride such as maleic anhydride using an acid anhydride such as acetic anhydride, propionic anhydride, or benzoic anhydride as a dehydrating agent. For example, when applied to the production of a maleimide monomer of aminophenol and maleic anhydride, the hydroxyl group of the aminophenol is esterified, making it impossible to produce an imide compound having a hydroxyl group in high yield.

Therefore, the conventionally known N-(p-hydroxyphenyl)
In the method for producing a maleimide-styrene copolymer, in order to return the hydroxyl group esterified in the monomer or polymer stage to a hydroxyl group by a transesterification reaction, for example, as disclosed in Belgian Patent No. 613801, A method of transesterification of maleimide whose hydroxyl group is esterified is employed.

[Problem that the invention seeks to solve]

The conventionally known method for producing N-(p-hydroxyphenyl)maleimide-styrene copolymer requires a step of converting the esterified hydroxyl group at the monomer or polymer stage into a hydroxyl group by a transesterification reaction, as described above. Since this transesterification reaction requires a long time, it is a very disadvantageous method industrially from the point of view of economic efficiency, etc.
When producing maleimide monomer from aminophenol and maleic anhydride, the unsaturated double bond of maleic anhydride is attacked by 7-minophenol, so the copolymer of maleimide monomer and styrene cannot be produced in high yield. There are problems such as the inability to synthesize.

Therefore, the object of the present invention is to provide N-(hydroxyphenyl)
To provide a method for producing an N-(hydroxyphenyl)maleimide copolymer by which the maleimide copolymer can be synthesized extremely easily and in high yield while retaining hydroxyl groups without going through a transesterification step. It is in.

[Means for solving problems]

The present invention has achieved the above object by preparing a copolymer of maleic anhydride and an unsaturated hydrocarbon compound, an aminophenol, and a primary amine having no group imparting solubility in an aqueous alkaline solution in an organic solvent. (wherein R1 and R2 are an aryl group, an alkyl group having 1 to 16 carbon atoms or a cycloalkyl group,
R8 is hydrogen or a lower alkyl group. Also, p and (1
+m+n), (i+m) and (n+m4-n), and l and B+) are respectively O〈□≦10, j! +m+n #+m+n J+m+n and 0.3□≦0.9. ] This was achieved by providing a method for producing an N-(hydroxyphenyl)maleimide copolymer, which is characterized by obtaining an N-(hydroxyphenyl)maleimide copolymer having a structural unit represented by β 0m .

The method for producing the rl-(hydroxyphenyl)maleimide copolymer of the present invention will be described in detail below.

The copolymer of maleic anhydride and an unsaturated hydrocarbon compound (hereinafter referred to as maleic anhydride copolymer) used in the production method of the present invention is: (wherein R2 is an aryl group, 1 to 16 carbon atoms) is an alkyl group or a cycloalkyl group having R2 is hydrogen or a lower alkyl group.Also, the ratio of a and b is O<-≦10. Preferably a O□≦5.) It is a copolymer having the structural units shown below, and suitable unsaturated hydrocarbon compounds include, for example, styrene,
Examples include α-methylstyrene, vinylnaphthalene, isobutylene, 3-methylbutene-1, hexene-1, and vinylcyclohexene.

In the maleic anhydride copolymer, the ratio (b/a) of the structural units represented by the above formula (V) and the structural units represented by the above formula (Vl) is determined to The above formula (1) in the copolymer, (
n) and (1), respectively, and the above formula (
The ratio (p, / (z +
m+n)). If this ratio exceeds 10, the properties are almost the same as homopolymers of unsaturated hydrocarbon compounds, and N-(hydroxyphenyl)maleimide has no heat resistance and cannot be used as a base polymer for photosensitive polymers. It is not suitable because only polymers can be produced. Furthermore, if the b/a ratio is too small, the coating of the N-(hydroxyphenyl)maleimide copolymer will become weak or sluggish, which is not appropriate.

Further, as the above-mentioned maleic anhydride copolymer, it is preferable to use one having a number average molecular weight ("1") of 1,000 to 500,000.

