JP2000026595A - Azo group-containing polyamide and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an azo group-containing polyamide having >=500 number- average molecular weight and containing a polyamide synthesized from various kinds of monomers as a constituent component and to provide a method for producing the azo group-containing polyamide. SOLUTION: This azo group-containing polyamide is produced by carrying out a polycondensation reaction of a polyamide having at least one amino group and 500-40,000 number-average molecular weight with an azo group- containing dicarboxylic acid halide represented by the formula [X denotes a halogen atom; R1 and R2 denote each hydrogen atom, a 1-6C alkyl group or nitrile group; (a) denotes 0 or an integer of 1-6] in the presence or absence of water and/or an alcohol in one or more kinds of solvents selected from a phenolic solvent and a halogenated inorganic substance-containing amide-based solvent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an azo group-containing polyamide having radical polymerization activity and a method for producing the same.
More specifically, the present invention relates to an azo group-containing polyamide having a polyamide unit having practical properties as a constituent unit and a production method thereof by a solution polycondensation reaction.

[0002]

2. Description of the Related Art An azo group-containing polyamide is known as a radical polymerization initiator or a kind of a collapsible polymer when producing a copolymer of a vinyl polymer and a polyamide.
Regarding the azo group-containing polyamide and its production method, see JP-A-49-17895, J. Polym. Sci. Polym Chem.
Ed, Vol.22, 1611 (1984) and Collection of Polymers, Vol.33, 131
(1976), Osaka Industrial Research Institute Report, 84th (1989), etc.

For example, Japanese Patent Application Laid-Open No. 49-17895 discloses a general formula (1)

Embedded image (Wherein X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom,
It represents an alkyl group or a nitrile group having 1 to 6 carbon atoms, and a represents 0 or an integer of 1 to 6. A) an aliphatic, alicyclic or aromatic diamine having 1 to 10 carbon atoms in the presence or absence of an azo group-containing dicarboxylic acid halide and an aliphatic, alicyclic or aromatic dicarboxylic acid halide represented by (Hereinafter referred to as "diamine monomer") and an azo group-containing polyamide to be polycondensed and a method for producing the same.

[0004]

The azo group-containing polyamide of the prior art is obtained by polycondensation of an azo group-containing dicarboxylic acid halide and a diamine monomer.
Polyamide consisting of repeating units of azo group and amide group.It contains many azo groups in its molecular chain, so it is easy to decompose, has low mechanical properties, and has low value as a practical polymer material. Met. Further, when polycondensation of an azo group-containing dicarboxylic acid halide and a diamine monomer in the presence of a dicarboxylic acid halide, a polyamide having a number average molecular weight of about several thousands between azo groups and having practical properties may be generated. . However, since the number average molecular weight of the produced polyamide has a distribution and a large number of structures having only one amide bond between azo groups, the practical properties are not so large as compared with those described above and the practical properties are not improved. In addition, there is a problem that a polyamide not containing an azo group, such as a reaction product of a dicarboxylic acid halide and a diamine monomer, is easily produced as a reaction product, and the yield of the azo group-containing polyamide is reduced.

Further, the polyamide unit of the conventional method is a polyamide obtained from a limited monomer such as a compound having an acid halide group (acid halogen group) and a diamine monomer, and the molecular structure of the obtained polyamide is limited. For example, an azo group-containing polyamide having a structural unit of a polyamide synthesized from aminocarboxylic acid or lacram could not be produced.

It is described that an interfacial polycondensation method and a solution polycondensation method can be applied to the production method. However, the method specifically disclosed is an interfacial polycondensation method which is considered to be difficult to apply to industrialization, and a solution polycondensation method which is easy to apply to industrialization and control of reaction conditions is a specific example. No technical description is given. This may be related to the fact that no suitable solvent has been found for this polycondensation reaction.

An object of the present invention is to provide an azo group-containing polyamide having a number average molecular weight of 500 or more and comprising a polyamide synthesized from various monomers as a component, and a method for producing the same by a solution polycondensation method.

[0008]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the presence of a polyamide having a number average molecular weight of 500 or more between azo groups makes it possible to exhibit properties as a polyamide, and that at least one amino acid is used. Solvents having a group and capable of solution polycondensation of a polyamide having a number average molecular weight of 500 or more and an azo group-containing dicarboxylic acid halide have been found and have reached the present invention.

