JPH0689134B2 - Method for producing polyester, polyesteramide and polyamide - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a polyester, a polyesteramide, or a polyamide. More particularly, it relates to a direct process for producing polyesteramides or polyamides, especially aromatic polyesteramides or aromatic polyamides.

[Conventional technology]

Direct synthesis of aromatic polyesters, aromatic polyester amides and aromatic polyamides is generally considered difficult. However, although it is possible to synthesize directly by using a condensing agent, the high cost of the condensing agent has been a major drawback. The present inventor has diligently studied to find an inexpensive condensing agent, and as a result, an organic base, or /
And a compound represented by the general formula (G) as a condensing agent are dissolved in an aprotic amide compound, and a polymerization reaction is performed at a specific temperature in the presence of the dissolved product, resulting in a polyester, a polyesteramide and a polyamide having an extremely high degree of polymerization. Have been found to be easily manufactured.

[Object of the Invention]

Therefore, an object of the present invention is to provide an excellent method capable of producing a highly polymerized aromatic polyester, aromatic polyester amide and aromatic polyamide at a very low cost as compared with the conventional method.

That is, the gist of the present invention is to include a dicarboxylic acid represented by the general formula (A), HOOCR ¹ COOH ... (A) a diol represented by the general formula (B), HOR ² OH ... (B) a general formula (C). An oxycarboxylic acid represented by HOR ³ COOH (C) a diamine represented by the general formula (D), Aminocarboxylic acid represented by general formula (E) And a hydroxyamine represented by the general formula (F) [Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁷ and R ⁹ are divalent aromatic hydrocarbon groups, R ¹¹ —X—R ¹² groups (provided that R ¹¹ and R ¹² are divalent groups; It is an aromatic hydrocarbon group, and X represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, an ester group or a direct bond), a xylylene group and a divalent aliphatic hydrocarbon group. (However, R ¹ , R ² , R ³ , R ⁴ , R ⁷ ,
R ⁹ , R ¹¹ , R ¹² and the hydrogen atom of the aromatic ring of the xylylene group may be substituted with a halogen, a hydrocarbon group, an alkoxy group or a phenoxy group), and R ⁵ , R ⁶ , R ⁸ and R ¹⁰ are A hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group is shown. ] In general formula (A), (B), (C),
When polymerizing a combination of two or more components selected from the group consisting of (D), (E) and (F) or polymerizing using (C) or (E) alone, an organic base Or / and a compound represented by the general formula (G) as a condensing agent to the aprotic amide compound (Wherein X ¹ and X ² represent a halogen atom, Y represents an oxygen atom, and n is an integer of 1 or 2) and the polymerization reaction is carried out in the presence of the dissolved product at a temperature of 60 ° C. or higher. And a method for producing a high-polymerization degree polyester, polyesteramide, and polyamide characterized by carrying out.

[Structure of Invention]

To describe the present invention in detail, as the carboxylic acid used in the present invention, any of those represented by the general formula (A) can be used, and specific examples thereof include terephthalic acid, isophthalic acid, naphthalene-2, 6-dicarboxylic acid,
Naphthalene-1,5-dicarboxylic acid, diphenyl-4,4'-
Dicarboxylic acid, methyl terephthalic acid, methyl isophthalic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenyl thioether-4,4'-dicarboxylic acid, diphenyl sulfone-4,4'-dicarboxylic acid, diphenyl ketone-4 4,4'-dicarboxylic acid, 2,2-diphenylpropane-4,
Aromatic dicarboxylic acids such as 4'-dicarboxylic acid, 1,4-
Aralkylene-based dicarboxylic acids such as xylylenedicarboxylic acid and 1,3-xylylenedicarboxylic acid, chain aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid ,
Cyclic aliphatic dicarboxylic acids such as 1,4 cyclohexyl dicarboxylic acid, 1,3 cyclohexyl dicarboxylic acid, 1,2 cyclohexyl dicarboxylic acid, 1,3 cyclopentyl dicarboxylic acid, 1,2 cyclohexyl dicarboxylic acid, etc. It is not limited. They may also be used as a mixture.

