JPH0710911B2 - Method for producing azo group-containing polycarbonate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polycarbonate having an azo group in the polymer polymer main chain.

[Conventional technology]

Generally, azo compounds are decomposed by heat and generate radicals, and are therefore used as polymerization initiators. As a method for synthesizing a polymer having an easily decomposable azo group, a method for producing a polymer having an azo group in the side chain by copolymerizing a vinyl monomer having an azo group in the side chain with another vinyl monomer (Makromol.Chem ., 180 609 (1979)) A method for producing a polymer having an azo group in its side chain by reacting a hydroxyl group-containing polymer with a carboxyl group-containing azo compound (Makromol. Chem. 36 17 (1959)) having an azo group the method of manufacturing a polyurethane including an azo group in the main chain by reaction of a glycol and a diisocyanate compound (Angew.Makromol.Chem. 1 92 (1967) ) azo group-containing polyamides or polyesters from dicarboxylic acid chloride and diamine or glycol containing azo groups (Synthesis of Polymers 33 (3) 131 (197
6), J.Polym.Sci.A Polym.Chem., 24 406 (1986)) A method for synthesizing a polycarbonate having an azo group in the main chain from an azo group-containing dicarboxylic acid chloride and bisphenol A (JP-A-59- 27908) has been proposed.

Any azo group-containing polymer is useful for producing block copolymers and graft copolymers.

However, in this method, the synthesis of the azo group-containing vinyl monomer is complicated, and in the method of (1), it is difficult to completely react the azo compound because it is a polymer reaction. Further, the methods (1) and (2) have the drawback that they are complicated because the dicarboxylic acid chloride containing an azo group needs to be synthesized separately. In the further method, there is a description that an azo group-containing polycarbonate resin can be produced by using an azo group-containing diacid halide, a diol, a dialkylene halide, and a dicarboxylic acid, but other than the diacid halide, there are drawbacks such as difficulty in interfacial polymerization. is there.

[Object of the Invention]

The present inventors have arrived at the present invention as a result of extensive studies on a method for producing a polycarbonate having an azo group in the main chain which does not have the above-mentioned drawbacks.

The present invention contains one azo group in the molecular main chain represented by the following general formula (a), general formula (b), general formula (c), or general formula (d), and has an alcohol at both ends. Of a compound having a polymerizable hydroxyl group, salts of these compounds, dicarboxylic acid chloride, a carbonate precursor, and a method for producing a polycarbonate having an azo group in the main chain by interfacial polymerization from a bisphenol compound containing no azo group, if necessary, (Here, R ¹ and R ² represent hydrogen, a lower alkyl group, a nitrile group, or an aromatic group, and x represents an integer of 1 to 10.) (Wherein R ¹ , R ² and x have the same meanings as above) (Wherein R ¹ and R ² are as defined above, and A represents a lower alkylene group) (Where X and Y represent a divalent organic group, R ¹ and R ² represent hydrogen, a lower alkyl group or an aromatic group).

[Structure of Invention]

The compound having one azo group in the molecular main chain used in the present invention and having an alcoholic hydroxyl group at both ends (hereinafter, referred to as azobis alcohol) is represented by the general formula (Here, R ¹ and R ² are hydrogen, a lower alkyl group, a nitrile group,
Alternatively, x represents an aromatic group and x represents an integer of 1 to 10).

For example And so on.

Also the general formula (Where R ¹ , R ² , and x have the same meanings as above) Also the general formula (Wherein R ¹ and R ² have the same meanings as above, and A represents a lower alkylene group) And so on.

Also the general formula (Wherein X and Y represent a divalent organic group, R ¹ and R ² represent hydrogen, a lower alkyl group or an aromatic group) and salts thereof. And so on.

The dicarboxylic acid chloride used in the present invention is aliphatic,
It is an alicyclic or aromatic dichloride.

For example, isophthalic acid, diphenylmethanedicarboxylic acid,
1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,3'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid Acid, 4,4'-
Aromatic dicarboxylic acids such as diphenyl ketone dicarboxylic acid, 3,3'-diphenyl ketone dicarboxylic acid, 4,4'-diphenyl thioether dicarboxylic acid and 4,4'-diphenyl sulfone dicarboxylic acid, and dicarboxylic acid dichlorides of its derivatives, cyclohexane Dicarboxylic acids, dichlorides of alicyclic dicarboxylic acids such as cyclopentanedicarboxylic acid and derivatives thereof, succinic acid, adipic acid, azelaic acid, dichlorides of saturated aliphatic dicarboxylic acids such as sebacic acid, maleic acid, fumaric acid, citraconic acid, Examples thereof include dichlorides of unsaturated aliphatic dicarboxylic acids such as itaconic acid and dimer acid.

As the bisphenol compound used in the present invention, those represented by the following general formula are used.