That is, the first invention of the present invention has at least one amino group and has a number average molecular weight of 500
Up to 40,000 units composed of polyamide, and a compound represented by the general formula (1):

Embedded image (Wherein X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom,
It represents an alkyl group or a nitrile group having 1 to 6 carbon atoms, and a represents 0 or an integer of 1 to 6. And azo group-containing dicarboxylic acid halide represented by the formula (1).

The second invention of the present invention has at least one amino group and a number average molecular weight of 500 to 40,0.
00 and a general formula (1)

Embedded image (Wherein X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom,
It represents an alkyl group or a nitrile group having 1 to 6 carbon atoms, and a represents 0 or an integer of 1 to 6. With the azo group-containing dicarboxylic acid halide represented by the formula (1), in the presence or absence of water and / or alcohol, and at least one solvent selected from phenol solvents and amide solvents containing halogenated inorganic substances. This is a method for producing an azo group-containing polyamide in which a polycondensation reaction is carried out in a polyamide.

A phenolic solvent which is inactive or very low in reactivity with an acid halogen group or an amino group, and simultaneously dissolves an azo group-containing dicarboxylic acid halide and a polyamide having a number average molecular weight of 500 to 40,000 has been found. This is one of the features of the present invention. The discovery of this solvent has made it possible to provide the azo group-containing polyamide of the present invention. Another feature of the present invention is that an azo group-containing polyamide containing a polyamide synthesized from aminocarboxylic acid or lacram as a constituent component is obtained.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
In the present invention, a polyamide having at least one amino group and having a number average molecular weight of 500 to 40,000 (hereinafter, this polyamide is referred to as “raw material polyamide”) is obtained by diamine and dicarboxylic acid. Or a repeating unit composed of an ω-aminocarboxylic acid or a lactam ring-opened repeating unit.

As the diamine used, there are usually diamines having 2 to 24 carbon atoms, and specifically, ethylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, heptamethylene diamine, octa diamine. Methylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, hexadecamethylene diamine, octadecamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4 Aliphatic diamines such as 4-trimethylhexamethylenediamine, alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine, bis- (4,4'-aminocyclohexyl) methane, and xylylene And aromatic diamines such as diamine.

The dicarboxylic acid is usually a compound having 2 to 2 carbon atoms.
There are 24 dicarboxylic acids, specifically, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandionic acid, dodecandionic acid, tridecadionic acid, tetradecadione Acid, hexadecadionic acid, hexadecenedionic acid, octadecadionic acid, octadecenedonic acid, eicosandioic acid, eicosenedioic acid, eicosadienedioic acid, docosandioic acid, 2,2,4-trimethyladipate, etc. And aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and xylylenedicarboxylic acid.

Specific examples of the ω-aminocarboxylic acid include:
5-aminovaleric acid, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and the like. Can,
Specific examples of the lactam include the lactams of these aminocarboxylic acids, that is, pyrrolidone, methylpyrrolidone, caprolactam, enantholactam, undecanelactam, dodecalactam and the like.
These units derived from a diamine and a dicarboxylic acid, ω-aminocarboxylic acid and lactam may be used alone or in combination of two or more.
When the polyamide unit is derived from a copolymer, its structure may be any of a random copolymer, a block copolymer and an alternating copolymer.

The raw material polyamide is selected from the above diamines and dicarboxylic acids, ω-aminocarboxylic acids and lactams, and is produced by a known polyamide synthesis method such as melt polymerization, solution polymerization, solid phase polymerization, and interfacial polymerization. Is done.
For example, equal amounts of diamine and dicarboxylic acid, or ω
It is produced by a method in which an aminocarboxylic acid is subjected to polycondensation by heating with a small amount of water, if necessary, or a method in which a lactam is heated with a small amount of water to carry out ring-opening polymerization.

