JPH05320336A - Production of polyamide elastomer - Google Patents

Abstract

PURPOSE:To produce a transparent polyamide elastomer having flexibility and excellent elasticity recovering ability. CONSTITUTION:(A) A polyamide oligomer having 500-5,000 number-average molecular weight obtained from (a) a polymerized fatty acid, (b) azelaic acid/or sebacic acid and (c) a diamine is blended with (B) (d) a polyoxyalkylene glycol having 200-3,000 number-average molecular weight or a mixture of the polyoxyalkylene glycol and an alpha, delta-dihydroxyalkylene glycol having 200-3,000 number-average molecular weight and (e) a 6-20C dicarboxylic acid and subjected to polycondensation.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyamide elastomer. More specifically, the present invention relates to a method for producing a polyamide elastomer which is transparent and has excellent flexibility and elastic recovery ability.

[0002]

2. Description of the Related Art Thermoplastic polyamide elastomers have excellent physical properties such as water resistance, heat resistance, mechanical strength, and low temperature characteristics, and have good moldability, so that they can be used in industrial parts, sheets, hoses, tubes, etc. Is used for.

Known polyamide elastomers are polyether ester amides and polyether amides having polyamide as a hard segment and polyether as a soft segment. Nylon such as 12-nylon or 6-nylon is used as the polyamide component, and currently, mainly 12-nylon type is commercially available.

On the other hand, as the soft segment, polyoxyalkylene glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and α, ω-dihydroxy hydrocarbon are used. Resistance, water resistance,
Polyoxytetramethylene glycol is mainly used from the viewpoints of low temperature characteristics, elastic recovery, mechanical strength and the like. For example, examples of polyamide elastomers using polyoxytetramethylene glycol as a soft segment component include JP-A-50-159586, JP-A-53-104694, and JP-A-53-119997.
JP-A-53-126057 and JP-A-56-650.
26, JP-A-57-119925.

However, nylon 12 polyamide elastomers having polyoxytetramethylene glycol as a soft segment are not always satisfactory in elastic recovery.

In order to improve the flexibility of polyamide elastomers at low temperatures, a polyesteramide composed of a polyamide containing a polymerized fatty acid and a polyester of a polymerized fatty acid and a glycol is disclosed in JP-A-61-69831.
It is proposed in Japanese Patent Laid-Open No. 61-69832. Although these have improved flexibility at low temperatures, they do not have sufficient hot water resistance.

[0007]

[Means for Solving the Problems] As a result of intensive studies to solve the above problems, a polyamide oligomer containing a polymerized fatty acid produced from a polymerized fatty acid, a dicarboxylic acid and a diamine was used. By polycondensing a mixture of oxyalkylene glycol and α, ω-dihydroxy hydrocarbon and dicarboxylic acid, reduction of hot water resistance is suppressed, and a transparent, flexible and elastic recoverable polyamide elastomer is obtained. The present invention has been found out, and the present invention has been completed based on this finding. That is, an object of the present invention is to obtain a polyamide elastomer which is transparent, and has excellent flexibility and elastic recovery ability. The purpose is to (A) (a) a polymerized fatty acid having 20 to 48 carbon atoms, ( b) azelaic acid and / or sebacic acid, (c) a diamine having 2 to 20 carbon atoms, and the weight ratio (a) / (b) of (a) to (b) is 0.3 to 5 0.0 and the number average molecular weight obtained by polycondensation by mixing such that all amino groups are substantially equivalent to all carboxyl groups and polycondensation is 500 to 5.0.
00 polyamide oligomer, (B) (d) polyoxyalkylene glycol having a number average molecular weight of 200 to 3,000 or polyoxyalkylene glycol and α, ω-dihydroxy hydrocarbon having a number average molecular weight of 200 to 3,000. The mixture and (e) a dicarboxylic acid having 6 to 20 carbon atoms are substantially equivalent to all hydroxyl groups with respect to all hydroxyl groups, and the weight ratio of (B) to (A) is (B) / ( A) is mixed so as to be 5/95 to 80/20, and polycondensation is performed so that the melt viscosity at a temperature of 250 ° C. is 5 Pa · s or more.

