JP2000191772A - Block copolymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a thermally stable block copolymer composed of a polyamide unit and a vinyl polymer unit, with controlled polyamide production and the number-average molecular weight of the polyamide unit by making up from a specific polyamide and a vinyl polymer. SOLUTION: This copolymer is obtained by making up from (A) a polyamide derived from (i) an azo group-contg. polyamide of formula I (R1 and R2 are each H, a 1-6C alkyl or nitrile; (a) is 0 or 1-6; PA1 and PA2 are each a polyamide unit comprising a polyamide afforded from ω-aminocarboxylic acid and/or lactam) and/or (ii) another azo group-contg. polyamide of formula II (R3 and R4 are each H, a 1-6C alkyl or nitrile; (b) is 0 or 1-6; PA3 is a polyamide unit comprising a polyamide afforded from ω-aminocarboxylic acid and/or lactam; R5 is a 1-24C hydrocarbon) and (B) a vinyl polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a block copolymer and a method for producing the same. More specifically, the present invention relates to a block copolymer comprising a polyamide unit and a vinyl polymer unit obtained by polymerizing a vinyl monomer using an azo group-containing polyamide having a polyamide block at a molecular terminal as a polymerization initiator.

[0002]

2. Description of the Related Art At present, various types of plastics are provided on the market, and are used for applications taking advantage of their characteristics. In recent years, with diversification of required characteristics, a polymer material having new characteristics has been demanded. As one of them, a polymer material having both characteristics of an engineering plastic and a general-purpose polymer, such as a block copolymer having characteristics of a polyamide which is a representative of an engineering plastic and a vinyl polymer which is a representative of a general-purpose polymer. There is a request.

Conventionally, with respect to a method for producing a copolymer of a polyamide and a vinyl polymer, a method using an azo group-containing polyamide as a polymerization initiator for a vinyl monomer is disclosed in J. Polym. Sci. Polym Chem Ed, Vol. 22,1611 (198
4), Journal of Polymers, Vol. 33, 131 (1976), Osaka Municipal Industrial Research Institute Report, 84th (1989), etc.

[0004] J. Polym. Sci. Polym Chem Ed, Vol. 22, 1
611 (1984) includes a compound represented by the general formula (3) described in JP-A-49-17895.

Embedded image (Wherein X represents a halogen atom, R ₆ and R ₇ represent a hydrogen atom,
C represents an alkyl group or a nitrile group having 1 to 6 carbon atoms, and c represents 0 or an integer of 1 to 6; ) Is reacted with a diamine such as hexamethylene diamine by a general formula (4)

Embedded image (Wherein X represents a halogen atom, and R ₈ represents a divalent aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms) in the presence or absence of a dicarboxylic acid halide represented by the formula: ,
Nylon 66- obtained by polymerizing a styrene monomer using an azo group-containing polyamide obtained by the reaction as a polymerization initiator.
Polystyrene copolymers and nylon 610-polystyrene copolymers have been reported.

[0005]

The azo group-containing polyamide as a polymerization initiator used in the production of a copolymer comprising a polyamide and a vinyl polymer by the above-mentioned method is mainly described in JP-A-49-17895. A compound obtained by a method, for example, reacting an azo group-containing dicarboxylic acid halide with a diamine in the presence or absence of a dicarboxylic acid halide. When the dicarboxylic acid halide is not present, the azo group-containing polyamide is obtained by a condensation reaction between the azo group-containing dicarboxylic acid halide and a diamine, and the polyamide having a structure containing an azo group and a structure containing an amide group as a repeating unit. It is. Since it contains many azo groups in the molecular chain, it is an effective compound as a radical polymerization initiator. However, when all the azo groups are decomposed, the polyamide structure disappears, so that it is not possible to obtain a copolymer composed of a polyamide unit and a vinyl polymer unit. When the azo group partially remains, the resulting polyamide has an azo group in a molecular chain, and thus becomes thermally unstable.

