JPS61293223A - Polyether-polyamide multiblock copolymer and its production - Google Patents

Abstract

PURPOSE:To obtain the title copolymer having high heat stability and useful as, e.g., a thermoplastic elastomer, by polycondensing a specified polyether with a specified polyamide in the presence of an aromatic phosphite esters and a pyridine derivative. CONSTITUTION:An equimolar mixture of a polyether having an amino group on each end, represented by formula I (wherein R<2> is a 30C or lower bivalent organic group and m is 10-200) and a polyamide having a carboxyl group on each end, represented by formula IV (wherein R<1> is a bivalent organic group, Ar is a bivalent aromatic organic group, and n is 1-30) and prepared by reacting an aromatic diamine of formula II with a dicarboxlic acid of formula III is dissolved in a solvent mixture comprising an aromatic phosphite ester, a pyridine derivative and an organic solvent such as N-mehylpyrrolidone to form a solution of a concentration of 5-30wt%, and the monomers are allowed to react with each other at 60-140 deg.C for several min-20hr in the presence of an inert atmosphere such as nitrogen to obtain a polyether-polyamide multiblock copolymer of formula V (wherein x is 2-20).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyether-polyamide multi-block copolymer, particularly a thermally stable polyether-polyamide multi-block copolymer, and a method for producing the same.

(Prior art) Polyether has a flexible molecular structure.
Polyether block copolymers, typified by urethane block copolymers, are known as excellent elastic bodies. However, the decomposition temperature of urethane bonds is not necessarily high, and the thermal stability of polyether-urethane block copolymers has been problematic.

(Problems to be Solved by the Invention) As mentioned above, although the polyether-urethane block copolymer is an excellent elastic body, it does not have good thermal stability, which makes this copolymer commercially difficult. This was a major problem in usage. Therefore, the present invention aims to solve the problem of providing a polyether-polyamide multiblock copolymer with excellent thermal stability and a method for producing the same.

(Means for solving the problem) The present inventors focused on the fact that polyamide has strong intermolecular forces, and designed a new polymer having a polyether-polyamide multi-block copolymer skeleton. The present invention was achieved through the synthesis of .

The first invention of the present invention is based on the general formula (wherein R1 is a divalent organic group, R'' is a divalent organic group having 30 or less carbon atoms, Ar is a divalent aromatic organic group, m is an integer of 10 to 200, n is an integer of 1 to 30, X is 2 to 2
(represents an integer of 0) This is a polyether-polyamide multi-block copolymer represented by:

The second aspect of the present invention is that when producing the polyether-polyamide multi-block copolymer represented by the general formula I, the general formula (wherein R2 is a divalent organic compound having 30 or less carbon atoms) is used. base, m
is an integer from 10 to 200), and the general formula (wherein, R1 is a divalent organic group, Ar is a divalent aromatic organic group, n represents an integer from 1 to 30) and a polyamide having carboxyl groups at both ends, in the presence of an aromatic phosphite and a pyridine derivative. This is a method for producing a block copolymer. Said general formula! ,
m, n and X in n and ■ indicate the average degree of polymerization.

The polyether having amino groups at both ends, represented by the general formula (3), used in the present invention may be produced by any method that introduces amino groups at both ends of the polyether molecule. .

The polyamide having carboxyl groups at both ends, represented by the general formula (1), used in the present invention has the following general formula (1).
It is produced by reacting an aromatic diamine represented by the following with an excess amount of a dicarboxylic acid or its derivative represented by the general formula sell.

(IV) (V) However, in formula V, Indicates a halogen atom such as

Examples of the aromatic diamine represented by the formula (1) include metaphenylenediamine, paraphenylenediamine,
4.4'-diaminobiphenyl, 3゜3'-methylene dianiline, 4.4'-methylene dianiline, 4.4'-
Ethylenedianiline, 4゜4'-isopropylidenedianiline, 3.4'-oxydianiline, 4.4'-oxydianiline, 4.4'-thiodianiline, 3.3'-
Carbonyl dianiline, 4.4'-carbonyl dianiline, 3.3'-sulfonyl dianiline, 4.4'-sulfonyl dianiline, 1.4-naphthalenediamine, 1,
Examples include 5-naphthalenediamine and 2,6-naphthalenediamine.