Further, examples of the aminophenol used in the production method of the present invention include 0-aminophenol, m-aminophenol, p-aminophenol, and the like.

In addition, the primary amines used in the production method of the present invention include:
Any primary amine that does not have a group that imparts solubility in an alkaline aqueous solution such as a hydroxyl group or a carboxyl group may be used, such as o-7 minotoluene, m-aminotoluene, p-aminotoluene, 2,3-xylidine, 2.4
- Aromatic amines such as xylidine, 2.5-xylidine, 2,6-xylidine, 3゜4-xylidine, 3.5-xylidine, aminoethylbenzene, aminoisopropylbenzene, amino-t-butylbenzene, methylamine , ethylamine, propylamine, butylamine, hexylamine, octylamine, dodecylamine, and aliphatic amines, and cycloaliphatic amines such as cyclohexylamine.

The ratio of the maleic anhydride copolymer to the aminophenol and the -class amine is 1 mole of the maleic anhydride component [constituent unit represented by formula (V)] in the maleic anhydride copolymer. On the other hand, the total amount of aminophenol and -class amine is preferably 2 mol or less, more preferably 1.5 mol or less.

Further, the ratio of the aminophenol to the -class amine used is preferably 0.05 mol of the latter to 1 mol of the former.
~4 mol, more preferably 0.1-2 mol.

Furthermore, various polar solvents can be used as the organic solvent used as a reaction solvent in the present invention, and specifically, dimethylformamide, dimethylsulfoxide, N-
Examples include methyl-2-pyrrolidone, hexamethylene phosphoramide, and cyclohexanone.

The amount of the organic solvent used varies depending on the molecular weight of the maleic anhydride copolymer used and its solubility in the solvent, but it is usually 10 to 200 g per 10 g of the maleic anhydride copolymer.
1, preferably 20 to 100 ml.

Therefore, in a preferred embodiment of the production method of the present invention, for example, +11 maleic anhydride copolymer, aminophenol and -class amine are heated at 0 to 150°C, preferably at 10°C in a solvent such as dimethylformamide. After reacting for 1 to 20 hours at a reaction temperature of ~100°C to convert some or all of the maleic anhydride component into a maleamic acid component, a tertiary amine catalyst is added, and the water generated by cyclodehydration is added. Add an azeotropic solvent such as toluene or xylene to remove N-(hydroxyphenyl)maleimide, and perform a cyclization and dehydration reaction at a reaction temperature of 80 to 200°C, preferably 100 to 150°C for 1 to 20 hours to obtain N-(hydroxyphenyl)maleimide. Method for obtaining a copolymer, (2) A maleic anhydride copolymer, an aminophenol, and a -class amine are mixed in an organic solvent such as dimethylformamide in the presence of a tertiary amine catalyst at θ to 150°C, preferably at 1
React for 1 to 20 hours at a reaction temperature of 0 to 100°C, then add an azeotropic solvent such as toluene or xylene, and react for 80 to 20 hours.
React at a reaction temperature of 200° C., preferably 100° C. to 150° C. for 1 to 20 hours to cyclodehydrate some or all of the maleic anhydride component via maleamic acid,
A method for obtaining an N-(hydroxyphenyl)maleimide copolymer, and (3) a maleic anhydride copolymer, an aminophenol, and a -class amine in an organic solvent such as dimethylformamide, a tertiary amine catalyst, toluene, or xylene. 80-200℃, preferably 100℃-150℃ in the presence of an azeotropic solvent such as
Examples include a method of obtaining an N-(hydroxyphenyl)maleimide copolymer by reacting for 1 to 20 hours at a reaction temperature of °C to cyclodehydrate part or all of the maleic anhydride component through maleamic acid. be able to.

In addition, in any of the methods of the above embodiments (11 to (3)), an azeotropic solvent is not used during the cyclization dehydration reaction, and 100 to
Water produced at a reaction temperature of 200° C. can be removed, and the dehydration reaction can be effectively carried out by flowing nitrogen gas.