The details of the present invention will be described below. As the polymerized fatty acid having 20 to 48 carbon atoms used in the present invention, a polymerization obtained by polymerizing an unsaturated fatty acid, for example, a monobasic fatty acid having at least one double bond or triple bond having 10 to 24 carbon atoms. Fatty acids are used. As a specific example,
Examples thereof include dimers such as oleic acid, linoleic acid, and erucic acid.

[0009] Commercially available polymerized fatty acids usually contain dimerized fatty acid as a main component and also contain raw material fatty acid and trimerized fatty acid, but the dimerized fatty acid content is 70% or more,
It is preferably 95% by weight or more, and hydrogenated to reduce the degree of unsaturation. Especially, the pre-pole 10
09, the commercially available products such as PRIPOL 1004 (all manufactured by Unichema) and EMPOL 1010 (manufactured by Henkel) are preferable. Of course, mixtures of these are also used.

Examples of the dicarboxylic acid (b) used together with the polymerized fatty acid include azelaic acid, sebacic acid and a mixture of both, in view of polymerizability, copolymerizability with polymerized fatty acid and physical properties of the obtained polyamide elastomer. Be done.

The diamine used in the present invention is preferably a diamine having 2 to 20 carbon atoms, specifically, ethylenediamine, 1,4-diaminobutane, hexamethylenediamine, nonamethylenediamine, undecamethylenediamine. , Dodecamethylenediamine, 2,2,4-trimethylhexamethylenediamine, bis- (4,4'-
Aminocyclohexyl) methane, diamines such as metaxylylenediamine.

To produce a polyamide oligomer from polymerized fatty acid and azelaic acid and / or sebacic acid and diamine, the weight ratio (a) / (b) of polymerized fatty acid (a) to azelaic acid and / or sebacic acid (b) is used. Is 0.
It was 3 to 5.0 and charged into a reaction vessel in which the three members were sufficiently replaced with nitrogen so that all amino groups were substantially equivalent to all carboxyl groups, and the mixture was heated at 170 ° C to 230 ° C at 0.5 to 0.5 ° C.
React for 1.0 hour and number average molecular weight is 500-5,000
It suffices to stop the reaction when it becomes.

Weight ratio of polymerized fatty acid (a) to azelaic acid and / or sebacic acid (b) (a) /
When (b) is less than 0.3, the obtained polyamide elastomer has insufficient flexibility and elastic recovery ability. Also,
In the following block copolymerization step with polyether, the compatibility of polyamide oligomer and polyoxyalkylene glycol or α, ω-dihydroxy hydrocarbon decreases, and coarse phase separation occurs during polycondensation, resulting in uniform polycondensation. The molecular weight does not increase, the transparency of the obtained polyamide elastomer decreases, and the mechanical strength decreases.
When (a) / (b) exceeds 5.0, the cohesive force of the hard segment is lowered, so that the mechanical strength and the melting point are lowered, which is not preferable.

The number average molecular weight of the polyamide oligomer of the present invention must be in the range of 500 to 5,000. When the number average molecular weight is less than 500, the cohesive force of the hard segment decreases, and the mechanical strength and melting point of the polyamide elastomer decrease. On the other hand, if it exceeds 5,000, as in the case where the polymerized fatty acid content is too low, in the step of block copolymerizing the following polyether, the polyamide oligomer and the polyoxyalkylene glycol or α, ω-dihydroxy hydrocarbon are The compatibility decreases, coarse phase separation occurs during polycondensation, homogeneous polycondensation cannot be performed, the molecular weight does not increase, and the transparency and mechanical strength of the obtained polyamide elastomer decrease.