The dicarboxylic acid represented by the formula (2) and its derivatives may be any dicarboxylic acid such as aliphatic, alicyclic, aromatic, etc., but examples include co-acid, fumaric acid,
Glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, undecanniic acid, dodecanniic acid, 1.3-cyclohexanedicarboxylic acid, 1.4-
Cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 4.4'-biphenyldicarboxylic acid, 3.3'-
Methylene nibenzoic acid, 4.4゛-methylene nibenzoic acid,
4.4'-oxynibenzoic acid, 4.4'-thionibenzoic acid, 3,3'-carbonylnibenzoic acid, 4,4'-carbonylnibenzoic acid, 4,4-sulfonylnibenzoic acid, 1
, 4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, and derivatives thereof.

The production of the polyamide having carboxyl groups at both ends represented by the formula (2) by the reaction of the aromatic diamine represented by the formula (1) with an excess amount of the dicarboxylic acid represented by the formula (2) or its derivative can be carried out by any known method. There is no difference depending on the method.

Here, the average degree of polymerization n of the polyamide represented by the above formula (2) produced from a combination of these two reaction components is usually 1 to 30.

The aromatic phosphite used in the present invention includes triphenyl phosphite, diphenyl phosphite, tri-tolyl phosphite, di-o-1-lyl phosphite, and tri-m-lyl phosphite. Tolyl, di-m-)lyl phosphite, tri-P-)lyl phosphite, di-p-)lyl phosphite, tri-chlorophenyl phosphite, di-0-chlorophenyl phosphite, trilyl phosphite Examples include p-chlorophenyl and di-p-chlorophenyl phosphite.

Pyridine derivatives used in the present invention include pyridine, 2-picoline, 3-picoline, 4-vicoline, 2-picoline,
, 4-lutidine, 2,6-lutidine, 3,5-lutidine and the like.

In the present invention, a polyether having amino groups at both ends represented by the above formula (1) and a polyamide having carboxyl groups at both ends represented by the above formula (2) are combined in the presence of an aromatic phosphite and a pyridine derivative. Polycondensation is carried out, and for this reaction, a solution polymerization method using a mixed solvent containing a pyridine derivative is usually employed. The organic solvent used here is limited in that it does not substantially react with both components and the aromatic phosphite, but it must also be a good solvent for both reaction components and be a solvent for the reaction products. It is desirable that it is a good solvent for multi-block copolymers. Typical examples of such organic solvents are amide solvents such as N-methylpyrrolidone and N,N-dimethylacetamide. In order to obtain a multi-block copolymer with a high degree of polymerization, inorganic salts such as lithium chloride and calcium chloride, and organic salts such as triethylamine hydrochloride, tetrabutylammonium chloride, and cetyltrimethylammonium chloride are added to this reaction system. You can also do that.

To explain in more detail the method for producing a multi-block copolymer according to the present invention, a polyether having amino groups at both ends represented by the above formula (1) and a polyamide having carboxyl groups at both ends represented by the above formula (2) are used. Equimolar amounts are heated in a mixed solvent containing an organic solvent represented by N-methylpyrrolidone in the presence of an aromatic phosphite and a pyridine derivative under an inert atmosphere such as nitrogen. This makes it easier.

The amount of aromatic phosphite used here is usually equal to or more than an equimolar amount to the amino group of the polyether represented by the formula It's not a good idea.

