JPH01223127A - Production of azo group-containing polymer - Google Patents

Abstract

PURPOSE:To readily obtain the title polymer useful as a polymerization initiator, modifier for resin or compatibilizing agent, by subjecting a specific compound to polyaddition reaction with a tetracarboxylic dianhydride in an organic solvent so as to give polyamide acid. CONSTITUTION:A compound (e.g., compound expressed by the formula) containing one azo group in molecular main chain and having amino groups at both terminals is subjected to polyaddition reaction with a tetracarboxylic dianhydride (e.g., 2,3,6,7-naphthalene tetracarboxylic acid dianhydride) in an organic solvent (e.g., DMF) to provide the aimed polymer as polyamide acid or the resultant polyamide acid is further subjected to chemical ring closure to provide the aimed polymer as polyimide.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing polyamic acid and polyimide containing an azo group in the polymer main chain.

Generally, azo compounds decompose due to heat and generate radicals, so they serve as polymerization initiators. It is also useful as a modifier and compatibilizer for various resins.

[Conventional technology]

As a method for synthesizing a polymer having an easily decomposable azo group, (1) A method of copolymerizing a vinyl monomer having an azo group in the side chain with another vinyl monomer to produce a polymer having an azo group in the side chain (Malcromol).

0ham, /10 1,0ri (/ri7ri))■ Method for producing a polymer having an azo group in the side chain by reacting a hydroxyl group-containing polymer with a carboxyl group-containing azo compound (
Makromol, C! hem.

36 /7 (/RIJRI)) ■ Method for producing polyurethane containing an azo group in the main chain by reacting a glycol having an azo group with a diisocyanate compound (Angew, Ma-kromol, C
hem, Eta 2 (/ri67))■ Method for synthesizing azo group-containing polyamide or polyester from azo group-containing dicarboxylic acid chloride and diamine or glycol (Kobunshi Ronsen 77(3)/J/(/976) , J.

Polym, 8ci, A Polym, Chem
, Ju UO& (/rirg)■ Method for synthesizing polycarbonate having an azo group in the main chain from azo group-containing dicarboxylic acid chloride and bisphenol A (JP-A-5B
! 272or) etc. have been proposed.

[Problem that the invention seeks to solve]

Any azo group-containing polymer is useful in making block copolymers and graft copolymers.

However, in the method (2), the synthesis of the azo group-containing vinyl monomer is complicated, and in the method (2), it is difficult to completely react the azo compound because it involves a polymer reaction. In addition, the methods (1) and (2) have drawbacks such as the necessity of separately synthesizing the azo group-containing dicarboxylic acid chloride, which is complicated.

[Means for solving problems]

As a result of intensive study by the present inventors on a method for producing polyamic acid and polyimide having an azo group in the main chain without the above-mentioned drawbacks,
We have arrived at the present invention.

That is, the present invention involves polycondensation or further chemical ring closure of a compound containing one azo group in the molecular main chain and having amino groups at both ends, and if necessary, a diamine and a tetracarboxylic dianhydride. This is a characteristic method for producing an azo group-containing polymer having an azo group in its main chain.

The compound (hereinafter referred to as azobisamine) that has one azo group in the molecular main chain and amino groups at both ends (hereinafter referred to as azobisamine) used in the present invention is - maximum (here, R1 and R2 are hydrogen, (a lower alkyl group, a nitrile group, or an aromatic group, where Ar is a divalent aromatic group); and salts thereof, such as NH and HE.

H3 H3 υ
0 or - represented by the formula (II) (wherein 81%R2) Ar is the same as defined above), and salts thereof, such as, for example.

These can be used alone or in combination of two or more.

Furthermore, as the tetracarboxylic dianhydride used to produce the polyamic acid used in the present invention, any aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and heterocyclic tetracarboxylic acid may be used. It is also possible to use anhydrides, specific examples of which include pyromellitic anhydride, 2,3. t,7-naphthalenetetracarboxylic dianhydride, J, J', Hiroshi, 4
! /-diphenyltetracarboxylic dianhydride% /lλ
, j, 6-naphthalene tetracarboxylic dianhydride, 2.
2'.