In the present invention, the above-mentioned polymerized fatty acid,
Polyamide oligomer (A) having a number average molecular weight of 500 to 5,000 produced from dicarboxylic acid and diamine, and polyoxyalkylene glycol or polyoxyalkylene glycol having a number average molecular weight of 200 to 3,000, and α, ω- The mixture (d) of dihydroxy hydrocarbons and the dicarboxylic acid (e) are adjusted so that all carboxyl groups are substantially equivalent to all hydroxyl groups (B), and the weight ratio of (B) to (A). (B) /
(A) is mixed so as to be 5/95 to 80/20 and polycondensed to produce a polyamide elastomer.

The polyoxyalkylene glycol used in the present invention includes polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, a block or random copolymer of ethylene oxide and propylene oxide, ethylene oxide and tetrahydrofuran. Block or random copolymers and mixtures thereof. Polyoxytetramethylene glycol is often used because of the heat resistance, water resistance, mechanical strength and elastic recovery of the obtained polyamide elastomer.

The α, ω-dihydroxy hydrocarbon used in combination with polyoxyalkylene glycol is, for example, a polyolefin glycol obtained by polymerizing olefin or butadiene to form a hydroxyl group at the terminal and hydrogenating the double bond, or hydrogenated. Examples thereof include polybutadiene glycol. Α, ω to polyoxyalkylene glycol
However, when the content of α, ω-dihydroxy hydrocarbon exceeds 80% by weight, the mechanical strength and oil resistance of the obtained polyamide elastomer are lowered. However, it is not preferable.

The number average molecular weight of these polyoxyalkylene glycols and α, ω-dihydroxy hydrocarbons is 20.
It must be in the range of 0 to 3000. When the number average molecular weight is less than 200, the melting point of the obtained polyamide elastomer will be low and excellent physical properties cannot be obtained. On the other hand, when it exceeds 5,000, the compatibility with the polyamide oligomer is reduced, the number of reaction points is reduced, coarse phase separation is likely to occur during polycondensation, and uniform polycondensation cannot be performed. As a result, the molecular weight does not increase, and the transparency and mechanical strength of the obtained polyamide elastomer decrease, which is not preferable.

The dicarboxylic acid used together with the glycol in the present invention is preferably a dicarboxylic acid having 6 to 20 carbon atoms, specifically, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecanedioic acid,
Aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenoxyethanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexyl-4,
Examples thereof include alicyclic dicarboxylic acids such as 4'-dicarboxylic acid. In particular, dicarboxylic acids such as azelaic acid, sebacic acid, terephthalic acid, isophthalic acid and 1,4-cyclohexanedicarboxylic acid are preferably used from the viewpoint of polymerizability and physical properties of polyamide elastomer.

Ratio (B) of hard segment component (A) and soft segment component (B) of the polyamide containing polymerized fatty acid in the polyamide elastomer of the present invention.
/ (A) is selected in the range of 5/95 to 80/20 in weight ratio. If the polyamide component exceeds this range, the flexibility and low-temperature properties of the obtained polyamide elastomer will be impaired, and conversely, if it decreases, the mechanical strength and melting point will decrease, which is not preferable.

In order to produce the polyamide elastomer of the present invention, it is necessary to uniformly polycondense the polyamide oligomer, glycol such as polyoxyalkylene glycol, and dicarboxylic acid without causing coarse phase separation. However, polymerized fatty acid and azelaine are required. Since the polyamide oligomer containing the polymerized fatty acid of the present invention obtained from acid and / or sebacic acid and hexamethylenediamine has good compatibility with polyoxyalkylene glycol and α, ω-dihydroxy hydrocarbon, a complicated polymerization method is used. No need.

That is, a polyamide oligomer containing a predetermined amount of polymerized fatty acid and having a number average molecular weight of 500 to 5,000 and a polyoxyalkylene glycol or α, ω-dihydroxy hydrocarbon having a number average molecular weight of 200 to 3,000. The mixture and the dicarboxylic acid having 6 to 20 carbon atoms are substantially equivalent to all hydroxyl groups with respect to all hydroxyl groups, and the weight ratio (B) / (A) is 5/95 to 80/2.
It was charged in a reaction vessel sufficiently replaced with nitrogen so as to be 0, and heated to 200 to 280 ° C. in the presence of a small amount of a catalyst.
After reacting for 3 hours, a polyamide elastomer which is transparent, flexible and has excellent elastic recovery ability can be easily obtained by reacting under reduced pressure of about 1 mmHg until the melt viscosity at a temperature of 250 ° C. becomes 5 Pa · s or more. Obtainable.