From the viewpoint of reactivity with the azo group-containing dicarboxylic acid halide, the raw material polyamide preferably has one or two amino groups at the molecular terminal. The number average molecular weight of the raw material polyamide is 500 to 40,000, preferably 1,000 to 30,000, and more preferably 6,000 to 25,000. Number average molecular weight is 4
If it is larger than 000, the reactivity with the azo group-containing dicarboxylic acid halide is lowered, and the solution viscosity at the time of the reaction is increased, and it is difficult to make the reaction uniform, which is not preferable. On the other hand, if it is smaller than 500, the reduction in practical properties becomes large.

When it is necessary to adjust the number of amino groups and the number average molecular weight of the raw material polyamide, it becomes possible by adding a monoamine or a diamine when synthesizing the raw material polyamide. Examples of monoamines that can be added include linear and branched aliphatic monoamines having 1 to 18 carbon atoms such as laurylamine and stearylamine, aromatic monoamines such as benzylamine and β-phenylethylamine, and alicyclic monoamines such as cyclohexylamine. There is. As the diamine, the above-mentioned aliphatic diamine, alicyclic diamine,
And aromatic diamines. The addition amount of these monoamines and diamines is appropriately determined depending on the desired number average molecular weight.

The general formula (1) of the present invention

Embedded image (Wherein X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom,
It represents an alkyl group or a nitrile group having 1 to 6 carbon atoms, and a represents 0 or an integer of 1 to 6. The azo group-containing dicarboxylic acid halide represented by) is a chlorine compound selected from azo group-containing dicarboxylic acid and phosgene, thionyl chloride, phosphorus trioxide, phosphorus pentoxide, or bromine corresponding to these chlorine compounds. It is synthesized by a reaction with an iodine compound or an iodine compound. Note that R ₁ and R ₂ in the general formula (1) represent a hydrogen atom or a carbon atom having 1 carbon atom such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.
To 6 linear or branched alkyl groups or nitrile groups.

Specific examples of the azo group-containing dicarboxylic acid used in the synthesis of the azo group-containing dicarboxylic acid halide include 4,4′-azobis-cyanovaleric acid and 6,6 ′
-Azobis-6-cyanoheptanoic acid, 2,2'-azobis-2-methylpropionic acid, 5,5'-azobis-5
-Methylcaproic acid, 7,7'-azobiscaprylic acid,
4,4'-azobis-4-methylcaproic acid, 4,4'-
Azobis-4-propylheptanoic acid, 3,3'-azobispropionic acid and the like can be mentioned.

The azo group-containing polyamide of the present invention is produced by a condensation reaction between a raw material polyamide and an azo group-containing dicarboxylic acid halide. As a method for producing the azo group-containing polyamide with high productivity, a solution polycondensation method is a preferable method in consideration of the thermal stability of the azo group, the reactivity of the raw material polyamide, and the like. The solvent used in the reaction of the present invention has conditions such as simultaneous dissolution of the raw material polyamide and the azo group-containing dicarboxylic acid halide, and inactivity with the acid halogen group and the amino group of the polyamide. Conventionally, since a solvent having such a condition was not known, as a result of various investigations, a phenol-based solvent and a mixed solvent thereof and a hydrocarbon-based solvent, and a halogen-containing inorganic material containing a amide-based solvent mixed with a halogenated inorganic material Amide solvents and the like were found. Specific examples of the phenolic solvent include phenol, o-cresol, m-cresol and the like, and specific examples of the hydrocarbon-based solvent include aliphatic solvents such as pentane, hexane, heptane, octane, nonane, decane and dodecane. Examples thereof include hydrocarbons and aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene. When a phenol solvent and a hydrocarbon solvent are used as a mixture, the mixing ratio is 5 to 50 parts by weight of the hydrocarbon solvent with respect to 100 parts by weight of the phenol solvent. Specific examples of the halogenated inorganic substance include lithium chloride, calcium chloride, lithium bromide, calcium bromide, and the like. Specific examples of the amide-based solvent include N-methyl-2-pyrrolidone,
N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone and the like can be mentioned. The mixing ratio of the amide solvent and the halogenated inorganic substance is 5 to 20 parts by weight of the halogenated inorganic substance with respect to 100 parts by weight of the amide solvent.

