JP3508577B2 - Block copolymer and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention provides a lactamide arm and / or aliphatic polyamides resulting from the amino acids 2
The present invention relates to a block copolymer containing 0 to 100% by weight of a polyamide and a vinyl polymer and a method for producing the same.

[0002]

2. Description of the Related Art At present, various kinds of plastics have been developed and are used in applications utilizing their respective characteristics.
In recent years, with diversification of required characteristics, polymer materials having new characteristics have been demanded. As one of them, there is a demand for a polymer material having characteristics of both engineering plastics and general-purpose polymers. Among them, there is a strong demand for a copolymer having the characteristics of both polyamide, which is a typical engineering plastic, and vinyl polymer, which is a typical general-purpose polymer.

Conventionally, regarding a copolymer composed of a polyamide and a vinyl polymer, what is obtained by polymerizing a vinyl monomer using an azo group-containing polyamide as a polymerization initiator is described in J. Polym. Sci. Polym Chem Ed, Vol. 22,1611 (19
84), Journal of Polymers, Vol. 33, 131 (1976) and Osaka City Institute of Industrial Research, 84th (1989).

These reports are disclosed in Japanese Patent Application Laid-Open No. 49-17895.
Formula (1) described in Japanese Patent Publication

[Chemical 3] (In the formula, X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, and a represents 0 or an integer of 1 to 6.). An azo group-containing dicarboxylic acid halide and a diamine such as hexamethylenediamine are added to the compound represented by the general formula (2)

[Chemical 4] (In the formula, X represents a halogen atom, and R ₃ represents a divalent aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms.) In the absence or presence of the dicarboxylic acid halide. Nylon 6 obtained by polymerizing styrene with azo group-containing polyamide obtained by reaction as a polymerization initiator
The present invention relates to a 6-polystyrene copolymer, a nylon 610-polystyrene copolymer and a method for producing the same.

Further, a method of polymerizing a vinyl monomer using a polyamide in which an amide bond is partially nitrosated is described in J. Polym. Sci. Polym Chem Ed, Vol.
011 (1980) and J. Polym. Sci. Polym Chem Ed, Vol. 20, 19
35 (1980). In this method, a polyamide synthesized from caprolactam and / or 6-aminocarboxylic acid is treated with nitric oxide or the like, and a polyamide having a part of amide group nitrosated is used as a polymerization initiator to polymerize a vinyl monomer. And a method for producing the same.

[0006]

The azo group-containing polyamide as a polymerization initiator used in the production of a copolymer composed of a polyamide and a vinyl polymer by the former method is a halogenated dicarboxylic acid represented by the general formula (2). Manufactured by a method of reacting an azo group-containing dicarboxylic acid halide with a diamine in the absence or presence of a compound. When the reaction is carried out in the absence of the dicarboxylic acid halide, the azo group-containing polyamide is obtained by the condensation reaction of the azo group-containing dicarboxylic acid halide and the diamine, and has a chemical structure in which azo groups and amide groups are alternately repeated. Therefore, since it has a large number of azo groups in its molecular chain, it is highly active as a polymerization initiator, but when all the azo groups are decomposed, the molecular structure of the polyamide disappears. You can't get coalesced. Further, when the azo group is partially left, the obtained polyamide becomes thermally unstable, which is not practical.

