JPH0764978B2 - Polyamide composition for engineering and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a polyamide composition for engineering and a method for producing the same, and in particular, it has excellent heat-resistant thermoplastic resin aging properties, heat resistance, mechanical properties, The present invention relates to a polyamide composition for engineering which is excellent in moldability, that is, fluidity as well as a molded product having excellent chemical and physical properties, and a method for producing the same.

[Conventional technology]

In general, thermoplastic resins such as polyolefin, polyester, and polyamide have excellent moldability, so compression molding,
Although melt molding such as injection molding or extrusion molding can be easily performed, the engineering plastics are still unsatisfactory in any of the heat resistance, mechanical properties and chemical properties, so It is used in each general-purpose molding field by taking advantage of the characteristics of.

On the other hand, as engineering plastics superior in heat resistance, mechanical properties and chemical / physical properties than before,
Polytetrafluoroethylene known as Teflon®, polyparaphenylene terephthalamide known as Kevlar®, 4,4′-diaminodiphenyl ether and pyromellitic anhydride known as Kapton® Polyimide consisting of a condensate of poly (6,6-nylon), polyhexamethylene adipamide known as 6,6-nylon, poly (2,2,4-trimethylhexamethylene terephthalamide) known as Trogamide T (registered trademark), polyphenylene Ruffid, polyacetal and the like are used for various purposes.

However, of these, polytetrafluoroethylene,
Although polyparaphenylene terephthalamide and the above-mentioned polyimide have excellent heat resistance, mechanical properties, and chemical-physical properties, they cannot be melt-molded, so that their fields of use are extremely limited. Against these,
Polyphenylene sulfide, polyhexamethylene adipamide, 2,2,4-trimethylhexamethylene terephthalamide, polyacetal, etc. all have the advantage of being melt-molded, but on the other hand, polyphenylene sulfide Is inferior in heat resistance characteristics such as melting point, glass transition point and heat deformation temperature and mechanical characteristics such as impact strength and abrasion resistance, while
Polyamides such as polyhexamethylene adipamide and 2,4,4-trimethylhexamethylene terephthalamide are all heat resistant properties such as glass transition point, heat distortion temperature, tensile strength, bending strength, limit PV value, wear resistance. Etc. and chemical properties such as chemical resistance, boiling water resistance, and saturated water absorption are inferior. Further, polyacetal is inferior in heat resistance characteristics such as melting point and thermal deformation strength, and in mechanical strength such as bending strength, impact strength and abrasion resistance.

In order to solve the problems in the conventional engineering plastics as described above, the present inventors have already
A polyamide having an aromatic dicarboxylic acid component unit and an aliphatic alkynediamine component unit whose main component is a terephthalic acid component unit and having a melting point of 309 ° C. or higher has any of heat resistance property, mechanical strength, chemical-physical property and molding property. It has also been found that it has excellent sliding properties, in particular, Japanese Patent Application No. 59-12040. However, the present inventors have further conducted extensive studies on this polyamide in order to improve its heat aging resistance, and as a result, by adding a predetermined monocarboxylic acid or monoamine and hypophosphite, excellent heat resistance is obtained. It was found that it is possible to obtain a polyamide composition as a molding material which gives a molded article having aging properties, and in particular, a monocarboxylic acid or a monoamine and hypophosphorous acid at any stage of polycondensing a polyamide raw material to produce a polyamide. By adding a salt, it is possible to obtain a polyamide composition having remarkably excellent fluidity and excellent moldability,
Furthermore, the present inventors have found that this polyamide composition gives a molded article having excellent heat aging resistance, and have reached the present invention.

