JPS6060131A - Polyesteramide and polyamide manufacturing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyesteramides or polyamides. In particular, it relates to the direct production of polyesteramides or polyamides, in particular aromatic polyesteramides or aromatic polyamides.

It is generally considered difficult to directly synthesize aromatic polyesteramides and aromatic polyamides. However, although this becomes possible by using a phosphorus compound as a condensing agent, there is a drawback that the cost of the phosphorus compound used in this case is high.

As a result of intensive studies to find an inexpensive condensing agent to replace phosphorus compounds, the present inventor found that polyesteramide and polyamide can be easily produced by using a sulfonyl compound represented by the general formula [II] as a condensing agent. I found out what I can do.

That is, the gist of the present invention is the combination of an organic compound having seven amine groups and an alcoholic or phenolic hydroxyl group with one dicarboxylic acid in the molecule, the polycondensation of a dicarboxylic acid with a diamine, or the polycondensation of an amine group in the molecule with one dicarboxylic acid. In the production of polyester amide tJjld polyamide by M condensation reaction of a compound having a carboxyl group, the general formula [l]
(In the formula, R1, Re and Hs are hydrogen atoms, alkyl groups,
(representing an aryl group, an aralkyl group or a cycloalkyl group) or/and an amide compound represented by the general formula [
1) An amide compound represented by (wherein R4 represents an optionally branched alkylene group having 3 or more carbon atoms, and R' represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group) and general formula [1] R'-8O, (indicates an atom)
A method for producing polyesteramide or polyamide using a mixture with a halogenated sulfonyl compound represented by

To explain in detail the present invention, the dicarboxylic acid used in the present invention has the general formula [1v]HOOO-R' -
000H@@---- [:lv] (R? rr in the formula
ia aromatic group, R1)(tRe- group, 3Y4, where R1 and Re
is a covalent aromatic group, and represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, an alkylidene group, or an atom.

As a covalent aromatic group, Y? Y@ (indicating an atom or an alkyl group) is honored.

s y4 Indicates an elementary atom, a helogen atom, or an alkyl group.

Specific examples include terephthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, ? , Nani 7 Tallinn-/,
&-Dicarboxylic acid, dienyl-q, 1Il-dicarboxylic acid, methyl terephthal? , methyl isophthalic acid, diphenyl ether, l/'-dicarboxylic acid, dienylthioether-F, 1%'-dicarboxylic acid, diphenylsulfone-qua 9'-dicarphonic acid, diphenyl ketone, di'-dicarboxylic acid, , cordiphenylpropane-+, aromatic dicarbonyl r'L/, such as lI-'-dicarboxylic acid, ti-xylylene dicarboxylic acid P,
Aralkylene dicarboxylic acids such as i'3-xylyl/dicarfonic acid, malonic acid, succinic acid, glutaric acid,
Adipic acid.

Chain aliphatic dicarboxylic acids such as pimelic acid, speric acid, azelaic acid, /, cyclohexyl dicarboxylic acid #
/1. ? Cyclohexyldicarboxylic a%/IJ cyclohexyldicarboxylic +*, l+, y cyclopentyldicarboxylic acid, /1.2 cyclohexyldicarboxylic rf2'
Examples include cycloaliphatic dicarboxylic acids of No. 3, but are not necessarily limited to these. Moreover, these may be used as a mixture.

Organic compounds having an amino group and an alcoholic or phenolic hydroxyl group in the molecule include the general formula [V] (wherein R'' is a covalent aromatic group, a divalent aliphatic group, and Y
°~yltij indicates a hydrogen atom, a halogen atom, or an alkyl group. R'' represents a hydrogen atom, an aliphatic group or an aromatic group], where R'' and R'' are a covalent aliphatic group or a divalent aromatic group,
Xo is an 18λ elementary atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, an alkylidene group, or a 0-valent aromatic group (indicating an alkyl group).

AIIJ includes kuaminophenol, N-methyl d'l-aminophenol, guamino-hiro'-hydroxydiphenyl, 3-aminephenol, N-phenyl-3-aminoneenol, 3-methyl-guhydroxyg'-amino- diphenyl, 3. S-dimethyl-guhydroxyg'-amino-diphenyl, 3-methyl-
hydroxy-3'-methyl-q'-amino-diphenyl, 3-methyl-1-hydroxy-q'-amino diphenyl ether, 3. ! ;-Simethyl-guhydroxy--amino-diphenyl ether, 3-methyl-guhydroxy-! -Methyl-g'-aminodiphenyl ether, g-hydroxy-hiro'-aminodienyl ether, 3-methyl-der-hydroxy-l-aminodienyl sulfide, 3-methyl-g'-aminodiphenyl methane, 3 .3-dimethyl-derhydroxy-t'-amino-diphenylmethane,
2. +2-(3-methyluda-human90x-4/-ami/-diphenyl)-furonokun,yu,co/-(,3,
ni-dimethyl-guhydroxy-g'-aminodiphenyl)-brono(n, J, J, -(J, &-dimethyl-q-hydroxy-37-methyl-1I/-amino-diphenyl)pronokun, uj-(j -Inpropyl-Hiro-
Hydroxy-l-amino-diphenyl]-pronokun,
Co, Co'-(3-tert=Ptyruderhydroxyak'-amino-diphenyl)-Flopane, Kotny (J
-chloro-hydroxy-g'-amino-diphenyl)-fluoropane, co, 2-(j-methyl-q-hydroxy-g!-amino-diphenyl)-butane, 3.3'
-(,?-methyl-derhydroxy-gaminocyphenyl)-pentane, /, / -(j-methyl-<2-
Aromatic hydroxyamines (aminone enol) such as hydroxy-q'-minodiphenyl)cyclohexane, hydroxy-q'-aminodiphenyl)-prono; ethanolamine, 3-amino-n
-Pronoknol, N-methylethanolamine, 3-
Examples include aminoisobutanol, g-amino-n-octano group hydroxyamines, i,y-xylylene amino alcohol, l,3-xylylene amino alcohol, and aromatic hydroxyamines (aminone enols). It is preferable to use