The azo group-containing polyamide of the present invention is prepared by mixing the amino group of the raw material polyamide with the acid halide group of the azo group-containing dicarboxylic acid halide represented by the general formula (1) in a molar equivalent ratio of 1: 0.5 to 1: 1. The mixture is charged in the solvent at a ratio of 10 to 10, preferably 1 to 0.7 to 1 to 8, and 60
It is synthesized by reacting at a temperature of not more than 0 ° C, preferably 0 to 50 ° C for 0.1 hour or more.

When the compounding ratio of the acid halogen group is less than 0.5 molar equivalent or more than 10 molar equivalents with respect to 1 molar equivalent of the amino group, the reaction ratio is out of the range of the suitable reaction ratio. It is not preferable because the amount of the azo group-containing polyamide to be formed becomes small. Reaction temperature is 60 ° C
If it is higher, the azo group is easily decomposed, and it is difficult to obtain the target azo group-containing polyamide. On the other hand, when the reaction temperature is lower than 0 ° C., the reaction between the amino group and the acid halide group becomes slow, and the time until the completion of the reaction becomes extremely long, which is not preferable.

When the reaction is carried out in a state where the molar equivalent of the acid halide group of the azo group-containing dicarboxylic acid halide is larger than the molar equivalent of the amino group of the polyamide, unreacted acid halide groups remain in the reaction system. If unreacted acid halogen groups remain in the reaction system, various side reactions are likely to occur,
Not preferred. Therefore, water and / or alcohol are added for the purpose of eliminating the reactivity of the remaining acid halide groups. The amount of the water or alcohol to be added is at least a molar equivalent of the remaining acid-halogen group, and preferably at least 1.5 times the molar equivalent of the remaining acid-halogen group. Water or alcohol may be added before, during or after the reaction of the polyamide with the azo group-containing dicarboxylic acid halide.

The alcohol to be added is an alcohol having 1 to 24 carbon atoms, and specific examples include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, octyl alcohol, stearyl alcohol, cyclohexanol, benzyl alcohol, and furfuryl alcohol. Is mentioned.

In the present invention, a tertiary amine such as triethylamine, pyridine, quinoline and isoquinoline can be added as a catalyst to promote the reaction between the starting polyamide and the azo group-containing dicarboxylic acid halide.

When the reaction solution of the azo group-containing polyamide obtained by the solution polycondensation method of the present invention is used as an initiator for a vinyl monomer, it can be used as it is. When the azo group-containing polyamide is obtained as a single substance, the synthesized azo group-containing polyamide is precipitated by pouring the reaction solution into a large amount of a poor solvent, or conversely, adding a poor solvent to the reaction solution. After separating, it can be obtained by drying.

The azo group-containing polyamide obtained in the present invention can be used as a polymerization initiator for vinyl monomers such as methyl methacrylate, ethyl methacrylate, methacrylic acid, styrene, vinyl acetate, butadiene and isoprene. Further, a film can be produced from an azo group-containing polyamide solution by a casting method or the like.

[0029]

The present invention will be described in more detail with reference to the following examples. In addition, the characteristic evaluation described in the Example was performed by the following method.

1) Measurement of Solution Viscosity of Polyamide A solution viscosity of ηsp / c (unit: ml) was measured at 25 ° C. using a Ubbelohde viscometer at a concentration of 0.5 g / 100 ml using m-cresol as a solvent. / G). ηsp / c = {(t−t ₀ ) / t ₀ } / c where, t: outflow time of solution (second), t ₀ : outflow time of solvent only (second), c: solution concentration (g / ml) )

2) Measurement of amino group concentration Phenol / methanol (4/1; volume ratio) mixed solvent 4
After dissolving the sample in 0 ml and adding a few drops of thymol blue as an indicator, it was titrated with 1 / 20N hydrochloric acid at room temperature. The amino group concentration [NH ₂ ] (unit: mol / g) was calculated by the following equation. [NH ₂ ] = (L ₁ −L ₂ ) × f × 10 ⁻⁴ / (2 × S) where L ₁ ; titration of sample solution (ml), L ₂ ; titration of solvent alone (ml) , F: Factor of 1 / 20N hydrochloric acid, S: Sample amount (g)