On the other hand, when the reaction is carried out in the presence of a dicarboxylic acid halide, at least three kinds of reactions, namely,
Reactions between an azo group-containing dicarboxylic acid halide and a diamine, reactions between a dicarboxylic acid halide and a diamine, and reactions between a polyamide produced from a dicarboxylic acid halide and a diamine and an azo group-containing dicarboxylic acid halide occur concurrently. , A mixture of the respective reaction products is obtained. Among the reaction products, a polymerization initiator that can be used for producing a block copolymer composed of a target polyamide and a vinyl polymer is a polyamide produced from a dicarboxylic acid halide and a diamine, and an azo group-containing dicarboxylic acid halide. It is an azo group-containing polyamide obtained by the reaction of. However, it is difficult to control the production amount of the azo group-containing polyamide and the number average molecular weight of the polyamide portion because some reactions proceed in parallel. Also, it is difficult to isolate this azo group-containing polyamide from the product mixture. Further, the chemical structure of the polyamide part is limited to the structure of diamine and dicarboxylic acid halide, and a polyamide containing a structural unit of an aliphatic polyamide obtained from lactam and / or aminocarboxylic acid having good film properties and processing properties, and It is difficult to obtain a block copolymer composed of a vinyl polymer.

In the latter prior art method for producing a copolymer of a polyamide and a vinyl polymer using a partially nitrosated polyamide as a polymerization initiator, the nitrosation reaction occurs at amide groups at random positions. The number average molecular weight of the polyamide between the nitrosated amide groups cannot be controlled. Therefore, since the number average molecular weight of the polyamide portion of the block copolymer composed of the polyamide and vinyl polymer obtained by this method is not controlled, the reproducibility of the chemical structure of the obtained copolymer of the polyamide and vinyl polymer is poor and stable. It is difficult to obtain a copolymer having the above physical properties. Further, the polymerization initiator activity of the partially nitrosated polyamide is not so high.

The object of the present invention is to obtain aliphatic polyamides from lactams and / or aminocarboxylic acids in an amount of 20 to 1
It is intended to provide a block copolymer comprising a polyamide and a vinyl polymer, which is contained in an amount of 00% by weight, and a method for producing the block copolymer.

[0010]

Means for Solving the Problems As a result of studying the above-mentioned problems, the present inventors have previously prepared a polyamide having two amino groups and a specific number average molecular weight from lactam and / or aminocarboxylic acid as a main raw material. Then, by polymerizing a vinyl monomer using the azo group-containing polyamide obtained from the reaction of the synthesized polyamide and the azo group-containing dicarboxylic acid halide as a polymerization initiator, the block copolymer of the present invention can be obtained with good reproducibility. The present invention has been achieved and the present invention has been achieved.

[0011] That is, the first invention of the present invention, the lactamide <br/> arm and / or aliphatic polyamides resulting from aminocarboxylic acids containing 20 to 100 wt%, and the two amino
Polyamide having no group and general formula (1)

[Chemical 5] (In the formula, X is a halogen atom, and R ₁ and R ₂ are hydrogen atoms.
Child, an alkyl group having 1 to 6 carbon atoms or a nitrile group
, A represents 0 or an integer of 1 to 6. )
Obtained by reaction with zo group-containing dicarboxylic acid halide
Using azo group-containing polyamide as a polymerization initiator, vinyl mono
It is a block copolymer composed of a polyamide and a vinyl polymer obtained by polymerizing a mer .

[0012] Also, the second invention of the present invention, the lactamide arm and / or aliphatic polyamides resulting from aminocarboxylic acids containing 20 to 100 wt%, and polyamide and the general formula having two amino groups (1)