In addition, the amount of the pyridine derivative used here is determined by the formula
Although it is necessary that the amount is at least equimolar to the amino group of the polyether represented by, in reality, it is often used in large excess, including its role as a reaction solvent. A mixed solvent consisting of a pyridine derivative and an organic solvent typified by N-methylpyrrolidone is preferably used here, but the amount of the mixed solvent used is usually 5 to 30% by weight of the reaction component.
Only the amount that will be included will be used. The reaction temperature is usually preferably 60 to 140°C. The reaction time is influenced by the reaction temperature, but in any case it is advisable to stir the reaction system until the maximum viscosity, meaning the highest degree of polymerization, is obtained, often from a few minutes to 20 hours.

The average degree of polymerization X of the resulting multi-block copolymer represented by the formula I is determined by the polyether having amino groups at both ends represented by the formula (1) and the polyamide having carboxyl groups at both ends represented by the formula (2). limited by the amount of preparation. Under the reaction conditions,
When both reaction components are used in equimolar amounts, a multiblock copolymer having an average degree of polymerization X of about 10 can be produced.

Using an excess of either of the reactants limits the average degree of polymerization and is undesirable for normal purposes, but for specific purposes, using an excess of either will reduce the average polymer skin. You can also do that. After the reaction is complete, the reaction mixture is poured into a non-solvent such as methanol or hexane to separate the produced polymer, and further purified by reprecipitation to remove by-products and salts. You can get a combination.

The polyether polyamide multi-block copolymer produced as described above can be produced in a wide range of forms, from elastic bodies to tough resin-like substances, by selecting the molecular structure, molecular weight, etc. of both reaction components, and selecting the average degree of polymerization X. It can be obtained as a polymer with physical properties and is useful as a material for fibers and films.

The present invention will be described in detail with reference to Examples below, but the present invention is not limited to these.

(Example) 1.5 mmol (0,2
49g) isophthalic acid 2.0 mmol (0,332g
), triphenyl phosphite 4.8 mmol (0,6
61g), 6ml of pyridine and 4 mmol (0,550g) of triethylamine hydrochloride were placed in a flask.
The reaction was carried out by stirring at 100° C. for 2 hours under a nitrogen stream. To the resulting solution was added 0.5 mmol (1,270 g
) and 2 liters of pyridine were added thereto, and the mixture was further stirred at the same temperature for 4 hours. The obtained polymer solution was
ml of methanol, and the precipitated polymer was separated and washed with hot methanol. The intrinsic viscosity of the polymer thus obtained (in 0.5 g 7 dll dimethylacetamide,
(measured at 30°C) was 0.23.

叉鳳且-1 3,4′-oxydianiline 2.5 mmol (0,5
01g), isophthalic acid 3.0 mn+ol (0,49
8g), triphenyl phosphite 7.2 + imol (
2,234 g), 7 ml of pyridine, and 6 mmol (0,826' g) of triethylamine hydrochloride were placed in a flask, and the reaction was carried out by stirring at 100° C. for 2 hours under a nitrogen stream. The average molecular weight of the resulting solution was 2540.
polyoxytetramethylenediamine 0.5+u+ol
(1,270 g) and 3 ml of pyridine were added, and the mixture was further stirred at the same temperature for 4 hours. The resulting polymer solution was poured into 500 ml of methanol, and the precipitated polymer was separated and washed with hot methanol. The intrinsic viscosity of the polymer thus obtained (measured at 30° C. in 0.5 g/d 1 dimethylacetamide) was 0.23.

Daiotan-1 3,4'-oxydianiline 3.5 nv+ol (0,
701 g), isophthalic acid 4.0 mmol (0,66
4g), triphenyl phosphite 9.6 mmol (2
, 979 g) and 8 mmol (1,101 g) of pyridine 31111° triethylamine hydrochloride were placed in a flask and stirred at 100° C. for 2 hours under a nitrogen stream to carry out a reaction. 0.5 mmol (1,27
0 g) and 4 tal of pyridine were added thereto, and the mixture was further stirred at the same temperature for 4 hours. The obtained polymer solution was heated to 500 I
I11! The precipitated polymer was separated and washed with hot methanol. The intrinsic viscosity of the polymer thus obtained (in 0.5 g 7di dimethylacetamide,
(measured at 30°C) was 0.28.