[Structure of Invention]

The engineering polyamide composition according to the present invention comprises (A) (a) a terephthalic acid component unit of 60 to 100 mol%.
And an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit in the range of 0 to 40 mol%, and (b) an aliphatic alkylenediamine component having 6 to 18 carbon atoms. A unit having a melting point of 309 ° C. or higher, and (B) 0.01 to 5 mol% of aromatic monocarboxylic acid or aromatic monoprimary amine with respect to the aliphatic alkylenediamine component constituting the polyamide, 0.01-5 mol%
And a hypophosphite salt of. The method for producing a polyamide composition for engineering according to the present invention comprises (a) a terephthalic acid component unit in the range of 60 to 100 mol% and an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit of 0 to 40 mol%. And (b) an aliphatic alkylenediamine component unit having 6 to 18 carbon atoms and having a melting point of 309 ° C. or higher, (c) the above polyamide is constituted. 0.01 to 5 mol% of aromatic monocarboxylic acid or aromatic monoprimary amine with respect to the above aliphatic alkylenediamine component
In the coexistence of hypophosphite, polycondensation of the aromatic dicarboxylic acid component and the aliphatic alkylenediamine component,
Or polycondensing a nylon salt or oligomer thereof.

In the engineering polyamide composition according to the present invention, the polyamide (A) comprises (a) a terephthalic acid component unit in the range of 60 to 100 mol% and an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit of 0 to 40: It has an aromatic dicarboxylic acid component unit in the range of mol% and (b) an aliphatic alkylenediamine component unit having 6 to 18 carbon atoms and has a melting point of 309 ° C or higher.

The composition of the aromatic dicarboxylic acid component unit (a) may be a terephthalic acid component unit alone, but it is a mixture of a terephthalic acid component unit and an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit. You can buy it. Specific examples of the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit include component units such as isophthalic acid, phthalic acid, 2-methylterephthalic acid, and naphthalenedicarboxylic acid. Among these, an isophthalic acid component unit or a naphthalenedicarboxylic acid component unit, particularly an isophthalic acid component unit is preferably used.

In the present invention, terephthalic acid accounts for 60 to 100 mol% of the aromatic dicarboxylic acid component unit (a),
Aromatic dicarboxylic acid other than terephthalic acid component unit is 0
It must be in the range of 40 mol%. In the aromatic dicarboxylic acid component unit (a), when the content of terephthalic acid is less than 60 mol% and the content of the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit is more than 40 mol%, such a polyamide is included. Molded product obtained from the composition is inferior in heat aging resistance and heat resistance characteristics including heat distortion temperature, mechanical properties such as tensile strength, bending strength, and abrasion resistance, chemical resistance, chemical physical properties such as water resistance .

However, in the present invention, the aromatic dicarboxylic acid component unit (a) is used in a small amount, for example, about 10 mol% of adipine together with the terephthalic acid component unit and the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit. It does not make any difference to include a polycarboxylic acid component unit such as an acid, sebacic acid, trimellitic acid, or pyromellitic acid.

In the polyamide composition according to the present invention, the aliphatic alkylenediamine component unit (b) is a linear or branched alkylenediamine component unit having 6 to 18 carbon atoms. Specific examples of the alkylenediamine component unit include, for example, 1,4-diamino-1,1-dimethylbutane, 1,4-diamino-1-ethylbutane, 1,4-diamino-1,2-dimethylbutane, 1, 4-diamino-1,3-dimethylbutane, 1,4
-Diamino-1,4-dimethylbutane, 1,4-diamino-2,
3-dimethylbutane, 1,2-diamino-1-butylethane, 1,6-diaminohexane, 1,7-diaminoheptane,
1,8-diamonooctane, 1,6-diamino-2,5-dimethylhexane, 1,6-diamino-2,4-dimethylhexane,
1,6-diamino-3,3-dimethylhexane, 1,6-diamino-2,2-dimethylhexane, 1,9-diaminononane, 1,
6-diamino-2,2,4-trimethylhexane, 1,6-diamino-2,4,4-trimethylhexane, 1,7-diamino-2,
3-dimethylheptane, 1,7-diamino-2,4-dimethylheptane, 1,7-diamino-2,5-dimethylheptane, 1,
7-diamino-2,2-dimethylheptane, 1,10-diaminodecane, 1,8-diamino-1,3-dimethyloctane, 1,8
-Diamino-1,4-dimethyloctane, 1,8-diamino-
2,4-dimethyloctane, 1,8-diamino-3,4-dimethyloctane, 1,8-diamino-4,5-dimethyloctane,
1,8-diamino-2,2-dimethyloctane, 1,8-diamino-3,3-dimethyloctane, 1,8-diamino-4,4-dimethyloctane, 1,6-diamino-2,4-diethyl Examples of component units include hexane, 1,9-diamino-5-methylnonane, 1,11-diaminoundecane, and 1,12-diaminododecane.