[Chemical 6] (In the formula, X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, and a represents 0 or an integer of 1 to 6.). A method for producing a block copolymer comprising a polyamide and a vinyl polymer, which comprises polymerizing a vinyl monomer using an azo group-containing polyamide obtained by reaction with an azo group-containing dicarboxylic acid halide as a polymerization initiator.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
Azo group-containing polyamide used in the polymerization initiator in the present invention, in advance, lactamide arm and / or aliphatic polyamides resulting from the amino acids (hereinafter, "aliphatic polyamides"
And a azo group-containing dicarboxylic acid halide represented by the general formula (1) and synthesizing a polyamide having 20 to 100% by weight of 2) and two amino groups. It is a compound. Since the pre-synthesized polyamide is used, the azo group-containing polyamide containing the polyamide having a specific number average molecular weight can be reproducibly reproduced.
Obtainable. The number average molecular weight of the polyamide containing 20 to 100% by weight of an aliphatic polyamide and having two amino groups is 500 to 40,000, preferably 1,000 to 30,000, and more preferably 2,000.
It is 0 to 25,000. When the number average molecular weight of this polyamide is larger than 40,000, the reaction rate between this polyamide and the azo group-containing dicarboxylic acid halide decreases, and the production time of the azo group-containing polyamide becomes longer. On the other hand, if it is less than 500, it becomes difficult to obtain a block copolymer composed of a polyamide and a vinyl polymer, which has the original properties of polyamide. In the present invention, in order to obtain an azo group-containing polyamide by the reaction of a polyamide having a specific number average molecular weight synthesized in advance and an azo group-containing dicarboxylic acid halide, the azo group-containing polyamide containing a target polyamide block is reproducible. It can be easily produced and can be used as it is as a polymerization initiator for vinyl monomers without purification.

The polyamide containing 20 to 100% by weight of aliphatic polyamide and having two amino groups is an aliphatic polyamide obtained by condensation polymerization of aminocarboxylic acid or ring-opening polymerization of lactam, preferably 20 to 100% by weight. 5
It is composed of 0 to 100% by weight and 0 to 80% by weight, preferably 0 to 50% by weight of a polyamide obtained by polycondensation of a diamine and a dicarboxylic acid or a salt thereof. If the amount of this aliphatic polyamide is less than 20% by weight, the properties of the resulting polyamide and vinyl polymer may be deteriorated such as brittleness.

Specific examples of the lactam used in the present invention include pyrrolidone, methylpyrrolidone, caprolactam,
Enantholactam, undecanelactam, dodecalactam and the like can be mentioned, and specific examples of the aminocarboxylic acid include 5-aminovaleric acid, 6-aminocaproic acid, 7-
Examples thereof include aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid. These lactams and aminocarboxylic acids may be used alone or in appropriate combination of two or more.

The diamine which can be used in the present invention is usually a diamine having 2 to 24 carbon atoms, and specific examples thereof include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and heptamethylene. Diamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecamethylenediamine, hexadecamethylenediamine, octadecamethylenediamine, 2,2,2
Aliphatic diamines such as 4 (or 2,4,4) -trimethylhexamethylenediamine, cyclohexanediamine, methylcyclohexanediamine, bis- (4,4 ′)
Examples thereof include alicyclic diamines such as -aminocyclohexyl) methane and aromatic diamines such as xylylenediamine. These diamines may be used alone,
Further, two or more kinds may be appropriately combined and used.

The dicarboxylic acid usually has 2 to 2 carbon atoms.
24 dicarboxylic acids are used, and specific examples thereof include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecadioic acid, tetradeca acid. Dionic acid, hexadecadioic acid, hexadecenedioic acid, octadecadionic acid, octadecenedioic acid, eicosandioic acid, eicosendioic acid, eicosadiendioic acid, docosandionic acid, 2,2,4-trimethyladipic acid Aliphatic dicarboxylic acids, such as 1,
Examples thereof include alicyclic dicarboxylic acids such as 4-cyclohexanedicarboxylic acid, aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, and xylylenedicarboxylic acid. These dicarboxylic acids may be used alone or in combination of two or more kinds. The above-mentioned diamine and dicarboxylic acid are combined in an approximately equimolar blending ratio, or used as a nylon salt thereof.

The polyamide containing 20 to 100% by weight of aliphatic polyamide and having two amino groups is a known polyamide synthesized by melt polymerization or solution polymerization by adding a specific amount of diamine to the above monomers. Manufactured by the method. For example, a method of ring-opening polymerization by adding a specific amount of diamine and a small amount of water to a lactam, a method of polycondensing an aminocarboxylic acid by adding a specific amount of a diamine and a small amount of water if necessary, or a lactam and / or Aminocarboxylic acid in the required amount of diamine and dicarboxylic acid or nylon salts thereof,
It is produced by adding a specific amount of diamine and, if necessary, a small amount of water and polymerizing. Usually, the polymerization temperature during production is 200-330 ° C.

