JPS62112626A - Polyamide resin and its production - Google Patents

Abstract

PURPOSE:To obtain a polyamide resin being soluble in various organic solvents and having a high glass transition point and a high decomposition point and excellent processability, by reacting a diamine having a 1-iodo-3,5-phenylene group with a dicarboxylic acid under specified conditions. CONSTITUTION:A diamine of formula I (wherein Ar is a 1-iodo-3,5-phenylene group when one kind of Ar is used and one Ar is a 1-iodo-3,5-phenylene group and the other Ar groups are bivalent aromatic groups when two or more kinds of Ar are used), e.g., 3,5-diaminoiodobenzene, is prepared. This diamine is reacted with a dicarboxylic acid of formula II (wherein R is a bivalent aromatic group), e.g., terephthalic acid, in an organic solvent in the presence of an aromatic phosphite (e.g., triphenyl phosphite) and pyridine (derivative) to obtain the purpose polyamide resin of formula III (wherein n is 10-200).

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention provides polyamide resins, particularly soluble in various organic solvents,
The present invention also relates to a new polyamide resin having a high glass transition temperature and a method for producing the same.

(Prior Art) In the past, fully aromatic polyamide resins have been expected to be materials with high glass transition points and high decomposition points. but,
Many of the aromatic polyamides produced so far are insoluble in organic solvents and have a glass transition point of 300° C. or higher, so there are still problems with their moldability. In addition, although it has high thermal stability, it has poor moldability and there is no fully aromatic polyamide resin that has both heat resistance and processability, making it difficult to use this resin commercially. This was a big problem when doing so.

(Problems to be Solved by the Invention) Therefore, the present invention provides a novel polyamide resin that is soluble in organic solvents, has a high glass transition point, and at the same time has a high decomposition point, and has excellent processability, and a method for producing the same. The purpose is to solve problems that facilitate.

(Means for solving the problems) The first invention of the present invention is a novel polyamide resin having a structure and characteristics capable of solving the above problems, namely:
General formula % Formula % () (wherein, R is one or more divalent aromatic groups, Ar
When there is one type of Ar, it is a 1-iodo-3,5-)1 dicine group, and when there are two or more types of Ar, it is one of them. 1
-Iodo-3,5-phenylene group, other species are divalent aromatic groups, and n is an integer of 10 to 200.

The second aspect of the present invention is that when producing a polyamide resin represented by the general formula 1, the general formula 8% () (wherein, Ar is 1-iodo-3, 5
-phenylene group, in the case of two or more types of Ar, one type of "t" is a 1-iodo-3,5-phenylene group, and the other type is a divalent aromatic group). One or more types of dicarboxylic acids represented by the general formula % (wherein R represents a divalent aromatic group) and one or more types of dicarboxylic acids are combined to form an aromatic phosphite ester. Production of a polyamide resin by reacting it with a pyridine derivative in an organic solvent in the presence of a pyridine derivative; method A'5.

The polyamide resin represented by the general formula T in 1)i'I of the present invention is H2N-Ar-NH2([) (wherein, Ar is 1-iodo-3,5 when there is only one type of Ar).
-phenylene group, if Ar is two or more types, one of them is 1-iodo-3,5-phenylene group, other types are divalent aromatic groups). species or two or more species and one or more dicarboxylic acid cybalides represented by the general formula % (% formula %) (wherein R represents a divalent aromatic group and X represents a halogen atom) It can also be produced by reacting in an organic solvent.

The polyamide resin represented by the general formula 1 is made from a diamine represented by the general formula (1) and a dicarboxylic acid represented by the general formula (2), or a dicarboxylic acid civalide represented by the general formula (2). However, as for diamine, 8r is
A diamine consisting of a 1-iodo-3,5-phenylene group can be used alone, or a diamine consisting of 20 to 99
A diamine in which mol% of the Ar consists of a 1-iodo-3,5-phenylene group, and a diamine in which 80 to 1 mol% of the Ar consists of one or more divalent aromatic groups,
They can also be used in combination. When using a mixture of diamines, if the diamine consisting of 1-iodo-3,5-phenylene group is less than 20 mol%, the solubility in organic solvents and thermoformability, which are the characteristics of the present invention, are not fully satisfied. It disappears. As the diamine represented by the above general formula (2), a diamine in which Ar is a 1-iodo-3,5-phenylene group is used alone, and a dicarboxylic acid represented by the above general formula (2) or a dicarboxylic acid represented by the above general formula (2) is used. It is also possible to use one type or a mixture of two or more types of dicarboxylic acid cybalides.