Among these, especially 1,6-diaminohexane, 1,8
Component units such as -diaminooctane, 1,10-diaminodecane, and 1,12-diaminododecane, or mixed component units thereof are preferably used.

In the engineering polyamide composition according to the present invention, the aromatic dicarboxylic acid component unit (a) described above is used.
The composition is preferably selected according to the carbon number of the aliphatic alkylenediamine. Thus, when the composition of the aromatic dicarboxylic acid component unit (a) is selected according to the carbon number of the aliphatic alkylenediamine, in particular, the obtained polyamide composition has excellent moldability, heat aging resistance, and heat aging resistance. This is because a molded product having excellent heat resistance such as heat distortion temperature and mechanical properties such as bending strength and wear resistance is provided.

That is, when the aliphatic alkylenediamine has 6 carbon atoms, for example, the aromatic dicarboxylic acid component unit (a)
The composition is preferably in the range of 60 to 85 mol% of the terephthalic acid component unit and in the range of 15 to 40 mol% of the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit. When the number of carbon atoms of the aliphatic alkylenediamine is 8, for example, the composition of the aromatic dicarboxylic acid component unit (a) is preferably in the range of 65 to 100 mol% of terephthalic acid component unit, and other than the terephthalic acid component unit. The aromatic dicarboxylic acid component unit of is in the range of 0 to 35 mol%. The aliphatic alkylenediamine component unit (b) has, for example, 10 carbon atoms.
When it is -18, the composition of the aromatic dicarboxylic acid component unit (a) is preferably 75 terephthalic acid component units.
To 100 mol%, and the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit is in the range of 0 to 25 mol%.

In the engineering polyamide composition according to the present invention, the polyamide is soluble in concentrated sulfuric acid at a temperature of 50 ° C, and has an intrinsic viscosity [η] of 0.5 measured in concentrated sulfuric acid at a temperature of 30 ° C. It is preferably dl / g or more. [Η] is preferably 0.6 dl / g or more, particularly preferably in the range of 0.7 to 3.0 dl / g.

Such concentrated sulfuric acid-soluble polyamide can be obtained by a method already known in the art. For example, Po
lymer Reviews, 10 , Condensation Polymers by Interfac
ial and Solution Methods (PWMorgan, Interscie
nce Publishers (1965)) and Makromol.Chem., 47 , 93-
113 (1961)), it is obtained by polycondensing a diacid halide of an aromatic dicarboxylic acid, which is the above-mentioned polyamide constituent unit, and an aliphatic alkylenediamine by a solution method. You can It can also be obtained by an interfacial polymerization method. Alternatively,
In the presence or absence of a solvent such as water, the aromatic dicarboxylic acid and an alkylenediamine or a nylon salt thereof,
It can also be obtained by polycondensation by the melting method. Further, it can also be obtained by polycondensing the polyamide oligomer obtained by the former method by a solid phase polymerization method.