Examples of the tertiary amine catalyst used in the reaction of the above maleic anhydride copolymer with aminophenol and -class amine include triethylamine, tri-propylamine, tri-butylamine, tri-n-butylamine, and tri-n-propylamine. Pentylamine, tri-n-hexylamine, tri-rooctylamine, pyridine, N
-ethylmorpholine, N-dimethylbenzylamine, isoquinoline and the like.

The amount of these tertiary amine catalysts used is 0.0 per mole of maleic anhydride component in the maleic anhydride copolymer.
It is preferably 1 to 2 mol, particularly 0.1 to 1 mol.

Moreover, benzene, toluene, xylene, etc. can be mentioned as an azeotropic solvent used to remove water generated in the above-mentioned cyclization dehydration reaction.

The amount of these azeotropic solvents to be used is determined because 1 mole of water is generated from 1 mole of the maleamic acid component produced by the reaction of the maleic anhydride component in the maleic anhydride copolymer with the aminophenol and the -class amine. Any amount is sufficient as long as the amount is sufficient to azeotropically remove the produced water, and it is usually preferable to separate it from the azeotropically removed water and reflux it before use, and the volume ratio of the reaction solvent to the azeotropic solvent is preferably 1. :1 or less, more preferably 1j0.5 or less.

The azeotropic solvent may be added in a necessary amount in several portions as the reaction progresses, or may be refluxed while removing water azeotropically.

In the production method of the present invention, the embodiments (1) and (2)
When the reaction of maleic anhydride copolymer with aminophenol and -grade amine is carried out in two steps as in the case of The reaction temperature of the first stage reaction to form the coalescence is preferably in the range of 0 to 150°C, particularly in the range of 10 to 100'C. 0”c
If the temperature is below 150°C, the reaction rate will be extremely low and the reaction will hardly proceed, and if the temperature exceeds 150°C, the water produced by the cyclodehydration of the partially produced maleamic acid will easily react with the unreacted anhydride ring. Further, side reactions due to hydroxyl groups tend to occur, which is not preferable.

In addition, the reaction temperature of the second stage reaction of cyclizing and dehydrating the copolymer of maleamic acid, and the reaction temperature of the maleic anhydride copolymer with aminophenol and -class amine as in the case of embodiment (3) above are also discussed. When the reaction is carried out in one step in the presence of a tertiary amine and an azeotropic solvent for dehydration, the reaction temperature ranges from 80 to 200'c, in particular from 100 to 150'c, respectively.
It is preferable to keep it within the range of . If it is less than 80°C, the reaction rate is extremely low and the reaction hardly progresses, and if it exceeds 200°C, side reactions and intermolecular reactions due to hydroxyl groups tend to occur, which is not preferable.

In addition, in the production method of the present invention, the reaction time of the maleic anhydride copolymer, aminophenol, and -grade amine is determined by the reaction temperature, the amount of aminophenol and -grade amine used, and the desired reaction rate [maleic anhydride copolymer]. Although it varies depending on the degree of modification of the maleic anhydride component in the copolymer to maleimide, etc., the first stage reaction to produce a copolymer of maleamic acid usually involves cycling the copolymer for 1 to 20 hours. The second stage reaction, which is a dehydration reaction, is preferably carried out for 1 to 20 hours.

Further, when the reaction is carried out in one stage in the presence of a tertiary amine and an azeotropic solvent, the reaction time is usually 1 to 20 hours.

In the production method of the present invention, the proportion of the structural unit represented by the formula (1) and the proportion of the structural unit represented by the formula (II) in the target N-(hydroxyphenyl)maleimide copolymer are controlled. , aminophenol and -
This can be easily carried out by appropriately selecting the amount of the grade amine used, the reaction temperature, and the reaction time.

After the reaction is completed, the N-(hydroxyphenyl)maleimide copolymer can be easily recovered from the reaction solution by, for example, precipitating the polymer using an inert solvent such as water or ethers.