As the diol, any of those represented by the general formula (B) can be used, and specific examples thereof include hydroquinone, resorcin, methylhydroquinone, chlorohydroquinone, acetylhydroquinone, acetoxyhydroquinone, nitrohydroquinone, dimethylaminohydroquinone, 1,4- Dihydroxynaphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, 2,7-dihydroxynaphthol, 2,2′-bis (4-hydroxyphenyl) propane, 2,2 ′ -Bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2'-bis (4-hydroxy-3,5-dichlorophenyl) -propane, 2,2'-bis (4-hydroxy-3) -Methylphenyl) -propane, 2,2'-bis (4-hydroxy-3-chlorophenyl) ) Propane,
Bis (4-hydroxyphenyl) -methane, bis (4-
Hydroxy-3,5-dimethylphenyl) -methane, bis (4-hydroxy-3,5-dichlorophenyl) -methane, bis (4-hydroxy-3,5-dibromophenyl)
-Methane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenylbis (4
-Hydroxyphenyl) -ketone, bis (4-hydroxy-3,5-dimethylphenyl) -ketone, bis (4-hydroxy-3,5-dichlorophenyl) -ketone, bis (4-hydroxyphenyl) Sulfide, bis (4-hydroxy-3-chlorophenyl) sulfide, bis (4
-Hydroxyphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) ether, 1,4-butanediol, 1,4-cyclohexanediol, 1,6-hexamethylenediol, 1,4-cyclohexane Dimethanol,
Examples thereof include, but are not limited to, xylidene-1,4-diol and 1,3-cyclohexanediol. Moreover, you may use these as a mixture.

As the oxycarboxylic acid, any of those represented by the general formula (C) can be used, and specific examples thereof include p-hydroxybenzoic acid, m-hydroxybenzoic acid, syringer acid, vanillic acid and 4-hydroxy-4 '. -Carboxydiphenyl ether, 4-hydroxy-4'-carboxybiphenyl, 2,6-dichloro-p-hydroxybenzoic acid, 2-chloro-p-hydroxybenzoic acid, 2,6-difluoro-p-hydroxybenzoic acid , 2-hydroxy 6
-Naphthoic acid, 2-hydroxy-3-naphthoic acid, 1-hydroxy-4-naphthoic acid, 4-hydroxycyclohexanecarboxylic acid, 3-hydroxycyclohexanecarboxylic acid, β-hydroxyethanol, ω-hydroxycaproic acid, etc. These may be a mixture.

As the diamine, any of those represented by the general formula (D) can be used, and specific examples thereof include metaphenylenediamine, paraphenylenediamine and 2,2-bis (4
-Aminophenyl) propane, 4,4'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,
3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ketone, 1,5-diaminonaphthalene, 3,3'-dimethylbenzidine, 2,6-diaminonaphthalene, 4,4'-diaminodiphenyl ether, m-xylylenediamine, p-xylylenediamine, hexamethylenediamine, heptamethienediamine, octamethylenediamine, 2,2-dimethylpropylenediamine, 1,4-diaminocyclohexane, etc. And these can be used alone or as a mixture.

As the aminocarboxylic acid, any of those represented by the general formula (E) can be used, and specific examples thereof include glycine, glycylglycine, alanine, phenylalanine,
α-aminobutyric acid, valine, leucine, isoleucine, α
-Aminoenanthic acid, α-aminocaprylic acid, α-aminoundecanoic acid, α-aminostearic acid, α-aminoserotic acid, α-aminomelisic acid, β-alanine, β
-Aminobutyric acid, γ-aminovaleric acid, ω-aminoenanthic acid, 4-aminocyclohexanecarboxylic acid, m-aminobenzoic acid, p-aminobenzoic acid, p- (4-aminophenyl) benzoic acid, p- (4- Aminobenzyl) benzoic acid and the like can be mentioned. Moreover, these may be mixed and used.