3) Number average molecular weight of polyamide (hereinafter referred to as
Indicated by “Mn”. ) Mn (unit; g / mol) was measured by the method of 2) above.
Amino group concentration [NH _TwoIs calculated from the following equation.
Was. Mn = 1 / [NH_Two]

4) ¹ H-NMR Measurement of Azo Group-Containing Polyamide and Polyamide-Vinyl Polymer Copolymer Using JEOL EX-270 manufactured by JEOL Ltd., measurement was carried out using bisulfuric acid as a solvent. Measurement frequency: 300 MHz, measurement temperature: room temperature, sample concentration: 5% by weight, standard substance: trimethylsilane

5) Measurement of ¹ H-NMR of azo group-containing dicarboxylic acid halide The measurement was carried out using JEOL EX-270 manufactured by JEOL Ltd. with heavy chloroform as a solvent. Measurement frequency: 300 MHz, measurement temperature: room temperature, sample concentration: 5% by weight, standard substance: trimethylsilane

6) UV measurement of azo group-containing polyamide Otsuka Electronics Co., Ltd. instantaneous multi-photometry system MCPD-1
000 using hexafluoroisopropanol (H
FIP) as a solvent. The sample concentration is 0.05 mol / l.

Synthesis Example 1: Synthesis of polyamide (PA-1) having one amino group at the molecular terminal 11.3 parts by weight of ε-caprolactam, 0.5 part by weight of water and 0.6 part by weight of stearylamine were placed in an autoclave. After charging and replacing with nitrogen,
Polymerization was performed at 250 ° C. and a pressure of 5 atm for 5 hours. After the pressure was reduced to atmospheric pressure while maintaining the temperature, polymerization was further performed for 4 hours under a nitrogen stream. After that, take out the polymer, pulverize, Soxhlet extracted with methanol, and then dried,
A polyamide (hereinafter, referred to as “PA-1”) was obtained. P
The solution viscosity of A-1 was 0.26, and the number average molecular weight Mn calculated from the amino group concentration was 4,900.

Synthesis Example 2: Synthesis of Polyamide (PA-2) Having One Amino Group at the Molecular Terminus Equimolar Salt 1 of Adipic Acid and Hexamethylenediamine
5.0 parts by weight and 0.38 parts by weight of stearylamine were charged into an autoclave, replaced with nitrogen, and then cooled to 230 ° C. and a pressure of 15%.
Polymerization was performed at atmospheric pressure for 4 hours. After the temperature was raised to 260 ° C., the pressure was reduced to atmospheric pressure while maintaining the temperature, and then polymerization was carried out for 4 hours under a nitrogen stream. Thereafter, the polymer was taken out, pulverized, subjected to Soxhlet extraction with methanol, dried, and then polyamide (hereinafter referred to as “PA-2”).
I got The solution viscosity of PA-2 was 0.93, and the number average molecular weight Mn calculated from the amino group concentration was 11,000.

Synthesis Example 3: Synthesis of polyamide (PA-3) having one amino group at the molecular terminal 13 parts by weight of ε-caprolactam, 2.2 parts by weight of equimolar salt of terephthalic acid and hexamethylenediamine, and stearyl An autoclave was charged with 0.3 part by weight of an amine, and after purging with nitrogen, polymerization was performed at 240 ° C. and a pressure of 2 atm for 4 hours.
After the temperature was raised to 250 ° C., the pressure was reduced to atmospheric pressure while maintaining the temperature, and then polymerization was carried out for 4 hours under a nitrogen stream. Thereafter, the polymer was taken out, pulverized, subjected to Soxhlet extraction with methanol, dried, and treated with nylon 6/6.
T (hereinafter referred to as “PA-3”) was obtained. The solution viscosity of PA-3 was 0.89, and the number average molecular weight Mn calculated from the amino group concentration was 10,000.