In the case of the reaction in the presence of a dicarboxylic acid halide, at least three kinds of reactions, namely, a reaction of an azo group-containing dicarboxylic acid halide with a diamine,
The reaction between the dicarboxylic acid halide and the diamine and the reaction between the polyamide obtained from the dicarboxylic acid halide and the diamine and the azo group-containing dicarboxylic acid halide occur simultaneously. Among these reactions, an azo group-containing polyamide which is a polymerization initiator effective for synthesizing a block copolymer of a polyamide and a vinyl polymer is a polyamide obtained from a dicarboxylic acid halide and a diamine, and an azo group-containing dicarboxylic acid halogen. Formed by reaction with However, since this reaction occurs concurrently with other reactions, it is difficult to control the production amount of the azo group-containing polyamide and the number average molecular weight of the polyamide unit. In addition, this reaction cannot provide an azo group-containing polyamide containing a polyamide derived from ω-aminocarboxylic acid and / or lactam as a constituent unit, which is useful for a material for melt extrusion such as a film material.

An object of the present invention is to provide a block copolymer comprising a polyamide containing a polyamide obtained from ω-aminocarboxylic acid and / or lactam and a vinyl polymer, and a method for producing the same.

[0008]

Means for Solving the Problems As a result of studying the above problems, the present inventors have found that a compound obtained from ω-aminocarboxylic acid and / or lactam is contained at both terminals or one terminal of a compound containing a specific azo group. The present inventors have found that a desired block copolymer can be obtained by polymerizing a vinyl monomer using an azo group-containing polyamide to which a polyamide is bonded as a polymerization initiator, and have reached the present invention.

That is, the first invention of the present invention provides a compound represented by the general formula (1)

Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, a represents 0 or an integer of 1 to 6. PA ₁ and PA ₂ represent ω-aminocarboxylic acid.) And a polyamide unit containing a polyamide obtained from an acid and / or a lactam.) And / or a general formula (2)

Embedded image (Wherein, R ₃ and R ₄ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, b represents 0 or an integer of 1 to 6. PA ₃ represents an ω-aminocarboxylic acid and / or a lactam. And R ₅ represents a hydrocarbon group having 1 to 24 carbon atoms.) A block unit composed of a polyamide unit derived from an azo group-containing polyamide represented by It is a polymer.

Another aspect of the present invention relates to a compound represented by the general formula (1):

Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, a represents 0 or an integer of ₁ to 6. PA ₁ and PA ₂ represent ω-aminocarboxylic acid and And / or a polyamide unit containing a polyamide obtained from a lactam.) And / or a general formula (2)

Embedded image (Wherein, R ₃ and R ₄ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, b represents 0 or an integer of 1 to 6. PA ₃ represents an ω-aminocarboxylic acid and / or a lactam. Wherein R ₅ represents a hydrocarbon group having 1 to 24 carbon atoms, and a vinyl monomer is polymerized using an azo group-containing polyamide represented by the following formula: 3. The method for producing a block copolymer described in 1. above.

An azo group-containing polyamide in which a polyamide unit containing a polyamide obtained from ω-aminocarboxylic acid and / or lactam is bonded to both ends or one end of a compound containing an azo group as a polymerization initiator, It has been found that a block copolymer of a polyamide and a vinyl polymer containing a polyamide unit obtained from an aminocarboxylic acid and / or a lactam can be synthesized.
This is a feature of the present invention.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The azo group-containing polyamide used in the present invention is a compound represented by the general formula (1) or (2), has one amino group, and has ω-aminocarboxylic acid and / or lactam. And a azo group-containing dicarboxylic acid halide represented by the general formula (3). The number average molecular weight of the polyamide having one amide group is 500 to 4
000, preferably 1,000 to 30,000, more preferably 2,000 to 25,000. When the number average molecular weight of this polyamide is larger than 40,000, the reactivity between the polyamide and the azo group-containing dicarboxylic acid halide decreases, and the production time of the azo group-containing polyamide used in the present invention becomes longer. On the other hand, when the number average molecular weight is less than 500, a block copolymer having the properties of polyamide, which is the object of the present invention, cannot be obtained.