As the hydroxyamine, any of those represented by the general formula (F) can be used, and specific examples thereof include 4-aminophenol, N-methyl-4-aminophenol,
4-amino-4'-hydroxydiphenyl, 3-aminophenol, N-phenyl-3-aminophenol, 3
-Methyl-4-hydroxy-4'-amino-diphenyl, 3,5-dimethyl-4-hydroxy-4'-amino-
Diphenyl, 3-methyl-4-hydroxy-3'-methyl-4'-amino-diphenyl, 3-methyl-4-hydroxy-4'-aminodiphenyl ether, 3,5-dimethyl-4-hydroxy-4 ' -Amino-diphenyl ether, 3-methyl-4-hydroxy-3'-methyl-
4'-amino-diphenyl ether, 4-hydroxy-
4'-amino-diphenyl ether, 3-methyl-4-
Hydroxy-4'-amino-diphenyl sulfide,
3-Methyl-4-hydroxy-4'-amino-diphenylmethane, 3,5-dimethyl-4-hydroxy-4'-amino-diphenylmethane, 2,2- (3-methyl-4-hydroxy-4'-amino- Diphenyl) -propane, 2,
2 '-(3,5-Dimethyl-4-hydroxy-4'-aminodiphenyl) -propane, 2,2- (3,5-dimethyl-4-
Hydroxy-3'-methyl-4'-amino-diphenyl) propane, 2,2- (3-isopropyl-4-hydroxy-4'-amino-diphenyl) propane, 2,2 '
-(3-tert-Butyl-4-hydroxy-4'-amino-diphenyl) -propane, 2,2- (3-chloro-4-
Hydroxy-4'-amino-diphenyl) -propane,
2,2- (3-methyl-4-hydroxy-4'-amino-
Diphenyl) -butane, 3,3 '-(3-methyl-4-hydroxy-4'-amino-diphenyl) -pentane, 1,
Aromatic hydroxyamines (aminophenols) such as 1- (3-methyl-4-hydroxy-4'-amino-diphenyl) -cyclohexane and 2,2- (4-hydroxy-4'-amino-diphenyl) -propane; Aliphatic hydroxyamines such as ethanolamine, 3-amino-n-propanol, N-methylethanolamine, 3-aminoisobutanol, 8-amino-n-octanol, p-amino-n-nonanol and 1,4 -Xylylene amino alcohol, 1,3-xylylene amino alcohol and the like can be mentioned, but it is preferable to use aromatic hydroxyamine (aminophenol). Also, these may be used as a mixture.

As the organic base used in the present invention, pyridine, α-picoline, β-picoline, γ-picoline, 1,3 lutidine, 2,4 lutidine, 3,5 lutidine, pyridines such as 1,3,5 collidine, isoquinone, 2-methylisoline, quinoline, 2-
Quinolines such as methylisoline, quinoline, 2-methylquinoline, aliphatic amines such as triethylamine, tri-n-butylamine, cyclohexyldimethylamine, benzylamine, aralkylamines such as benzyldiethylamine, phenyldiethylamine, triphenyl. Aromatic amines such as amines, morpholine, triethylenediamine, 1,8-diazabicycloundecene-
Cyclic amines such as 7 and imidazoles such as N-methylimidazole, imidazole and 2methylimidazole are generally known as organic bases, and both tertiary amines and imidazole compounds can be used, but they are costly. To pyridine are preferred.

As the aprotic amide compound, N-methyl 2-pyrrolidone, N-phenyl 2-pyrrolidone, N-methyl 2-
Pyrrolidone, cyclic amide compounds such as 1,3-dimethyl-2-imidazolone, N, N-dimethylformamide, N, N-
Examples thereof include chain amide compounds such as dimethylacetamide, but any known aprotic amide compound can be used, and is not particularly limited to the above.

The amount of the organic base or / and the aprotic amide compound used may be equal to or more than the molar amount of the substrate.

Examples of the compound represented by the general formula (G) used in the present invention include general formula (G) such as thionyl chloride, thionyl bromide, thionyl iodide, thionyl chloride bromide, thionyl chloride, iodide, sulfuryl chloride, sulfuryl chloride and bromide. Although any of the compounds shown can be used, thionyl chloride is most preferred in terms of cost. The reaction is usually carried out using a base or / and an aprotic amide compound as a solvent, but a solvent may be used if necessary.

Examples of the solvent include chlorine-based solvents such as chlorobenzene, O-dichlorobenzene, carbon tetrachloride, dichloromethane and tetrachloroethane, pyridine, dimethylformamide, dimethylacetamide, N-methylpyrrolide and γ-.
Butyrolactone, dimethyl sulfoxide, sulfolane,
There may be mentioned polar solvents such as hexamethylphosphoramide and aromatic hydrocarbons such as benzene, toluene and xylene.

If necessary, additives such as lithium chloride, lithium bromide, calcium chloride and potassium chloride may be added.

