JPS59202220A - Production of copolyamide - Google Patents

Abstract

PURPOSE:To obtain a copolyamide excellent in heat resistance, oil resistance, etc., by reacting a hydrogenated, diene-containing polymer having a specified group with a polyamide having a group capable of reacting with the specified group to form an amide bond. CONSTITUTION:A hydrogenated, diene-containing polymer having a functional group such as caboxyl group, carboxylic acid-derived group or amino group on its terminals and/or side chains is prepared by hydrogenating a diene-containing polymer such as polybutadiene or polyisoprene and introducing carboxyl groups, carboxylic acid-derived groups or amino groups thereinto. The produced hydrogenerated polymer is reacted with a polyamide terminated with amino groups, carboxyl groups or carboxylic acid-derived groups which are capable of reacting with the above functional groups to form amide bonds, e.g., nylon 6 or nylon 12, to obtain the purpose copolyamide.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hydride of a diene-containing polymer having a carboxyl group, a carboxylic acid derivative group, or an amino group at the terminal and/or side chain, and an amide group, a carboxyl group, which can form an amino bond with the functional group. The present invention relates to a method for producing a cocondensation product with a polyamide having a terminal group or a carboxylic acid derivative group, and more specifically, a method for producing a copolyamide with well-balanced properties such as heat resistance, oil resistance, and rubber elasticity.

Conventionally, attempts have been made to copolymerize various monomers to improve the flexibility, water absorption, and other properties of polyamides such as nylon 6 and nylon 6.6.

For example, in JP-A No. 57-57720, in order to improve the flexibility of polyamide and obtain polyamide with low water absorption, polybutadiene, etc. having carboxyl groups or amino groups at both ends, was heated at 180°C to 250°C. A method of polymerizing under temperature conditions with a polyamide having a molecule i of 20,000 or less to form a copolyamide resin is disclosed. However, even when copolymerized at relatively low humidity, polybutadiene is easily crosslinked, and the resulting copolyamide has insufficient heat stability and weather resistance.

Similarly, JP-A No. 57-149529 exemplifies a block copolymer produced from a telegyric diene polymer containing a carboxyl group or a carboxylic acid ester group and a polyamide; Polyamide has insufficient heat stability and weather resistance.

On the other hand, JP-A No. 57-151622 discloses a copolymerized polyamide resin obtained by copolymerizing a polyamide component and a hydrogenated polybutadiene component. Expected to improve stability. However, this publication only discloses a method of polycondensing by simultaneously introducing single b1 compounds constituting the polyamide component, such as 12-aminododecanoic acid and hexamethylene diamine, together with hydrogenated polybutadiene, which has carboxyl groups at both ends. However, the copolyamide obtained by this method has polyamide segments ranging in length from long to short, which poses an obstacle in quality design according to required performance.

As a result of studies in view of the above-mentioned circumstances, the present inventors discovered that polyamides having polycondensed amino groups, carboxyl groups, or carboxylic acid-derived groups at their terminals, and carboxyl groups and carboxylic acid-derived groups that can form amide bonds with the functional groups. By copolymerizing a hydride of a diene-containing polymer having a group or an amino group at the terminal and/or side chain, a copolyamide with improved flexibility, rubber elasticity, toughness, impact strength, water absorption, etc. can be obtained. The present invention was achieved based on the discovery that

That is, the present invention relates to a method for producing a copolyamide, which is characterized by reacting a hydrogenated diene-containing polymer having a carboxyl group, a carboxylic acid derivative group, or an amino group at the terminal and/or side chain with a polyamide.

The hydride of the diene-containing polymer having a carboxyl group, a carboxylic acid derivative, or an amine group at the terminal and/or side chain used in the present invention can be obtained by hydrogenating the diene-containing polymer by a conventionally known method, and then hydrogenating the diene-containing polymer by a conventionally known method. It is prepared by introducing a derivative group or an amine 7 group. Examples of the diene-containing polymer used as a raw material include 1. Ro-butadiene, 2,3-dimethylbutadiene, 1,3-
There are homopolymers or copolymers obtained by polymerizing at least one monomer selected from pentadiene, chloroprene, and isoprene, among which conjugated diene polymers, particularly polybutadiene and polyisoprene, are preferably used.