Since polyamide elastomers having a melt viscosity at a temperature of 250 ° C. of less than 5 Pa · s have low mechanical strength and elastic recovery property, they are 5 Pa · s or more, preferably 10 to 300 Pa.
・ It is necessary to set to s.

Examples of the catalyst used here include phosphoric acid-based catalysts such as phosphoric acid, metaphosphoric acid and polyphosphoric acid, tetraalkyl orthotitanates such as tetrabutyl orthotitanate and tetraisopropyl orthotitanate,
A tin-based catalyst such as dibutyltin oxide, dibutyltin laurate and monobutylhydroxytin oxide, a manganese-based catalyst such as manganese acetate and a lead-based catalyst such as lead acetate are used.

In the polyamide elastomer of the present invention, an antioxidant, a thermal decomposition inhibitor, or a compound which is used after the polymerization or before the molding before the molding,
A heat and light resistance stabilizer such as an ultraviolet absorber can be added. As the heat resistance stabilizer, for example, 4,4′-bis (2,6-di-t-butylphenol), 1,3,5-
Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3 (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Various hindered phenols such as methane, N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxycinnamic acid amide), N, N'-bis (β-naphthyl) -P-phenylenediamine And aromatic amines such as 4,4'-bis (4-α, α-dimethylbenzyl) diphenylamine, sulfur compounds such as dilaurylthiodipropinate, phosphorus compounds, alkaline earth metal oxides, Schiff base nickel Examples thereof include salt, cuprous iodide, and / or potassium iodide.

As the light resistance stabilizer, substituted benzophenones, benzotriazoles and bis (2,2,6,6) are used.
Examples thereof include piperidine compounds such as -tetramethyl-4-piperidine) sebacate and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine.

Further, a reinforcing agent, a filler, a lubricant, a release agent, a plasticizer, a flame retardant, a hydrolysis resistance improver and the like can be added to the polyamide elastomer of the present invention depending on the use.

[0028]

INDUSTRIAL APPLICABILITY The polyamide elastomer of the present invention is transparent and has an excellent elastic recovery ability, and is used in fields requiring these properties, for example, hoses, tubes, films, sheets and modifiers for polymers. It has high industrial value.

[0029]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples. Each property in the examples was measured by the following methods. (1) Melt viscosity Using a flow tester CFT-500 manufactured by Shimadzu Corporation,
Measurement temperature 250 ℃, die 1mm (diameter) × 10mm (length), load 10k
It was measured under the condition of g. (2) Acid value and amine value 1 g of a sample was dissolved in 50 g of benzyl alcohol, the acid value was 1/10 N NaOH in methanol and a phenolphthalein indicator was used, and the amine value was 1/10 N hydrochloric acid in methanol and bromphenol blue. Titrated with indicator. (3) Melting point and crystallization temperature Using a differential scanning calorimeter (DSC), a temperature rising rate of 10 ° C /
The melting point was measured at min, the temperature was lowered at 10 ° C./min, and the crystallization temperature was measured. (4) Tensile test An elastomer was formed into a sheet having a thickness of 2 mm by using a hot press, punched out from a dumbbell No. 2 type test piece, and a tensile test was conducted in accordance with JIS K 6301. (5) Permanent elongation (PS) According to JIS K 6301, a dumbbell type 2 test piece was pulled for 10 minutes at a length equivalent to 1/2 of the tensile elongation (%), and then suddenly without rebounding. It was determined by shrinking and 10 minutes later, and measuring the distance between marked lines. L ₀ : Distance between marked lines (mm) l ₁ : Length between marked lines after shrinking and standing for a specified time (mm) (6) Elastic recovery rate Elastic recovery from the following formula based on the permanent elongation measurement method. I asked for the rate. L ₀ : Distance between marked lines (mm) L ₁ : Length between marked lines when cutting (mm) l ₁ : Length between marked lines after shrinking and leaving for a specified time (mm) (7) Shore hardness durometer Was measured in accordance with JIS K 7215. (8) Dynamic Viscoelasticity A storage elastic modulus from −145 ° C. to around the melting point was measured at a temperature rising rate of 2 ° C./min using a dynamic viscoelasticity device (DMS110 manufactured by Seiko Denshi KK).

