JPH05320335A - Production of polyamide copolymer - Google Patents

Abstract

PURPOSE:To obtain a polyamide copolymer having the same flexibility as that of (external plasticizing) nylon 12 and excellent chemical resistance by blending a polymerization fatty acid with azelaic acid, sebacic acid and a diamine in a specific ratio and subjecting the blend to polycondensation. CONSTITUTION:(A) A 20-28C polymerization fatty acid (e.g. oleic acid) is blended with (B) azelaic acid and/or sebacic acid and (C) a 2-20C diamine (e.g. ethylenediamine) in the weight ratio of the component A/B of 0.25-5.2 so as to make the whole amino group equivalent to the whole carboxyl group and subjected to polycondensation to give the objective copolymer having 15Pa.s melt viscosity at 250 deg.C. The polycondensation is preferably carried out by heating the reaction system to 200-280 deg.C in the presence of a molecular weight modifier such as stearic acid and a small amount of a polycondensation catalyst such as phosphoric acid, reacting for 1-3 hours and then reacting under 160mmHg reduced pressure for 0.5-2 hours.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyamide copolymer. More specifically, it relates to a method for producing a polyamide copolymer having flexibility equivalent to that of nylon 12 and external plasticized nylon 12.

[0002]

2. Description of the Related Art Nylon 12 has been widely used as an externally plasticized nylon 12 mainly for applications such as tubes and hoses by adding a plasticizer such as higher alcohol, hydroxybenzoic acid or aromatic sulfonamide. .. However, these plasticizers have a problem that flexibility does not continue due to bleeding and volatilization at high temperature, and flexibility decreases with the passage of time.

In order to impart flexibility to polyamide, polyamide copolymers containing caprolactam, polymerized fatty acid, hexamethylenediamine or adipic acid, polymerized fatty acid, and polymerized fatty acid produced from hexamethylenediamine are disclosed in Japanese Patent Application Laid-Open 54-71191, JP-A-56-582.
4, JP-A-61-200125, JP-A-63-23
No. 927 and JP-A-2-53823. All of them have insufficient flexibility and cannot be used for the outer plasticized nylon 12. In the case of copolymerization of caprolactam, polymerized fatty acid and hexamethylenediamine, it is necessary to add water in order to accelerate the ring-opening polymerization rate of caprolactam, and in the case of copolymerization of adipic acid, polymerized fatty acid and hexamethylenediamine, adipine Since the melting point of the salt of acid and hexamethylenediamine is as high as 183 ° C., pressure polymerization is performed after forming an aqueous solution for uniform polymerization, or polymerization is performed after first forming a prepolymer from adipic acid and hexamethylenediamine. A complicated two-step polymerization in which a fatty acid and hexamethylenediamine are polymerized is used.

[0004]

[Means for Solving the Problems] As a result of intensive studies to solve the above-mentioned problems, as a result, polymerized fatty acid, azelaic acid and / or
It was also found that a polyamide copolymer having flexibility equivalent to that of nylon 12 and externally plasticized nylon 12 can be produced by polycondensing sebacic acid and diamine, and based on this finding, the present invention was accomplished. ..

That is, the object of the present invention is to obtain a polyamide copolymer having flexibility equivalent to that of nylon 12 and external plasticized nylon 12, and the purpose thereof is (A) having 20 carbon atoms. ~ 48 polymerized fatty acids, and (B)
Azelaic acid and / or sebacic acid and (C) a diamine having 2 to 20 carbon atoms are used, and the weight ratio (A) / (B) of (A) to (B) is 0.25 to 5. 2 and mixed so that all amino groups are substantially equivalent to all carboxyl groups, and the melt viscosity at a temperature of 250 ° C. is 5
This is achieved by polycondensation until it reaches Pa · s or higher.

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.

[0007] Commercially available polymerized fatty acids usually contain dimerized fatty acid as a main component and other raw material fatty acids and trimerized fatty acids, 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.

As the dicarboxylic acid (B) used together with the polymerized fatty acid, azelaic acid, sebacic acid and a mixture of the two are used in view of the polymerizability, the copolymerizability with the polymerized fatty acid and the physical properties of the obtained polyamide copolymer. Is mentioned.

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.

In the present invention, (A) a polymerized fatty acid having 20 to 48 carbon atoms, (B) azelaic acid and / or sebacic acid, and (C) a diamine having 2 to 20 carbon atoms are selected from the above (B). The weight ratio of (A) to (A) / (B) is 0.2
It should be mixed in a polycondensation ratio of 5 to 5.2 so that all amino groups are substantially equivalent to all carboxyl groups. It is necessary to set this (A) / (B) to 0.25 to 5.2 in order to obtain a polyamide copolymer having flexibility equivalent to that of nylon 12 and external plasticized nylon 12. When (A) / (B) is less than 0.25, the obtained polyamide copolymer has insufficient flexibility, while when it is more than 5.2, it is too soft and the heat resistance is remarkably lowered. To obtain a polyamide copolymer. Further, if the melt viscosity of the polyamide copolymer at a temperature of 250 ° C. is less than 5 Pa · s, the mechanical strength becomes too low, and 5 Pa · s or more, preferably 10 to 500.
It is necessary to set Pa · s.