The N-(hydroxyphenyl)maleimide copolymer of the present invention obtained as described above contains dimethylformamide,
Because it is soluble in organic solvents such as cyclohexanone, tetrahydrofuran, and ethyl cellosolve, it is useful as a thin film coating resin, and because it has a phenolic hydroxyl group, it is soluble in alkaline aqueous solutions, so it can be used as a base polymer for photosensitive resins, etc. It is useful and can be used in a wide range of applications as a heat-resistant resin.

〔Example〕

EXAMPLES The present invention will be explained in more detail by giving examples below. In addition, in the following examples, the modification rate of the maleic anhydride component in the maleic anhydride copolymer to maleimide was determined from the nitrogen content in elemental analysis, and the ratio to the maleic anhydride component in the maleic anhydride copolymer was determined from the nitrogen content in elemental analysis. Furthermore, the ratio of the structural unit (1) represented by the formula (1') and the structural unit (m) represented by the formula (II) in the N-(hydroxyphenyl)maleimide copolymer is as follows:
It was determined by proton NMR and was shown as 47m. In addition, the infrared absorption spectrum was determined using the KBrBr method, and the number average molecular weight (
Mn) is a polystyrene-equivalent value determined by the GPC method using tetrahydrofuran as a solvent using a standard polystyrene calibration curve. Further, the glass transition temperature (Tg) was measured using a DuPont 990 thermal analyzer DSC.

Example 1 Maleic anhydride was added to a fourth flask of 200+ ml capacity equipped with a stirrer, temperature needle, water metering receiver and nitrogen inlet tube.
Isobutylene copolymer (copolymerization ratio 1:1, trade name Isohan-04 manufactured by Clarei Soprene Chemical Co., Ltd.) 10
g and 50 ml of dehydrated dimethylformamide were added, stirred and dissolved, and then 3.02 g of aniline and 3.57 g of p-aminophenol were added and dissolved, and reacted at 80°C for 3 hours with stirring as the first stage reaction. , N-(p-hydroxyphenyl)maleamic acid and N-phenylmaleamic acid copolymers were produced. Next, as a second stage reaction, 7 g of tri-n-butylamine and 15 ml of toluene were added, and after 1 hour, while passing nitrogen gas at 140°C, the water produced in the cyclization dehydration reaction was azeotroped with toluene and taken out of the reaction system. 10 ml of toluene was added, and then the toluene was refluxed by overflowing from the water content receiver, and the cyclization and dehydration reaction was carried out for 4 hours.

After the reaction is completed, the temperature of the solution is cooled to 40°C or less, and then
The polymer was added to 300 ml of ethyl ether to precipitate the polymer. After standing still, the supernatant was removed, and the precipitated polymer was washed with 200 ml of ethyl ether, followed by 150 ml of THF.
and then the solution was diluted with ethyl ether 700+wl.
was gradually dropped into the solution to precipitate a powdery polymer. Next, the polymer was separated every day, dissolved again in THF-ethyl ether, purified by precipitation, and vacuum-dried at 100°C for 24 hours to obtain the N-(p-hydroxyphenyl)maleimide-N-phenylmaleimide-isobutylene copolymer. Obtained.

The polymer yield was 12.2 g, and the elemental analysis was C
= 68.24%, H = 6.86%, N = 4.86%, and 80% of the maleic anhydride component of the maleic anhydride-isobutylene copolymer was modified into an imide component. In addition, the ratio of N-(p-hydroxyphenyl)maleimide component to N-phenylmaleimide component (g 7m> is 6
It was 0/40. Further, Mn was 33,800, and Tg was 215°C. Moreover, the infrared absorption spectrum is shown in FIG.

Examples 2 to 4 N-
A (p-hydroxyphenyl)maleimide-N-phenylmaleimide-isobutylene copolymer was obtained. The yields and measurement results of various physical properties of these copolymers are shown in Table 1 below.

Example 5 Maleic anhydride-isobutylene copolymer (isopan-0
4) Instead of 10g, maleic anhydride-styrene copolymer (copolymerization ratio 1:1, product name SMA-1 manufactured by Kawa Yuka Kaisha)
An N-(p-hydroxyphenyl)maleimide-N-phenylmaleimide-styrene copolymer was obtained in the same manner as in Example 1 except that 13.1 g of N-(p-hydroxyphenyl)maleimide was used.