Among the diamines represented by the general formula (1), the diamine in which Ar is a 1-iodo-3,5-phenylene group is a diamine consisting of a 1-iodo-3,5-phenylene group having the structure of the following formula V. Diamines are suitable.

(In the formula, J represents an iodine atom) This diamine can be produced using 1,3-dinitrobenzene and iodine, which are industrially available at low cost, as raw materials.
- Dinitro-1-iodobengyne can be added to various conventionally known j
Obtained by reduction using the oxidation method.

Examples of diamines containing a divalent aromatic group behind the diamine represented by the general formula (1) include meta-phenylene diamine, para-phenylene diamine, 4,4'-diaminophenyl, and 3,3'-methylene dianiline. ,4.
4'-methylene dianiline, 4.4'-ethylene dianiline, 4.4'-isopropylidene dianiline,
3.4'-oxydianiline, 4.4'-oxydianiline, 4゜4'-buodianiline, 3.3'-carbonyldianiline, 4.4'-carbonyldianiline, 3.3'-sulfonyldianiline Examples include aniline, 4,4'-sulfonyldianiline, i,4-naphthalenediamine, 1,5-naphthalenediamine, and 2,6-naphthalenediamine.

As the dicarboxylic acid consisting of a divalent aromatic group represented by the general formula (2), the following dicarboxylic acids can be exemplified. Zunawara, terephthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid,
4.4'-diphenyl ether dicarboxylic acid, 3.3
' -diphenyl ether dicarboxylic acid, 4,4' -
diphenylmethanedicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 3,3
'-diphenylsulfonedicarboxylic acid and the like can be exemplified.

As the dicarboxylic acid cybaride consisting of a divalent aromatic group represented by the general formula (2), the following dicarboxylic acid dichloride, difluoride, and dibromide can be exemplified. Namely, terephthalic acid, isophthalic acid,
1.4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid 2.6-naphthalene dicarboxylic acid, 4,
4'-diphenyl ether dicarboxylic acid, 4.4'-diphenylmethane dicarboxylic acid, 3.3'-diphenylmethane dicarboxylic acid 3
, 3'-diphenylsulfone dicarbonichloride,
Difluoride and dibromide can be expressed as '/11.

The production of the polyamide resin represented by the general formula (2) is carried out by combining the diamine represented by the general formula (IF-r) and the dicarboxylic acid represented by the general formula (2) with an aromatic phosphite and a pyridine derivative. The reaction is carried out by reacting at 20 to 200° C. for several minutes to several days in the presence of a chemical. In this method, the molecular weight of the polyamide resin represented by the general formula D is limited by the amount of the diamine represented by the general formula II and the dicarboxylic acid represented by the general formula II, and equimolar amounts of these reaction components are used. Then, a high molecular weight polyamide resin represented by the general formula can be produced.

The aromatic substinthium PIi ester used in the present invention includes triphenyl phosphite, diphenyl phosphite,
Phosphite trilyl, phosphite di-tolyl, phosphorous acid trilyl, phosphorous acid di-m-tolyl, phosphorous acid trilyl, phosphorous acid trilyl, phosphorous acid di-p-tolyl, phosphorous acid di-p- Examples include hryl, tri-o-talolophenyl phosphite, di-0-chlorophenyl phosphite, tri-p-chlorophenyl phosphite, and di-p-chlorophenyl phosphite.

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

Typical organic solvents that can be used in this method are:
These are amide solvents such as N-methylpyrrolidone and N,N-dimethylacetamide. In order to obtain a polyamide resin with a high degree of polymerization, non-n 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 it.

Furthermore, in the production of the polyamide resin represented by the general formula (1), the diamine represented by the general formula (1) and the dicarboxylic acid civalide represented by the general formula (IV) are mixed in an organic solvent.
This is carried out by reacting at 20 to 200°C for several minutes to several days. In this method, the molecular weight of the polyamide resin represented by the general formula 1 is limited by the charge (2) of the diamine represented by the general formula (1) and the dicarboxylic acid civalide represented by the general formula IV, and these reaction components are mixed in equimolar amounts. When used for a long time, a high molecular weight polyamide resin represented by the general formula 1 can be produced.

The organic solvent that can be used in this method is N.