In the present invention, two or more components of the compounds represented by the general formulas (A) to (F) are used in combination, or the compound represented by the general formula (C) or the general formula (E) is used alone. In order to produce a polyester, a polyesteramide, or a polyamide having a desired structure, the organic base or / and the aprotic amide compound is used in the reaction system in the present invention,
It is necessary to react in the presence of the condensing agent represented by the general formula (G). As a method for polymerizing, the condensing agent is dissolved in an organic base, and a solvent is used if necessary, but all known polymerization methods in solution polymerization can be adopted.
The amount of the compound of the general formula (G) used is such that the equivalent of sulfur is 0.8 to 2 with respect to the produced ester or / and amide bond.
A range of 0 is chosen.

The polycondensation temperature varies depending on the type of solvent used and the type of raw material compound, but is usually about 60 to 300 ° C., preferably 6
A temperature of about 5 to 200 ° C is used, and a polymerization time of about 10 minutes to 24 hours is used.

The system during polymerization varies depending on the homogeneous system, the precipitation system, the combination of gel-like systems and the monomers used, the solvent, and the type of additive, but the isolation of the polymer is carried out in an organic solvent such as a lower alcohol or a lower ketone. It can be carried out by re-precipitation in the interior, re-precipitation with water only, or washing.

In the present invention, the condensing agent represented by the general formula (G) is dissolved in an organic base or / and an aprotic amide compound and used, but it is very inexpensive as compared with conventional condensing agents, In addition to being an economically advantageous method, the reaction progresses via the mixed acid anhydride formed by reacting an organic base or an aprotic amide compound with an active intermediate to react with a carboxylic acid. Therefore, it is presumed that the reaction is carried out by another mechanism of the conventional reaction using acid chloride.

〔The invention's effect〕

According to the method of the present invention, a polycondensation reaction using two or more components of the compounds represented by the general formulas (A) to (F) in combination can be easily promoted, and a polyester having excellent quantitative yield can be obtained. , Polyesteramides, or polyamides can be obtained.

Similarly, in the homopolymerization of the compound represented by the general formula (C) or (E), the reaction can be remarkably accelerated, and an excellent polyester or polyamide can be easily obtained.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples, but is not particularly limited to the Examples as long as the gist of the present invention is not exceeded.

Example 1 Pyridine (10 m) was added to thionyl chloride (11 mmol) cooled with ice.
l) was added slowly (about 10 minutes), and this solution was cooled to 30
After allowing to stand for about 20 minutes, add about 20 ml of a solution of isophthalic acid (2.5 mmol) and terephthalic acid (2.5 mmol) in pyridine (10 ml).
Dropped over minutes. After the dropping, the mixture was allowed to stand at room temperature for 20 minutes, and then 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) (5 mmol) of pyridine (10 m
l) The solution was added and heated in an oil bath at 80 ° C. for 4 hours. The polymer was separated by pouring into methanol after diluting the reaction mixture with pyridine and washing in hot methanol. The yield was quantitative. The logarithmic viscosity of the polymer is 2.28 dl / g (phenol / 1,1,2,2, -tetra-chloroethane = 60/40, 0.5 g / d
(measured at 30 ° C. at a concentration of 1).

Examples 2 to 5 The same operation as in Example 1 was carried out except that the dicarboxylic acid and bisphenol were changed, and the results shown in the following table were obtained.

Example 6 A solution of thionyl chloride (11 mmol) produced in the same manner as in Example 1 in pyridine (10 ml) was cooled with ice while isophthalic acid (2.5 mmol), terephthalic acid (2.5 mmol) and bisphenol A (5 mmol) were added. ) Pyridine solution (20m
l) was added dropwise over about 20 minutes and then left at room temperature for 20 minutes. The reaction mixture was heated in an 80 ° C. oil bath for a further 3 hours. The procedure of Example 1 was repeated to obtain a polymer having a logarithmic viscosity of 2.00 dl / g in a quantitative yield.

Examples 7-9 The procedure of Example 6 was repeated except that various combinations of oxycarboxylic acids (5 mmol) were used instead of isophthalic acid, terephthalic acid and bisphenol, and the following results were obtained in quantitative yield. Got

Examples 10 to 14 Dicarboxylic acid (2.5 mmol), bisphenol (2.5 mmol) and oxycarboxylic acid (5 mmol) were used in place of dicarboxylic acid and bisphenol A, and the reaction time was 5 hours. The procedure of Example 6 was repeated except that the following results were obtained in quantitative yield.