Furthermore, in the engineering polyamide composition according to the present invention, the polyamide is not only the concentrated sulfuric acid-soluble polyamide described above, but has a composition in the same range as this concentrated sulfuric acid-soluble polyamide, but contains a polyamide insoluble in concentrated sulfuric acid at 50 ° C. You may have. Here, the polyamide insoluble in concentrated sulfuric acid at 50 ° C. is crushed polyamide, and a concentrated 1% by weight concentrated sulfuric acid solution of polyamide at 32 ° C. is passed at 50 ° C.
After heating and stirring for 10 hours, it refers to a polyamide from which soluble parts have been removed by filtration with a 2 G glass filter at a temperature of 50 ° C. Such concentrated sulfuric acid insoluble polyamide is not particularly limited, but the melt viscosity (MFR) at 360 ° C. and a load of 2.16 kg is usually 20 g / 10 minutes or less, preferably 5
g / 10 minutes or less, particularly preferably 0.1 g / 10 minutes or less.

Such concentrated sulfuric acid-insoluble polyamide can be produced as a by-product during the production of the concentrated sulfuric acid-soluble polyamide. In addition, the production amount can be intentionally increased by selecting the reaction conditions. Therefore, in such a case, a mixture of concentrated sulfuric acid-soluble polyamide and concentrated sulfuric acid-insoluble polyamide can be obtained. Further, if necessary, the concentrated sulfuric acid-soluble polyamide or the mixture of the concentrated sulfuric acid-soluble polyamide and the concentrated sulfuric acid-insoluble polyamide may be further crosslinked to have a high molecular weight so that the concentrated sulfuric acid is insoluble.

Therefore, as a method for producing a concentrated sulfuric acid insoluble polyamide or a mixture of concentrated sulfuric acid insoluble polyamide and concentrated sulfuric acid insoluble polyamide, for example, without any limitation, for example,
A method for further solid-phase polymerization of the concentrated sulfuric acid-soluble polyamide,
When producing concentrated sulfuric acid-soluble polyamide by melt polycondensation, the polycondensation temperature is set higher, for example, about 340 ° C finally.
The above method, the charge molar ratio of the alkylenediamine and the aromatic dicarboxylic acid to 1.03 or more, polycondensation of these, together with the alkylenediamine and the aromatic dicarboxylic acid, trifunctional or higher polyamine or polycarboxylic acid in combination Then, a method of polycondensing this can be exemplified.

In the engineering polyamide composition according to the present invention, the concentrated sulfuric acid-insoluble polyamide is preferably contained in an amount of 1000 parts by weight or less based on 100 parts by weight of concentrated sulfuric acid-soluble polyamide. In particular, according to the present invention, the concentrated sulfuric acid-insoluble polyamide is contained in the range of 2-1000 parts by weight, preferably 3-600 parts by weight, particularly preferably 5-400 parts by weight, based on 100 parts by weight of concentrated sulfuric acid-soluble polyamide. In this case, a molded product obtained from such a polyamide composition has excellent mechanical strength such as bending strength.

Here, the ratio of the concentrated sulfuric acid-soluble polyamide and the concentrated sulfuric acid-insoluble polyamide in the polyamide is determined by the following method. That is, a 1% by weight concentrated sulfuric acid solution of a polyamide mixture crushed into 32 mesh passes at a temperature of 50 ° C. with stirring.
After heating for 10 hours and cooling to room temperature, the mixture was filtered with a 2G glass filter, and the polyamide obtained as a precipitate and the polyamide obtained by precipitating the polyamide contained in the filtrate with water were dried, Weigh each one.

The engineering polyamide composition according to the present invention,
It contains an aromatic monocarboxylic acid or an aromatic monoprimary amine. Examples of the aromatic monocarboxylic acid include benzenecarboxylic acid which may have an alkyl substituent, and the like. More specifically, benzoic acid, toluic acid, naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and the like can be mentioned.

Examples of the aromatic mono-primary amine include aniline, toluidine, diphenylamine, naphthylamine and the like.