The diamine used for producing polyamide has the general formula [Vl:] H,N-RI4-NH,...[Vl:] (wherein R" is a covalent aromatic group, 2 valence I]tT aliphatic group Y1.
Y'' represents an atom or alkyl group), RIM X41=11
(represents a @- group) where R" and R" are a divalent aliphatic group or a λ-valent aromatic group, and X4 is an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an alkylene group, an alkylidene group. , or none. A covalent aromatic compound Y"Y" representing a halogen atom or an alkyl group is honored.

Specific examples include metaphenylene diamine, paraphenyl diamine, co-corbis(cou-aminophenylbropan% +, +'-diaminodiphenylmethane, benzidine, g, p'-diaminodiphenyl sulfide,
<z, lI'-diaminodiphenylsulfone, J,
J'-Shifumi/ Synenyl sulfone, μpl-diaminodiphenyl ether, +, ll'-diaminodiphenyl ketone%/, , S--diaminonaphthalene 1
．． 7. ．． 7'-dimethylbenzidiy, 2,6-diaminonaphthalene, u, 4t'-diaminodiphenyl ether, m-xylylene diamine, p-xylylene diamine,
Examples include hexamethylene diamine, heptamethylene diamine, octamethylene diamine, u, +2-dimethylpropylene diamine, and 4t-71 diaminocyclohexane, which can be used alone or as a mixture. Further, any of the general formula [v1] can be used, and is not limited to these specific examples.

In addition, as a compound having an amine group and a carboxyl group in the molecule used for polyamide synthesis, the general formula [V11
] % Formula % (In the formula, R' represents a straight chain, branched chain, or cyclic aliphatic hydrocarbon base and 5 aromatic hydrocarbon groups, and one or more of these groups are bonded by a 10ONH- group. ), and specific examples thereof include glycine, glycylglycine, acinine, phenylalanine, α-aminobutyric acid, valine, leucine, inleucine, α-amino acid, α-amizukaglyric acid, α-aminoundecanoic acid, α
-Aminostearic acid, α-aminocellodine r-α-amithumelycin, β-alanine, β-aminoNir+
′! , γ-aminoyoshifu r41, 0-amino p-(guaminobenzyl)an 7 (one incense, one dilambda, etc.) can be hung, but it is not necessarily difficult to use, and it is not necessary to set the number 1 hair. do not have.

As the Ryomid compound used in the present invention, any of those shown in Table 1 with the general formula [11) and/or [11] can be used, but N,N-dimethylformamide, N , N-diethylacetamide, N,N-dibutylpho, Ilzmamide, N-methylbormamide;
i; lumamide, N, N-dimethylacetamide, N,
N-diethylacetamide, N-methylacetamide,
Acetani IJ)”, N, 11-diphenylformamide, benzyl I, T mido, N, N-dimethylbenzoylamimethyl benzoylamide, N, N-diegyl acetylamide Particularly preferred are those in which R3, R8 and R1 in 111 are hydrogen atoms, alkyl groups and aryl groups.
From the viewpoint of cost, N-methylcobyrolidone is preferred as the compound represented by.

As the sulfonyl compound used in the present invention, any compound represented by the general formula Cl) can be used, but
p-Toluenesulfonyl chloride, phenylsulfonyl chloride, p-p10 mophenylsulfonyl chloride +7
) 11, p-nitrophenylsulfonyl chloride IJ)”
% p-chlorophenylsulfonyl chloride, m-chlorophenylsulfonyl chloride. ,2,lI,A-
1-limethylphenylsulfonyl chloride, λ, q
, t. -) lisofurovirsulfonylchloride IJ)
"% Methanesulfonyl chloride Ensulfonium bromide, p-toluenesulfonyl iotide, p-)luenesulfonyl fluoride, benzylsulfonyl chloride, where R' is an aryl group, an alkyl group, or a benzyl group in the forefoot general formula (1) is particularly preferred.

It is necessary to use 7,730 moles or more of the amide compound per 27 moles of dicarboxylic acid or aminocarboxylic acid, and the sulfonyl compound used M is preferably 2 to 70 times the mole per mole of dicarboxylic acid or aminocarboxylic acid. It is necessary to use twice as many moles.