Example 1 1000 ml of 4 equipped with a stirrer, nitrogen inlet and distillation tube
In the neck flask, the composition of the obtained polyamide copolymer,
By weight ratio, hexamethylenediamine-polymerized fatty acid polycondensate / hexamethylenediamine-azelaic acid polycondensate = 6
Hydrogenated type polymerized fatty acid (carbon number to 0/40)
36, product name Pripol 1009, manufactured by Unichema) 12
4.6 g, azelaic acid 61.8 g, and hexamethylenediamine 63.6 g were charged together with a 5% phosphorous acid aqueous solution 0.8 g, and the temperature was raised while flowing a fixed amount of nitrogen.
Water generated by the polycondensation reaction came out from 8 ° C.
The content at this time was a uniform transparent liquid. When the temperature was raised to 190 ° C., the contents were sampled, and the acid value and the amine value were adjusted so as to have an equivalent relationship. Finally, a transparent polyamide oligomer having a terminal group concentration of 40.2 mgKOH / g and a number average molecular weight of 1396 was obtained. 57 g of azelaic acid was added at this temperature, and when the contents became transparent, 193.2 g of polyoxytetramethylene glycol having a number average molecular weight of 319 and N, N'-hexamethylene-bis (3,5-di-t- Butyl-4-hydroxycinnamic acid amide) (Product name Irganox 1098, antioxidant)
1.0 g was sequentially added, and when they became uniform, 0.1 g of antimony trioxide and 0.1 g of monobutylhydroxytin oxide were added. Then, the temperature was raised to 270 ° C. while distilling off the water produced by the reaction, and the temperature was maintained for 30 minutes. Next, at this temperature, the pressure was reduced to 25 mmHg, the reaction was continued for 30 minutes, then the pressure was reduced to 1 mmHg, and the reaction was further advanced. After 3 hours and 30 minutes, the melt viscosity was 86 Pa · s / 250.
C., melting point 157.5.degree. C., crystallization temperature 129.9.degree. C., and hard segment (polyamide copolymer) / soft segment (azelaic acid to polyoxytetramethylene glycol) = 50/50 (weight ratio) of a transparent elastomer. Was obtained.

Example 2 After synthesizing a polyamide oligomer in the same manner as in Example 1,
Azelaic acid, polyoxytetramethylene glycol having a number average molecular weight of 638, Irganox 1098, antimony trioxide, monobutylhydroxy according to the charging order of Example 1 so that the hard segment / soft segment = 70/30 (weight ratio). Add tin oxide,
The reaction proceeded under the same conditions as in Example 1. After 3 hours and 30 minutes, melt viscosity 100 Pa · s / 250 ° C., melting point 165.
A transparent elastomer with a temperature of 5 ° C. and a crystallization temperature of 139.9 ° C. was obtained.

Example 3 After synthesizing a polyamide oligomer in the same manner as in Example 1,
Azelaic acid, polyoxytetramethylene glycol having a number average molecular weight of 638, Irganox 1098, antimony trioxide, monobutylhydroxy according to the charging order of Example 1 so that the hard segment / soft segment = 30/70 (weight ratio). Add tin oxide,
The reaction proceeded under the same conditions as in Example 1. After 2 hours and 10 minutes, melt viscosity 96 Pa · s / 250 ° C., melting point 141.5
A transparent elastomer having a crystallization temperature of 114.9 ° C. was obtained.

Example 4 The reaction was carried out in the same manner as in Example 3 except that polyoxytetramethylene glycol having a number average molecular weight of 2018 was used. After 3 hours, melt viscosity 80 Pa · s / 250 ° C.,
A transparent elastomer having a melting point of 144.0 ° C. and a crystallization temperature of 126.3 ° C. was obtained.