Diene-containing polymers include polymers using catalysts such as radicals, cations, anions, and coordinating anions, and can be used without particular limitation in the present invention. For example, a living anionic polymerization method using an alkali metal-based initiator, a radical polymerization method using a peroxide as an initiator, or a coordination anionic polymerization method using a Ziegler type catalyst. There is a way to do it. It is also possible to adopt a method in which a small amount of other monomer is copolymerized together with the diene monomer, for example, in a proportion of 40 mol % or less of the constituent monomers. Other copolymerizable monomers include styrene, α-methylstyrene, 0
Examples include vinyl monomers such as - or p-vinyltoluene, vinylxylene, acrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, and vinylpyridine.

Furthermore, linear, branched, and branched polymers in which the same or different living polymers are coupled together using a polyfunctional coupling agent such as methylene chloride, xylylene dibromide, terephthalic acid dichloride, silicon tetrachloride, etc. in the presence of the initiator; Although radial diene-containing polymers can also be used, linear ones are usually preferred.

To hydrogenate diene-containing polymers, methods well known to those skilled in the art are employed. As the hydrogenation catalyst, catalysts such as nickel, diatomaceous earth, Raney nickel, finely ground platinum, palladium, and carbon-supported palladium can be used. The conditions for hydrogenation are not particularly limited, and are, for example, atmospheric pressure to about 300 atm, typically 5 to about 200 atm, room temperature to about 620°C for about 0.1 to about 24 hours, preferably about Hydrogenation can be carried out for 0.2 to about 10 hours.

Hydrogenated diene-containing polymers are preferably those whose average degree of unsaturation (residual rate of unsaturated bonds determined from iodine value) has been reduced to 30% or less of its original value, especially those whose average degree of unsaturation has been reduced to 30% or less of its original value. Preference is given to those whose strength is reduced to 20% of the original value.

Methods well known to those skilled in the art are employed to introduce carboxyl groups, carboxylic acid-derived groups or ami-7 groups into the hydrides of diene-containing polymers.

For example, in order to obtain a hydrogenated product of a diene-containing polymer having a carboxyl group or a carboxylic acid derivative group at the terminal, for example, a living polymer of a diene compound is reacted with carbon dioxide, and then hydrogenated. Examples include a method in which a diene compound is radically polymerized using an initiator having a carboxyl group or a carboxylic acid derivative group such as (4-cyanovaleric acid), and then hydrogenated. A method of introducing an acyl halide group by reacting the polymer with a compound having a plurality of acyl halide groups using a hydride of a polymer as a raw material, a method of introducing a carboxyl group by hydrolyzing the acyl halide group, and a method of introducing a carboxyl group by hydrolyzing the acyl halide group. Examples include a method in which a carboxylic acid ester group is introduced by further reacting an alcohol such as methanol or phenol with a halide group.In the above reaction,
When a diene-containing polymer having a hydroxyl group is used as a raw material, a method of introducing a carboxyl group or a carboxylic acid-derived group and then hydrogenating the polymer may also be adopted.

To obtain a diene-containing polymer having a hydroxyl group as a raw material, for example, a method of reacting a living polymer of a diene compound with ethylene oxide, etc.
(There is a method in which a diene compound is radically polymerized using 4-cyano-n-amylalcoholne as an initiator.

Examples of the compound having a plurality of acyl halide groups used in the above reaction include phosgene and a dicarboxylic acid dihalide represented by the following general formula (1).

However, in general formula (1), there are compounds in which X is a halogen, R is a divalent hydrocarbon group or a divalent hydrocarbon group having an ether or thioether bond in the main chain, and m is zero or 1. Examples of divalent hydrocarbon groups include alkylene groups having 1 to 10 carbon atoms, phenylene groups, alkyl-substituted phenylene groups, diphenylene groups, and naphthalene groups, and halogens include chlorine and bromine. There are divalent hydrocarbon radicals with ether linkages of atoms.