Polyamides having two amino groups are obtained by adding a specific amount of diamine during polyamide synthesis. The diamine added has 2 to 24 carbon atoms.
Diamine is used, and specific examples include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, Aliphatic diamines such as dodecamethylenediamine, tridecamethylenediamine, hexadecamethylenediamine, octadecamethylenediamine, 2,2,4 (or 2,4,4) -trimethylhexamethylenediamine, cyclohexanediamine, methylcyclohexanediamine Alicyclic diamines such as bis- (4,4′-aminocyclohexyl) methane, aromatic diamines such as xylylenediamine, and the like.
These diamines may be used alone or in combination of two or more kinds. The amount of the diamine added is 0.0001 to 0.2 mol, preferably 0.1%, relative to 1 mol of the lactam and / or aminocarboxylic acid.
It is 001-0.1 mol. If it exceeds the upper limit, the number average molecular weight of the polyamide may become too small. On the other hand, if it is less than the lower limit, the number average molecular weight of the polyamide may become too large, or a polyamide having two amino groups may not be produced.

The azo group-containing dicarboxylic acid halide represented by the general formula (1) is represented by the general formula (3)

[Chemical 7] (In the formula, R ₄ and R ₅ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, and b represents 0 or an integer of 1 to 6.) of the azo group-containing dicarboxylic acid Chloride, bromide or iodide, obtained by reacting an azo group-containing dicarboxylic acid with a chlorine-based compound such as phosgene, thionyl chloride, phosphorus trichloride, phosphorus pentachloride, or a corresponding bromine-based compound or iodine-based compound To be 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 the polyamide containing 20 to 100% by weight of the aliphatic polyamide and having two amino groups and the azo group-containing dicarboxylic acid halide represented by the general formula (1) is carried out by the reaction of the polyamide amino group. 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, relative to 1 molar equivalent. When the amount of acid halogen group is less than 0.5 molar equivalent to 1 molar equivalent of amino group,
A large amount of unreacted polyamide containing no azo group remains. On the other hand, when the proportion of acid halogen groups is more than 10 molar equivalents relative to 1 molar equivalent of amino groups, a large amount of unreacted azo group-containing dicarboxylic acid halide not bound to polyamide remains.

The synthesis of the azo group-containing polyamide of the present invention is
Considering the thermal stability of the azo group, it is necessary to carry out the reaction under the condition that the azo group is not decomposed as much as possible, the control of the reaction temperature is important, and the solution reaction is preferable. As a solvent that can be used in this solution reaction, a solvent that dissolves polyamide and has no reactivity with acid halogen groups or amino groups or has very low reactivity is selected. Specific examples of such a solvent include phenol, phenol-based solvents such as cresol and mixed solvents of these and hydrocarbon-based solvents, lithium chloride, N-methyl-2-pyrrolidone in which halogenated inorganic substances such as calcium chloride are dissolved. , N, N-
Dimethylacetamide, N, N-dimethylformamide,
Examples thereof include amide solvents such as 1,3-dimethyl-2-imidazolinone.

The reaction temperature is 6 considering the decomposition temperature of the azo group.
The temperature is 0 ° C. or lower, preferably 0 to 50 ° C., and the reaction time varies depending on the reaction temperature, but usually 0.1 hour or more is required. When the reaction temperature is higher than 60 ° C., the azo group is decomposed in a short time, and it becomes difficult to obtain the target azo group-containing polyamide. On the other hand, when the reaction temperature is excessively low, the reaction rate becomes extremely slow.

