JPH0513166B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to hydrophilic polyamide elastomers. Polyether ester amide, in which a polyamide segment and a polyether ester segment are bonded together, is known as a hydrophilic polyamide (Japanese Patent Application Laid-Open No. 159586/1986). This polyether ester amide uses poly(alkylene oxide) glycol in the polyether ester segment, so it is a polymer that exhibits considerable flexibility and also has some degree of hydrophilicity, but it is used in fields that require even more hydrophilicity. When applied to , the hydrophilic ability is insufficient, and the mechanical strength, especially the breaking strength, is insufficient. Therefore, the present inventors have developed a polyether ester amide that has at least the same flexibility as the known polyether ester amide.
Moreover, as a result of intensive studies aimed at obtaining a hydrophilic polyamide elastomer with further improved hydrophilicity and mechanical strength, the present invention was achieved. That is, the present invention provides a polyamide derived from an aliphatic dicarboxylic acid having 4 to 10 carbon atoms (component a), an aliphatic diamine having 4 to 6 carbon atoms (component b), and a diamine having piperazine or a piperidine ring (component c). Poly(alkylene oxide) with unit (A unit) 5-70% by weight and number average molecular weight 250-4000
A polyether ester amide consisting of glycol (d component) and 95 to 30% by weight of polyether ester units (B units) derived from a dicarboxylic acid having 4 to 20 carbon atoms (e component), in which the c component is b
Contains 1 to 70 mol% based on the total amount of component and c component, each unit is present in the polymer in a statistical distribution depending on the copolymerization ratio, and in orthochlorophenol,
Relative viscosity (ηr) measured at 25℃ and 0.5% concentration is 1.6
to 1.9, particularly a hydrophilic polyamide elastomer in which a part or all of the basic nitrogen in the c-component ring is converted into a quaternary ammonium salt. The method for producing the hydrophilic polyamide elastomer and the properties and characteristics of the hydrophilic polyamide elastomer according to the present invention will be specifically described below. The polyamide elastomer of the present invention is basically composed of polyamide units and polyether ester units, and the polyamide units are
and component c, and the polyetherester unit is obtained from components d and e. The above component a includes succinic acid, glutaric acid,
Examples include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and particularly preferred are adipic acid, azelaic acid, and sebacic acid. Examples of the component b include tetramethylene diamine, pentamethylene diamine, and hexamethylene diamine, with hexamethylene diamine being particularly preferred. Further, as the c component, piperidine, N,
N'-bis(aminomethyl)piperazine, N,
N'-bis(β-aminoethyl)piperazine, N,
N'-bis(β-aminoethyl)methylpiperazine, N-(aminomethyl)-N'-(β-aminoethyl)piperazine, N,N'-bis(γ-aminopropyl)piperazine, N-(β- aminoethyl)
piperazine, N-(γ-aminopropyl)piperazine, N-(ω-aminohexyl)piperazine,
N-(δ-aminocyclohexyl)piperazine,
N-(β-aminoethyl)-3-methylpiperazine, N-(β-aminoethyl)-2,5-dimethylpiperazine, N-(β-aminopropyl)-3-methylpiperazine, N-(γ-amino propyl)−
2,5-methylpiperazine, 1,4-bis(aminomethyl)piperidine, 1,4-bis(β-aminoethyl)piperidine, 1,4-bis(γ-aminopropyl)piperidine, 1-aminomethyl-4
-(β-aminoethyl)piperidine, 1-(β-aminoethyl)-4-aminomethylpiperidine, 4
-aminomethylpiperidine, 4-(β-aminoethyl)piperidine, 4-(γ-aminopropyl)
Examples include diamines such as piperidine, preferably N,N'-bis(γ-aminopropyl)piperazine, N-(β-aminoethyl)piperazine,
Piperazine, 4-aminomethylpiperidine is used. The poly(alkylene oxide) glycol having a number average molecular weight of 250 to 4,000, which is component (d), includes poly(ethylene oxide) glycol, poly(1,2
- and 1,3-propylene oxide) glycol, poly(tetramethylene oxide) glycol, poly(hexamethylene oxide) glycol, (block or random copolymer of ethylene oxide and propylene oxide) glycol,
(Block or random copolymer of ethylene oxide and tetrahydrofuran) glycol, among others poly(ethylene oxide) glycol, poly(1,2-propylene oxide)
By using glycol and the copolymer glycol described above, it is possible to obtain an elastomer with particularly excellent hydrophilicity. The optimum molecular weight range differs depending on the type of poly(alkylene oxide) glycol, but in the case of poly(ethylene oxide) glycol and the above-mentioned copolymer glycol, 250 to 4000, particularly preferably 350 to 3000, is the range for poly(propylene oxide) glycol. In the case of poly(tetramethylene oxide) glycol, those having a molecular weight in the range of 250 to 2,000, particularly preferably 500 to 1,200 are used, and in the case of poly(tetramethylene oxide) glycol, those having a molecular weight in the range of 250 to 2,500, particularly preferably 500 to 1,500 are used. (e) Ingredients include terephthalic acid, isophthalic acid,