In the polyamide composition according to the present invention, these aromatic monocarboxylic acids or aromatic mono-primary amines are in the range of 0.01 to 5 mol%, preferably 0.02 to 10% with respect to the aliphatic alkylenediamine component constituting the polyamide. The amount is 2 mol%, particularly preferably 0.05 to 1 mol%. When the content of the monocarboxylic acid or monoamine is less than 0.01 mol% with respect to the aliphatic alkylenediamine component, the heat aging resistance of the molded product obtained from such a polyamide composition is not sufficiently improved, while 5 mol %, The mechanical strength such as tensile strength and bending strength will decrease. In particular, as will be described later, when a polyamide composition is produced by polycondensing a polyamide raw material in the presence of a monocarboxylic acid or a monoamine, since the molecular weight of the obtained polyamide does not become sufficiently large, the tensile strength and bending strength are lowered. Come to do.

Furthermore, the engineering polyamide composition according to the present invention preferably contains a hypophosphite, particularly an alkali metal hypophosphite, as an additive together with the above-mentioned monocarboxylic acid or monoamine. Specifically as such hypophosphite, potassium hypophosphite, sodium hypophosphite, calcium hypophosphite, barium hypophosphite, magnesium hypophosphite, manganese hypophosphite, hypophosphite Examples include nickel and cobalt hypophosphite.

In the engineering polyamide composition according to the present invention, these hypophosphites are also contained in an amount of 0.01 to 5 relative to the aliphatic alkylenediamine component constituting the polyamide.
The content is in the range of mol%, preferably 0.02 to 2 mol%, particularly preferably 0.05 to 1 mol%. When a large amount of hypophosphite exceeds 5 mol%, the tensile strength and bending strength of the molded product from the obtained polyamide composition are the same as those described for the monocarboxylic acid or monoamine. It is not preferable because it lowers the mechanical strength such as.

As described above, the polyamide can be obtained by any method such as a melting method, a solid phase method, and a combination thereof, and the engineering polyamide composition according to the present invention can be obtained by these methods. It can be obtained by adding the above-mentioned monocarboxylic acid or monoamine at any stage of the production of polyamide, and preferably by adding the above-mentioned hypophosphite together with these monocarboxylic acid or monoamine. However, the timing of adding these additives does not have to be the same. It can also be obtained by adding and mixing a monocarboxylic acid or monoamine and a hypophosphite to the polyamide obtained by any method.

However, in the present invention, the monocarboxylic acid or monoamine and the hypophosphite are used in combination at the stage of polycondensing the dicarboxylic acid component and the aliphatic alkylenediamine component, or a nylon salt or oligomer thereof. According to this, a polyamide composition having particularly excellent fluidity can be obtained, and further, such a polyamide composition gives a molded article particularly excellent in heat aging resistance.

In the polyamide composition according to the present invention, in addition to the above-mentioned monocarboxylic acid or monoamine and hypophosphite, if necessary, conventionally known polymers, stabilizers, plasticizers, release agents, lubricants , A filler, etc. may be contained.
Examples of the polymer include polyamides such as nylon 66 and nylon 6 and the like.

As the filler, conventionally known powder, plate,
Organic or inorganic substances having various forms such as transition or cross can be used.

As the inorganic filler, for example, silica, alumina, silica alumina, talc, diatomaceous earth, clay, kaolin, quartz, glass, mica, graphite, molybdenum disulfide, gypsum, red iron oxide, titanium dioxide, zinc oxide, aluminum, Powdery or plate-like materials such as copper and stainless steel,
Glass fiber, carbon fiber, boron fiber, ceramic fiber,
Examples thereof include fibrous materials such as asbestos fibers and stainless steel fibers, or cloth-shaped materials as secondary processed products thereof.