Synthesis Example 4 Synthesis of Polyamide (PA-4) Having Two Amino Groups at the Molecular Terminal 12.8 parts by weight of ε-caprolactam, 2.1 parts by weight of equimolar salt of terephthalic acid and hexamethylenediamine And 0.15 parts by weight of hexamethylenediamine were charged into an autoclave, and after purging with nitrogen, polymerization was carried out at 240 ° C. and a pressure of 2 atm for 4 hours. After the temperature was raised to 250 ° C., the pressure was reduced to atmospheric pressure while maintaining the temperature, and then polymerization was carried out for 4 hours under a nitrogen stream. After that, take out the polymer, pulverize, Soxhlet extracted with methanol, and then dried,
Nylon 6 / 6T (hereinafter referred to as "PA-4") was obtained. The solution viscosity of PA-4 was 0.83, and the number average molecular weight Mn calculated from the amino group concentration was 9,400.

Example 1 1,2-dimethyl-containing 10% by weight of lithium chloride dissolved
2-imidazolidinone (DMI) 500 parts by weight, PA
-1 and 5 parts by weight of triethylamine and 1.5 parts by weight of
Dissolved at 60 ° C. While cooling with ice, 4,4′-azobis-cyanovaleric acid dichloride (ACPC) 0.16
5 parts by weight of tetrahydrofuran (THF) having 2 parts by weight dissolved therein were added dropwise. After the dropwise addition, the mixture was reacted while stirring at 20 ° C. for 1 hour. The reaction solution was poured into a large amount of methanol to precipitate a reaction product, which was separated by filtration and dried under reduced pressure. The solution viscosity of the obtained reaction product was 0.51. From the UV spectrum measurement of the reaction product, absorption based on an azo group was observed at around 350 nm, and from the ¹ H-NMR measurement, 0.9 to ¹ .
A signal based on nylon 6 was observed at around 5 ppm, 2.22 ppm, and 3.07 ppm, indicating that this reaction product was an azo group-containing polyamide. 2.5 parts by weight of the azo group-containing polyamide was mixed with a phenol-methanol mixed solvent (phenol: methanol = 4: 1, volume ratio) 2
The solution was dissolved in 00 parts by weight at room temperature, and 10 parts by weight of methyl methacrylate was added to the solution. Then, under a nitrogen atmosphere, 60
The polymerization was carried out at 24 ° C. for 24 hours under stirring. Thereafter, the reaction solution was poured into methanol to precipitate a polymer, which was filtered and dried under reduced pressure. By ¹ H-NMR measurement, a signal of nylon 6 and a signal of poly (methyl methacrylate) were observed, and the obtained polymer was a copolymer of polyamide and poly (methyl methacrylate). From this, it was confirmed that the obtained azo group-containing polyamide had a polyamide structure of nylon 6 and also had a function as a polymerization initiator of methyl methacrylate.

Example 2 8 parts by weight of PA-2 and 1.5 parts by weight of triethylamine were dissolved in 200 parts by weight of a mixed solvent consisting of 25 parts by weight of methanol and 75 parts by weight of phenol. While cooling on ice
15 parts by weight of tetrahydrofuran (THF) in which 0.61 parts by weight of 4,4'-azobis-cyanovaleric acid dichloride (ACPC) was dissolved were added dropwise. After dropping, 20 ° C
While stirring for 2 hours. The reaction solution was poured into a large amount of methanol to precipitate a reaction product, which was separated by filtration and dried under reduced pressure. The solution viscosity of the obtained reaction product was 0.9.
It was 4. No amino group was measured by titration. The azo group was determined to be ¹ H-
From NMR measurement, a signal based on nylon 66 was observed, and this reaction product was found to be an azo group-containing polyamide. Methyl methacrylate was polymerized in the same manner as in Example 1 except for using 3 parts by weight of the azo group-containing polyamide to obtain a polymer. By ¹ H-NMR measurement, a signal of nylon 66 and a signal of poly (methyl methacrylate) were observed in this polymer, and it was a copolymer of polyamide and poly (methyl methacrylate). This indicates that the obtained azo group-containing polyamide is nylon 6
It was confirmed that the resin had a polyamide structure of No. 6 and had a function as a polymerization initiator of methyl methacrylate.