Example 5 After synthesizing a polyamide oligomer in the same manner as in Example 1,
Azelaic acid, polyoxytetramethylene glycol having a number average molecular weight of 341, Irganox 1098, antimony trioxide, and monobutylhydroxy according to the charging order of Example 1 so that the hard segment / soft segment = 90/10 (weight ratio). Add tin oxide,
The reaction proceeded under the same conditions as in Example 1. After 2 hours and 10 minutes, melt viscosity 96 Pa · s / 250 ° C., melting point 141.5
A transparent elastomer having a crystallization temperature of 114.9 ° C. was obtained.

Example 6 In the same apparatus as in Example 1, the composition of the obtained polyamide copolymer was such that the weight ratio of hexamethylenediamine to polymerized fatty acid polycondensate / hexamethylenediamine to azelaic acid polycondensate was 70 /. Prepol 1009 to be 30
When 145.4 g, azelaic acid 46.4 g and hexamethylenediamine 58.2 g were charged and the temperature was raised while flowing a fixed amount of nitrogen, water generated by the polycondensation reaction was distilled out from 162 ° C. The content at this time was a uniform transparent liquid. When the temperature was raised to 220 ° C., the contents were sampled and the acid value and the amine value were adjusted so as to have an equivalent relationship. Finally, a transparent polyamide oligomer having a terminal group concentration of 12.4 mgKOH / g and a number average molecular weight of 4524 was obtained. 56.8 g of azelaic acid was added at this temperature, and when the contents became transparent, 193.2 g of polyoxytetramethylene glycol having a number average molecular weight of 319 and Irganox 1098, 3.6 g were sequentially added. Liquid temperature is 1
Although the temperature dropped to 80 ° C., when it became uniform at this temperature, 0.06 g of antimony trioxide and 0.06 g of monobutylhydroxytin oxide were added. After this, the reaction was allowed to proceed under the same conditions as in Example 1. After 3 hours, the melt viscosity was 36 Pa · s / 250 ° C., the melting point was 150.0 ° C., the crystallization temperature was 124.9 ° C., and the hard segment / soft segment = 50. A transparent elastomer of / 50 (weight ratio) was obtained.

Example 7 In the same apparatus as in Example 1, the composition of the obtained polyamide copolymer was such that the weight ratio of hexamethylenediamine-polymerized fatty acid polycondensate / hexamethylenediamine-sebacic acid polycondensate = 60 / Prepol 1009,1 to be 40
62.0 g, sebacic acid 82.6 g, and hexamethylenediamine 80.6 g were charged and synthesized in the same manner as in Example 1 to obtain a terminal group concentration of 27.1 mg KOH / g and a number average molecular weight of 207.
0 transparent polyamide oligomer was obtained. 190 ° C
Then, 33.2 g of sebacic acid was added, and when the content became transparent, 167.0 g of polyoxytetramethylene glycol having a number average molecular weight of 514 and Irganox 109
8,3.6 g were sequentially added. When a uniform solution was obtained, 0.24 g of antimony trioxide and 0.24 g of monobutylhydroxytin oxide were added. Then, the reaction was allowed to proceed under the same conditions as in Example 1, and after 2 hours, the melt viscosity was 90 Pa · s / 250 ° C., the melting point was 195.0 ° C., the crystallization temperature was 154.2 ° C., and the hard segment / soft segment = 60. A translucent elastomer of / 40 (weight ratio) was obtained.