The polyamide having one amino group according to the present invention may be a polyamide obtained by polycondensation of ω-aminocarboxylic acid and / or ring-opening polymerization of lactam in an amount of 50 to 100.
% By weight. Polyamides other than polyamides obtained from ω-aminocarboxylic acids and / or lactams include polyamides obtained by polycondensation of diamines with dicarboxylic acids or salts thereof. Specific examples of the ω-aminocarboxylic acid used in the present invention 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,
Specific examples of lactams include pyrrolidone, methylpyrrolidone, caprolactam, enantholactam, undecanelactam, dodecalactam and the like.
These ω-aminocarboxylic acids and lactams may be used alone or in combination of two or more.

As the diamine used for synthesizing the polyamide, a diamine having 2 to 24 carbon atoms is usually used. Specific examples thereof include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. Heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, hexadecamethylenediamine, octadecamethylenediamine, 2,2,4 (or 2, Aliphatic diamines such as 4,4) -trimethylhexamethylenediamine, cyclohexanediamine, methylcyclohexanediamine,
Examples include alicyclic diamines such as bis (4,4'-aminocyclohexyl) methane and aromatic diamines such as xylylenediamine.

On the other hand, as the dicarboxylic acid, a dicarboxylic acid having 2 to 24 carbon atoms is usually used. Specific examples thereof include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and the like. Sebacic acid, undecandionic acid, dodecandionic acid, tridecadionic acid, tetradecadionic acid, hexadecadionic acid, hexadecenedionic acid, octadecadionic acid, octadecenedionic acid, eicosandioic acid, eicosenedioic acid, eicosadi Endionic acid, docosandioic acid, 2,2,4
An aliphatic dicarboxylic acid such as trimethyladipic acid,
Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid,
Aromatic dicarboxylic acids such as xylylene dicarboxylic acid are exemplified. These diamines and dicarboxylic acids can be used in an appropriate combination in an approximately equimolar ratio.

A polyamide containing one amino group and containing a polyamide obtained from ω-aminocarboxylic acid and / or lactam can be produced by a known polyamide synthesis method such as melt polymerization, solution polymerization or solid phase polymerization. Is done. For example, ω-aminocarboxylic acid may be heated with a small amount of water for polycondensation if necessary, lactam may be heated with a small amount of water to perform ring-opening polymerization, or if necessary, diamine and dicarboxylic acid or There is a method in which these nylon salts are mixed with ω-aminocarboxylic acid or lactam and heated to polymerize. The heating temperature during these polymerizations is usually from 200 to 300 ° C.

Generally, a polyamide produced by a known method generally has an amino group at one of the terminal groups of the molecule and a carboxyl group at the other. In the present invention, the polyamide to be reacted with the azo group-containing dicarboxylic acid halide has one end group having an amino group and the other having a non-reactive structure such as an alkyl group. Polyamide of such a structure,
It is produced by adding a monoamine during the synthesis of polyamide. Specific examples of the monoamine to be added include:
1-2 carbon atoms such as laurylamine and stearylamine
4, straight-chain and branched aliphatic monoamines, aromatic monoamines such as benzylamine and β-phenylethylamine, and alicyclic monoamines such as cyclohexylamine. When these are added, the synthesized polyamide has almost no carboxyl terminal group, and the terminal groups other than the amino group mainly become residues of the above-mentioned monoamine. The addition amount of these monoamines is appropriately determined according to the amino group concentration and the number average molecular weight of the polyamide to be synthesized. Usually, monoamine is 0.0001 to 1 mol of a polyamide material such as ω-aminocarboxylic acid or lactam.
０．２0.2 mol.