Examples of such dicarboxylic acid halides include oxalic acid dichloride, oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, sebacic acid dichloride, cyclohexanedicarboxylic acid dichloride, terephthalic acid dichloride, and isophthalic acid dichloride. Examples include dichloride, phthalic acid dichloride, xylene dicarboxylic acid dichloride, 2,6-naphthalenedicarboxylic acid dichloride, and bis(4-carboxyphenyl ether dichloride).

Other ways to introduce carboxyl groups or carboxylic acid derived groups into monos with these groups? An example is a method of graft copolymerizing - to a hydride of a diene-containing polymer.

Monomers having a carboxyl group or a carboxylic acid derivative group include, for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, chloromaleic acid, -itaconic acid, or derivatives thereof, such as methanol, phenol esters, m-water, etc. There are acid anhydrides such as maleic acid.

These monomers may be added to the hydride of the diene-containing polymer as a carboxylic acid derivative, or the carboxyl group may be converted to the corresponding derivative after addition of the carboxylic acid or its anhydride.

Graft copolymerization of a monomer having a carboxyl group or a carboxylic acid-derived group onto a hydride of a diene-containing polymer is carried out with both in a molten state or in a solution state, with or without the use of a radical initiator.

In addition, methods for introducing amino groups include a method in which the hydroxyl groups of the diene-containing polymer into which the hydroxyl groups have been introduced are cyanoethylated with acrylonitrile and then hydrogenated, or the hydroxyl groups are treated with a halogenating agent such as thionyl chloride. A method in which this is converted into a halide and further aminated with liquid ammonia or an amidide of an alkali metal, or a living polymer of a diene compound is reacted with para-bromomethylnitrobenzene to introduce a nitro group at the terminal, and hydrogen For example, how to During this hydrogenation, the diene-containing polymer can also be hydrogenated simultaneously.

Also exemplified is a method in which a hydride of a diene-containing polymer having a terminal carboxyl group synthesized by anionic polymerization or radical polymerization is reacted with a diamino compound such as hexamethylene diamine.

Also exemplified is a method in which the hydride of the diene-containing polymer into which the hydroxyl group has been introduced is reacted with a compound having a plurality of acyl halide groups to introduce an acyl halide group, and then a diamino compound such as hexamethylene diamine is reacted. The compound having a plurality of acyl halide groups is the same as the phosgene or the carboxylic acid acyl halide represented by the general formula (I), and the diamino compounds include, for example, ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, etc. Examples include aliphatic diamines, alicyclic cyamines such as cyclohexane diamine, piperazine, and inphorone diamine, and aromatic diamines such as p-phenylene diamine, m-phenylene diamine, and baraxylylene diamine.

Diene-containing polymers having a carboxyl group and their hydrides, or diene-containing polymers and their hydrides that are commercially available as raw materials for introducing polar groups selected from carboxyl groups, carboxylic acid-derived groups, and ami-7 groups. Polybutadiene polymers or copolymers having hydroxyl or carboxyl groups as well as their hydrides can be used, for example N15s
OPB G-1000 Nippon Soda 2000 3000 〃 G knee 1000 tt2000 -3000 tt 〃(!-1QQQ tt 〃 C knee 1000 //Polytail H Mitsubishi Kasei〃 HA 〃Hy
car-CTB Gutudrich C! T
BN tt // CT
BN-X ttTelagen C
T General Tire Eutarez CT
Examples include L. Phillips.

In the present invention, a preferable hydride of a diene-containing polymer having a carboxyl group, a carboxylic acid derivative group, or an amino group at the end and/or side chain is a polymer having a carboxyl group at the end of the hydride of the diene-containing polymer. be.

Furthermore, a preferred example of a hydrogenated diene-containing polymer having a terminal carboxyl group has a molecular weight of about 300 to about 1.
00,000, particularly preferably about 500 to about 50,000, and the carboxyl group has a hydride width of about 0.00,000, particularly preferably from about 500 to about 50,000, and the carboxyl group has a hydride width of about 0.00,000, particularly preferably about 500 to about 50,000.
0.02 meq/g to about 7 meq/g, especially about 0.04 meq/g to about 4 meq/g.