The polymer yield was 15.8 g, and the elemental analysis was C
= 75.09%, H = 5.84%, and N = 4.53%, and 93% of the maleic anhydride component of the maleic anhydride-styrene copolymer was modified into an imide component. Also,
N-(p-hydroxyphenyl)maleimide component and N
-The ratio with phenylmaleimide component (17m) is 501
It was 50. Also, Mn is 4,070. Tg is 192
It was ℃. Moreover, the infrared absorption spectrum is shown in FIG.

Example 6 3.02 g of aniline was replaced with 3 p-aminotoluene
．． N-(p-hydroxyphenyl)maleimide-N-(p-
-methylphenyl)maleimide-isobutylene copolymer (white polymer) was obtained.

The polymer yield was 12.7 g, and the elemental analysis was C
= 70.88%, H = 6.80%, and N = 5.45%, and 92% of the maleic anhydride component of the maleic anhydride-isobutylene copolymer was modified into an imide component. Further, the ratio (j!/m) of the N-(p-hydroxyphenyl)maleimide component and the N-(p-methylphenyl)maleimide component was 50,150. Also, Mn is 32
,000XTg was 225°C.

Example 7 N-(p-hydroxyphenyl)maleimide-N was prepared in the same manner as in Example 1 except that 2.38 g of mono-n-butylamine was used instead of 3.02 g of aniline.
-Butylmaleimide-isobutylene copolymer (white polymer) was obtained.

The polymer yield was 13.3 g, and the elemental analysis was C
= 67.16%, I (= 8.39%, N = 5.11%), and 77% of the maleic anhydride component of the maleic anhydride-isobutylene copolymer was modified into an imide component.

Furthermore, the ratio (#/m) of the N-(p-hydroxyphenyl)maleimide component and the N-butylmaleimide component is 4.
It was 0/60. Moreover, Mn was 23,000 and Tg was 180°C.

Moreover, the infrared absorption spectrum is shown in FIG.

〔Effect of the invention〕

According to the method for producing the N-(hydroxyphenyl)maleimide copolymer of the present invention, the N- (Hydroxyphenyl)maleimide copolymer can be synthesized extremely easily and in high yield while retaining hydroxyl groups without going through a transesterification step, and N-(hydroxyphenyl)maleimide copolymer It is also easy to control the total imide composition of the formula (I) in the total imide composition.
) It is also easy to control the ratio of the structural unit represented by formula (II) to the structural unit represented by formula (II), so that the resulting N-(hydroxyphenyl)
The solubility of the maleimide copolymer in an alkaline aqueous solution can be easily controlled, and the production method of the present invention is industrially extremely advantageous.

[Brief explanation of drawings]

FIG. 1 shows an infrared absorption spectrum chart of the N-(p-hydroxyphenyl)maleimide-isobutylene copolymer obtained in Example 1, and FIG. -Hydroxyphenyl)maleimide-styrene copolymer - Figure 3 shows an infrared absorption spectrum of the N-(p-hydroxyphenyl)maleimide-isobutylene copolymer obtained in Example 7. Shows the chart.

Claims (1)

[Claims] A copolymer of maleic anhydride and an unsaturated hydrocarbon compound, an aminophenol, and a primary amine having no group imparting solubility in an aqueous alkaline solution are reacted in an organic solvent. Formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ Formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are aryl groups, 1 to 16 carbon atoms and R_3 is hydrogen or a lower alkyl group. Also,
The ratio of p and (l+m+n), (l+m) and (l+m+
The ratio between l and (l+m) is 0<p/(l+m+n)≦10, 0<(l+m)/(l+m+n)≦1 and 0<l/(l+m), respectively.
+m)<1. ] A method for producing an N-(hydroxyphenyl)maleimide copolymer, which comprises obtaining an N-(hydroxyphenyl)maleimide copolymer having the structural unit shown below.