3.3I-diphenyltetracarboxylic dianhydride, λ,
2-Upper 2-39 μm dicarboxyphenyl)butylene dianhydride, bis(J,44-dicarboxyphenyl)sulfone dianhydride, s, p, y, t o -he+) lentithoracarboxylic dianhydride mono, bis(3,≠-dicarboxyphenyl)ether dianhydride, ethylenetetracarboxylic dianhydride, naphthalene-l, co, 4c, j-tetracarboxylic dianhydride, naphthalene/, II, j, r- Tetracarboxylic dianhydride, bis(3,II-dicarboxyphenyl)ketone dianhydride, decahydronaphthalene
7,≠,z,r-tetracarboxylic dianhydride,≠,za-
Dimethyl-l.

Tip 3. Yu', 4, 7-hexahydronaphthalene-
/, 2. ir.

6-tetracarboxylic dianhydride, λ, 6-dichloronaphthalene-7. μ,! ,! -tetracarcaric dianhydride,
-2,7-dichlornaphthalene-i, tt, s, ir
-tetracarboxylic dianhydride, λ, 3. t,7-titrachlornaphthalene/, II, j, I-tetracarboxylic dianhydride, phenanthrene-/, r, 10-tetracarboxylic dianhydride, cyclopentane-/, 2,3
．． ≠-Tetracarboxylic dianhydride, pyrrolidine-2,3
,u,! -tetracarboxylic dianhydride, pyrazine-λ,
3. j, l, -tetracarboxylic dianhydride, -2, -2
-bis(,2,J-dicarboxyphenyl)propanihydride, l,/-bis(2,3-dicarboxyphenyl)ethane dianhydride, /,/-bis(J,Hiro-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,≠-dicarboxyphenyl)methane dianhydride, benzene-/, 2,
3. II-tetracarboxylic dianhydride, /, 2,3. μ
m-butanetetracarboxylic dianhydride, thiophene-2,
3,≠.

Examples include j-tetracarboxylic dianhydride, which may be used alone or as a mixture.

Furthermore, any aromatic diamine, aliphatic diamine, and heterocyclic diamine can be used as the azo group-free diamine used to produce the polyamic acid used in the present invention, but specific examples thereof include: as metaphenylenediamine, paraphenylenediamine, ≠
pl-diaminodiphenylpropane, 44.4! '-diaminodiphenylmethane, benzidine, Hiroyo' -diaminodiphenylsulfide, ≠, Hiro'-diaminodiphenylsulfone, 3.3'-diaminodiphenylsulfone, Hiro, Hiro'-diaminodiphenyl ether, 2,6
-diamitupyridine, bis-(quaminophenyl)diethylsilane, bis-(quaminophenyl)phosphine oxide, bis-(p-aminophenyl)-N-methylamine, /, j-diaminonaphthalene, 3.3'
-dimethyl-benzidine, 3.3'-dimethoxy-benzene, 2) Hiro-bis-(β-amino-t-butyl)toluene, bis-(para-β-amino-t-butylphenyl)ether, para-bis (2-methyl-p-7minopentyl)benzene, para-bis(l,l-dimethyl-y-aminopentyl)benzene, m-xylene diamine,
p-xylylenediamine, bis(para-amino-cyclohexyl)methane, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 3-methyl-heptamethylenediamine, ≠, Hiro'-dimethyl Hebutamethylenediamine, 1//-diaminododecane, 1,2-bis-(3-aminopropoxy)-ethane, 2. Codimethylpropylene diamine, 3-methoxy-hexamethylene diamine, λ,! -dimethylhexamethylenediamine,
2. ! -dimethylhebutamethylenediamine, j-methylnonamethylenediamine, /, 4! -Diamino-cyclohexane, l,12-diaminooctadecane, co,! −
Examples include diaminol, 31 μm oxadiazole, and the like, which may be used alone or as a mixture.

Regarding the amounts of azobisamine and optionally azo group-free diamine used in the present invention and tetracarboxylic dianhydride, the ratio of the amine group to the acid anhydride is used in a substantially equivalent amount.