Carboxyl group, carboxylic acid derivative group or ami7 at the end
Polyamides having groups can be prepared by known methods. Such methods include, for example, polycondensation of lactams, polycondensation of amino acids, or polycondensation of dicarboxylic acids and diamines.

These polycondensation reactions are carried out in the presence of an excess of dicarboxylic acid, dicarboxylic acid derivative or diamine.

These excess dicarboxylic acids, dicarboxylic acid derivatives, or diamines act as chain limiters, so by appropriately selecting the amount of dicarboxylic acids, dicarboxylic acid derivatives, or diamines, the length of one polymer chain, that is, the average molecular weight of the polyamide can be adjusted. can do.

Among the compounds used as chain limiters, diamines include aliphatic, alicyclic and aromatic diamines, such as ethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, cyclohexanediamine, piperazine, isophoronediamine, p-phenylene. Examples include diamine, m-phenylenediamine, and p-xylylenediamine. The dicarboxylic acids used as chain limiters are aliphatic, cycloaliphatic and aromatic dicarboxylic acids, such as adipic acid, pimelic acid, sebacic acid, toticandioic acid, cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, etc. .

Further, dicarboxylic acid derivatives used as chain limiters include esters and acid chlorides of the above dicarboxylic acids. The polycondensation reaction is usually carried out in the melt without a solvent, but it can also be carried out at the interface by dissolving the dicarboxylic acid chloride and the diamine in an organic solvent or in two or more solvents that are immiscible with each other. It is possible. Further, an excess dicarboxylic acid, dicarboxylic acid derivative, or diamine as a chain limiter can be added at the initial stage, intermediate stage, or final stage of the reaction. It is also possible to prepare a polyamide having the functional group at the end by adding an l-limiting agent to a high molecular weight polyamide and carrying out the reaction.

The polyamide mentioned here can be produced, for example, by condensing an aliphatic, alicyclic, or aromatic dicarboxylic acid with an aliphatic, aliphatic, or aromatic diamine. These polyamides can also be produced from the amine and acid-forming derivatives and amine-forming derivatives, such as esters, acid chlorides, amine salts, and the like.

Typical dicarboxylic acids used to produce polyamides include adipic acid, pimelic acid, superric acid, sebacic acid, dodecanoic acid, cyclohexane diamic acid,
There are terephthalic acid and isophthalic acid. On the other hand, representative diamines include hegisamethylene diamine, octamethylene diamine, cyclohexane diamine, isophorone diamine, piperazine, and phenylene diamine. Furthermore, polyamides can also be produced by self-condensation of lactams. Examples of polyamides include polyhexamethylene adivamide (nylon 6.6), polyhexamethylene azelamide (nylon 6.9), polyhexamethylene adipamide (nylon 6.10) and polyhexamethylene Dodecanoamide (nylon 6.12L polybis(4-aminocyclohexyl)methandodecanoamide, or polyamide produced by ring opening of lactams or condensation of aminocarboxylic acids, i.e. polyε
- caprolactam (nylon 6), poly-ω-laurinlactam (nylon 12) or poly-11-aminoundecanoic acid (nylon 11). It is also possible to use polyamides produced by polymerization of at least two amines or acids used to produce the polyamides mentioned above, for example polymers made from adipic acid and isophthalic acid and hexamethylene diamine. .

It is also possible to use blends of polyamides, such as mixtures of nylon 6.6 and nylon 6. The integrated polyamides used in the present invention are preferably polyhexamethylene adipamide (nylon 6.6), polyhexamethylene sebaamide (nylon 6.10), polyε-caprolactam (nylon 6), polyω - laurinlactam (nylon 12) and poly-11-aminoundecanoic acid (nylon 11). 7 amino groups at the end,
Preferred examples of these polyamides having carboxyl groups or carboxylic acid derived groups have a molecular weight of about 600 to about i
oo, ooo, particularly preferably about 500 to about 50,000.

A hydride of a diene-containing polymer having a carboxyl group, a carboxylic acid derivative group, or an amide 7 group at the terminal and/or side chain, and an amide bond capable of forming an amide bond with the functional group;
Polyamides having a carboxyl group or a carboxylic acid derivative group at the end are melt-mixed under heating to obtain a copolyamide in which the hydride segment of the diene-containing polymer and the polyamide segment are linked by an amide bond.

