JPH01167329A - Production of polyester, polyester amide or polyamide - Google Patents

Abstract

PURPOSE:To obtain the title polymer with a simple operation at a low cost, by arbitrarily combining a dicarboxylic acid, a diol, a hydroxycarboxylic acid, a diamine and a hydroxiamine, etc., and polymerizing the compounds in the presence of an organic base using a phosphorus pentahalide as a condensation agent. CONSTITUTION:The objective polymer can be produced by using a combination of two or more components selected from (A) a dicarboxylic acid of formula I (R<1> is bivalent aromatic hydrocarbon group, xylylene, bivalent aliphatic hydrocarbon group, etc.), (B) a diol of formula II (R<2> is same as R<1>), (C) a hydroxycarboxylic acid of formula III (R<3> is same as R<1>), (D) a diamine of formula IV (R<4> is same as R<1>; R<5> and R<6> are H, hydrocarbon group, etc.), (E) an aminocarboxylic acid of formula V (R<7> is same as R<1>; R<8> is same as R<5>) and (F) a hydroxylamine of formula VI (R<9> is same as R<1>; R<10> is same as R<5>) or using the component C or component E as a sole component and reacting the components in the presence of an organic base using a phosphorus pentahalide of formula VII (X<1>-X<5> are halogen) as a condensation agent.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing polyesters, polyesteramides or polyamides.

In particular, it relates to the direct production of polyesters, polyesteramides or polyamides, in particular aromatic polyesters, aromatic polyesteramides or aromatic polyamides.

[Conventional technology]

It is generally considered difficult to directly synthesize aromatic polyesters, aromatic polyesteramides, and aromatic polyamides. Therefore, indirect synthesis methods such as transesterification and acid chloride methods in which raw material monomers are activated in advance are currently the main synthesis methods. but,
Direct synthesis is possible by using a condensing agent, but the high cost of the condensing agent is a major drawback.

As a means to overcome this drawback, a method using phosphorus oxytrihalides such as phosphorus oxychloride, phosphorus trihalides sulfide, and dihalophosphates such as phenyl dichlorophosphate as an inexpensive condensing agent (especially; n
However, this method using phosphorus oxychloride, etc. requires complicated operations such as the need to react with water in the presence of metal salts, and also Dihalophosphates are expensive condensing agents and cannot be said to have solved the above problems.

[Problem that the invention seeks to solve]

The present invention has been made based on the above-mentioned circumstances, and its purpose is to produce polyester, polyester amide, and polyamide, particularly aromatic polyester, aromatic polyester amide, and aromatic polyamide, at a significantly lower cost compared to conventional methods. Moreover, it is an object of the present invention to provide a manufacturing method which is extremely superior in practical use and can be manufactured by simple operations.

[Means for solving problems]

As a result of extensive research in order to solve the above problems, the present inventors found that a method using an inexpensive specific compound as a condensing agent satisfies the above object, and based on this knowledge, the present invention I was able to complete it.

That is, the present invention provides a dicarboxylic acid represented by the general formula (A), a diol represented by +10OCR'C0OH(A)-maximum(B), ItOR''011(B)-e
Hydroxycarboxylic acid represented by formula (C), HOR3C
OOH (C) - diamine represented by max (D), - aminocarboxylic acid represented by max (sn), ＼ N-R'-COOII (E) / f and - max (F) Hydroxyamine RIO \ N-R'-OH / ■ [In the formula, R1, R'', R3, R', R' and R9 are divalent aromatic hydrocarbon groups, R11X RI2 group (However, R+
+ and R12 are divalent aromatic hydrocarbon groups, 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. ), represents a xylylene group or a divalent aliphatic hydrocarbon group (however, R1, RZ, Rs, R', R?, R', R's, R
The hydrogen atom of the aromatic ring of I2 and the xylylene group may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, or a phenoxy group. ) Also, R5, R65R11
and RIO represents a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. ], when polymerizing two or more components selected from the group consisting of (F) in combination, or using (C) or (E) alone, the general maximum % formula %) (In the formula, xl, X2, X'3, x4 and X5 represent halogen atoms.) is used as a condensing agent, and the reaction is carried out in the presence of an organic base.

The present invention will be explained in detail below.

