JPH0689133B2 - 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 conducted extensive studies to find an inexpensive condensing agent, and as a result, in the presence of an organic base, the compound represented by the general formula (G) and the compound represented by the general formula (H) shown above as metal salts are used as a metal salt. It was found that polyesters, polyesteramides and polyamides can be easily produced by using a compound previously reacted in the presence of, and / or a compound represented by the general formula (I).

OBJECT OF THE INVENTION Accordingly, an object of the present invention is to provide an excellent method for producing an aromatic polyester, an aromatic polyesteramide and an aromatic polyamide at a very low cost as compared with a conventional method.

That is, the gist of the present invention is that the dicarboxylic acid represented by the general formula (A) HOOCR ¹ COOH (A) the diol represented by the general formula (B) HOR ² OH (B) the oxycarboxylic acid HOR represented by the general formula (C) ³ COOH (C) Diamine represented by general formula (D) Aminocarboxylic acid represented by general formula (E) Hydroxyamine represented by 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; X 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 or 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 halogen, a hydrocarbon group, an alkoxy group or a phenoxy group), and R ⁵ , R ⁶ , R ⁸ and R ¹⁰ are hydrogen atoms. , An aliphatic hydrocarbon group or an aromatic hydrocarbon group. ] 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, A compound represented by (G) and a compound represented by the general formula (H), which have been previously reacted in the presence of a metal salt. R ¹³ —OH (H) and / or compound represented by general formula (I) (In the formula, X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a halogen atom, R ¹³ represents a hydrogen atom, R ¹⁴ represents a hydrogen atom, an aromatic hydrocarbon group, an aralkyl group or an aliphatic carbon atom. A hydrogen group, Y represents an oxygen atom or a sulfur atom) as a condensing agent,
A method for producing polyesters, polyesteramides and polyamides is characterized by carrying out the reaction in the presence of an organic base.

[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'-dicarboxylic acid, 2,2'-diphenylpropane-
Aromatic dicarboxylic acids such as 4,4'-dicarboxylic acid, 1,4
-Xylylenedicarboxylic acid, aralkylene-based dicarboxylic acids such as 1,3-xylylenedicarboxylic acid, malonic acid,
Chain aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid, 1,4 cyclohexyl dicarboxylic acid, 1,3-cyclohexyl dicarboxylic acid, 1,2 cyclohexyl dicarboxylic acid,
Examples thereof include cycloaliphatic dicarboxylic acids such as 1,3 cyclopentyl dicarboxylic acid and 1,2 cyclohexyl dicarboxylic acid, but are not necessarily limited thereto. 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, 2,2′-bis (4-aminophenyl) propane, 4, 4'-diaminodiphenylmethane, benzidine, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone 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-diaminosilane Rohekisan, and the like. These may 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, 1,1
-(3-Methyl-4-hydroxy-4'-amino-diphenyl) -cyclohexane, 2,2- (4-hydroxy-
Aromatic hydroxyamine (aminophenol) such as 4'-amino-diphenyl) -propane; ethanolamine, 3-amino-n-propanol, N-methylethanolamine, 3-aminoisobutanol, 8-amino-
Aliphatic hydroxyamines such as n-octanol and p-amino-n-nonanol and 1,4-xylyleneaminoalcohol and 1,3-xylyleneaminoalcohol may be mentioned, but aromatic hydroxyamines (aminophenols) may be mentioned. ) Is preferably used. 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, quinolines such as 2-methylquinoline, triethylamine,
Aliphatic amines such as tri-n-butylamine and cyclohexyldimethylamine, aralkylamines such as benzylamine and benzyldiethylamine, aromatic amines such as phenyldiethylamine and triphenylamine,
Cyclic amines such as morpholine, triethylenediamine, 1,8-diazabicycloundecene-7, imidazoles such as N-methylimidazole, imidazole and 2-methylimidazole are generally known as organic bases and are tertiary. Both amine and imidazole compounds can be used, but pyridine is preferable from the viewpoint of cost.

The amount of the organic base used may be equal to or more than the molar amount of the substrate.

The compound represented by the general formula (G) used in the present invention includes phosphorus oxychloride, phosphorus oxybromide, phosphorus oxyiodide, dichlorobromophosphate, dichloroiodophosphate, trichlorothiophosphite. Examples include notebooks, but not limited to these, any of those represented by the general formula (G) can be used, but phosphorus oxychloride is most preferable from the viewpoint of cost.

The compound represented by the general formula (H) is water. Water can also be used as water of crystallization of metal salts or water of adhesion. Further, the reaction between (G) and (H) is carried out at an arbitrary temperature, and it is possible even at 0 ° C. or lower.

The amount of (H) used relative to (G) is preferably 0.3 to 2 times, and the reaction may be performed in the presence of a solvent.

Examples of the compound represented by the general formula (I) include phenyldichlorophosphonate, cyclohexyldichlorophosphonate, ethyldichlorophosphate, stearyldichlorophosphonate, benzyldichlorophosphonate,
Nonylphenyl dibromophosphonate, etc. General formula (I)
Although any of the compounds represented by can be used, phenyldichlorophosphonate is preferable. The reaction is usually carried out using a base as a solvent, but a solvent may be used if necessary.

Examples of the solvent include chlorine-based solvents such as chlorobenzene, 0-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.

The metal salts used in the present invention include lithium chloride, lithium bromide, calcium chloride, potassium chloride, potassium bromide, calcium carbonate, magnesium chloride, zinc chloride, nickel chloride, cupric chloride and the like. As the salt, an alkali metal salt or an alkaline earth metal salt is preferable, and a metal salt halide thereof is particularly preferable.