Melt mixing under heating can be carried out in the presence of an organic diluent, but is usually carried out in its absence.

It is not particularly necessary to add a catalyst during melt mixing. In addition, water, alcohol, etc. produced as the reaction progresses can be naturally distilled off through inert gas such as nitrogen, or
Alternatively, it can be distilled off under reduced pressure.

Further, during melt mixing, other additives such as colorants, stabilizers, inorganic fillers, organic fillers, etc. can be added at the initial stage, intermediate stage, or final stage.

The charging ratio of the hydride of the diene-containing polymer and the polyamide to be melt-mixed is not particularly limited, and depends on the molecular weight of both components used, the hydride of the diene-containing polymer and the carboxyl group in the polyamide, It can be changed as appropriate depending on the concentration of carboxylic acid derivative groups or amine groups, heating temperature, types and proportions of other additives present. Usually, the weight ratio of diene-containing polymer to polyamide is from about 6/97 to about 9715, particularly preferably from about 10,790 to about 90/10.

For melt-mixing the mixture of both components (or even other additives), conventionally known devices such as a stirred pod reactor, a screw or twin-screw extruder, a Banbury mixer, a Nigu, a mixing roll, etc. are used. These kneading devices can be used alone or in combination.

The reaction temperature is usually higher than the melting point of the hydride of the diene-containing polymer and the polyamide, but it is also possible to complete the reaction in the solid phase after mixing both components using the above-mentioned kneading device.

For example, when using a hydride of a diene-containing polymer having a terminal carboxyl group and a polyamide having a terminal amine 7 group, the temperature is generally about 150 to about 370°C, and preferably about 200 to about 550"C. is desirable.

If it is less than 150°C, there are disadvantages such as the polymerization rate being too slow, and if it exceeds 70'C, there are disadvantages such as side reactions such as decomposition and crosslinking.

The time required for the reaction is usually about 1 hour to about 10 hours.

In the production method of the present invention, it is not always necessary to react all the components, and the reaction may be completed in such a manner that unreacted diene-containing polymer hydride and/or polyamide remain. In this case, unreacted substances can be separated and removed if necessary.

The copolyamide obtained by the present invention has excellent performance with well-balanced properties such as heat resistance, oil resistance, and rubber elasticity, and can be used alone or in combination with other additives.

The copolyamides provided herein have a ratio of the total weight of the hydride segments of the diene-containing polymer to the total weight of the polyamide segments from about 6/97 to about 97/3, more particularly about 10,790. or about 907
It is desirable to set it to 10.

If the weight ratio is less than 6/97, elongation and rubber elasticity will be insufficient, and if the weight ratio exceeds 97/3, mechanical strength and heat resistance will be insufficient.

The copolymer provided by the present invention is also suitable for use in blending with conventional polyamides such as nylon 6 in order to modify their properties. The copolymer provided by the present invention can be blended with polyamides together with various polymers, such as additives conventionally blended as modifiers for polyamides, such as hydrogenated polybutadiene, to improve modification effects, such as impact resistance. There are uses for expressing it.

When blending in these uses, an organic diluent can be added as required.

The organic diluent in the present invention has the property of dissolving or swelling the diene-containing polymer hydride or polyamide, does not adversely affect the mixed components, and can be easily removed from the yarn by drying or other methods. liquid, such as benzene, toluene, xylene, cyclohexane, n
-Hydrocarbons such as octane, ethylbenzene, cumene, methylcyclohexane, and ethylcyclohexane, ketones such as methyl isobutyl getone, N-methylformamide, N, Jtl'-dimethylpolamide, N,
N-methylacetamide, dimenalsulfoxide, tetramethylurea, acetonitrile, nitrobenzene, pyridine, N-methylpyrrolidone, γ-butyrolactone,
Examples of hexamethylphosphoramide include afrotic polar solvents, halogenated hydrocarbons such as trichloroethane and tetrachloroethane, and ethers. etc. are suitable.