In order to promptly proceed the reaction between the polyamide containing 20 to 100% by weight of the aliphatic polyamide and having two amino groups and the azo group-containing dicarboxylic acid halide represented by the general formula (1), A basic catalyst such as a tertiary amine such as triethylamine, pyridine, quinoline or isoquinoline may be added.

After completion of the synthetic 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. Further, when the azo group-containing polyamide is obtained as a simple substance, the reaction solution is poured into a large amount of a poor solvent, or conversely, the poor solvent is added to the reaction solution to precipitate the synthesized azo group-containing polyamide and filter it. After that, it can be obtained by drying.

The azo group-containing polyamide obtained by the above method is a compound effective as a polymerization initiator for vinyl monomers. The vinyl monomer used in the present invention may be any monomer that can be polymerized by a radical reaction without particular limitation. Examples of such a monomer include ethylene, propylene, butene, isobutene, butadiene, isoprene, chloroprene, styrene, α-methylstyrene, acrylonitrile, vinylidene cyanide, acrylamide, methacrylamide, acrylic acid, methyl acrylate, and acrylic acid. Acrylic esters such as ethyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, glycidyl methacrylate, methacrylic acid esters such as 2-ethylhexyl methacrylate,
Maleic anhydride, dimethyl maleate, maleates such as diethyl maleate, dimethyl fumarate, fumarates such as diethyl fumarate, maleimide,
N-methyl maleimide, N-cyclohexyl maleimide,
N-substituted maleimides such as N-phenylmaleimide, vinyl acetates such as vinyl acetate, vinyl propionate and vinyl benzoate, vinyl ethers such as methyl vinyl ether and phenyl vinyl ether, vinyl chloride, vinylidene chloride and tetrafluoroethylene. , Vinylpyridine, N-vinylpyrrolidone and the like, and these may be used alone or in an appropriate combination of two or more kinds.

When the azo group-containing polyamide of the present invention is used as a polymerization initiator and the above vinyl monomer is polymerized,
The solution method is preferred because it is easy to handle and polymerizes in a stable state. The solvent used is not particularly limited as long as it dissolves the azo group-containing polyamide at room temperature. Specific examples thereof include phenol, phenol-based solvents such as cresol and mixed solvents of these and hydrocarbon-based solvents, lithium chloride, N-methyl-2-pyrrolidone in which halogenated inorganic substances such as calcium chloride are dissolved,
N, N-dimethylacetamide, N, N-dimethylformamide, 1,3-dimethyl-2-imidazolidinone and other amide solvents, mixed solutions of phenol solvents and alcohol solvents such as methanol and ethanol, trifluoro Examples thereof include fluorine-based alcohols such as ethanol and hexafluoroisopropanol, organic acids such as formic acid.

The polymerization of the vinyl monomer is used in such a ratio that the number of moles of azo groups in the azo group-containing polyamide is 0.0001 to 1 mole per 1 mole of the vinyl monomer. When the amount of the azo group-containing polyamide used is less than the above lower limit,
It is not preferable because the polymerization rate of the vinyl monomer becomes very slow. On the other hand, when it is more than the upper limit, the number average molecular weight of the synthesized vinyl polymer does not become so large, and it becomes difficult to obtain a copolymer having the characteristics of the vinyl polymer.

The polymerization reaction of the vinyl monomer is initiated by dissolving the azo group-containing polyamide and the vinyl monomer in a solvent and then generating a radical by a known method such as heating or irradiating with light or an electron beam. Polymerization temperature is 30 ℃
As described above, the temperature is preferably in the range of 35 to 150 ° C. When the polymerization temperature is lower than 30 ° C, the polymerization time becomes extremely long. 1
When the temperature is higher than 50 ° C, the decomposition rate of the azo group becomes too fast, and it becomes difficult to polymerize in a stable state. The polymerization time varies depending on the polymerization temperature, but is usually 0.5 hour or more. A known radical initiator, photosensitizer, or the like may be used in combination during the polymerization reaction.