The azo group-containing dicarboxylic acid halide is a chloride, bromide or iodide of the azo group-containing dicarboxylic acid. The azo group-containing dicarboxylic acid and a chlorine compound such as phosgene, thionyl chloride, phosphorus trioxide and phosphorus pentoxide. Alternatively, it can be obtained by reaction with a corresponding bromine compound or iodine compound. Specific examples of the azo group-containing dicarboxylic acid include 4,4′-azobis-cyanovaleric acid, 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 reaction between a polyamide having one amino group and an azo group-containing dicarboxylic acid halide represented by the general formula (3) is carried out in the presence or absence of water and / or an alcohol. The reaction is performed in such a manner that the acid halogen group of the azo group-containing dicarboxylic acid halide is 0.5 to 10 molar equivalents, preferably 0.7 to 8 molar equivalents, per 1 molar equivalent. If the amount of the acid halogen group is less than 0.5 molar equivalent relative to the amino group, a large amount of unreacted polyamide containing no azo group remains, and the yield of the azo group-containing polyamide is undesirably low. When the ratio of the acid halogen group is more than 10 molar equivalents with respect to the amino group, a large amount of unreacted azo group-containing dicarboxylic acid halide not bonded to the polyamide remains, and the yield of the azo group-containing polyamide is low. Is not preferred. In the present invention, the azo group-containing polyamide in which the molecular weight of the polyamide is controlled can be easily obtained because the polyamide having one amino group and the azo group-containing dicarboxylic acid halide which has been previously polymerized and having a known molecular weight are directly reacted. Can be.

When no water and / or alcohol is present, an azo group-containing polyamide represented by the general formula (1) is obtained. On the other hand, when water and / or alcohol is present, a mixture of the azo group-containing polyamides represented by the general formulas (1) and (2) is obtained. The ratio of obtaining the azo group-containing polyamide represented by the general formula (2) increases as the amount of water and / or alcohol added increases.

When adding water and / or alcohol,
The amount of these additives is an excess of the acid halide group, that is,
It is an amount equal to or more than the number of molar equivalents corresponding to (number of acid halogen groups−number of amino groups). Water and / or alcohol may be added at any time before, during or after the reaction of the polyamide with the azo group-containing dicarboxylic acid halide. The alcohol to be added has 1 to 24 carbon atoms.
And specific examples thereof include methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, octyl alcohol, stearyl alcohol, cyclohexanol, benzyl alcohol, and furfuryl alcohol.

The synthesis of the azo group-containing polyamide used in the present invention must be carried out under conditions in which the azo group is not decomposed as much as possible in consideration of the thermal stability of the azo group. It is preferable to carry out the reaction by a suitable solution reaction. Solvents that can be used for the synthesis reaction are selected from those that dissolve the polyamide and have no or very low reactivity with acid halogen groups or amino groups. Specific examples of such a solvent include phenolic solvents such as phenol and cresol, and mixed solvents of these with hydrocarbon solvents, and N-methyl-2-pyrrolidone in which halogenated inorganic substances such as lithium chloride and calcium chloride are dissolved. And amide solvents such as N, N-dimethylacetamide, N, N-dimethylformamide, and 1,3-dimethyl-2-imidazolidinone.

The reaction temperature is preferably lower than the decomposition temperature of the azo group, usually 60 ° C. or lower, preferably 0 to 50 ° C.
C., and the reaction time is preferably 0.1 to 150 hours. When the reaction temperature is higher than 60 ° C., the azo group may be decomposed in a short time, and it becomes difficult to obtain the target azo group-containing polyamide. On the other hand, if the reaction temperature is excessively low, the reaction rate becomes extremely slow, which is not preferable.

The reaction between a polyamide having one amino group and containing a polyamide obtained from ω-aminocaproic acid and / or a lactam, and an azo group-containing dicarboxylic acid halide represented by the general formula (3) is quickly carried out. A known basic catalyst such as a tertiary amine such as triethylamine, pyridine, quinoline, or isoquinoline may be added.

After the completion of the synthesis reaction of the azo group-containing polyamide,
The reaction solution containing the azo group-containing polyamide can be used as it is as a polymerization initiator for a vinyl monomer. When the azo group-containing polyamide is obtained as a simple substance, the synthesized azo group-containing polyamide is precipitated by pouring the reaction solution into a large amount of a poor solvent, or adding a large amount of the poor solvent to the reaction solution, and filtering the solution. It is obtained by drying after separating.