Amide solvents such as N-dimethylacetamide and N-methyl-2-pyrrolidone, aromatic solvents such as benzene, anisole, diphenyl ether, nitrobenzene, and benzonitrile, and chloroform, dichloromethane, 1
．． Examples include organic solvents such as halogenated solvents such as 2-dichloroethane and 1.1,2.2-tetrachloroethane.

It is effective to carry out the reaction by allowing an acid acceptor such as pyridine or triethylamine to coexist with such an organic solvent, or by using a two-way system with an alkaline aqueous solution in the case of a solvent that is immiscible with water.

First, when an amide solvent such as N,N-dimethylacetamide or N-methyl-2-pyrrolidone is used, these solvents themselves become acid acceptors and a high polymer polyamide resin can be obtained.

In the polyamide resin represented by the above general formula, n is 1
The reason for limiting n to an integer between 0 and 200 is that if n is smaller than 10, the mechanical properties and heat resistance of the molded product formed into a film etc. will not be sufficient, and if n exceeds 200, it will be difficult to dissolve in paid solvents, etc. This is because the sex becomes worse.

The thus produced polyamide resin represented by the above general formula is composed of the diamine represented by the above general formula (1) used and the dicarboxylic acid represented by the above general formula (2) or the dicarboxylic acid represented by the general formula (2) used. The solubility varies depending on the type of sybaride, but chloroform, tetrachloroethane, N.

It becomes soluble in all or part of solvents such as N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, cresol, chlorobenzene, 0-chlorophenol, and pyridine.

The polyamide resin represented by the general formula 1 has remarkable ffl even when heated to around 400℃! 2 No change observed.

(Example) Hereinafter, the present invention will be roughly described in detail using reference examples and examples.

Reference Example 1 m-Dinitrobenzene eo9 (0,357 mol) and 47 g (0,185 mol) of iodine were dissolved in 25% oleum and gradually heated to 150°C. Stirred at this temperature until no white smoke was generated. After that, the reaction mixture was cooled and poured into ice to obtain crystals of the composition.Pure 3,5-dinitroiodobenzene was obtained by recrystallization from ethanol. Yield: 72.6y (69%) .Melting point: 96°C (Literature value: 99-100°C) Reference Example 2 In 300°C of ethanol, 29.4g (0.1ml) of 3,5-dinitroiodobenzene, 1% stannous chloride
80.5 g (0.8 mol) was dissolved and stirred at 70° C. for 30 minutes under a nitrogen stream. After the reaction, the reaction mixture was poured into ice water and adjusted to pH with 5% aqueous sodium bicarbonate solution.
Adjusted to 7-8. The resulting solution was extracted with ethyl acetate, dried over sodium fA acid, and then the solvent was distilled off under reduced pressure.

The obtained 3,5-diaminoiodobenzene was recrystallized from benzene. Yield 8,16 y (35%).

Melting point 128°C Example 1 Isophthalic acid 0.83 g (5 mmol), 3,5-
Diaminoiodobenzene i, 17 y (5 mmol)
, triphenyl phosphite 3.10 g (10 mmo
1) 2.5 parts of pyridine, 0.50 parts of lithium chloride and 10 parts of N-methyl-2-pyrrolidone were stirred at 100 DEG C. for 3 hours under a nitrogen atmosphere. After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Income FJ 1.82
g (100%). Intrinsic viscosity 0.59 (0 in sulfuric acid)
．． 59/dL of 41, measured at 30°C).

Table 1 shows the 10% weight loss temperature determined by thermogravimetry, the glass transition temperature at 415°C by thermomechanical measurement, and the solubility of the produced polymer at 278°C.

Example 2 Terephthalic acid 0.83 g (5m+++ol), 3.5
-Diaminoiodobenzene 1.179 (5 mmol)
, triphenyl phosphite 3.10 g (10 mmol
), pyridine 2.5-1 lithium chloride 0.50, and N-methyl-2-pyrrolidone 10- were stirred at 100° C. for 3 hours in a nitrogen atmosphere F. After the reaction, the polymerization solution was poured into methanol to obtain a polymer. Collection 5i 1
．． 82.

(ioo%). Intrinsic viscosity 0.73 (Ili!! 0.73 in acid)
5. /dl, measured at 30°C).

The 10% weight loss temperature determined by thermogravimetry, the glass transition temperature determined by thermomechanical measurement at 435°C, and the solubility of the produced polymer at 318°C are shown in Table 1.

Example 3 2.6-naphthalene dicarboxylic acid LO8g (5mlIl
ol), 3,5-diaminoiodobenzene 1,17.