In addition, the additives in the present invention include colorants, stabilizers, inorganic fillers, organic fillers, etc., and more specifically, dyes such as nitrosine, cadmium sulfide, phthalocyanine, carbon Examples include pigments such as black, titanium oxide, etc., antioxidants and heat stabilizers such as stabilizers phenol, hydroquinone, thioether, phosphites and substituted products and combinations thereof, resorcinol, salicylate, benzotriazole, Ultraviolet absorbers such as benzophenone, higher fatty acids such as stearic acid and montanic acid, and hiso (7J
Various lubricants and mold release agents including derivatives such as metal salts, esters, Hafestel, stearyl'T alcohol, and stearamide, flame retardant aids such as antimony oxide, sodium dodecylbenzenesulfonate, polyalkylene glycols, etc. Examples include antistatic agents, crystallization promoters, silane coupling agents, etc. Inorganic fillers include fibrous materials such as glass fiber, carbon fiber, and ceramic fiber, plate-like materials such as mica, Examples include granular and powdered materials such as glass beads, silica, barium titanate, hydrotalcite, and zeolite.

Organic fillers include fluororesins such as Teflon, wholly aromatic polyamide resin fibers such as Kevlar, and phenol resin fibers. The blending amount of these additives is determined as appropriate, but when blending fillers such as inorganic fillers and organic fillers, about 0.1 to about 200 parts by weight per 100 parts by weight of the copolyamide, Especially about 1 to about 15
It is preferable to melt and mix at a ratio of 0 parts by weight.

Polymers used as additives include polybutadiene, polyisoprene, or their (7) hydrides, ethylene propylene rubber, ethylene propylene diene rubber, styrene butadiene rubber, hydrogenated styrene butadiene rubber, or acrylic acid, male anhydride. Modified rubber obtained by graft copolymerization with acids, etc., polyethylene, polypropylene, ethylene-1-butene copolymer, ethylene-4-methyl-1-pentene copolymer, 4-methyl-1
- Extensible olefin resins such as penten-decene copolymers, or ionomer resins such as bolastomers, polymethacrylic acid, acrylic resins such as ethylene-ethyl acrylate copolymers, and zinc salts of ethylene-methacrylic acid copolymers , ethylene-vinyl acetate copolymer, polyacetal, polycarbonate, polysulfone, polyphenylene oxide, fluororesin, phenol resin, melamine resin, unsaturated or saturated polyester resin, silicone resin, epoxy resin and the like.

The amount of the above-mentioned additives to be blended is determined as appropriate, taking into account the various properties of the polyamide, if necessary.

The compositions obtained by these methods can be processed by various melt molding methods,
For example, it can be used for various molded products, such as industrial parts, by methods such as injection molding and extrusion molding.

Next, the present invention will be explained with reference to Examples.

In the Examples, the following methods were used for molding and evaluating the physical properties of the products.

Molding: The dried copolymerized polyamide was molded using a press molding machine at a molding temperature of 240°C and a molding pressure of 501 g/cnr2.
Under nitrogen atmosphere conditions, 11X 11 X Ooo 5
01L (A) and 5 x 5 x O53Gl (B)
A sheet having the shape of was prepared.

Tensile test: Length 5 C17r from sheet (A),
A tumble-shaped test piece with a parallel portion width Q of 5 CM was punched out and tested using a tensile tester model 1122 manufactured by Instron at 23° C. and a crosshead speed of 50 mm/min.

Permanent strain: Determined from the hysteresis curve of one tensile test. That is, 50mm/mi? The specimen was stretched 100% at a crosshead speed of 1, then the crosshead was lowered to the pre-test position at the same speed, and the sample was further stretched to 100%. In this test, the strain remaining during the second stretching was defined as permanent strain.

Glass transition point Tg: Measured using a dynamic mechanical analyzer (DMA) model 981 manufactured by DuPont.

屹; Point Tm: Manufactured by Birkin Elmer, differential scanning thermal I
It was measured using a J-meter Motel DSO-2.

Vi cat softening point: Using the sheet of (E), J process 5
Measured according to K7206.

Hardness = (B) (7) Using : rx
Measured according to s K6301.