In the polycondensation of (A) polymerized fatty acid, (B) azelaic acid and / or sebacic acid, and (C) hexamethylenediamine of the present invention, a salt of polymerized fatty acid and hexamethylenediamine and azelaic acid and / or Alternatively, since the melting point of the salt of sebacic acid and hexamethylenediamine is relatively low and the polycondensation rate of these is relatively fast, caprolactam, polymerized fatty acid, hexamethylenediamine type or adipic acid, polymerized fatty acid, hexamethylenediamine type, etc. It is not necessary to add water to the system in order to accelerate the ring-opening polymerization reaction or to carry out homogeneous polymerization, and therefore it is not necessary to use a pressure reaction vessel. It is not necessary to use a complicated two-step polymerization method in which a prepolymer is first produced from adipic acid and hexamethylenediamine and then polycondensation of polymerized fatty acid and hexamethylenediamine is performed.

In the present invention, (A) polymerized fatty acid, (B) azelaic acid and //
Alternatively, sebacic acid and (C) hexamethylenediamine are added to the above (B) in a weight ratio of (A) / (A) /
(B) is 0.25 to 5.2, and is charged so that all amino groups are substantially equivalent to all carboxyl groups, and a predetermined amount of a molecular weight modifier such as stearic acid and a small amount of phosphoric acid and the like are added. In the presence of a polycondensation catalyst, the temperature is raised to 200 to 280 ° C.
After reacting for 3 hours and then reacting under a reduced pressure of about 160 mmHg for 0.5 to 2 hours, a polyamide copolymer having a high molecular weight of melt viscosity at a temperature of 250 ° C. of 5 Pa · s or more and excellent flexibility is obtained. can get.

As the catalyst used here, for example, phosphoric acid type catalysts such as phosphoric acid, metaphosphoric acid, polyphosphoric acid and the like are used.

To the polyamide copolymer of the present invention, a heat and light resistance stabilizer such as an antioxidant, a thermal decomposition inhibitor and an ultraviolet absorber can be added at the time of polymerization or before molding before molding. 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.

The polyamide copolymer of the present invention also comprises
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 depending on the application.

[0017]

INDUSTRIAL APPLICABILITY The polyamide copolymer produced by the method of the present invention has excellent flexibility and chemical resistance, and like nylon 12 and external plasticized nylon 12, injection molding, extrusion molding, blow molding, compression molding and the like. Can be molded by various molding methods. Further, in fields where these characteristics are required, for example, fuel tubes, brake pipes, tubes such as exhaust gas system parts, pipes, sheets, electrical system parts such as connectors, gears, valves, oil vans, cooling fans, It is useful for radiator tanks, cylinder heads, canisters, etc. and has high industrial value.

[0018]

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 obtained as follows. (1) Melt viscosity Using a flow tester CFT-500 manufactured by Shimadzu Corporation,
Measurement temperature 250 ℃, die 1mm (diameter) x 10mm
(Long), the load was measured under the condition of 10 kg. (2) Acid value and amine value 1 g of a sample is dissolved in 50 g of benzyl alcohol, the acid value is 1/10 N NaOH in methanol solution and phenolphthalein indicator is used, and the amine value is 1/10 N in hydrochloric acid methanol solution. Titrated with blue 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) Dynamic viscoelasticity Using a dynamic viscoelasticity device (DMS110 manufactured by Seiko Electronics Co., Ltd.)
The storage elastic modulus, the glass transition point due to the E ′ and tan δ peaks, and Tg were measured at a heating rate of 2 ° C./min. (5) Tensile test An elastomer was molded into a sheet having a thickness of 2 mm by using a hot press, and then a dumbbell No. 2 type test piece was punched out, and a tensile test was performed according to JIS K6301.

Example 1 1000 m equipped with a stirrer, nitrogen inlet and distillation tube
In a separable flask of 1 l, hydrogenated type so that the composition of the obtained polyamide copolymer is hexamethylenediamine-polymerized fatty acid polycondensate / hexamethylenediamine-azelaic acid polycondensate = 60/40 by weight ratio. Polymerized fatty acid of 36 (carbon number 36, product name Pripol 1009, manufactured by Unichema) 322.6 g, azelaic acid 174.8 g, hexamethylenediamine 177.5 g, stearic acid 2.
When 6 g was charged at once with 0.005 g of phosphoric acid and the temperature was raised while flowing a fixed amount of nitrogen, water generated by the polycondensation reaction was distilled out from 158 ° C. The content at this time was a uniform transparent liquid. After the temperature was raised to 250 ° C. and the temperature was maintained at this temperature for 1 hour, the contents were sampled and the acid value and the amine value were adjusted so as to have an equivalent relationship. Next, when the pressure was reduced to 160 mmHg at this temperature and the reaction was continued, after 30 minutes, the number average molecular weight was 52,000 and the melt viscosity was 92 Pa · s /.
A transparent polyamide copolymer having a temperature of 250 ° C., a melting point of 170 ° C. and a crystallization temperature of 130 ° C. was obtained. Then, N, N'-hexamethylene-bis (3,5-di-t-butyl-4-hydroxycinnamic acid amide) (trade name Irganox 109
2.5 g of (8. antioxidant) was added, and when uniform, it was extracted in a strand form, pelletized and dried.