After the completion of the polymerization reaction, the synthesized block copolymer of polyamide and vinyl polymer is removed by a known method such as evaporation of the reaction solvent and then dried.
The reaction solution is poured into a large amount of a poor solvent, or conversely, a poor solvent is added to the reaction solution to precipitate a block copolymer composed of the synthesized polyamide and vinyl polymer, which is filtered and dried. It can be obtained by the method. When a homopolymer of vinyl polymer is produced as a by-product, the vinyl polymer can be removed by a purification method such as extraction or reprecipitation, if necessary.

[0031]

EXAMPLES The present invention will be described in more detail below with reference to examples. The characteristic evaluations described in the examples were performed by the following methods.

1) Measurement of solution viscosity of polyamide Measured with an Ubbelohde viscometer at 25 ° C. using m-cresol as a solvent at a concentration of 0.5 g / 100 ml, and the solution viscosity ηsp / c (unit: ml) / G) was determined. ηsp / c = {(t−t ₀ ) / t ₀ } / c where t: outflow time of solution (sec), t ₀ ; outflow time of solvent only (sec), c; solution concentration (g / ml) )

2) Measurement of amino group concentration Phenol / methanol (4/1; volume ratio) mixed solvent 4
The sample was dissolved in 0 ml, several drops of thymol blue was added as an indicator, and then titrated with 1 / 20N hydrochloric acid at room temperature. The amino group concentration [NH ₂ ] (unit: mol / g) was calculated by the following formula. [NH ₂ ] = (L ₁ −L ₂ ) × f × 10 ⁻⁴ / (2 × S) where L ₁ ; titer of sample solution (ml), L ₂ ; titer of solvent only (ml) , F; 1 / 20N hydrochloric acid factor, S; sample amount (g)

3) Number average molecular weight of polyamide (hereinafter,
"Mn" indicates Mn is the amino group concentration [NH] measured by the method of 2) above.
₂ ] and calculated from the following formula. Mn = 1 / [NH ₂ ]

4) ¹ H-of azo group-containing polyamide and block copolymer composed of polyamide and vinyl polymer
Measurement of NMR Using JEOL EX-270 manufactured by JEOL Ltd., measurement was performed under the following conditions using bisulfate as a solvent. Measurement conditions Measurement frequency: 300 MHz, measurement temperature: room temperature, sample concentration: 5 wt%, standard substance: trimethylsilane

5) Measurement of infrared absorption spectrum (IR) of block copolymer composed of polyamide and polystyrene It was measured by a KBr method using a Fourier transform infrared spectrophotometer 1750 manufactured by Perkin-Elmer.

6) Evaluation of compression-molded film 1 g of a block copolymer composed of polyamide and vinyl polymer dried under reduced pressure at 50 ° C. for 48 hours was sandwiched between FelloW plates, and a compression-molding machine (F-37 manufactured by Shinto Metal Industry Co., Ltd.) was used. Used, and after degassing at 235 ° C, the temperature was 235
Compression molding was performed under the conditions of ℃, pressure of 20 kg / cm ² · G and compression time of 3 minutes. Then, the ferro-plate was taken out, cooled in air, and then taken out of the film for evaluation.