Composition ratio of copolymer: Calculated by quantifying the weight of nitrogen contained in the copolymer using elemental analysis.

Intrinsic viscosity of copolymer: Measured in m-cresol/toluene (1/iwt ratio) solution at 30°C.

Molecular weight of polyamide: Calculated by quantifying terminal amino groups and carboxyl groups. Ami7 group was obtained by dissolving polyamide in m-cresol and using thymol blue as an indicator. INp-) Titrated with luenesulfonic acid m-cresol solution. The carboxyl group was determined by converting the polyamide into benzylalco/' mN, using phenolphthalein as an indicator, and adding 0.0 mN to the polyamide. Titrated with IN NaOH/benzyl alcohol solution.

Example 1 370 g of 6-aminocaproic acid and 60.76 g of hexamethylene diamine were introduced into a stirred reactor.

The reaction mixture was heated to 200-260° C. for 5 hours and further heated at 260° C. under immHg vacuum for 4 hours to obtain a polyamide with an average molecular weight of 1500 and a terminal amine 7 group. Polyamide 2 with an amine group at the end
6.3 g (18 mmol) and 41.9 g (18 mmol) of hydrogenated polybutadiene having a carboxyl group at the terminal (manufactured by Nippon Soda Co., Ltd., trade name Nko 5SO-PB C-nee 1000, number average molecular weight determined from acid value: 2500)
) was introduced into a reactor equipped with a stirrer. The reaction mixture was placed under a nitrogen atmosphere and heated until the temperature reached 260°C.

The mixture was then placed under high vacuum (0.7 mmHg) and the reaction continued for 7 hours with stirring. By continuing the reaction for 7 hours, a very smooth melt was produced. The melt was cooled and powdered. Unreacted hydrogenated polybutadiene and polyamide contained in this crudely produced polymer were extracted with toluene and formic acid, respectively, to isolate only the copolymerized polyamide. The ratio of the copolyamide to the crude polymer was 50%. As a result of examining the composition of this copolymer by elemental analysis, the weight composition ratio of the hydrogenated polybutadiene component and the polyamide component was 60/40.

Further, the intrinsic viscosity was 1.0ag/g, and the melting point was 197°C. Table 1 shows the results of measuring the physical properties of the press sheet.

Example 2 Using 104.94 g of 6-aminocaproic acid and 7.26 g of hexamethylene diamine, a polyamide having an average molecular weight of 125 oo and terminal amine groups was obtained according to Example 1. Polyamide 36.8 having an amino group at this end
6 g (15 mmol) and 34.92 g (15 mmol) of hydrogenated polybutadiene (Cny 1000) having an average molecular weight of 12,300 and having a carboxyl group at the end were introduced into a reactor equipped with a stirrer. The reaction mixture was placed under a nitrogen atmosphere and heated until the temperature reached 260°C.

The mixture was then placed under high vacuum (1 mmng) and the reaction continued for 6 hours with stirring.

The product obtained was processed according to Example 1.

The results are shown in Table 1.

Example 3 According to Example 1, using 104.94 g of 6-amide/capron and 4.05 g of hexamethylene diamine, a polyamide having an average molecular weight of 3800 and having amide 7 groups at the ends was obtained. 42.14 g of polyamide having 7 amino groups at the end and polybutadiene (C-nee 1000) having an average molecular weight of 2300 and a carboxyl group at the end.
25.61 g were introduced into the reactor using a stirrer. The reaction mixture was placed under nitrogen atmosphere and heated until the temperature reached 260°C. The mixture was then placed under high vacuum (1 mmHg) and the reaction continued with stirring for 6 hours.

The product obtained was processed according to Example 1.

Example 4 Anhydrous THF 700 in a reactor equipped with a condenser and a crab stirrer
Me, 130 g of isoprene was charged, and a THF solution containing 6.28 g of sodium naphthalene was added dropwise with strong stirring, followed by reaction at room temperature under an argon atmosphere for 5 hours. Then,
While cooling the reactor in a water bath and bubbling CO2,
C, the reaction was continued for 2 hours and then for 12 hours at room temperature. The reaction solution was precipitated into a large excess of MeOH to isolate polyisoprene having carboxyl groups at the ends. As a result of GPC measurement using THF solvent, the number average molecular weight was approximately 6200 in terms of polyisoprene. Further, the acid value was '58.