The carboxylic acid used in the present invention has the formula -C (
Any of those represented by A) can be used, and specific examples include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, diphenyl-4,4' -Dicarboxylic acid, methyl terephthalic acid, methyl terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylthioether-4,4'-dicarboxylic acid, diphenyl sulfone-
4,4'-dicarboxylic acid, diphenylketone-4,4'
-dicarboxylic acid, 2,2-diphenylpropane-4,4
Aromatic dicarboxylic acids such as '-dicarboxylic acids, l, 4
-Aralkylene dicarboxylic acids such as xylylene dicarboxylic acid and 1,3-xylylene dicarboxylic acid; chain aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, and azelaic acid; acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclopenkunedicarboxylic acid, l
, cycloaliphatic dicarboxylic acids such as 2-cyclopenkune dicarboxylic acid, but are not necessarily limited thereto. Mixtures of these may also be used.

Any diol represented by the general formula (B) can be used, and specific examples include hydroquinone, resorcinol, methylhydroquinone, chlorohydroquinone, acetylhydroquinone, acetoxyhydroquinone, nitrohydroquinone, dimethylaminohydroquinone, 1 .4-dihydroxynaphthalene, 1.5
-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2゜7-dihydroxynaphthalene, 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
'-dihy-10oxydiphenyl, bis(4-hydroxyphenyl)ketone, bis(4-hydroquine-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 , l,4-butanediol, 1.
4-cyclohexanediol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, l,4-bis(hydroxymethyl)benzene, l,3
-cyclohexanediol, etc., but are not necessarily limited to these. Moreover, these may be used as a mixture.

As the hydroquine carboxylic acid, any one represented by the general formula (C) can be used, and specific examples thereof include p-hydroxybenzoic acid, m-hydroxybenzoic acid, Schlinger's acid, vanillic acid, and 4-hydroxybenzoic acid. 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, l-hydroxy-4-naphthoic acid, 4-hydroxycyclohexanecarboxylic acid, 3-hydroxycyclohexanecarboxylic acid, β-hydroxyethanol,
Examples include, but are not limited to, ω-hydroxycaproic acid. Moreover, these may be used as a mixture.

As the diamine, any diamine represented by the general formula (D) can be used, and specific examples thereof include, for example, 1.3-
Diaminobenzene, 1,4-diaminobenzene, 2.2
'-Bis(4-aminophenyl)propane, 4.4'
-Diaminodiphenylmethane, benzidine, 4.4'-
Diaminodiphenyl sulfide, 4.4'-diaminodiphenylsulfone, 3.3'-diaminodiphenylsulfone, 4.4'-diaminodiphenyl ether, 4°4'-diaminodiphenyl ketone, 1.5-diaminonaphthalene, 3.3' -dimethylhenzidine, 2,6-diaminonaphthalene, 4,4'-diaminodiphenyl ether, m-xylylene diamine (1,3-bis(diaminomethyl)benzene), p-xylylene diamine, hexamethylene diamine, heptamethylene Examples include diamine, octamethylene diamine, 2,2-dimethylpropylene diamine, (1), 4-diaminocyclohexane, but are not necessarily limited to these.

In addition, these can be used individually or as a mixture of two or more types.

As the aminocarboxylic acid, any of those represented by the general formula (E) can be used, and specific examples include glycine, glycylglycine, alanine, phenylalanine, α-aminoacetic acid, valine, leucine, isoleucine,
α-aminoenanthic acid, α-aminocaprylic acid, α-aminoundecanoic acid, α-aminostearic acid, α-aminocerotic acid, α-amithumelicic acid, β-alanine,
β-aminobutyric acid, T-aminovaleric acid, ω-aminoenantoic acid, 4-aminocyclohexanecarboxylic acid, m-aminobenzoic acid: p-aminobenzoic acid, p-(4-aminophenyl)benzoic acid, p-( Examples include 4-aminohensyl)benzoic acid.

Moreover, these may be used in combination.