Example 8 In the same apparatus as in Example 1, the composition of the obtained polyamide copolymer was such that the weight ratio of hexamethylenediamine to polymerized fatty acid polycondensate / hexamethylenediamine to azelaic acid polycondensate was 60 /. Hydrogenated type polymerized fatty acid (carbon number 44, trade name Pripol 1004, manufactured by Unichema) 130.3 g, azelaic acid 63.0 g, and hexamethylenediamine 61.4 g were charged to 40, and the same as in Example 1. A transparent polyamide oligomer having a terminal group concentration of 43.0 mgKOH / g and a number average molecular weight of 1305 was obtained by the synthesis. At 190 ° C., 56.3 g of azelaic acid was added, and when the contents became transparent, 193.9 g of polyoxytetramethylene glycol having a number average molecular weight of 319 and 1.098 g of Irganox 1098 were sequentially added. When a uniform solution was obtained, 0.1 g of antimony trioxide and 0.1 g of monobutylhydroxytin oxide were added. Then, the reaction was carried out in the same manner as in Example 1, and after 2 hours, the melt viscosity was 46 Pa · s / 250 ° C. and the melting point was 157.
A transparent elastomer having a hard segment / soft segment = 50/50 (weight ratio) was obtained at 0 ° C. and a crystallization temperature of 134.0 ° C.

Example 9 In the same apparatus as in Example 1, the composition of the obtained polyamide copolymer was such that the weight ratio of hexamethylenediamine to polymerized fatty acid polycondensate / hexamethylenediamine to azelaic acid polycondensate was 70 /. Prepol 1004 to be 30
151.7 g, azelaic acid 47.1 g, and hexamethylenediamine 55.3 g were charged and synthesized in the same manner as in Example 1 to obtain a terminal group concentration of 38.8 mgKOH / g and a number average molecular weight of 1.
446 transparent polyamide oligomers were obtained. 19
45.9 g of azelaic acid was added at 0 ° C., and when the contents became transparent, 105.6 g of polyoxytetramethylene glycol with a number average molecular weight of 341 and a number average molecular weight of 22
Hydrogenated polyolefin glycol of No. 00 (Polytail HA manufactured by Mitsubishi Kasei Co., Ltd.) (105.6 g) and Irganox 1098 (1.0 g) were sequentially added. When a uniform solution was obtained, 0.1 g of antimony trioxide and 0.1 g of monobutylhydroxytin oxide were added. Thereafter, the reaction was allowed to proceed under the same conditions as in Example 1, and after 2 hours and 30 minutes, a melt viscosity of 64 Pa · s / 250 ° C. and a melting point of 1
A transparent elastomer having a hard segment / soft segment = 50/50 (weight ratio) was obtained at 56.0 ° C. and a crystallization temperature of 128.0 ° C.

Example 10 In a device similar to that of Example 1, the composition of the obtained polyamide copolymer was such that the weight ratio of hexamethylenediamine to polymerized fatty acid polycondensate / hexamethylenediamine to azelaic acid polycondensate was 60 /. Prepol 1009 to be 40,
133.3 g, azelaic acid 121.0 g, and hexamethylenediamine 88.4 g were charged and synthesized in the same manner as in Example 1 to obtain a transparent polyamide oligomer having a terminal group concentration of 39.8 mg KOH / g and a number average molecular weight of 1410. Was given.
At 190 ° C., 33.3 g of azelaic acid was added, and when the contents became transparent, 174 g of polyethylene glycol having a number average molecular weight of 501 and Irganox 1098,1.
0 g was sequentially added. When a uniform solution was obtained, 0.1 g of antimony trioxide and 0.1 g of monobutylhydroxytin oxide were added. After that, when the reaction was allowed to proceed under the same conditions as in Example 1, the melt viscosity was 24 after 3 hours and 30 minutes.
Pa · s / 250 ° C, melting point 166.0 ° C, crystallization temperature 1
Hard segment / soft segment = 6 at 45.2 ℃
A 0/40 (weight ratio) transparent elastomer was obtained.

