JPH06102725B2 - Method for producing high polymer of polyether polymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyether polymer high polymer having a carbazole-based substituent in a side chain, which is useful as an organic photosensitive material, and a method for producing the same. .

(Prior Art and Problems to be Solved by the Invention) Polyvinylcarbazole is a well-known polymer as an organic photosensitive material for copying machines, but it has a chemical structure similar to that of poly [1] having an ether bond in the main chain. -N- (2,3-
Epoxypropyl) carbazole] (hereinafter referred to as “PEPCz”) is also known as a photosensitive material (V. Gaid
elis et al., Thin Solid Films, 38 , 9 (1976)). Especially PEPCz
Has a lower glass transition temperature than polyvinylcarbazole. It has attracted attention because of its excellent flexibility and adhesiveness. However, in the case of a homopolymer, the known PEPCz has a weight average molecular weight of about 100,000 at most, and a polymer having a higher molecular weight and soluble in a solvent capable of forming a coating film has been demanded. The reason is that, for example, when used as a photocrosslinking negative resist, the minimum energy required to insolubilize a polymer by light irradiation is considered to be inversely proportional to its weight average molecular weight. This is because it is expected to indicate

As a method for obtaining high molecular weight PEPCz, 1-N- (2,3-
A method of ring-opening polymerization of an epoxypropyl) carbazole monomer and a method of polymer reaction in which a halogen atom of polyepihalohydrin is replaced with carbazole have been tried.

However, in the former method, when polymerized in the presence of an inorganic base or an acid catalyst, only a polymer having a molecular weight of about several thousand can be obtained, and when polymerized with a coordination polymerization catalyst which can usually be expected to have a high polymerization reaction, the molecular weight is unknown. Only insoluble polymers can be obtained (Urio et al., Polymer Review, 47 , 543 (1990)).

In the latter method, a solvent-soluble polymer can be obtained according to the conventional reaction method, but a considerable amount of main chain cleavage reaction cannot be avoided as a side reaction of the substitution reaction, and the weight average molecular weight is at most
Only about 100,000 was obtained (Japanese Patent Publication No. 50-33858).
See issue. ).

(Means for Solving the Problems) In view of the above points, the present inventors have made earnest studies for the purpose of obtaining a solvent-soluble PEPCz capable of forming a coating film having a high molecular weight. As a result, they have found that the above object can be sufficiently achieved by substituting a halogen atom of polyepihalohydrin with a carbazole or a derivative under a specific condition at a high substitution rate, and have completed the present invention.

The present invention, when the halogen atom of the epihalohydrin homopolymer or epihalohydrin-alkylene oxide copolymer is substituted with a carbazole or a carbazole derivative in an organic solvent, an inorganic base and a phenolic radical are added to the organic solvent under an inert gas atmosphere. A method for producing a high polymer of a polyether polymer having a carbazole type substituent in a side chain, which is characterized in that a chain inhibitor is present.

The epihalohydrin homopolymer or epihalohydrin-alkylene oxide copolymer of the raw material polymer of the present invention includes epifluorohydrin, epichlorohydrin, epibromohydrin or epiiodohydrin, which is economical. From the viewpoint, epichlorohydrin or epibromohydrin is preferable.

The alkylene oxide is ethylene oxide,
Examples thereof include propylene oxide and 1,2-butene oxide.

The epihalohydrin-alkylene oxide copolymer used in the present invention preferably has an epihalohydrin unit of 40 mol% or more. If it is less than 40 mol%, the photosensitivity of the substitution product is not sufficient. The raw material polymer used in the present invention preferably has a molecular weight of 100,000 or more.

The carbazole derivative used in the present invention has an aromatic hydrogen atom substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, and an iodine atom as the bromine atom. , 6-
Alternatively, the 3,6-position is preferable.

The amount of the carbazole or carbazole derivative used in the present invention is 0.5 to the halogen atom in the raw material polymer.
A range of 5 times equivalent is suitable.

If the amount is less than 0.5 times the equivalent, the carbazole substitution rate decreases, and if the amount exceeds 5 times the equivalent, there is no advantage.