Any of the hydroxyamines represented by the general formula (F) can be used, but specific examples include 4-aminophenol, N-methyl-4-aminophenol, 4-amino-4'-hydroxy Phenyl, 3-aminophenol, N-phenyl-3-aminophenol, 3-methyl-4-hydroxy-4'-amino-diphenyl, 3,5-dimethyl-4-hydroxy-4'-amino-biphenyl, 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 sulfite, 3-methyl-4-hydroxy-4'-aminodiphenylmethane, 3,5-dimethyl-4-hydroxy-4'
-amino-diphenylmethane, 2,2-(3-methyl-
4-hydroxy-4'-amino)diphenylpropane,
2.2-(3,5-dimethyl-4-hydroxy-4'
-amino)diphenylpropane, 2,2- (3,5-
Dimethyl-4-hydroxy-3'-methyl-4'-amino)diphenylpropane, 2.2-(3-isopropyl-4-hydroxy-4'-amino)diphenylpropane, 2°2 (3tert-butyl-4- hydroxy-
4'-amino)diphenylpropane, 2.1-(3-chloro-4-hydroxy-4'-amino)diphenylpropane, 2.2-(3-methyl-4-hydroxy-4'-
amino) diphenylbutane, 3,3-(3-methyl-4
-Hydroxy-4'-amino)diphenylpenkun, l
.

Aromatic hydroxyamine w4 (aminophenols) such as 1-(3-methyl-4-hydroxy-4'-amino)diphenylcyclohexane, 2.2-(4-hydroxy-4'-amino)diphenylpropane: ethanolamine , 3-amino-n-propanol, N-methylethanolamine, 3-amino-2-methylpropanol, T-amino-n-octatool, ω-amino-n-nonanol; l
.

4-xylylene amino alcohol (1-hydroxymethyl-4-aminomethylhensen), 1. Examples include 3-xylylene amino alcohol, among which aromatic hydroxyamines (aminophenols) are preferably used. Moreover, these may be used in combination.

Examples of organic bases used in the present invention include pyridine, α-picoline, β-pyricone, T-vinyline, 1°3-lutidine, 2,4-lutidine, 3,5-lutidine, 1,3.
Pyridines such as 5-collidine, quinolines such as quinoline, isoquinoline, 2-methylisoquinoline, 2-methylquinoline, aliphatic amines such as triethylamine, tri-n-butylamine, cyclohexyldimethylamine, hensylamine, benzyldiethylamine Aromatic amines such as aralkylamines, phenyldiethylamine, triphenylamine, cyclic amines such as morpholine, triethylenediamine, 1,8-diazabicycloundecene-7, N-methylimidazole, imidazole, 2-methyl Although tertiary amines and imidazole compounds generally known as organic bases such as imidazole such as imidazole can be used, pyridine is preferred from the viewpoint of cost.

The amount of organic base used may be at least equimolar to the amount of the substrate.

Further, compounds represented by the general formula (G) used in the present invention include phosphorus pentachloride, phosphorus pentabromide, etc., but are not limited to these. , can be used alone or as a mixture of two or more, but phosphorus pentachloride is particularly preferred from the viewpoint of cost.

In the present invention, the reaction can usually be carried out using the organic base as a solvent, but other solvents may be used as necessary.

The solvents include chlorobenzene, O-dichlorobenzene, carbon tetrachloride, dichloromethane, chlorinated solvents such as tetrachloroethane, pyridine, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, T
- Polar solvents such as butyrolactone, dimethyl sulfoxide, sulfolane, hexamethylphosphoramide, aromatic hydrocarbons such as benzene, toluene, xylene, and the like.

These may be used as a mixed solvent if desired.

In the present invention, - two or more of the compounds represented by (A) to (F) are used in combination, or -
The compound represented by max. (C) or -max. In this step, the organic base and the condensing agent represented by the general formula (G) are made to exist in the reaction system, and the reaction is carried out.

As a polymerization method, a well-known solution polymerization method can be applied,
The order of addition of the monomer, the organic base, the condensing agent, and the thin medium used if desired is not particularly limited, but for example, the condensing agent is dissolved in the organic base, and this A method of mixing - with a solution prepared by dissolving the above-mentioned solvent or the above-mentioned organic base, etc. can be suitably employed.

The amount of the compound represented by maximum (G) to be used is usually selected such that the equivalent amount of phosphorus is in the range of 0.3 to 20 with respect to the ester or/and amide bond to be produced.

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 about 80 to 200°C, and the polymerization time is about 10 minutes to 24 hours. Ru.

The system during polymerization varies depending on the combination of monomers used, solvent, and additives, such as homogeneous system, precipitation system, and gel-like system, but the isolation of the polymer is performed in an organic solvent such as a lower alcohol or lower ketone. ITE by re-sedimentation or water only
This can be done by settling, washing, etc.