Phthalic acid, naphthalene-2,6-dicarboxylic acid,
Aromatic dicarboxylic acids such as naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethane dicarboxylic acid, sodium 5-sulfoisophthalate, 1,4-cyclohexane dicarboxylic acid, 1,2- Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid, and aliphatic dicarboxylic acids such as succinic acid, oxalic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid (decanedicarboxylic acid). can be mentioned.
In particular, the same dicarboxylic acids as the component a, such as adipic acid, suberic acid, and sebacic acid, are preferred;
Dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, and dodecanedioic acid are also preferably used from the viewpoint of polymerizability, color tone, and physical properties of the polymer. Once the starting materials are prepared, they are subjected to a polymerization reaction, and in order to obtain a polyamide elastomer with specific properties, polyamide units and polyether ester units are separated from each other in the final polyether ester amide. 5-70% by weight preferably 10-60% by weight and 95-30% by weight preferably 90
The starting materials are supplied to the polymerization reaction system so that the proportion is 40% by weight, and component c is contained in an amount of 1 to 70 mol%, preferably 10 to 60 mol%, based on the total amount of components b and c. Note that component a, the combination of b and c, and components d and e are used in substantially equal molar amounts; however, if some of the starting materials are dissipated during the polymerization reaction process, It is not necessary to use strictly equimolar amounts as long as an excess amount is supplied to the polymerization reaction system and the obtained polymer has the above-mentioned copolymerization ratio and does not impair the effects of the present invention described below. Further, components a and b and components a and c may be supplied to the polymerization reaction system in the form of salts. The polymerization reaction proceeds through two operations.
One is a homogenization operation in which the starting materials are fed into a heatable container and heated and stirred to form a transparent homogeneous reaction mixture, and the other is a homogenization operation in which the reaction mixture obtained by the homogenization operation is heated under high vacuum. This is a polymerization operation in which the mixture is heated and stirred at the bottom. In the homogenization operation, the starting materials are homogeneously mixed and at the same time some reaction occurs. Homogenization is carried out at 150-260°C, preferably 180-250°C, under normal pressure for about 20-80 minutes under an inert gas atmosphere,
Polymerization is preferably carried out at 220-290°C in the presence of a polymerization catalyst.
This is carried out by heating at 240-285° C. under high vacuum for 2-7 hours and stirring until a predetermined degree of polymerization is reached. Here, high vacuum is about 15 mmHg or less, preferably 5 mm
It refers to a reduced pressure state of Hg or less, more preferably 1 mmHg or less. Polymerization catalysts include titanium-based catalysts, tin-based catalysts,
Zirconium-based catalysts, hafnium-based catalysts, lead-based catalysts, etc. are used. Furthermore, 4,4'-bis(2,6-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butylphenol), 1,3,5-trimethyl-2,4,6-tris(3,5-di tert-butyl-4-hydroxybenzyl)benzene, tetrakis[methylene-3
Various hinderers such as (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid amide) Dophenols or aromatic amines such as N,N'-bis(β-naphthyl)-p-phenylenediamine and 4,4'-bis(4-α,α-dimethylbenzyl)diphenylamine are added. Further, as a viscosity increasing agent, a polyfunctional compound such as trimesic acid, glycerin, pentaerythritol, etc. may be added to the polymerization reaction system as long as the polyether ester amide does not gel. By the above method, 5 to 70% by weight of polyamide units and 95 to 30% by weight of polyether ester units are combined, and each unit is present in the polymer in a statistical distribution depending on the copolymerization ratio. A hydrophilic ether ester amide containing a specific amount of piperazine or a diamine residue having a piperidine ring and having a relative