Examples of the inorganic base used in the present invention include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like. The amount of the inorganic base used is appropriately in the range of 0.5 to 10 times equivalent to the halogen atom in the raw material polymer. If it is less than 0.5 times the equivalent, the substitution rate will be reduced, and if it is used in excess of 10 times the equivalent, there is no advantage.

The substitution reaction of the present invention is carried out in an organic solvent. As the solvent used in the reaction, an aprotic polar solvent such as hexamethylphosphoramide, dimethylsulfoxide, N-methylpyrrolidone, N, N-dimethylformamide, or an aromatic such as benzene, toluene, xylene or chlorobenzene is used. Group hydrocarbons may be mentioned.

The inert gas atmosphere of the present invention means replacement with an inert gas such as nitrogen gas or argon gas and allowing the gas to stay or flowing as it is. Further, bubbling of not only the gas phase but also the liquid phase with an inert gas is included. In addition, during the reaction, bubbling an inert gas into the liquid phase of the reaction system, reducing the pressure of the reaction system to 400 Torr or less, and then effectively reacting in an inert gas atmosphere are also included.

Examples of the phenolic radical chain inhibitor used in the present invention include 2,6-ditertiary butyl-p-cresol, 2,6-ditertiary.
Butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-hydroxymethylphenol, 2,6-di-tert-butyl-α-dimethylamino-p-
Cresol, 2,5-ditertiary butyl-4-ethylphenol), 4,4'-bis (2,6-ditertiary butylphenol), 2,
2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis (4-ethyl-6-
Tertiary butylphenol), 4,4'-methylene-bis (6-
Tert-butyl-o-cresol), 4,4'-methylene-bis (2,6-tert-butylphenol), 4,4'-butylidene-
Bis (3-methyl-6-tert-butylphenol), 4,4 '
-Thiobis (6-di-tert-butyl-3-methylphenol), bis (3-methyl-4-hydroxy-5-tert-butylbenzyl) sulfide, 4,4'-thiobis (6-tertiary
Butyl-o-cresol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), hexamethylene glycol-bis [β- (3,5-tert-butyl-4-hydroxyphenol) propionate], Tris (3,5-ditertiarybutyl-4-hydroxyphenyl) isocyanurate, 3,5-ditertiarybutyl-4-hydroxyanisole, 3-
A compound containing a phenol group having a tert-butyl group at one or two ortho positions of a benzene ring such as tert-butyl-4-hydroxyanisole, 2,2'-methylene-bis (4-
Methyl-6-cyclohexylphenol), 2,2'-dihydroxy-3,3'-di (α-methylcyclohexyl)-
A compound containing a phenol group having a cycloalkyl group at one or two ortho positions of a benzene ring such as 5,5'-dimethyl-diphenylmethane, 4-methoxyphenol, 2-
1 with a strong electron-donating group such as tert-butyl-4-hydroxyanisole, 4,4'-isopropylidene bisphenol
One or more substituted phenols, condensed ring aromatic phenols such as α or β-naphthol, hydroquinone, 2,5-ditertiary butyl hydroquinone, catechol, 4-
A compound having a plurality of phenolic hydroxyl groups on the same benzene ring such as tert-butylcatechol, phenol on a benzophenone skeleton such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2-hydroxy-4-benzyloxybenzophenone And the like having a hydroxyl group.

The amount of the phenolic radical chain inhibitor used is appropriately in the range of 0.1 to 20% by weight based on the raw material polymer.

The reaction of the present invention is preferably carried out at a reaction temperature of 30 to 120 ° C. and a reaction time of 1 to 20 hours, and the reaction system is preferably stirred. When the reaction temperature is lower than 30 ° C, the substitution reaction does not proceed at a practical rate, and when it exceeds 120 ° C, a high molecular weight polymer cannot be obtained.

The reaction of the present invention is carried out as follows. That is, a predetermined amount of an epihalohydrin homopolymer or epihalohydrin-alkylene oxide copolymer, an inorganic base, a carbazole or a carbazole derivative, a phenolic radical chain inhibitor and a solvent are charged, and the mixture is stirred under an inert gas atmosphere or under The reaction is performed at a predetermined reaction temperature for a predetermined reaction time without stirring. Bubbling by injecting an inert gas into the liquid phase before the reaction or reducing the pressure of the reaction system to 400 Torr or less makes it possible to obtain a polymer having a higher molecular weight.