Synthesis Example 1 Azo group-containing polyamide (PA
-1) Synthetic caprolactam 13 parts by weight, 2.2 parts by weight of a nylon salt obtained from equimolar amounts of terephthalic acid and hexamethylenediamine, and 0.15 parts by weight of hexamethylenediamine are charged into an autoclave and, after nitrogen substitution, 240 ° C. Polymerization was carried out at a pressure of 2 atm for 4 hours. After raising the temperature to 250 ° C., the pressure was reduced to atmospheric pressure while maintaining the temperature. Polymerization was further continued for 4 hours under a nitrogen stream. Then, the polymer was taken out, pulverized, Soxhlet-extracted with methanol, and dried to obtain nylon 6 and 6T having two amino end groups.
(T represents a terephthalic acid unit.) Copolymer (hereinafter,
"Nylon 6 / 6T") was obtained. The solution viscosity of the obtained nylon 6 / 6T was 0.87, and the number average molecular weight Mn calculated from the amino group concentration was 9,300.
10 parts by weight of the obtained nylon 6 / 6T 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 benzene and 75 parts by weight of phenol.
While cooling with ice, 15 parts by weight of tetrahydrofuran (THF) in which 0.35 parts by weight of 4,4′-azobis-cyanovaleric acid dichloride (ACPC) was dissolved was added dropwise. After the dropping, the reaction was performed while stirring at 20 ° C. for 2 hours. The reaction solution was poured into a large amount of methanol to precipitate the reaction product, which was then filtered and dried under reduced pressure to obtain an azo group-containing polyamide (hereinafter referred to as "PA-1"). The solution viscosity of PA-1 was 1.40, and amino groups were not measured by titration. Also, in the ultraviolet absorption measurement, absorption of an azo group was observed at 348 nm.

Synthesis Example 2 Azo group-containing polyamide (PA
In the same manner as in Synthesis Example 1 except that 6-aminocaproic acid was used instead of the synthetic caprolactam of -2), nylon 6 / 6T having two amino end groups was obtained. The solution viscosity of the obtained nylon 6 / 6T was 0.85, and the number average molecular weight Mn calculated from the amino group concentration was 9,000. Using this polyamide, an azo group-containing polyamide (hereinafter referred to as “PA-2”) was obtained in the same manner as in Synthesis Example 1. The solution viscosity of PA-2 was 1.38, and amino groups were not measured by titration. Also, in the ultraviolet absorption measurement, absorption of an azo group was observed at 348 nm. Synthesis Example 3 Synthesis of Azo Group-Containing Polyamide (PA-3) 11.3 parts by weight of caprolactam, 0.5 parts by weight of water and 0.27 parts by weight of hexamethylenediamine were charged into an autoclave, and after nitrogen substitution, 240 ° C., pressure 2 Polymerization was carried out 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 the polymerization was further continued for 4 hours under a nitrogen stream. Then, take out the polymer, crush,
Soxhlet extraction with methanol and drying yielded nylon 6 with two amino end groups. The solution viscosity of this nylon 6 was 0.26, and the number average molecular weight Mn calculated from the amino group concentration was 5000. The same procedure as in Synthesis Example 1 was conducted except that 10 parts by weight of the obtained nylon 6 and 0.63 parts by weight of 4,4′-azobis-cyanovaleric acid dichloride (ACPC) were used, and an azo group-containing polyamide ( Hereinafter, "PA-3" was obtained). P
The solution viscosity of A-3 was 1.32, and no amino group was measured by titration. Also, in the ultraviolet absorption measurement, 348
Absorption of the azo group was observed at nm.

Synthesis Example 4 Azo group-containing polyamide (PA-
4) The same method as in the synthesis example except that 2 parts by weight of caprolactam, 13.2 parts by weight of a nylon salt obtained from equimolar hexamethylenediamine and adipic acid, and 0.15 parts by weight of hexamethylenediamine are used. By carrying out, a nylon 6/66 copolymer having two amino end groups was obtained. The solution viscosity of the obtained nylon 6/66 was 0.88, and the number average molecular weight Mn calculated from the amino group concentration was 9,600. Using this polyamide, a azo group-containing polyamide (hereinafter referred to as “PA-
4 ”). The solution viscosity of PA-4 was 1.40, and amino groups were not measured by titration. Also, in the ultraviolet absorption measurement, absorption of an azo group was observed at 348 nm.