The azo group-containing polyamide obtained as described above can be used as a polymerization initiator for a vinyl monomer. The vinyl monomer used in the present invention is not particularly limited as long as it is a monomer polymerized by a radical reaction. Specific examples of such a monomer include ethylene, propylene, butene, isobutene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, acrylonitrile, vinylidene cyanide, acrylic acid, methyl acrylate, and acrylic acid such as ethyl acrylate. Esters, acrylamide, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, glycidyl methacrylate, methacrylic acid esters such as methacrylic acid 121-ethylhexyl, methacrylamide, maleic anhydride, maleic acid Maleic esters such as dimethyl and diethyl maleate; fumaric esters such as dimethyl fumarate and diethyl fumarate; maleimide; N-methylmaleimide; N-cyclohexylmaleimide; N- substituted maleimide such as sulfonyl maleimides, vinyl acetate,
Vinyl carboxylate such as vinyl propionate and vinyl benzoate, vinyl ethers such as methyl vinyl ether and phenyl vinyl ether, vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinyl pyridine,
N-vinylpyrrolidone and the like can be mentioned, and these can be used alone or in combination of two or more.

When the above-mentioned vinyl monomer is polymerized by using the azo group-containing polyamide of the present invention as a polymerization initiator, the polymerization operation and the polymerization reaction are carried out in a uniform state. Preferably, The solvent used in this polymerization is not particularly limited as long as the azo group-containing polyamide can be dissolved at room temperature.
Specific examples of such a solvent include phenolic solvents such as phenol and cresol, and mixed solvents of these with hydrocarbon solvents, and N-methyl-2-pyrrolidone in which halogenated inorganic substances such as lithium chloride and calcium chloride are dissolved. Amide solvents such as N, N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone, mixed solutions of phenol solvents and alcohol solvents, trifluoroethanol, hexafluoro Fluorinated alcohols such as isopropanol; organic acids such as formic acid;

The azo group-containing polyamide is a vinyl monomer 1
It is used in such a ratio that the number of moles of the azo group in the azo group-containing polyamide is 0.0001 to 1 mole per mole. When the amount of the azo group-containing polyamide is less than the lower limit,
The polymerization of the vinyl monomer hardly proceeds. or,
If it exceeds the upper limit, the number average molecular weight of the synthesized vinyl polymer tends to be small, and it is difficult to obtain a copolymer having the characteristics of a vinyl polymer.

The polymerization reaction of the vinyl monomer is started by dissolving the azo group-containing polyamide and the vinyl monomer in a solvent and then generating radicals by a known method such as heating or irradiation with light or an electron beam. Polymerization temperature is 3
The reaction is carried out at a temperature of 0 ° C. or higher, preferably 35 to 150 ° C. The polymerization time is usually at least 0.5 hour. When the polymerization temperature is lower than 30 ° C., the polymerization rate becomes extremely slow. At the time of the polymerization reaction, other radical initiators, photosensitizers and the like may be added.

After completion of the polymerization reaction, the synthesized block copolymer composed of polyamide and vinyl polymer is removed by a known method such as evaporation of the reaction solvent and then dried, or the reaction solution is poured into a large amount of poor solvent. Or conversely,
By adding a poor solvent to the reaction solution, the synthesized polyamide-vinyl polymer block copolymer can be precipitated, filtered, and dried. Further, if necessary, purification operations such as extraction and reprecipitation may be performed to remove by-products such as homopolymers of vinyl polymers.

[0031]

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 Measured at a concentration of 0.5 g / 100 ml using m-cresol as a solvent at 25 ° C. using an Ubbelohde viscometer, and according to the formula (1), the solution viscosity ηsp / c (unit: ; Ml / g).

Ηsp / c = {(t−t ₀ ) / t ₀ } / c (1) 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 equation (2).

[NH ₂ ] = (L ₁ −L ₂ ) × f × 10 ⁻⁴ / (2 × S) (2) where L ₁ ; titration of sample solution (ml), L ₂ ; solvent Titer (ml), f: factor of 1 / 20N hydrochloric acid, S: sample amount (g)

3) Number average molecular weight of polyamide (hereinafter referred to as
Mn (unit: g / mol) is measured by the method described in 2) above.
Amino group concentration [NH _Two] And calculated by equation (3).
Calculated.