30g of this polyisoprene, 7oomg of cyclohegisan
, 15g of palladium on carbon carrier (5% palladium supported) was placed in an autoclave, and hydrogen pressure was 1o otcg.
/cm' at 140'C for 14 hours. The reaction solution was filtered and washed with water, and then precipitated in methanol to obtain hydrogenated polyisoprene having carboxyl groups at the ends. The iodine value of this hydrogenated polyisoprene was 14.

The reaction was carried out under the same conditions as in Example 1, except that hydrogenated polyisoprene having carboxyl groups at both ends synthesized in this way was used instead of hydrogenated polybutadiene C-1ooo having carboxyl groups at both ends. went. The results are shown in Table 1.

Example 5 15.7 g (6.3 mmol) of the polyamide used in Example 2 with an average molecular weight of 2500 and having 7 amino groups at the end
) and 29.8 g (6,5
mmol) was introduced into the reactor using a stirrer. The reaction mixture was heated under a nitrogen atmosphere until the humidity reached 260°C. The mixture was then placed under high vacuum (1 mmHg) and the reaction continued with stirring for 6 hours.

? The purified product was processed according to Example 1.

As a result, the copolymer yield of the obtained copolyamide was 53%. In addition, the diene-containing polymer hydride/polyamide composition ratio in the obtained copolyamide was 60/40. Intrinsic viscosity 1.0 (d(?/g), melting point 20
0°C1 elongation at break 340%, permanent set 13%, hardness 8
It was 2.

Claims (8)

[Claims] (1) An amino group, a carboxyl group, or a carboxylic acid that can react with a hydride of a diene-containing polymer having a carboxyl group, a carboxylic acid derivative group, or an amine group at the terminal and/or side chain and the functional group to form an amide bond. A method for producing a copolyamide, which comprises reacting the polyamide with a polyamide having a derivative group at the end. (2) As a hydrogenated product of a diene-containing polymer having a carboxyl group, a carboxylic acid derivative group, or an amine group at the terminal and/or side chain, the average degree of unsaturation is the average degree of unsaturation of the diene-containing polymer before hydrogenation. The manufacturing method according to claim (1), characterized in that the amount is reduced to 30% or less. (3) Carboxyl group, carboxylic acid derivative group or amide 7
Claim (1) or (1), wherein the hydride of a diene-containing polymer having a group at its terminal and/or side chain is a hydride of a diene-containing polymer having a carboxyl group at its terminal. The manufacturing method described in section 2). (4) The molecular weight of the hydride of the diene-containing polymer having a carboxyl group at the end is 300 to 100.000.
The manufacturing method according to claim (3), characterized in that: (5) Polyamides having amino groups, carboxyl groups, or carboxylic acid-derived groups at the ends include polyhexamethylene adipamide (nylon 6.6), polyhexamethylene sebaamide (nylon 6, io), polyε- Claim No. 1 characterized in that it is caprolactam (nylon 6), poly-ω-laurinlactam (nylon 12) or poly-11-aminoundecanoic acid (nylon 11).
The manufacturing method described in ). (6) Claims (1) or (5) characterized in that the polyamide having an amine group, a carboxyl group, or a carboxylic acid-derived group at its terminal has a molecular weight of 600 to 100,000. Manufacturing method described. (7) Claim No. 3, characterized in that the ratio of the total weight of the hydride segments of the diene-containing polymer to the total weight of the polyamide segments is from 3/97 to 97/6. 4), the manufacturing method according to any one of (5) and (6). (8) A hydride of a diene-containing polymer having a carboxyl group, a carboxylic acid derivative group, or an amine group at the end and/or a side chain, and an amino group, a carboxyl group, or a carboxylic acid derivative group that can form an amide bond with the functional group at the end. 0.1 to 20 parts of filler per 100 parts of copolymerized polyamide obtained by reacting with polyamide having
A method for producing a copolyamide according to claim (1), characterized in that melt mixing is carried out at a ratio of 0 parts by weight.