Azobisamine can be polycondensed alone with tetracarboxylic dianhydride in an equivalent amount, or can be used in combination with a diamine. When used in combination, the amount of azobisamine used must be 0.02 molti or more based on the diamine.

If the amount is less than this, the polymer has no meaning as an azo group-containing polymer. That is, when used as a radical polymerization initiator, its initiation ability is extremely poor.

The organic solvent used to prepare the polyamic acid is one that does not react with either the reactant diamine or the tetracarboxylic dianhydride. Further, this organic solvent must not react with polyamic acid and must dissolve polyamic acid. Such solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, N-methylcaprolactam, dimethylsulfoxide, N-methyl-
2-pyrrolidone, tetramethylurea, tetramethylthiourea, pyridine, dimethylsulfone, hexamethylphosphoramide, tetramethylenesulfone, formamide, N-methylformamide, butyrolactone and N
Examples include, but are not limited to, -acetyl-copyrrolidone.

Solvents can be used alone or in combination,
Alternatively, it can be used in combination with poor solvents such as benzene, benzonitrile, dioxane, xylene, toluene and cyclohexane. In this case, the concentration of polyamic acid in the organic solvent is /-! 0%, preferably 3 to 30 inches.

Polyamic acid is produced according to conventional methods. For example, it can be produced by mixing tetracarboxylic dianhydride with a solvent solution of azobisamine and other diamines and stirring the mixture at around room temperature.

Methods for imidizing polyamic acid by chemically ring-closing include a method of adding and mixing an imidization catalyst such as a base and an acid anhydride to a polyamic acid solution, and a method of imidizing a polyamic acid solution by adding and mixing a base and an imidization catalyst such as an acid anhydride. There is a method of imidization in an organic solvent containing. The imidization temperature must be such that the imide groups in the polyamic acid are not substantially decomposed; however, if the temperature is too low, the imidization time becomes long and is not industrially practical. It is usually carried out at temperatures ranging from around room temperature to below j0°C.

As the acid anhydride, any of aliphatic carboxylic acid anhydrides, aromatic carboxylic acid anhydrides, alicyclic carboxylic acid anhydrides, and heterocyclic carboxylic acid anhydrides can be used. Acetic anhydride, propionic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, formic anhydride, malonic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride compounds, o, m and p-) ruyl acid anhydride, m and p-ethylbenzoic anhydride, p
-n-propylbenzoic anhydride, p-isopropylbenzoic anhydride, anilic anhydride, o, m and p-nitrobenzoic anhydride, o, m and p-chlorobenzoic anhydride, various dibromo and dichlorobenzoic anhydride,
Tribromo and trichlorobenzoic anhydride, hemeritic anhydride 1.3. v-xylylic anhydride, isoxylylic anhydride, mesitylenic anhydride, peratrumic anhydride, trimethoxybenzoic anhydride, α and β-naphthoic anhydride, p-phenylbenzoic anhydride, hexahydrophthalic anhydride, Tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride,
Examples include nadic anhydride, chlorendic anhydride, nicotinic anhydride, isonicotinic anhydride, picolinic anhydride, quinolinic anhydride, etc., but are not necessarily limited to these. The amount of such carboxylic acid-anhydride used is at least the main mole, preferably at least 1 mole, based on the amide bond of the polyamic acid.

As the base, aliphatic N-based compounds, aromatic N-based compounds, imidazoles, etc. are used. Examples of aliphatic N compounds include triethylamine, tributylamine, triethylenediamine, dimethylbenzylamine, and dermethylmorpholine.

Examples of aromatic N compounds include pyridine, quinoline, isoquinoline, α-picoline, β-,picoline, r-picoline, 3. ! Lutidine, 3. taltidine, J, j lutidine, co, 4c lutidine, 2-16 collidine, l, 2. μ
triazine, pyrimidine, pyrazine, /, J, j triazine, pyridazine, l-dimethylaminopyridine,
Examples include dermorpholinopyridine, pyrrolidinopyridine, biperazinoviridine, and the like.

Examples of imidazoles include N-cyanoethyl-coethyl-methylimidazole, N-cyanoethyl-comethylimidazole, N-cyanoethyl-2-phenylimidazole, 2-methylbenzimidazole,! -methylimidazole, N-7enylimidazole, cophenylphenyl-methylimidazole, and the like.