Specific examples of the bisphenol compound that can be used in the present invention include bis- (4-hydroxyphenyl) methane, 1,1-bis- (4-hydroxyphenyl) ethane, and 1,1-bis- (4-hydroxyphenyl). ) Propane, 2,2-bis- (4-hydroxyphenyl) propane (ie bisphenol A), 2,2-bis- (4-hydroxyphenyl) butane, 2,2-bis- (4-hydroxyphenyl) pentane, 2,2-bis- (4-hydroxyphenyl) -3-methylbutane, 2,2-bis- (4-hydroxyphenyl) hexane, 2,2-bis- (4-hydroxyphenyl) -4-methylpentane, 1 1,1-bis- (4-hydroxyphenyl) phenylmethane, 1,1-bis- (4-hydroxyphenyl) cyclopentane, 1,1-bis- (4-hydroxyphenyl) cyclo Hexane 2,2-bis - (4-hydroxy-3-chlorophenyl)
Bisphenol compounds such as propane, 2,2-bis- (4-hydroxy-3,5-dimethylphenyl) propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxydiphenylsulfide Can be mentioned.

The bisphenol compound is necessary when the carbonate precursor described below is phosgene or the like, but is not necessarily present when the precursor is a polycarbonate oligomer.

The carbonate precursor used in the present invention is one that reacts with a bisphenol compound to produce a polycarbonate and a polycarbonate oligomer, and specifically, bisphenol bischloroformates such as phosgene, bisphenol A and hydroquinone, and those. Oligomers, bischloroformate of ethylene glycol and neopentyl glycol. Preferred carbonate precursor materials are phosgene, bisphenol bischloroformates and their oligomers.

In the present invention, the azobis alcohol and the dicarboxylic acid chloride are preliminarily reacted with each other prior to the interfacial polymerization, but this reaction is generally preferably carried out in an organic solvent which does not react with the reactant.

As such a solvent, N, N-dimethylformamide,
N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, N-methylcaprolactam, dimethylsulfoxide, N-methyl-
2-pyrrolidone, tetramethylurea, tenoramethylthiourea, pyridine, dimethyl sulfone, hexamethylphosphoramide, tetramethylene sulfone, formamide, N-methylformamide, butyrolactone and N
-Acetyl-2-pyrrolidone can be mentioned, but it is not necessarily limited thereto.

The solvent can be used alone, or a combination of solvents can be used,
Alternatively, a combination of poor solvents such as benzene, benzonitrile, dioxane, xylene, toluene and cyclohexane can be used.

The polycarbonate of the present invention is produced by interfacial polymerization among the well-known conventional methods.

In the interfacial polymerization method, a caustic soda aqueous solution, a non-water-soluble organic solvent such as methylene chloride, bisphenol, azobis alcohol, a carbonate precursor and, if necessary, a catalyst and a molecular weight modifier are used.

As the catalyst, any well-known catalyst that accelerates the polycarbonate forming reaction may be used. These catalysts include, but are not limited to, tertiary amines such as triethylamine, quaternary ammonium salts and quaternary phosphonium salts.

As the molecular weight regulator, any of well-known compounds that regulate the molecular weight of polycarbonate by a chain termination mechanism may be used.

These compounds are phenol, chlorophenol, p-
Examples include, but are not limited to, tert-butylphenol.

The amount of azobis alcohol used in the present invention must be 0.05 mol% or more based on the bisphenol unit in the polymer. This is because if it is less than 0.05 mol%, the meaning as a polymer having an azo group is lost.
That is, when the azo group-containing polycarbonate is used as a radical polymerization initiator, its polymerization initiation ability becomes extremely poor.

When the azobis alcohol and the dicarboxylic acid chloride are reacted in advance, the ratio of both is 1.1 mol or more and 10 mol or less, preferably 2 mol or more and 5 mol or less, relative to 1 mol of the azobis alcohol. 1.
If it is less than 1 mol, polycondensation of azobis alcohol and dicarboxylic acid chloride will proceed, and it will not be possible to randomly introduce azo groups into the polycarbonate, and the molecular end of the reaction product will become an alcoholic OH group, resulting in dicarboxylic acid chloride. The meaning of reacting in advance disappears. Also
If it is used in excess of 10 moles, the properties as polycarbonate will be impaired.

A bisphenol compound may be used together when the azobis alcohol and the dicarboxylic acid chloride are previously reacted. The amount of the bisphenol compound is not limited as long as it can be adjusted during the production of the polycarbonate, but it is preferable to use the bisphenol compound in an amount equal to or more than the difference between the azobis alcohol and the dicarboxylic acid chloride.

It is necessary to carry out the reaction at a relatively low temperature such that the azo group is not decomposed in both the interfacial polymerization and the preliminary reaction,
It is usually carried out at -10 to 40 ° C, preferably 0 to 30 ° C.