Mn = 1 / [NH ₂ ] (3)

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 performed using bisulfuric acid as a solvent under the following conditions. Measurement frequency: 300 MHz, measurement temperature: room temperature, sample concentration: 5% by weight, standard substance: trimethylsilane 5) Infrared absorption spectrum (IR) of polyamide-polystyrene copolymer Fourier transform infrared spectroscopy manufactured by Perkin-Elmer It was measured by the KBr method using an apparatus 1750.

6) UV measurement of azo group-containing polyamide Instant multi-photometry system MCPD-1 by Otsuka Electronics Co., Ltd.
Hexafluoroisopropanol (HF
The measurement was carried out under the condition of a sample concentration of 0.05 mol / l using IP) as a solvent.

Synthesis Example 1 Azo group-containing polyamide (PA-
Synthesis of 1) 11.3 parts by weight of ε-caprolactam, 0.5 part by weight of water and 0.6 part by weight of stearylamine were charged into an autoclave, and after purging with nitrogen, polymerization was carried out 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. Thereafter, the polymer was taken out, pulverized, subjected to Soxhlet extraction with methanol, and then dried to obtain a polyamide (nylon 6). The solution viscosity of this polyamide was 0.50, and the number average molecular weight Mn calculated from the amino group concentration was 4,900. 5 parts by weight of the obtained polyamide and 1.5 parts by weight of triethylamine were dissolved at 60 ° C. in 500 parts by weight of a solvent obtained by dissolving 10% by weight of lithium chloride in 1,2-dimethyl-2-imidazolidinone (DMI). . While cooling on ice
5 parts by weight of a tetrahydrofuran (THF) solution in which 0.162 parts by weight of 4,4′-azobis-cyanovaleric acid dichloride (ACPC) was dissolved was added dropwise. After dripping, 1
The reaction was carried out at 0 ° C. with stirring for 40 hours. After pouring the reaction solution into a large amount of methanol to precipitate a reaction product,
It was separated by filtration and dried under reduced pressure. An azo group was observed from the UV spectrum measurement of the reaction product, and a signal based on nylon 6 was observed from the ¹ H-NMR measurement. The obtained reaction product was an azo group-containing polyamide (hereinafter, referred to as “PA-1”). It was confirmed that.

Synthesis Example 2 Azo group-containing polyamide (PA-
Synthesis of 2) Polymerization was carried out in the same manner as in Synthesis Example 1 except that the amount of stearylamine used was changed to 0.4 part by weight to obtain a polyamide (nylon 6). The solution viscosity of this polyamide is 0.97
And the number average molecular weight Mn calculated from the amino group concentration was 8,300. 5 parts by weight of the obtained polyamide, 1.5 parts by weight of triethylamine and 25 parts by weight of methanol were dissolved in 75 parts by weight of phenol. While cooling with ice, 5 parts by weight of a tetrahydrofuran (THF) solution in which 0.30 parts by weight of 4,4′-azobis-cyanovaleric acid dichloride (ACPC) was dissolved was added dropwise. After dripping, 1
The reaction was carried out at 0 ° C. with stirring for 40 hours. After pouring the reaction solution into a large amount of methanol to precipitate the reaction product,
It was separated by filtration and dried under reduced pressure. ^{From the 1} H-NMR measurement, a signal based on the terminal methoxy group was observed in the reaction product, and from this signal intensity and the signal intensity based on polyamide (nylon 6), 98 mol% of the reaction product had an azo group having a terminal methoxy group. Group-containing polyamide (hereinafter “PA-2”)
Indicated by ).