When combining the blades, it is appropriate to mix the amide compound and the sulfonyl compound with a base alone or with a base and a solvent and then mix and heat the monomers, and the reaction temperature is usually about θ to SO ℃, preferably about room temperature. . Bases used for this purpose include pyridine, α-picoline, β-picoline, γ-picoline, 3. S-lutidine,
3.Courtidine, -,Courtidine, 2.6-Lutidine,Co,3-Lutidine,Co,5-Lutidine,2. +.

Examples include 6-collidine, quinoline, isoquinoline, dimethylaniline, etc., but any tertiary amine can be used.

Examples of solvents include chlorinated solvents such as chlorobenzene, 0-dichlorobenzene, carbon tetrachloride, dichloromethane, and tetrachloroethane, dimethylformamide, dimethylacetamide, N-methyl birolide, γ-butyrolactone, dimethyl sulfoxide, sulfolane, and hexane. Examples include polar solvents such as methylphosphoramide, aromatic hydrocarbons such as toluene and xylene.
The temperature is about 0°C, preferably about 100°C to 20°C.

In addition, in the present invention, Li0 is used as an additive to adjust the solubility and swelling property of the polymer produced during the 1l-I'A reaction, and as an auxiliary agent to increase the degree of polymerization.
40a07. , MgOAt, LiBrn (of any alkali or alkaline earth metal), polyesters with a high degree of polymerization and a very narrow molecular pair distribution can be easily obtained by VC without the addition of halogenides.

The system during polymerization varies depending on the combination of monomers used, such as homogeneous system, precipitation system, and gel-like system, as well as the type of solvent and additives. This can be carried out by reprecipitation in a solvent such as 41, or by reprecipitation with water alone, washing, etc.

The present invention will be explained in detail below using examples.

Example 1 p-)Luenesulfonylchlori)” (/3 mmol)
N,N-dimethylformamide (DMF, !; mmol) was added to the pyridine (/θ) solution of and left under stirring at room temperature for 30 minutes. Isophthalic acid solution? 2 (j mmol) in pyridine (tOrnl) and heated at room temperature for 10 minutes, and then heated in an oil bath at 10°C for 10 minutes, followed by a solution of p-mininophenol (j mmol) in pyridine (10 ml). Add the solution and incubate in an oil bath at /20”C for 30 minutes.
heated for an hour. By injecting the reaction solution into methanol, the quantitative yield was ηinh of 0.1.9 eLll/g.
A polyesteramide was obtained.

In addition, the actual h1! Viscosity (η1n
h) was measured at 30°C in N-methylpyrrolidone (0.5).

Example 3. Comparative example: The following results were obtained by performing the same procedure as in the example except for changing the starvation of DMF. ! Also.

Example 1 A polymer with ηinh of O, co'7 dl, and Q/ was obtained in quantitative yield by the same procedure as in Example 1, except that p-aminone enol was changed to m-amine phenol.

Example S Insophthalic acid (2,j mmol)
A polymer with ηinh of o and q z 4747 g was obtained in the same manner as in Example 1 with a quantitative yield, except that a mixture of and terephthalic acid (J, j mmol) was used.

, Example B: Isophthalic acid (S, S mmol) instead of isophthalic acid
The procedure was repeated in the same manner as in Example 1, except that m-amine phenol was used in place of p-aminone enol and a mixture of terephthalic acid (2.5 mmol) and p-aminone phenol.
With the desired yield, ηinh is o, t, t.

(167 g of polymer was obtained.

Example 7 Example 1i except that N,N-diethylformamide was used instead of DMF! i The same procedure as in Example 1 was carried out to obtain a quantitative yield with ηinh of 0. A, 2 eLl/11 polymer was obtained.

Example g? A polymer of p-)luenesulfonyl chloride was obtained in quantitative yield by operating in the same manner as in Example 1 of Actual A11i, except that the following compound was used for W.

Example 10. // Using the following diamine instead of p-aminone enol,
After adding isophthalic acid pyridine liquor solution, leave at room temperature for 70 minutes.
The following polyamide was prepared in the same manner as in Example 1, except that after heating in a 100°C oil bath for 70 minutes, diamine (tamimole) was added and the JQ reaction was carried out in a 700°C oil bath. A constant J14 yield was obtained.

Claims (1)

[Claims] (1) Polycondensation of an organic compound having an amino group and an alcoholic or phenolic hydroxyl group in the molecule with a dicarboxylic acid, a polycondensation of a dicarboxylic acid and a diamine, or a compound having an amine group and a carboxyl group in the molecule. In the production of polyesteramide or polyamide by polycondensation reaction, general formula [1] (wherein R1, R1 and R8 are hydrogen atoms, alkyl groups,
aryl group, aralkyl group or cycloalkyl group) or/and the general formula [
■] (In the formula, R4 represents an optionally branched alkylene group having 3 or more carbon atoms, and represents an R'U hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group) Compounds and halogenated sulfonyl compounds represented by the general formula [River] A method for producing polyesteramide or L-polyamide, characterized by using a mixture of.