The amount of these bases to be used is 0.007-3 mol, preferably 0.07-1 mol, per 1 mol of amide bond of polyamic acid.
It is a mole.

The azo group-containing polymer of the present invention thus obtained is useful as a polymer initiator for producing various block copolymers.

Example 1 2,2'-azobis(N-(+-aminophenyl)-λ-methylpropionamidine]tetrahydrochloride j, 243f (
/Ommol), triethylamine u, 0ulf
(4fiOmmol) and N-methyl-copyrolide 7' (abbreviated as NMP)! 0t was added. Next/
2. J, II-butanetetracarboxylic dianhydride 1. 4/P (10 mmol) was added thereto and the mixture was reacted for 2 hours at room temperature with stirring, to obtain a pale yellow viscous polymer solution. A portion of this is taken and poured into a large amount of methanol to precipitate it,
The ηin of the polymer was washed and vacuum-dried for 2ψ hours at room temperature.
h is 13dl/t (0,1f/d1%NMP, j
(0°C).

From the infrared absorption spectrum! Amic acid absorption (NH) was observed at 210 crIL.

Next, add acetic anhydride, / 1 (see 〇 m) to the above polymer solution.
mol), isoquinoline 0. lit (44 mmol
) and NMP 109 were added to 4 ct at room temperature.
When the reaction was stirred for a period of time, a yellow polymer solution was obtained. This was poured into a large amount of methanol to precipitate a polymer, washed several times with methanol, and then dried at room temperature for 24 hours to obtain a pale yellow powdered polymer. Yield is high! It was more than that.

+71nh of this polymer is /, j dll f (0
, j t /d11NMP, j7℃) In the infrared absorption spectrum, strong imide absorption was newly observed at t'yro and 730CrlL, while J2tOcrt
The absorption of N-H at r completely disappeared.

In differential thermal analysis of the polyamic acid and polyimide obtained as above, a broad exothermic peak was observed at 100-160°C, but no exothermic peak was observed in the above temperature range for the polymer that had been previously heat-treated at 110°C for 3 hours. I couldn't. This exothermic peak was consistent with that of the starting material, azobisamine.

Example λ In a 300-four-hole flask, J-bis(Hiroshi-aminophenoxy)benzene 1.770 f (j Ommol
), co, 2'-azobis(N-(J-aminophenyl)
-2-Methylpropionamidine cotetrahydrochloride/, 0! J f (2,0 mmol), triethylamine y 0.1/t (I mmol) and NMp 1zot were added. Then J, 31. u, 44
'-hyphenyltetracarboxylic dianhydride, II/
! f (JJmmol) was added and reacted with stirring at room temperature for 2 hours to obtain a pale yellow viscous polymer solution. A portion of this was poured into a large amount of methanol to precipitate it, wash it, and dry it under vacuum at room temperature for several hours to obtain the polymer ηi.
nh is ko, / dll? (0,1t/di%IMP
, JO°C). 3210 from infrared absorption spectrum
Absorption of amic acid was observed in 3.

Next, add 20% of acetic anhydride to the above polymer solution. II f(Jo
ommol) and dimethylaminopyridine o, prr(
A solution consisting of <cmmol) and NMP IOy was added and reacted with stirring at room temperature for an hour, yielding a yellow polymer solution. This was poured into a large amount of methanol to precipitate the polymer, washed several times with methanol, and then heated to room temperature for 2 hours.
Vacuum dried for μ hours. The yield was over 77%. ηinh Idλ, Ode/? of this polymer? In the infrared absorption spectrum, i'yrocIIL and 7JOC
Strong imide absorption was newly observed for I11, while for 3
210c! The N-H absorption of IL had completely disappeared.

In the differential thermal analysis of the polyamic acid and polyimide obtained as above, a broad exothermic peak was observed at 100-160°C, but in the polymer that had been previously heat-treated at 110°C for 3 hours, there was no exothermic peak in the above temperature range. I was not able to admit.