Synthesis Example 3 Azo group-containing polyamide (PA-
Synthesis of 3) 13 parts by weight of ε-caprolactam, 2.2 parts by weight of an equimolar salt of terephthalic acid and hexamethylenediamine and 0.3 parts by weight of stearylamine were charged into an autoclave. Polymerization was performed at atmospheric pressure 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. The obtained polymer was taken out, pulverized, subjected to Soxhlet extraction with methanol, dried, and dried with polyamide (6 /
6T copolymerized nylon) was obtained. The solution viscosity of this polyamide was 0.89, and the number average molecular weight Mn calculated from the amino group concentration was 10,000. 200 parts by weight of a mixed solvent comprising 10 parts by weight of the obtained polyamide, 0.86 parts by weight of 4,4'-azobis-cyanovaleric acid dichloride (ACPC) and 1.5 parts by weight of triethylamine, 25 parts by weight of methanol and 75 parts by weight of phenol Dissolves in the part. While cooling with ice, 15 parts by weight of a tetrahydrofuran (THF) solution in which 0.61 part by weight of 4,4′-azobis-cyanovaleric acid dichloride (ACPC) was dissolved was added dropwise. After the dropwise addition, the mixture was reacted at 20 ° C. for 2 hours with stirring. 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. 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. This reaction product was an azo group-containing polyamide (hereinafter, referred to as “PA-3”).
Was confirmed.

Synthesis Example 4 Azo group-containing polyamide (PA-
Synthesis of 4) 11.3 parts by weight of ε-caprolactam, 0.5 part by weight of water
Synthetic except that 0.1 parts by weight of stearylamine was used.
Polymerized in the same manner as in Example 1, and polyamide (nylon 6)
I got The solution viscosity of this polyamide is 1.52,
The number average molecular weight Mn calculated from the amino group concentration is 17,
000. 10 parts by weight of this polyamide
2.5 parts by weight, and then 4,4 ^'-Azobis
0.55 parts by weight of 4-cyanovaleric acid dichloride
After dropping, the mixture is stirred at 5 ° C for 30 minutes, and then at 20 ° C for 1 hour.
A reaction was conducted in the same manner as in Synthesis Example 2 except that the reaction was carried out while stirring.
A reaction was obtained.¹From H-NMR, it was found that nylon 6
Signal was observed, and azo
The presence of a group was observed, and the azo group-containing polyamide
Described as "PA-4". ) Was confirmed.

Example 1 2.5 parts by weight of PA-1 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
Methyl methacrylate was polymerized at a temperature of 24 ° C. under stirring for 24 hours. Thereafter, the reaction solution was poured into methanol to precipitate a polymer, which was filtered and dried under reduced pressure. The obtained polymer was measured by ¹ H-NMR, and a signal of nylon 6 and a signal of poly (methyl methacrylate) were observed. Thus, it was a block copolymer of polyamide and poly (methyl methacrylate).

Example 2 Methyl methacrylate was polymerized in the same manner as in Example 1 except that 2.5 parts by weight of PA-2 was used instead of PA-1 to obtain a polymer. The obtained polymer is ¹ H-NM
From the measurement of R, signals of nylon 6 and poly (methyl methacrylate) were observed, and it was found that the copolymer was a copolymer of polyamide and poly (methyl methacrylate).
The structure of the copolymer is a block copolymer consisting of a nylon 6 block and a poly (methyl methacrylate) block, and a block copolymer consisting of a nylon 6 block, a poly (methyl methacrylate) block and a nylon 6 block. It is estimated to be a mixture with Example 3 A polymerization reaction was carried out in the same manner as in Example 1 except that the amount of PA-1 was changed to 5.0 parts by weight, and 5.1 parts by weight of styrene was used instead of methyl methacrylate. I got
From the IR measurement, signals of nylon 6 and polystyrene were observed, and the obtained polymer was a block copolymer of polyamide 6 and polystyrene. Example 4 2.5 parts by weight of PA-2 was added to trifluoroethanol 2
In 100 parts by weight at room temperature.
Parts by weight were added. Next, vinyl acetate was polymerized under a nitrogen atmosphere at 60 ° C. with stirring for 24 hours. afterwards,
The reaction solution was poured into methanol to precipitate a polymer, which was filtered and dried under reduced pressure. The obtained polymer is ¹ H-NM
From the measurement of R, signals of nylon 6 and poly (vinyl acetate) were observed, and it was found that the block copolymer was a block copolymer of nylon 6 and poly (vinyl acetate).