Example 3 10 parts by weight of PA-3 and 4,4'-azobis-cyanonova
Use 0.86 parts by weight of rellianic acid dichloride (ACPC)
Azo group-containing polymer
Mido was obtained. The solution viscosity of the obtained reaction product was 0.91.
Was. No amino group was measured by titration. reaction
From the UV spectrum measurement of the product, ¹H-NMR measurement
From the measurement, a signal based on nylon 6 / 6T was observed.
The reaction product was found to be an azo group-containing polyamide.
Was. After using 2.5 parts by weight of the azo group-containing polyamide,
Outside, methyl methacrylate was superposed in the same manner as in Example 1.
Then, a polymer was obtained. This polymer is¹H-NMR measurement
The signal of nylon 6 / 6T and poly (meth
(Methyl acrylate) signal was observed.
It is found to be a copolymer with poly (methyl methacrylate).
won. From this, the obtained azo group-containing polyamide was
Has a polyamide structure of nylon 6 / 6T, and
It has a function as a polymerization initiator for methyl methacrylate.
Was confirmed.

Example 4 The procedure was carried out except that 10 parts by weight of PA-4 and 0.31 part by weight of 4,4'-azobis-cyanovaleric acid dichloride (ACPC) were used, and 25 parts by weight of benzene was used instead of methanol. In the same manner as in Example 2, an azo group-containing polyamide was obtained. The solution viscosity of the obtained azo group-containing polyamide was 1.92. No amino group was measured by titration. An azo group was observed from the UV spectrum measurement of the reaction product, and a signal based on nylon 6 / 6T was observed from the ¹ H-NMR measurement, indicating that this reaction product was an azo group-containing polyamide. This azo group-containing polyamide 2.5
Methyl methacrylate was polymerized in the same manner as in Example 1 except for using parts by weight to obtain a polymer. This polymer is
^{By 1} H-NMR measurement, a signal of nylon 6 / 6T and a signal of poly (methyl methacrylate) were observed,
It was found to be a copolymer of polyamide and poly (methyl methacrylate). From this, it was confirmed that the obtained azo group-containing polyamide had a polyamide structure of nylon 6 / 6T and had a function as a polymerization initiator of methyl methacrylate.

[0044]

The azo group-containing polyamide of the present invention comprises:
Polyamide having at least one amino group and having a number average molecular weight of 500 to 40,000 and a general formula (1)

Embedded image (Wherein X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom,
It represents an alkyl group or a nitrile group having 1 to 6 carbon atoms, and a represents 0 or an integer of 1 to 6. The azo group-containing dicarboxylic acid halide represented by the formula (1) is subjected to a solution polycondensation reaction in one or more solvents selected from phenol solvents and halogenated inorganic substance-containing amide solvents.

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Claims (5)

[Claims] (1) having at least one amino group, and
A unit comprising a polyamide having a number average molecular weight of 500 to 40,000 and a general formula (1) (Wherein X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom,
It represents an alkyl group or a nitrile group having 1 to 6 carbon atoms, and a represents 0 or an integer of 1 to 6. Azo group-containing polyamide characterized by comprising, as a component, a unit comprising an azo group-containing dicarboxylic acid halide represented by the formula (1). (2) having at least one amino group, and
A polyamide having a number average molecular weight of 500 to 40,000 and a general formula (1) (Wherein X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom,
It represents an alkyl group or a nitrile group having 1 to 6 carbon atoms, and a represents 0 or an integer of 1 to 6. With the azo group-containing dicarboxylic acid halide represented by the above) in the presence or absence of water and / or alcohol in one or more solvents selected from phenol solvents and amide solvents containing halogenated inorganic substances. The method for producing an azo group-containing polyamide according to claim 1, wherein a polycondensation reaction is performed. 3. The method according to claim 1, wherein the amino group of the polyamide and the acid halide group of the azo group-containing dicarboxylic acid halide are in a molar equivalent ratio of 1 to 1.
The method for producing an azo group-containing polyamide according to claim 1 or 2, wherein the reaction is performed at a ratio of 0.5 to 1:10. 4. The method according to claim 1, wherein the phenolic solvent comprises at least one solvent selected from the group consisting of phenol, cresol and a mixture thereof with a hydrocarbon solvent.
4. The method for producing an azo group-containing polyamide according to any one of the above items 3. 5. An N-methylpyrrolidone in which an amide-based solvent containing a halogenated inorganic substance dissolves a halogenated inorganic substance, N, N
4. It comprises one or more kinds of solvents selected from -dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone. For producing azo group-containing polyamides.