Example 1 1 part by weight of PA-1 was mixed with 200 parts of a phenol-methanol mixed solvent (phenol: methanol = 4: 1, volume ratio).
It was dissolved in 1 part by weight at room temperature, and 4 parts by weight of methyl methacrylate was added to the solution. Then, polymerization was carried out at 60 ° C. for 24 hours under stirring in a nitrogen atmosphere. Then, the reaction solution was poured into methanol to precipitate a polymer, which was filtered and dried under reduced pressure. The polymerization yield was 80%. The polymer obtained is a block copolymer of polyamide and poly (methyl methacrylate), in which a signal of nylon 6 / 6T and a signal of poly (methyl methacrylate) are observed by ¹ H-NMR measurement. Was confirmed. Flexible films were obtained from this block copolymer by compression molding.

Comparative Example 1 The procedure of Example 1 was repeated, except that PA-4 was used instead of PA-1. The obtained polymer is a block copolymer of polyamide and poly (methyl methacrylate), in which a signal of nylon 6/66 and a signal of poly (methyl methacrylate) are observed by ¹ H-NMR measurement. Was confirmed. A film was made from this block copolymer by compression molding, but when it was bent, it was fragile and quickly broken.

Example 2 Methyl methacrylate was polymerized in the same manner as in Example 1 except that 2.5 parts by weight of PA-2 and 10 parts by weight of methyl methacrylate were used to obtain a polymer. This polymer is ¹ H
By NMR measurement, a signal of nylon 6 / 6T and a signal of poly (methyl methacrylate) were observed, and it was confirmed that the block copolymer was a polyamide and poly (methyl methacrylate).

Example 3 Styrene was polymerized in the same manner as in Example 1 except that 2.0 parts by weight of PA-3 and 5.5 parts by weight of styrene were used to obtain a polymer. From the IR measurement, absorption of nylon 6 and polystyrene was observed in this polymer, and it was confirmed that the polymer was a block copolymer of nylon 6 and polystyrene.

[0045]

According to the present invention the aliphatic polyamides resulting from lactamide arm and / or ω- amino acids 20 to 10
A block copolymer comprising 0% by weight of a polyamide and a vinyl polymer, the block copolymer containing 20 to 100% by weight of an aliphatic polyamide obtained from lacrum and / or an aminocarboxylic acid, and Polyamide having amino group and general formula (1)

[Chemical 8] (In the formula, X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, and a represents 0 or an integer of 1 to 6.). It can be obtained with good reproducibility by polymerizing a vinyl monomer with an azo group-containing polyamide obtained by a reaction with an azo group-containing dicarboxylic acid halide as a polymerization initiator.

─────────────────────────────────────────────────── ─── Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08G 69/00-69/50 C08F 4/00-4/58 C08F 4/72-4/82 C08F 251 / 00-283/00 510 C08F 283/02-289/00 C08F 291/00-297/08

Claims (2)

(57) [Claims] 1. A lactamide arm and / or 20 to 100 wt% of aliphatic polyamides resulting from the amino acids
And a polyamide having two amino groups and a general formula
(1) [Chemical formula 1] (In the formula, X is a halogen atom, and R ₁ and R ₂ are hydrogen atoms.
Child, an alkyl group having 1 to 6 carbon atoms or a nitrile group
, A represents 0 or an integer of 1 to 6. )
Obtained by reaction with zo group-containing dicarboxylic acid halide
Using azo group-containing polyamide as a polymerization initiator, vinyl mono
A block copolymer comprising a polyamide obtained by polymerizing a mer and a vinyl polymer. Wherein the lactamide arm and / or aliphatic polyamides resulting from aminocarboxylic acids containing 20 to 100 wt%, and polyamide and the general formula having two amino groups (1) ## STR2 ## (In the formula, X represents a halogen atom, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a nitrile group, and a represents 0 or an integer of 1 to 6.). 2. A block copolymer comprising a polyamide and a vinyl polymer according to claim 1, wherein the vinyl monomer is polymerized using an azo group-containing polyamide obtained by reaction with an azo group-containing dicarboxylic acid halide as a polymerization initiator. Manufacturing method.