Example 5 Methyl methacrylate was polymerized in the same manner as in Example 1 except that 2.5 parts by weight of PA-3 was used instead of PA-1 to obtain a polymer. The obtained polymer is ¹ H-NM
From the measurement of R, signals of nylon 6 / 6T and poly (methyl methacrylate) were observed, and polyamide 6/6
It was a block copolymer of T and poly (methyl methacrylate).

Example 6 2.5 parts by weight of PA-4 and 10 parts by weight of hydroxyethyl methacrylate were dissolved in 20 parts by weight of 2,2,2-trifluoroethanol, and stirred at 60 ° C. under a nitrogen atmosphere. The hydroxyethyl methacrylate was polymerized for 24 hours. Then, the reaction solution was poured into methanol,
The polymer was precipitated, filtered and dried under reduced pressure. The resulting polymer is
^{By 1} H-NMR measurement, a signal of nylon 6 and a signal of poly (hydroxyethyl methacrylate) were observed, and it was a block copolymer of nylon 6 and poly (hydroxyethyl methacrylate).

[0045]

According to the present invention, an ω-aminocarboxylic acid and / or
Or a block copolymer comprising a polyamide containing a polyamide obtained from a lactam and a vinyl polymer, and the block copolymer is represented by the general formula (1)

Embedded image (Wherein, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, a represents 0 or an integer of ₁ to 6. PA ₁ and PA ₂ represent ω-aminocarboxylic acid and And / or a polyamide unit containing a polyamide obtained from a lactam.)
Or the general formula (2)

Embedded image (Wherein, R ₃ and R ₄ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, b represents 0 or an integer of 1 to 6. PA ₃ represents an ω-aminocarboxylic acid and / or a lactam. A polyamide unit containing a polyamide obtained from
R ₅ represents a hydrocarbon group having 1 to 24 carbon atoms. Can be obtained by polymerizing a vinyl monomer using the azo group-containing polyamide represented by the formula (1) as a polymerization initiator.

Claims (3)

[Claims] 1. A compound of the general formula (1) (In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group or a nitrile group having 1 to 6 carbon atoms, a represents 0 or an integer of 1 to 6. PA ₁ and PA ₂ represent ω-aminocarboxylic acid. Acid and / or
Or a polyamide unit containing a polyamide obtained from a lactam. And / or an azo group-containing polyamide represented by the general formula (2): (Wherein, R ₃ and R ₄ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, b represents 0 or an integer of 1 to 6. PA ₃ represents an ω-aminocarboxylic acid and / or a lactam. A polyamide unit containing a polyamide obtained from
R ₅ represents a hydrocarbon group having 1 to 24 carbon atoms. A block copolymer comprising a polyamide derived from the azo group-containing polyamide represented by the formula (1) and a vinyl polymer. 2. The block copolymer according to claim 1, wherein the polyamide unit in the azo group-containing polyamide contains 50 to 100% by weight of a polyamide obtained from an aminocarboxylic acid and / or a lactam. 3. A compound of the general formula (1) (In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group or a nitrile group having 1 to 6 carbon atoms, a represents 0 or an integer of 1 to 6. PA ₁ and PA ₂ represent ω-aminocarboxylic acid. Acid and / or
Or a polyamide unit containing a polyamide obtained from a lactam. And / or an azo group-containing polyamide represented by the general formula (2): (Wherein, R ₃ and R ₄ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, b represents 0 or an integer of 1 to 6. PA ₃ represents an ω-aminocarboxylic acid and / or a lactam. A polyamide unit containing a polyamide obtained from
R ₅ represents a hydrocarbon group having 1 to 24 carbon atoms. 3. The method for producing a block copolymer according to claim 1, wherein the vinyl monomer is polymerized using the azo group-containing polyamide represented by the formula (1) as a polymerization initiator.