〔Example〕

Example 1 8.3 g (0.05 mol) of isophthalic acid was placed in a 500 ml three-ronus flask with a stirrer.
With pyridine roomR? I made them understand 8. To this is added lymph pentachloride, 3 g (0,035 mol) of pyridine (100 a
i)? After adding PI solution at room temperature, I 0 minutes at room temperature,
Furthermore, it was heated for 10 minutes in an oil solution of l 00 ''C.

This reaction mixture was added with 5.4 g of m-phenylenediamine (
A solution of 0.05 mol) of pyridine (100++ff1) was added all at once and heated at l 00 ''C for 3 hours.

The polymer was triturated with the reaction mixture in methanol and washed with hot methanol. The yield of the obtained polymer was 12 g and the logarithmic viscosity was 2.00 dilg in Rho 1□S Os.
．． A polyamide with a concentration of 5 g/d1 (measured at 30'C) was obtained.

Example 2 In a 500 d flask similar to Example 1, 6.9 g (0.05 mol) of p-aminobenzoic acid and 9.9 g of syringic acid were added.
g (0.05 mol) of pyridine (200 relative) solution was added and preheated (15 minutes) in an oil solution at 120°C. To this was added dropwise a solution of pentachloride phosphorus, 3 g (0,035 mol) of pyridine (100 aliquots) at 120°C over 20 minutes, and the mixture was further heated for 3 hours. Separated and washed.

Polymer yield is 15Il! Logarithmic viscosity at 2.50 dil
g (N,N-dimethylacetamide/lithium chloride (5
%) of polyesteramide (measured at 30° C. at D concentration) was obtained.

Example 3 Pyridine (1
00ai)? Yong? Pour the mixture into a 500 ml flask,
A solution of 8.3 g (0.04 mol) of phosphorus pentachloride in pyridine (100 ye) was added to this at room temperature, and the mixture was stirred at room temperature for 10 minutes and further heated in an oil bath at 120°C for 10 minutes. Then, methylhydroquinone 6 was added to this reaction product.
．． 2 g (0.05 mol) of pyridine (100ai>/8
After dropping the liquid at 120°C over 30 minutes,
heated for an hour. The polymer was separated by diluting the reaction mixture with pyridine, pouring into methanol, and washing in hot methanol. The yield of polymer was 13 g and the logarithmic viscosity was 1.
00di/g (in p-chlorophenol, 0.5
A polyester with a concentration of g/L0U (measured at 50'C) was obtained.

[Effects of the Invention] According to the present invention, since a specific inexpensive and effective condensation agent is used, the desired polycondensation reaction can be easily promoted with a quantitative yield. To provide a method for producing polyesters, polyesteramides and polyamides which is extremely advantageous in practice and can obtain polyesters, polyesteramides and polyamides such as aromatic polyesters, aromatic polyesteramides and aromatic polyamides at low cost through simple operations. Can be done.

Claims (1)

[Claims] 1. Dicarboxylic acid represented by general formula (A), HOOCR
^1COOH (A) Diol represented by general formula (B), HOR^2OH (B) Hydroxycarboxylic acid represented by general formula (C), HOR^3COOH (C) Represented by general formula (D) Diamine, ▲There are mathematical formulas, chemical formulas, tables, etc.▼(D) Aminocarboxylic acid represented by the general formula (E), ▲There are mathematical formulas, chemical formulas, tables, etc.▼Represented by (E) and general formula (F) Hydroxyamine ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (F) [In the formula, R^1, R^2, R^3, R^4, R^7 and R^9 are divalent aromatic hydrocarbon groups , R^1^1-X-R
^1^2 groups (where R^1^1 and R^1^2 are divalent aromatic hydrocarbon groups, and X is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, an ester group, or ), represents a xylylene group or a divalent aliphatic hydrocarbon group (however, R^1, R^2, R^3
, R^4, R^7, R^9, R^1^1, R^1^2, and the hydrogen atom of the aromatic ring of the xylylene group is substituted with a halogen atom, a hydrocarbon group, an alkoxy group, or a phenoxy group. You can leave it there. ) Furthermore, R^5, R^6, R^8 and R^1^0 represent a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. ], the general formula (A), (
B), (C), (D), (E) and (F) are combined and polymerized, or (C) or (E)
When polymerizing using alone, the compound represented by the general formula (G) ▲Mathematical formula, chemical formula, table, etc.▼(G) (In the formula, X^1, X^2, X^3,
^4 and X^5 represent halogen atoms. ) as a condensing agent and the reaction is carried out in the presence of an organic base.