After completion of the reaction, the reaction system was returned to room temperature, the supernatant was poured into methanol, and the deposited precipitate was separated and dried to obtain poly [1-N- (2,3-epoxypropyl) carbazole from the starting epihalohydrin homopolymer. ] Is obtained.

This is a high polymer having a repeating unit represented by the following formula (I).

Further, a high polymer containing the structural unit of the above formula (I) can be obtained from the raw material epihalohydrin-alkylene oxide copolymer.

Any high polymer obtained from these two raw material polymers has a molecular weight of 200,000 to 1,000,000 and is soluble in organic solvents such as chloroform, dichloromethane and chlorobenzene.

(Effect of the invention) According to the production method of the present invention, having a carbazole-based substituent in the side chain and having a molecular weight of 200,000 to 1,000,000, a solvent-soluble polyether high polymer can be obtained in high yield. It can be said to be industrially useful.

(Examples) Examples 1-2 An epichlorohydrin homopolymer was placed in a three-necked flask having a capacity of 200 ml equipped with a nitrogen inlet tube having a length to be immersed in the reaction solution, a nitrogen outlet, a thermometer and a magnetic stirrer. ("Epichromer H" manufactured by Daiso, molecular weight M _w 600,00
0) 1.5 g (16.2 meq), carbazole 4.0 g, N, N-dimethylformamide 110 m dried with molecular sieve 4A
l, pulverized sodium hydroxide 1.5 g and the phenolic radical chain inhibitor shown in Table 1 were added, and then 20 l / hr of nitrogen gas was vigorously introduced into the liquid through the nitrogen introduction tube while stirring.
Continue this for 1 hour. Then, while introducing nitrogen gas gently so that the outside air does not enter, warm it to 70 ° C and leave it at 70
Continue the reaction at ~ 75 ° C for 8 hours. After the reaction is completed, return to room temperature,
Pour the supernatant into 110 ml of methanol. The deposited precipitate was washed with methanol and dried to obtain poly [1-N- (2,3
-Epoxypropyl) carbazole] is obtained. The yield and properties of the obtained high polymer are shown in Table 1.

However, the reduced viscosity is 80 ℃ in 0.1g / dl chlorobenzene solution.
And the weight average molecular weight M _w is a value calculated in terms of polystyrene using a gel permeation chromatograph (GPC).

Further, all of the obtained high polymers were soluble in chloroform, dichloromethane and chlorobezene.

IR (KBr, cm ^-1 ) 720,744,1100,1321,1455,1482,1595,2
910,3040 UV (CHCl ₃ ) λ _max 343,328,293,262,248nm Examples 3 to 5 Epichlorohydrin was placed in a three-necked flask with a capacity of 200 ml equipped with a three-way cock connected to a vacuum line, a nitrogen introduction tube, a thermometer, and a magnetic stirrer. Homopolymer ("Epichromer H" manufactured by Daiso, molecular weight _Mw 600,000) 1.5 g (16.2 milliequivalent), carbazole 4.0 g, N, N-dimethylformamide 110 ml dried with molecular sieve 4A, crushed sodium hydroxide 1.5 g and After adding the phenolic radical chain inhibitors shown in Table 2, reduce the pressure of the reaction system to 10 Torr and
After a lapse of minutes, nitrogen gas is introduced to bring the pressure to normal pressure. After performing this operation of depressurization and introduction of nitrogen gas three times in succession, the mixture was heated to 70 ° C while stirring in a nitrogen gas atmosphere, and kept at 70 to 75 ° C for 8 hours.
Keep reacting for hours. After the reaction is completed, the temperature is returned to room temperature, and the supernatant is poured into 110 ml of methanol. The precipitated precipitate is filtered, washed with methanol and dried to obtain poly [1-N- (2,3-epoxypropyl) carbazole].

The yield of the obtained high polymer and the result of measurement in the same manner as in Example 1 are shown in Table 2.