Example 3 29,2'-azobis(N-(≠-aminophenyl)-2-methylpropionamide) 0.7619 (2, Ommol), /,
J-diaminodiphenyl ether &, 007 f(z
o mmol) and NMP/109 were added. Then J, J',≠4(/-benzophenonetetracarboxylic dianhydride/0.3//f (J 2 mmol
) was added and reacted for 2 μh at room temperature with stirring to obtain a pale yellow viscous polymer solution. A portion of this was taken, poured into a large amount of methanol, precipitated, washed, and vacuum-dried at room temperature for 2 hours. The polymer has ηinh/, r dl/? Met. From the infrared absorption spectrum, absorption of amic acid was observed at 32rocrIL''.

Next, add 20% of acetic anhydride to the above polymer solution. II t(Jo
ommol) and isoquinoline x, z r t (20 m
A solution consisting of NMP 709 and NMP 709 was added, and the mixture was stirred and reacted at room temperature for an hour, yielding a yellow polymer solution. This was poured into a large amount of methanol to precipitate a polymer, washed several times with methanol, and then vacuum-dried at room temperature for 2 hours. The yield was over 21%. The ηinh of this polymer is i, trdt7t, and the infrared absorption spectrum shows /7 r o crIL''' and 7
Strong imide absorption was newly observed in JOCIIL-'', while amic acid absorption in J2103-' was completely eliminated.

In the differential thermal analysis of the polyamic acid and polyimide obtained as described above, a broad exothermic peak was observed between ioo and ito°C, but the exothermic peak was no longer in the above temperature range for the polymer that had been previously heat-treated at 110°C for 3 hours. was not recognized.

Reference Example 1 Azo group-containing polyimide obtained in Example 1 λ, Of%N
MP JOf and butyl acrylate 109 to 300
After placing in a four-ml flask and purging with nitrogen while stirring, 70
Polymerization was carried out at ℃ for a period of time. The polymerization solution was poured into a large amount of methanol, washed several times with methanol, and then dried under vacuum at room temperature for 2 hours to obtain a transparent rubbery polymer. The polymerization rate is data, j
It was Chi.

Next, 10 t of the above rubbery polymer IOf%NMP and 20 t of styrene were added and polymerized at 70° C. for a long time in the same manner as above, and then further polymerized at 30° C. for 1 hour to obtain a white powdery polymer. The styrene polymerization rate was 7%.

Reference example λ Azo group-containing polyimide obtained in Example 2 IOf%NM
P 1009 and styrene 209 were placed in a JOO, 1 four-bottle flask, and the flask was purged with nitrogen while stirring, and then polymerized at 70° C. for t hours. The polymerization solution was poured into a large amount of methanol, washed several times with methanol, and then vacuum-dried at IOOO°C for 3 hours to obtain a white powdery polymer. The polymerization rate of styrene is $
! , j %, and 171nh of the polymer is /, J d
l/f (0,j wt%, NMP, 30°C).

Reference Example 3 Styrene was polymerized in exactly the same manner as in Reference Example 2 except that the azo group-containing polyamic acid 10f obtained in Example 3 was used, and the polymerization rate of styrene was 4! OJ%, ηin
h was t, oa/l.

〔Effect of the invention〕

As described above, the azo group-containing polyamic acid or polyimide obtained in the present invention is relatively easily obtained and suitably used as a polymerization initiator.

Sender: Mitsubishi Chemical Industries, Ltd. Representative Patent Attorney Hase - 1 other person

Claims (3)

[Claims] (1) A polyamic acid is obtained by polyadding a compound containing one azo group in the molecular main chain and having amino groups at both ends and a tetracarboxylic dianhydride in an organic solvent. , method for producing azo group-containing polymer (2) A method for producing an azo group-containing polymer, which comprises chemically ring-closing the polyamic acid obtained in claim 1 to obtain a polyimide. (3) A compound containing one azo group in the molecular main chain and amino groups at both ends, a diamine that does not contain an azo group, and a tetracarboxylic dianhydride are polyadded in an organic solvent to produce polyamic acid. A method for producing an azo group-containing polymer according to claim 1 or 2, characterized in that the azo group-containing polymer is further chemically ring-closed to form a polyimide.