Daishen - raw 3.4'-oxydianiline 5.0 m + * ol (1,
001 g), isophthalic acid 5.5 mmol (0,91
4 g), triphenyl phosphite 13.2 mmol (4
,096g), pyridine 10n+It.

Triethylamine hydrochloride 11 mmol (1,514 g)
was placed in a flask and stirred at 100° C. for 2 hours under a nitrogen stream to carry out a reaction. The resulting solution has an average molecular weight of 2
540 polyoxytetramethylene diamine 0.5mm
Add ol (1,270g) and pyridine 5ral,
The mixture was further stirred at the same temperature for 4 hours. The resulting polymer solution was poured into 500 ml of methanol, and the precipitated polymer was separated and washed with hot methanol. The intrinsic viscosity of the polymer thus obtained (measured in 0.5 g/dl dimethylacetamide at 30° C.) was 0.37.

Yukiyong-1 3,4'-oxydianiline 10.5 mmol (2,
102 g), isophthalic acid 11.0 mmol (1,8
27g), triphenyl phosphite 26.4 a+mol
(8,192 g) and 22 mmol (3,028 g) of pyridine 16Il11 triethylamine hydrochloride were placed in a flask, and the reaction was carried out by stirring at 100° C. for 2 hours under a nitrogen stream. 0.5 mmol (1,2
70g) and pyridine 811 were added thereto, and the mixture was further stirred at the same temperature for 4 hours. The obtained polymer solution was
ml of methanol to separate the precipitated polymer,
Washed with hot methanol. The intrinsic viscosity of the polymer thus obtained (0.5 g/dx in dimethylacetamide, 30
) was 0.50.

(Effects of the Invention) As described above, the present invention uses a polyether-polyamide multi-block copolymer represented by the general formula I, a polyether having an amino group at both ends, and a polyamide having a carboxyl group at both ends. A method for producing a polyether-polyamide multi-block copolymer which is polycondensed in the presence of a group-face phosphate ester and a pyridine derivative, the method comprising:
The polycondensation reaction proceeds easily at low temperatures, and the multiblock copolymer with good regularity can be obtained. According to the present invention, high temperatures are not required during polycondensation, and transamide reactions and decomposition reactions of polyether chains can be avoided. In addition, easy-to-handle carboxylic acids can be used instead of unstable carboxylic acid chlorides. Since it is used as it is, a multiblock copolymer with a controlled structure can be easily produced, which has a great advantage over other amide-generating polycondensation methods.

Furthermore, the polyether-polyamide multipropylene copolymer of the present invention has high thermal stability and is highly useful for thermoplastic elastomers and the like.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 is a divalent organic group, R^2 has 30 carbon atoms.
or less divalent organic group, Ar is a divalent aromatic organic group,
m is an integer from 10 to 200, n is an integer from 1 to 30, x is 2
A polyether-polyamide multi-block copolymer represented by: 2. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 is a divalent organic group, and R^2 has 30 carbon atoms.
or less divalent organic group, Ar is a divalent aromatic organic group,
m is an integer from 10 to 200, n is an integer from 1 to 30, x is 2
In producing a polyether-polyamide multi-block copolymer represented by (representing an integer of ~20),
General formula H_2N-R^2-(CH_2-CH_2-CH_2-
CH_2-O)-_mR^2-NH_2, (in the formula, R^
2 is a divalent organic group having 30 or less carbon atoms, m is 10 to 2
There are polyethers with amino groups at both ends represented by the general formula ▲ numerical formula, chemical formula, table, etc. ▼ (in the formula, R^1 is a divalent organic group, and Ar is a divalent organic group). A polyamide having carboxyl groups at both ends represented by an aromatic organic group (n is an integer of 1 to 30) is polycondensed in the presence of an aromatic phosphite and a pyridine derivative. A method for producing a polyether-polyamide multi-block copolymer.