(5 mmol), triVxylsulfite 3.10 g
(40 miol), pyridine 2.5-1 lithium chloride 0.50 p and N-methyl-2-pyrrolidone 10-
, under a nitrogen atmosphere. The mixture was stirred at 100°C for 3 hours. After the reaction, the polymerization solution was poured into methanol to obtain a polymer.
Yield fl 2.07, (400%). Intrinsic viscosity i, i
+ (concentration of 0.59/dL in sulfuric acid, measured at 30°C)
.

Table 1 shows the solubility of the polymer produced at 445° C. with a 10% overlapping reduction in humidity by heat measurement.

Example 4 1.17 g of 3.5-diaminoiodobenzene (5 m...0
1) was dissolved in 10 strips of N,N-dimethylacetamide and completely frozen on a dry ice-acetone bath. 1.029 (5 mmo) of isophthalic acid chloride was added to the generated solid.
1) was added, and the mixture was stirred at 0°C under a nitrogen atmosphere for 3 hours.

After the reaction, the polymerization solution was poured into water to obtain a polymer. yield
1.829 (100%).

Intrinsic viscosity 0.43 (concentration of 0.59/dL in tiii1 acid, measured at 30°C).

10% weight loss temperature by thermogravimetry. 414℃ Glass transition temperature according to thermomechanical 1Q11 standard method. The solubility of the polymer produced at 278°C is shown in Table 1.

Example 5 3.5-diaminoiodobenzene 1.17, (5
m+1101) was dissolved in 10 ml of N21N-dimethylacetamide and completely frozen on a dry ice-7 setone bath. 1.0% of terephthalic acid chloride was added to the generated solid.
2 g (5 mmol) was dried and stirred under a nitrogen atmosphere for 3 hours. After the reaction, the polymerization solution was poured into methanol to cover 1 tsubo of polymer. 18. m 1.82 g
(100%). Intrinsic viscosity 0.75 (0.5 in sulfuric acid
9/dl- measured at 30°C).

10% weight loss (temperature, 417°C) by thermogravimetry
Table 1 shows the glass transition temperature of 318° C. and the solubility of the produced polymer as determined by thermomechanical cell measurement.

Example 6 3.5-Diaminoiodobenzene 1. +79 (5 mmo
f> was dissolved in 10 ml of N,N-dimethylacetamide and completely frozen on a dry ice-acetone bath. 2.6-naphthalene dicarpho>acid'y in the generated solid
Add 1.27 g (5 mmol) of O'C
1. The mixture was stirred for 3 hours under a nitrogen atmosphere. After the reaction l; i5, the polymerization solution was poured into water and the polymer was (q. Yield ψ2,03
.

(98%). Intrinsic viscosity 0.47 (0.59/in sulfuric acid)
dL concentration, measured at 30°C>.

Thermogravimetric 11111 10% weight loss temperature by standard method, 44
The solubility of the polymer produced at 4°C is shown in Table 1.

Table 1 NMP: N-methyl-2-pyrrolidone DMAc: N,N-dimethylacetamide DMF:
N,N-dimethylformamide DMSO dimethyl sulfoxide (Effects of the Invention) The present invention provides a polyamide resin represented by the general formula (1) and an advantageous method for producing the polyamide resin. The polyamide resin of the present invention is different from the conventional aromatic polyamide resin.
Engineering plastics that are insoluble in organic solvents and thermally infusible, leaving problems with moldability, are soluble in various organic solvents and can be solution molded, as well as heat moldable. It has high industrial value.

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is one or more divalent aromatic groups, Ar
is a 1-iodo-3,5-phenylene group when there is one type of Ar, and a 1-iodo-3,5-phenylene group when there are two or more types of Ar, and a divalent group as the other type. (n is an integer of 10 to 200) A polyamide resin represented by: 2. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is one or more divalent aromatic groups, Ar
is a 1-iodo-3,5-phenylene group when there is one type of Ar, and a 1-iodo-3,5-phenylene group when there are two or more types of Ar, and a divalent group as the other type. is an aromatic group, and n is an integer of 10 to 200. Iodine-3,5
- phenylene group, if there are two or more types of Ar, one type of diamine is a 1-iodo-3,5-phenylene group, and the other type is a divalent aromatic group) or two or more types, and one or more dicarboxylic acids represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R represents a divalent aromatic group) A method for producing a polyamide resin, which comprises reacting in an organic solvent in the presence of a phosphite and a pyridine derivative.