Example 2 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 30 /. Prepol 1009 to be 70,
127.4 g, azelaic acid 239.7 g, hexamethylenediamine 177.5 g and stearic acid 2.6 g were charged all at once, and the mixture was produced in the same manner as in Example 1. The number average molecular weight was 53,000 and the melt viscosity was 161 Pa · s / 25.
A transparent polyamide copolymer having a temperature of 0 ° C., a melting point of 179 ° C. and a crystallization temperature of 160 ° C. was obtained.

Example 3 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 50 /. Prepol 1009 to be 50,
246.2 g, 200.2 g of azelaic acid, 177.5 g of hexamethylenediamine and 2.6 g of stearic acid were charged all at once, and the mixture was produced in the same manner as in Example 1. The number average molecular weight was 45,000 and the melt viscosity was 61 Pa · s / 250.
As a result, a transparent polyamide copolymer having a melting point of 176 ° C. and a crystallization temperature of 140 ° C. was obtained.

Example 4 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 50 /. Hydrogenated type polymerized fatty acid (carbon number 44, trade name Pripol 1004, manufactured by Unichema Co.) 262.1 g, azelaic acid 208.7 g, hexamethylenediamine 177.5 g and stearic acid 2.6 so as to be 50.
g was added at once, and the product was produced in the same manner as in Example 1. The number average molecular weight was 51,000 and the melt viscosity was 101 Pa · s.
A transparent polyamide copolymer having a melting point of / 250 ° C, a melting point of 177 ° C and a crystallization temperature of 153 ° C was obtained.

Example 5 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 = 60 / Prepol 1004 to be 40
262.1 g, 208.7 g of azelaic acid, 177.5 g of hexamethylenediamine and 2.6 g of stearic acid were charged all at once, and the mixture was produced in the same manner as in Example 1. The number average molecular weight was 62,000 and the melt viscosity was 101 Pa · s / 25.
A transparent polyamide copolymer having a temperature of 0 ° C., a melting point of 175 ° C. and a crystallization temperature of 147 ° C. 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 of hexamethylenediamine-polymerized fatty acid polycondensate / hexamethylenediamine-adipic acid polycondensate = 60/40. Prepol 1009, 280.8g,
Adipic acid-hexamethylenediamine salt 50% aqueous solution 4
When 94.0 g and 58.8 g of hexamethylenediamine were charged at once together with 0.05 g of phosphoric acid and the temperature was raised while flowing a fixed amount of nitrogen, water was distilled off from 157 ° C. The contents at this time remained cloudy. After the temperature was raised to 270 ° C. and kept at this temperature for 1 hour, the contents were sampled and the acid value and the amine value were adjusted so as to have an equivalent relationship. The contents at this time remained cloudy. next,
When the pressure was reduced to 160 mmHg at this temperature and the reaction was continued,
A polyamide copolymer having a number average molecular weight of 24,400 was obtained. However, the obtained product was cloudy and brittle.

The physical properties obtained in the above examples are shown in Table 1. Further, in Comparative Examples 2, 3 and 4, the melt viscosity is 194 respectively.
Pa · s / 250 ° C, melting point 179 ° C, crystallization temperature 155
C. Nylon 12 (Comparative Example 2) and melt viscosity 75 Pa.
s / 250 ° C., melting point 172 ° C., crystallization temperature 143 ° C. (Comparative Example 3), melt viscosity 115 Pa · s / 250 ° C., melting point 1
The physical properties of the external plasticized nylon 12 at 74 ° C. and the crystallization temperature of 147 ° C. (Comparative Example 4) were shown.

Table 1 Storage Modulus Tg Yield Tensile Tensile Break Tensile E ', 23 ° C Strength Elongation Strength Elongation kgf / mm ² ° C kgf / cm ² % kgf / cm ² % Example 1 141 37 308 26 536 466 Example 2 229 59 482 12 566 375 Example 3 175 44 372 22 450 450 394 Example 4 117 117 314 314 27 459 435 Example 5 75 75 17 253 33 33 594 439 Comparative Example 2 222 60 490 11 529 283 292 29 2 Comparative Example 518 414 Comparative Example 4 128 36 36 335 25 461 326

Claims (1)

[Claims] 1. (A) polymerized fatty acid having 20 to 48 carbon atoms, (B) azelaic acid and / or sebacic acid,
(C) The diamine having 2 to 20 carbon atoms has a weight ratio (A) / (B) of (A) to (B) of 0.2.
The melt viscosity at a temperature of 250 ° C. is 5 Pa · 5 to 5.2, and all the amino groups are mixed and polycondensed so that all the amino groups are substantially equivalent to all the carboxyl groups.
Method for producing polyamide copolymer having s or more