The polyamide having an azo group in the main chain of the present invention is useful as a polymer polymerization initiator for producing various block copolymers.

Example 1 <Production of Oligomer> Bisphenol A 100 parts Sodium hydroxide 37 parts Water 670 parts The above mixture was charged into a reactor equipped with a stirrer, and 360 parts of methylene chloride was added while stirring at 800 rpm. Then, while cooling the mixed solution to 20 ° C or less, 60 g of 54 g of phosgene was added.
Blowing in for minutes, oligomerization was carried out. After the reaction was completed, only the methylene chloride solution containing the polycarbonate oligomer was collected.

The analysis result of the methylene chloride solution of the obtained oligomer is
It was as follows.

Oligomer concentration 22.9% (Note 1) Terminal chloroformate group concentration 0.50N (Note 2) Terminal phenolic hydroxyl group concentration 0.02N (Note 3) (Note 1) Measured by evaporation to dryness (Note 2) Reaction with aniline The resulting aniline hydrochloride was neutralized and titrated with a 0.2N aqueous sodium hydroxide solution.

(Note 3) Colorimetric determination at 546 nm of color development when dissolved in titanium tetrachloride and acetic acid solution.

The oligomer solution obtained by the above method is hereinafter abbreviated as oligomer solution A.

<Preliminary reaction> In a 100 ml four-necked flask, 2,2'-azobis [2-methyl-
N- (2-hydroxyethyl) propionamide] 1.13
A uniform solution was prepared by charging 6 g and 30 g of N-methyl-2-pyrrolidone (NMP).

To this solution, 3.200 g of isophthalic acid chloride was charged, and the mixture was stirred and reacted at room temperature for 30 minutes.

<Manufacture of polymer> 2 parts of 177 ml of oligomer solution A and 31 ml of methylene chloride
It was charged into the reactor equipped with a stirrer and stirred at 600 rpm. Then 2
0.9% by weight of triethylamine aqueous solution, 30 ml of methylene chloride, 41 ml of water and 31 ml of 25% by weight aqueous solution of caustic soda were added to 500 ml of methylene chloride.
Was added and interfacial polymerization was performed at room temperature for 3 hours.

After separating the polymerization solution into an aqueous layer and a methylene chloride layer containing polycarbonate, the methylene chloride layer is washed successively with aqueous sodium hydroxide solution, aqueous hydrochloric acid solution and demineralized water, and finally methylene chloride is poured into a large amount of methanol to remove the polymer. Precipitated. After passing the precipitated polymer, it was vacuum dried at room temperature for 24 hours to obtain a white powdery polymer.

The yield of this polymer was 91% and ηinh was 0.38 dl / g (0.5
g / dl, 30 ° C in methylene chloride).

In the differential thermal analysis (DSC) of this polymer, a broad exothermic peak was observed at 130 to 160 ° C. This polymer 130
When heat-treated at 5 ° C. for 5 hours, the exothermic peak in the above temperature range was no longer observed. In addition, the ultraviolet absorption spectrum (UV) of the chloroform solution of this polymer showed a maximum absorption at 350 nm. In the polycarbonate obtained by polymerization without using 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide, an exothermic peak at DSC and a maximum absorption at 350 nm at UV were observed. There wasn't. In addition, 2,2'-azobis [2-methyl-N-
DSC and U of (2-hydroxyethyl) propionamide
In V, the exothermic peak in the above temperature range and maximum absorption at 350 nm were exhibited.

Example 2 <Preliminary reaction>2,2'-azobis [2-methyl-] was added to a 100 ml four-necked flask.
N- (2-hydroxyethyl) propionamide] 1,13
A uniform solution was prepared by charging 6 g and 30 g of NMP. To this solution, 3.200 g of isophthalic acid chloride was charged, and after stirring and reacting at room temperature for 30 minutes, 2.699 g of bisphenol A was added and further reacted for 30 minutes.

<Production of Polymer> Interfacial polymerization was performed in the same manner as in the production of the polymer of Example 1 except that the preliminary reaction liquid obtained above was used in place of the preliminary reaction liquid of Example 1.

The polymer yield was 97% and ηinh was 0.65 dl / g. A broad exothermic peak was observed by DSC at 130-160 ℃, and a maximum absorption was observed by UV at 350 nm.

Comparative Example 1 In the preparation of the polymer of Example 1, 1.136 g of 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) propionamide] was dissolved in 15 g of NMP and 3.200 g of isophthalic acid was dissolved in 15 g of NMP. Interfacial polymerization was performed in exactly the same manner as in Example 1 except that the above solution was added without preliminary reaction.

The polymer yield was 88% and ηinh was 0.23 dl / g. D
No exothermic peak is observed at 130-160 ℃ in SC and 350n in UV
No absorption was observed in m.