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. To produce a polyester, polyesteramide, or polyamide having a desired structure, respectively. In the present invention, the organic base and the general formulas (G) and (H) are used in the reaction system. It is necessary to allow the reaction product with and / or the condensing agent represented by (I) to exist and react. 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 compounds of the general formulas (G) and (H) used is selected such that the phosphorus equivalent is 0.8 to 20 with respect to the resulting ester or / and amide bond.

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 8
A temperature of about 0 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 combination of homogeneous system, precipitation system, gel-like system and monomers to be used, solvent and kind of additives, but the isolation of the polymer is carried out in an organic solvent such as a lower alcohol or a lower ketone. Reprecipitation, or reprecipitation with water only, or washing.

〔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 Lithium chloride hydrate (12 ml) dissolved in pyridine (15 ml)
Solution of phosphorus oxychloride (12 mmol) in pyridine (5 ml) previously reacted under ice cooling was added to the solution at room temperature, and the mixture was allowed to stand for 30 minutes at room temperature. Isophthalic acid (2.5 mmol) and terephthalic acid (2.5 mmol) were added to this mixture.
Of pyridine (10 ml) was added, and the mixture was kept at room temperature for 10 minutes at 120 ℃
After heating in an oil bath for 10 minutes, a solution of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A, 5 mmol) in pyridine (10 ml) was added dropwise at 120 ° C over 20 minutes. , Heated for an additional 3 hours.

The polymer was separated by pouring into methanol after diluting the reaction mixture with pyridine and washing in hot methanol. A polymer with a logarithmic viscosity of 1.26 dl / g (measured in phenol / 1,1,2,2, -tetra-chloroethane = 60/40 at a concentration of 0.5 g / dl at 30 ° C.) was obtained in quantitative yield.

Examples 2 to 4 The same results were obtained as in Example 1 except that the dicarboxylic acid and bisphenol were changed.

Example 5 A solution of phenyldichlorophosphate (8 mmol) in pyridine (10 ml) was preheated (5) in an oil bath at 120 ° C.
1 minute at 120 ° C. in a solution of p-aminobenzoic acid (5 mmol) and syringic acid (5 mmol) in pyridine (20 ml).
After dropping for 0 minutes, the mixture was further heated for 3 hours. The polymer was triturated with methanol in the reaction mixture and washed in hot methanol. Quantitative yield of logarithmic viscosity 2.88dl / g (N, N-
0.5g in dimethylacetamide / lithium chloride (5%)
(measured at a concentration of / dl at 30 ° C.).

Examples 6 to 10 The following results were obtained by operating in the same manner as in Example 5 except that the relative contents of p-aminobenzoic acid and silingaic acid were changed.

Example 11 To a solution of isophthalic acid (2.5 mmol) and terephthalic acid (2.5 mmol) in pyridine (10 ml) was added a solution of phenyldichlorophosphate (8 mmol) in pyridine (10 ml) at room temperature, and then at room temperature for 10 minutes. Further, it was heated in an oil bath at 120 ° C. for 1 minute.

A pyridine (5 ml) solution of bisphenol A (2.5 mmol) was added dropwise to the reaction mixture at 120 ° C. over 5 minutes, and then a 4,4′-oxydianiline (2.5 mmol) solution of pyridine (5 ml) was added. It was added dropwise over 5 minutes and the mixture was further heated at 120 ° C. for 3 hours. The polymer was separated and washed in the same manner as in Example 5 to give a quantitative yield of logarithmic viscosity of 1.23 dl / g.
(Phenol / 1,1,2,2-tetrachloroethane = 60/40
(Measured at 30 ° C. in the medium).

Examples 12 to 15 The following results were obtained by operating in the same manner as in Example 11 except that the diamine and bisphenol were changed.

Comparative Example 1 Isophthalic acid (2.5 mmol), terephthalic acid (2.5 mmol) and phosphoric acid trimethyl ester (5 mmol)
A pyridine (20 ml) solution of was heated at room temperature for 30 minutes and at 120 ° C. for 10 minutes in the same manner as in Example 1, and then bisphenol A was added.
A solution of (5 mmol) in pyridine (10 ml) was added dropwise at 120 ° C. over 20 minutes, and the mixture was further heated for 3 hours.

An attempt was made to separate the polymer by pouring the reaction solution into methanol, but no polymer was obtained.

─────────────────────────────────────────────────── ─── 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) An oxycarboxylic acid represented by the general formula (C), HOR ³ COOH (C) 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. 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 or a divalent aliphatic hydrocarbon group. (However, R ¹ , R ² , R ³ , R ⁴ , R ⁷ ,
R ^9, R ^11, a hydrogen atom of an aromatic ring of R ¹² and xylylene group is a halogen atom, a hydrocarbon group, may be substituted with an alkoxy group or a phenoxy group), also R ^5, R ^6, R ⁸ and R ¹⁰ represents a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. ] In general formula (A), (B),
To polymerize by combining two or more components selected from the group consisting of (C), (D), (E) and (F), or by polymerizing using (C) or (E) alone. That is, the compound represented by the general formula (G) and the compound represented by the general formula (H) are previously reacted in the presence of a metal salt. R ¹³ —OH (H) and / or compound represented by general formula (I) (In the formula, X ¹ , X ² , X ³ , X ⁴ and X ⁵ represent a halogen atom, R ¹³ represents a hydrogen atom, R ¹⁴ represents a hydrogen atom, an aromatic hydrocarbon group, an aralkyl group or an aliphatic carbon atom. A hydrogen group and Y represents an oxygen atom or a sulfur atom) as a condensing agent,
A process for producing polyesters, polyesteramides and polyamides, which comprises reacting in the presence of an organic base.