Comparative Example 1 The composition of the polyamide copolymer obtained in the same apparatus as in Example 1 was such that the weight ratio was hexamethylenediamine-polymerized fatty acid polycondensate / hexamethylenediamine-adipic acid polycondensate = 70/30. To become a pre-pole 1009,19
6.2 g, adipic acid to hexamethylenediamine salt 50
% Aqueous solution 99.8 g, hexamethylenediamine 44.0
g was charged together, and the temperature was raised to 190 ° C. while distilling the reaction water and water while flowing a fixed amount of nitrogen. The contents at this time remained cloudy. The contents were sampled at this temperature, and the acid value and the amine value were adjusted so as to have an equivalent relationship. Finally, a cloudy polyamide oligomer having a terminal group concentration of 43.6 mgKOH / g and a number average molecular weight of 1287 was obtained. Adipic acid 20.8g, number average molecular weight 5 at this temperature
14 polyoxytetramethylene glycol 146.2
g and Irganox 1098, 1.8 g were added, and when uniform, 0.2 g of antimony trioxide and 0.2 g of monobutylhydroxytin oxide were added. After that, the reaction was allowed to proceed under the same conditions as in Example 1, but the contents remained cloudy even after 4 hours, and no sharp increase in viscosity was observed. The obtained product was cloudy and brittle.

Comparative Example 2 In the same apparatus as in Example 1, 272.8 g of 12-aminododecanoic acid, which is a synthetic raw material of nylon 12, 67.0 g of dodecanedioic acid, and 193.5 g of polyoxytetramethylene glycol having a number average molecular weight of 319. , Irganox 109
Charged with 8,1.0 g, antimony trioxide 0.08 g, and monobutylhydroxytin oxide 0.08 g, 22
The temperature was raised to 0 ° C. After stirring at this temperature for 30 minutes to form a uniform solution, the temperature is increased and reduced according to the depressurization program.
The polymerization conditions of 270 ° C. and 1 mmHg were reached over time. When the reaction was allowed to proceed for 2 hours and 30 minutes under these conditions, the melt viscosity was 583 poise / 250 ° C, the melting point was 154.0 ° C, the crystallization temperature was 113.3 ° C, and the hard segment (nylon 1
2) / soft segment (dodecanedioic acid-polyoxytetramethylene glycol condensate) = 50/50 (weight ratio), a transparent elastomer was obtained.

The physical properties of the elastomers obtained in the above Examples are shown in Table 1, and FIG. 1 shows the changes in the storage elastic modulus of Examples 1, 8 and Comparative Example 2 as a representative. Table 1 Shore Yield Tensile Rupture Tension Permanent Elasticity Hardness Strength Elongation Strength Elongation Elongation Recovery D Kg / cm ² % Kg / cm ² %%% Example 1 43 85 52 52 330 963 214 214 Example 2 52 130 32 475 689 174 56 Example 3 35 206 1220 169 72 72 Example 4 31 147 1295 122 75 Example 5 216 29 553 535 166 652 52 Example 6 40 75 75 47 242 1103 245 59 Example 7 48 105 42 374 780 Example 191 40 84 58 334 930 190 58 Example 9 37 210 950 197 66 Example 10 47 105 51 51 361 847 208 52 52 Comparative Example 2 40 92 47 312 312 865 359 25 25

[0043]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing changes in storage elastic modulus of Example 1, Example 8 and Comparative Example 2 with respect to heating temperature.

Claims (1)

[Claims] 1. (A) (a) a polymerized fatty acid having 20 to 48 carbon atoms, (b) azelaic acid and / or sebacic acid,
And (c) the diamine having 2 to 20 carbon atoms, the weight ratio (a) / (b) of (a) to (b) is 0.3.
To 5.0, and a polyamide oligomer having a number average molecular weight of 500 to 5,000, obtained by mixing and polycondensing so that all amino groups are substantially equivalent to all carboxyl groups, and (B) (D) Number average molecular weight is 200 to 3,000
No. 0 polyoxyalkylene glycol or polyoxyalkylene glycol and a number average molecular weight of 200 to 3.0
A mixture of 00 with α, ω-dihydroxy hydrocarbons,
(E) a dicarboxylic acid having 6 to 20 carbon atoms, a total equivalent of all carboxyl groups to all hydroxyl groups, and a weight ratio (B) / (A) of (B) to (A) above. The melt viscosity at a temperature of 250 ° C. is 5 Pa ·, which is characterized by being mixed and polycondensed so as to be 5/95 to 80/20.
A method for producing a polyamide elastomer of s or more.