Comparative Example 2 In Comparative Example 1, 2,2'-azobis [2-methyl-N-
(2-hydroxyethyl) propynamide] 1.136 g NM
Polymerization was carried out in the same manner as in Comparative Example 1 except that dicarboxylic acid chloride was not used, using only the solution dissolved in P30 g.

The polymer yield was 90% and ηinh was 0.31 dl / g, but no exothermic peak or maximum absorption due to an azo group was observed in DSC and UV.

Example 3 <Preliminary reaction> A 100 ml four-necked flask was charged with 1.2 g of 2,2'-azobis (2-cyanopropanol) and 30 g of NMP to prepare a uniform solution. Charge 2.80 g of terephthaloyl chloride to this solution and mix at room temperature for 3
After reacting for 0 minutes, add 2.5 g of bisphenol A for another 30
Reacted for minutes.

<Production of Polymer> Polymerization was carried out in the same manner as the polymer of Example 1 except that the preliminary reaction liquid obtained above was used in place of the preliminary reaction liquid of Example 1.

The polymer yield was 95% and ηinh was 0.62 dl / g. A broad exothermic peak was observed at 120 to 140 ° C by DSC and a maximum absorption at 350 nm was observed by UV.

Example 4 <Preliminary reaction>2,2'-azobis {2 [1- (2
-Hydroxyethyl) -2-imidazolin-2-yl]
Propane} 1.354 g and NMP 30 g were added to make a uniform solution. To this solution 3.6 g of sebacyl chloride and bisphenol
A2.7 g was added and reacted for 30 minutes.

<Production of Polymer> Polymerization was carried out in the same manner as the polymer of Example 1 except that the preliminary reaction liquid obtained above was used in place of the preliminary reaction liquid of Example 1.

The polymer yield was 93% and ηinh was 0.54 dl / g. A broad exothermic peak was observed at 120 to 180 ° C by DSC and a maximum absorption at 350 nm was observed by UV.

Reference Example 1 3.0 g of the azo group-containing polycarbonate obtained in Example 1,
NMP (37 g) and styrene (7.0 g) were placed in a 300 ml four-necked flask, the atmosphere was replaced with nitrogen while stirring, and the mixture was polymerized at 75 ° C for 5 hours and at 130 ° C for 1 hour. The polymerization solution was poured into a large amount of methanol, washed several times with methanol, and vacuum dried at 100 ° C. for 24 hours to obtain a white powdery polymer.

The polymerization rate of styrene is 45%, and the polymer ηinh is 0.44d.
l / g (0.5% by weight, 30 ° C. in NMP). A styrene homopolymer was extracted from this polymer with Soxhlet using cyclohexane as an extraction solvent. The IR spectrum and'H-NMR of the remaining polymer confirmed that it was a block polymer with styrene units and carbonate bonds present.

In addition, the ratio of block-copolymerized styrene to the polymerized styrene (block efficiency) was 57%. Further, in an experiment in which styrene was thermally polymerized without using the azo group-containing polycarbonate under the above conditions, the block efficiency of styrene was 9%.

Reference Example 2 3.0 g of the azo group-containing polycarbonate obtained in Example 2,
37 g of NMP and 7.0 g of styrene were placed in a 300 ml four-necked flask and polymerized and post-treated in the same manner as in Reference Example 1. The polymerization rate of styrene was 47%, and the polymer ηinh was 0.58 dl / g.
The block efficiency was 64%.

〔The invention's effect〕

According to the method of the present invention, an azo group-containing polycarbonate resin can be obtained relatively easily, and by using it as an initiator, a block copolymer can be obtained at a high polymerization rate.

Claims (2)

[Claims] 1. An azo group having one azo group in the main chain of a molecule represented by the following general formula (a), general formula (b), general formula (c) or general formula (d) and having an alcoholic property at both ends. In producing an azo group-containing polycarbonate by interfacial polymerization from a compound having a hydroxyl group or salts of these compounds, a dicarboxylic acid chloride, a carbonate precursor, and optionally a bisphenol compound containing no azo group, the azo group-containing compound And a dicarboxylic acid chloride are preliminarily reacted with each other, a method for producing an azo group-containing polycarbonate. (Here, R ¹ and R ² represent hydrogen, a lower alkyl group, a nitrile group, or an aromatic group, and x represents an integer of 1 to 10.) (Wherein R ¹ , R ² and x have the same meanings as above) (Here, R ¹ and R ² are as defined above, and A represents a lower alkylene group.) (Here, X and Y are divalent organic groups, R ¹ and R ² are hydrogen, a lower alkyl group or an aromatic group.) 2. The production method according to claim 1, wherein bisphenols are used in combination when the azo group-containing compound and the dicarboxylic acid chloride are previously reacted.