All of the obtained high polymers were soluble in chloroform, dichloromethane and chlorobenzene.

Examples 6 to 7 1.5 g of epichlorohydrin-ethylene oxide copolymer (“Epichromer C” manufactured by Daiso Co., Ltd., epichlorohydrin: ethylene oxide = 47: 53 (molar ratio), molecular weight M _w 750,000) as a raw material polymer, 1.5 g, Table 3 shows the results of the same tests as in Examples 3 to 5 except that argon was used instead of nitrogen.

All of the obtained high polymers were soluble in chloroform, dichloromethane and chlorobezene.

IR (KBr, cm ^-1 ) 720,744,1090,1321,1455,1480,1595,2
850,3040 UV (CHCl ₃ ) λ _max 344,330,294,260,250 Comparative Example 1 Co-epichlorohydrin homopolymer (“Epichromer H”) was added to a three-necked frass with a capacity of 200 ml equipped with a nitrogen inlet tube, a nitrogen outlet, a thermometer and a magnetic stirrer. Made by Daiso,
Molecular weight M _w 600,000) 1.5 g (16.2 meq), carbazole 4.0 g, N, N-dimethylformamide 110 ml dried with molecular sieve 4A and ground sodium hydroxide 1.5 g Flow rate 20l /
Hour nitrogen gas for 3 hours. After that, decrease the flow rate of nitrogen gas and heat the reaction system to 70 ° C in a nitrogen gas atmosphere.
Continue the reaction for 8 hours at 70-75 ° C. After the reaction is completed, the temperature is returned to room temperature, and the supernatant is poured into 110 ml of methanol. The precipitated precipitate was washed with methanol, dried and dried to give poly [1-N-
(2,3-Epoxypropyl) carbazole] was obtained. The yield of the obtained high polymer and the result of the same test as in Example 1 were as follows. Yield 75%, chlorine content 0.5% or less, reduced viscosity 0.32, weight average molecular weight _Mw 116,000.

Comparative Examples 2 to 3 Epichlorohydrin homopolymer ("Epichromer H" manufactured by Daiso Co., Ltd., molecular weight _{Mw) was} added to a three-necked frass having a volume of 200 ml equipped with a calcium chloride tube, a thermometer and a magnetic stirrer.
600,000) 1.5g (16.2 milliequivalent), carbazole 4.0g, N, N-dimethylformamide 110ml dried with molecular sieve 4A, crushed sodium hydroxide 1.5g and phenol radical radical chain inhibitor in the presence or absence Shinaga is heated to 70 ° C, and the reaction is continued at 70 to 55 ° C for 8 hours. After the reaction was completed, the temperature was returned to room temperature, and the supernatant was added to 110 ml of methanol.
Pour into. The precipitated precipitate is filtered, washed with methanol and dried to obtain poly [1-N- (2,3-epoxypropyl) carbazole]. The yield of the obtained high polymer and the result of the same test as in Example 1 are shown in Table 4.

From the results of Examples 1 to 7 and Comparative Examples 1 to 3, it is not possible to obtain a high-molecular-weight high polymer by the substitution reaction in the air or a low-grade inert gas atmosphere in which only the gas phase is substituted, Alternatively, a high polymer having a large molecular weight cannot be obtained even by a substitution reaction in the presence of a phenolic radical chain inhibitor in air, only by a substitution reaction in an inert gas atmosphere and in the presence of a phenolic radical chain inhibitor. A high polymer having a large molecular weight can be obtained, and even when an epihalohydrin homopolymer as well as an epihalohydrin-alkylene oxide copolymer is used as a raw material polymer, a high polymer having a large molecular weight can be obtained by the substitution reaction of the present invention. I understand.

Claims (1)

[Claims] 1. When replacing a halogen atom of an epihalohydrin homopolymer or an epihalohydrin-alkylene oxide copolymer with a carbazole or a carbazole derivative in an organic solvent, an inorganic base and a phenol-based compound are added to the organic solvent in an inert gas atmosphere. A method for producing a high polymer of a polyether polymer having a carbazole-based substituent in a side chain, which is characterized by containing a radical chain inhibitor.