Example 15 N-Methylpyrrolidone (10 ml) was gently added to ice-cooled thionyl chloride (11 mmol) (about 2-3 minutes), and the solution was left under ice-cooling for 10 minutes and further at room temperature for 10 minutes. ,
A solution of isophthalic acid (5 mmol) in N-methylpyrrolidone (10 ml) was added at room temperature and left for 320 minutes. 4,4'-oxydianiline (5 mmol) was added to the reaction mixture.
Solution of N-methylpyrrolidone (10 ml) was added and the mixture was added at 70 ° C for 2
Heated for hours. Separate the polymer as in Example 1,
It was washed and had a logarithmic viscosity of 1.23 dl / g (in concentrated sulfuric acid, in quantitative yield,
(Measured at 30 ° C. at a concentration of 0.5 g / dl).

Examples 16 to 19 The following results were obtained by operating in the same manner as in Example 15 except that the types of dicarboxylic acid and diamine were changed.

Comparative Example 1 Pyridine was used instead of N-methylpyrrolidone,
And the same experiment as in Example 15 was conducted except that the reaction temperature was changed from 70 ° C. to room temperature, and the logarithmic viscosity was 0.20 dl in quantitative yield.
/ g (measured in concentrated sulfuric acid at a concentration of 0.5 g / dl at 30 ° C.) was obtained.

Comparative Example 2 A solution of isophthalic acid (2.5 mmol) and terephthalic acid (2.5 mmol) in pyridine (10 ml) was ice-cooled and then 2,2-bis (4-hydroxyphenyl) propane (5 mmol).
And thionyl chloride (11 mmol) were added, pyridine (20 ml) was added, and the mixture was allowed to polymerize at room temperature for 17 hours. The polymer was treated as in Example 1. The yield was 91%. The logarithmic viscosity of the polymer is 0.43 dl / g (solvent for measurement, concentration,
The temperature was the same as in Example 1).

Comparative Example 3 Instead of carrying out the polymerization reaction at room temperature for 17 hours in Comparative Example 2,
The procedure of Comparative Example 2 was repeated except that the polymerization reaction was carried out at 80 ° C. for 4 hours. The yield was 97%. The logarithmic viscosity of a polymer is
0.47 dl / g (measurement solvent, concentration and temperature are the same as in Example 1)
Met.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08G 69/08 NRZ 9286-4J 69/28 NSC 9286-4J 69/44 NSS 9286-4J

Claims (1)

[Claims] 1. A dicarboxylic acid represented by the general formula (A): HOOCR ¹ COOH (A) A diol represented by the general formula (B), HOR ² OH (B) a general formula ( An oxycarboxylic acid represented by C), HOR ³ COOH (C) a diamine represented by the general formula (D), Aminocarboxylic acid represented by general formula (E) And a hydroxyamine represented by the general formula (F) [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁷ and R ⁹ are divalent aromatic hydrocarbon groups and R ¹¹ -X-R ¹² groups (wherein R ¹¹ and R ¹² are divalent aromatic groups. It is a group hydrocarbon group, and X represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, an ester group or a direct bond), a xylylene group and a divalent aliphatic hydrocarbon group. (However, the hydrogen atom of R ¹ , R ² , R ³ , R ⁴ , R ⁷ , R ⁹ , R ¹¹ , R ¹² and the aromatic ring of the xylylene group is substituted with a halogen atom, a hydrocarbon group, an alkoxy group or a phenoxy group. R ⁵ , R ⁶ , R ⁸ and R ^{10 each} represent a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. ], Two or more components selected from the group consisting of the general formulas (A), (B), (C), (D), (E) and (F) are combined and polymerized, or (C) Or a compound represented by the general formula (G) as a condensing agent for an organic base or / and an aprotic amide compound in the polymerization using (E) alone. (Wherein, X ¹ and X ² represent a halogen atom, Y represents an oxygen atom, and n is an integer of 1 or 2), and in the presence of the dissolved product, at a temperature of 60 ° C. or higher. Polyester characterized by causing a polymerization reaction,
Method for producing polyesteramide and polyamide.