viscosity (ηr) of 1.6 to 1.9 when measured in orthochlorophenol at 25°C and 0.5%. A copolymer is obtained. However, in order to make the copolymer more hydrophilic, part or all of the basic nitrogen in the ring of component c in the copolymer is converted into a quaternary ammonium salt. Converts to quaternary ammonium salt. Quaternization is obtained by reacting the copolymer with a quaternizing agent. Methods for reacting the quaternizing agent include a method of dissolving and mixing the polyether ester amide and the quaternizing agent in an organic solvent and stirring at a temperature below the boiling point of the solvent, and a method of mixing both at the melting temperature. be. As the quaternizing agent, known agents such as protonic acids and halogenated hydrocarbons can be used. Examples of protonic acids include inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as formic acid, acetic acid, maleic acid, adipic acid, and acrylic acid. Examples of halogenated hydrocarbons include ethyl chloride, butyl chloride, methyl bromide, butyl bromide, and methyl iodide. Among these, organic acids such as acrylic acid, maleic acid, and adipic acid are preferred, and acrylic acid is particularly preferred. The rate of quaternary ammonium salting is appropriately selected depending on the desired hydrophilicity. The polyether ester amide obtained by the above method is obtained from a specific starting material, a specific amount of polyamide units and polyether ester units are copolymerized, and the c component is a specific amount. Since the amount contained in the polyamide unit, this polymer has the following characteristics. (1) Extremely hydrophilic, with low water solubility or water absorption
Shows 200% water absorption. (2) As shown below, it is extremely flexible (tensile modulus), has high strength, and has high rubber-like elasticity (elastic recovery rate, rebound modulus). Breaking strength > 75Kg/cm ² Elongation at break > 200% Tensile modulus 10-1000Kg/cm ² Elastic recovery rate (after 50% elongation) > 40% Repulsion modulus > 40% (3) High transparency. (4) A product with a high degree of polymerization can be obtained by the method described above. The polyether ester amide of the present invention can be molded by any conventional molding method for thermoplastic plastics or rubber, such as injection molding, extrusion molding, compression molding, blow molding, calendering, coating, etc. It can be made into a body. Examples of molded products include photosensitive resin substrates, hygroscopic/water-absorbing fibers, antistatic fibers, hygroscopic foams, conductive composites, separation membranes, medical tubes, and disposable products. The present invention will be explained below with reference to Examples. In the examples, parts mean parts by weight unless otherwise specified. Example 1 11.6 parts of nylon 6.6 salt (AH salt) prepared in advance from hexamethylene diamine and adipic acid, N,
11.2 parts of a pre-prepared salt of N'-bis(γ-aminopropyl)piperazine and adipic acid, 67.6 parts of poly(ethylene oxide) glycol with a number average molecular weight of 600, and 16.45 parts of adipic acid were added to "Irganox" 1098 (antioxidant). 0.20 parts of tetrabutyl titanate catalyst and 0.05 parts of tetrabutyl titanate catalyst were charged into a reaction vessel equipped with a helical ribbon stirring blade, purged with _N2 , heated and stirred at 240°C for 40 minutes to obtain a transparent homogeneous solution, and then subjected to a temperature increase and pressure reduction program. Therefore 260℃,
The polymerization conditions were brought to below 0.5 mmHg. When the polymerization reaction was carried out under these conditions for 5 hours and 30 minutes, a viscous, colorless and transparent molten polymer was obtained. The polymer was discharged onto a cooling belt and pelletized. In this polyetheresteramide (), the diamine having a piperazine ring in the polyamide unit accounts for 42.2 mol% of the total diamine component, and the polyetherester unit accounts for 80% by weight of the total copolymer. The polyamide unit is the same as polyether ester amide (), and four types of polyether ester amide () ~
() was similarly polymerized. Polymerization reactivity of these polymers, 0.5% at 25°C in orthochlorophenol
Table 1 shows the relative viscosity (ηr) measured in terms of concentration, and the results of measuring water absorption to water solubility and mechanical properties of the polymer formed into a 1 mm thick sheet by hot pressing.
Note that () remained liquid and could not be formed into a sheet. In addition, the shore hardness and rebound modulus are values measured by stacking four sheets.

[Table] Example 2 16.9 parts of nylon 6.10 salt pre-prepared from hexamethylene diamine and sebacic acid, 28.1 parts of a pre-prepared salt from N-(β-aminoethyl)piperazine and sebacic acid, with a number average molecular weight of 1000. Polyether ester amide () was polymerized in the same manner as in Example 1 using 51.5 parts of poly(ethylene oxide) glycol and 10.4 parts of sebacic acid. In this polyetheresteramide (), the diamine having a piperazine ring in the polyamide unit accounts for 61.4 mol% of the total diamine component, and the polyetherester unit accounts for 60% by weight of the total copolymer. In addition, the composition and copolymerization amount of the polyether ester unit are the same as that of polyether ester amide (), and the polyamide unit is N-
Polyether ester amide () without copolymerizing (β-aminoethyl) piperazine and polyether ester amide () in which N-(β-aminoethyl) piperazine accounts for 95 mol% of the total diamine component in the polyamide unit are similarly polymerized. did. The physical properties of these polymers were measured in the same manner as in Example 1, and the results are shown in Table 2.

【table】

[Table] This is a comparative example.
Example 3 23.6 parts of nylon 4.6 salt pre-prepared from tetramethylenediamine and adipic acid, salt pre-prepared from 4-aminomethylpiperidine and adipic acid
Polyether ester amide () was polymerized in the same manner as in Example 1 using 11.6 parts of poly(ethylene oxide) glycol having a number average molecular weight of 1000 and 9.2 parts of adipic acid. This polyether ester amide () has a diamine having a piperidine ring in the polyamide unit, which accounts for the total diamine component.
It accounts for 30.6 mol%, and the polyether ester unit accounts for 70% by weight of the total copolymer. In addition, polyether ester amide resins () to () with different poly(alkylene oxide) glycols as shown in Table 3 were prepared by making the copolymerization amount of polyether ester units and the composition of polyamide units similar to those of polyether ester amide ().
was polymerized. Table 3 shows the results of measuring the physical properties of these polymers in the same manner as in Example 1.

【table】

[Table] Example 4 100 parts of polyether ester amide (), 13.9 parts of acrylic acid as a quaternizing agent, and 400 parts of ethyl alcohol were dissolved in a flask at 70°C and reacted. The reaction solution was cast on a Teflon-coated metal plate, the ethanol was evaporated, and then vacuum dried to obtain a transparent film with a thickness of about 0.3 mm.
This film was dissolved by immersion in water at 23°C for 1 day.

Claims (1)

[Scope of Claims] 1. Aliphatic dicarboxylic acid having 4 to 10 carbon atoms (component a), aliphatic diamine having 4 to 6 carbon atoms (component b)
and 5 to 70% by weight of polyamide units (A units) derived from piperazine or a diamine having a piperidine ring (component c), and a number average molecular weight of 250
~4000 poly(alkylene oxide) glycol (d component) and a dicarboxylic acid having 4 to 20 carbon atoms (e
A polyetherester amide consisting of 95 to 30% by weight of polyetherester units (B units) derived from component), and containing 1 to 70 mol% of component c based on the total amount of components b and c. , each unit exists in the polymer in a statistical distribution depending on the copolymerization ratio, in orthochlorophenol, 25°C, 0.5%
Hydrophilic polyamide elastomer with a relative viscosity (ηr) measured in concentration of 1.6 to 1.9. 2 Aliphatic dicarboxylic acid having 4 to 10 carbon atoms (component a), aliphatic diamine having 4 to 6 carbon atoms (component b)
and 5 to 70% by weight of polyamide units (A units) derived from piperazine or a diamine having a piperidine ring (component c), and a number average molecular weight of 250
~4000 poly(alkylene oxide) glycol (d component) and a dicarboxylic acid having 4 to 20 carbon atoms (e
A polyetherester amide consisting of 95 to 30% by weight of polyetherester units (B units) derived from component), which contains component c in an amount of 1 to 70 mol% based on the total amount of components b and c, Each unit exists in the polymer in a statistical distribution depending on the copolymerization ratio, and the relative viscosity (ηr) measured in orthochlorophenol at 25°C at a concentration of 0.5% is 1.6 to 1.9, and c A hydrophilic polyamide elastomer in which some or all of the basic nitrogens in the rings of the components are converted into quaternary ammonium salts.