Examples of the organic filler include polyparaphenylene terephthalamide, polymetaphenylene terephthalamide, polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, diaminodiphenyl ether and terephthalic acid and / or isophthalic acid. Condensates with acids, wholly aromatic polyamides such as condensates of para- or meta-aminobenzoic acid, wholly aromatic polyamideimides such as condensates of diaminodiphenyl ether and trimellitic anhydride and / or pyromellitic acid, wholly aromatic Group polyimide, polybenzimidazole, heterocycle-containing polymer such as polyimidazophenanthroline, powdered material such as polytetrafluoroethylene, plate-shaped material, fibrous material or cross-shaped material as a secondary processed product thereof. Can be mentioned.

The above-mentioned fillers are blended alone or as a mixture, and if necessary, these fillers may be treated with a silane coupling agent, a titanium coupling agent or the like.

Among the above-mentioned fillers, as the powdery material, silica, silica-alumina, alumina, titanium dioxide, graphite, molybdenum disulfide, polytetrafluoroethylene and the like are preferably used, but in particular, graphite, molybdenum disulfide and Polytetrafluoroethylene is used to determine the dynamic friction coefficient, Taber wear, and limit of molded products obtained from the composition.
It is preferably used because it improves abrasion resistance such as PV value. Such a filler is preferable when the average particle diameter is usually in the range of 0.1 mμ to 200 μ, particularly in the range of 1 mμ to 100 μ, because the abrasion resistance of the obtained molded product is remarkably improved.

The amount of the powdery filler as described above is the polyamide composition.
With respect to 100 parts by weight, 200 parts by weight or less, preferably 100 parts by weight or less, particularly preferably 0.5 to 50 parts by weight.

Further, when a fiber made of the wholly aromatic polyamide is used as the filler, the tensile strength of the molded product obtained from the composition, mechanical properties such as Izod impact strength, and heat resistance properties such as heat distortion temperature are further improved. . When glass fiber, carbon fiber or boron fiber is used as the fibrous inorganic filler, mechanical properties such as tensile strength, bending strength and bending elastic modulus of the molded product obtained from the composition, heat deformation temperature, etc. The heat resistance and chemical / physical properties such as water resistance are further improved.

These fibrous fillers are usually 0.1 to 20 mm, especially 1 to 1
It is preferable to have an average length in the range of 0 mm. The blending amount is usually 200 parts by weight or less, preferably 5 to 180 parts by weight, and particularly preferably 5 to 150 parts by weight with respect to 100 parts by weight of polyamide.

The engineering polyamide composition according to the present invention,
It can be molded by a usual melt molding such as compression molding, injection molding or extrusion molding.

(Effect of the invention) The engineering polyamide composition according to the present invention comprises:
As described above, a polyamide having a predetermined composition, a monocarboxylic acid or a monoamine and a hypophosphite are contained, and a molded article obtained from such a polyamide composition is remarkably improved in its heat aging resistance. ing. Of course, heat resistance characteristics such as melting point, glass transition point and heat deformation temperature, tensile strength, bending strength, impact characteristics, dynamic friction coefficient, mechanical characteristics such as Taber abrasion, chemical resistance, boiling water resistance, chemistry such as saturated water absorption rate, etc. Physical properties, fluidity of melted composition, melt compression moldability, melt injection moldability, melt extrusion moldability, and other molding characteristics.

In particular, when producing a polyamide having a high molecular weight as well as having a component unit composition specified in the present invention, for example, by melt polymerization or solid phase polymerization, high temperature conditions are required. By polycondensing the polyamide raw material in the presence of carboxylic acid or monoamine and hypophosphite, thermal degradation of the polymer is prevented even during polycondensation,
Furthermore, an engineering polyamide composition having excellent fluidity can be obtained. Further, this composition gives a molded article having excellent heat aging resistance.

〔Example〕

The present invention will be described below with reference to examples, but the present invention is not limited to these examples. still,
In the table below, the abbreviations indicate the following compounds, respectively.

TA: terephthalic acid IA: isophthalic acid C ₆ DA: 1,6-hexamethylenediamine C ₁₀ DA: 1,10-decamethylenediamine The method for preparing the test piece and the evaluation method for each performance are as follows.

[Preparation of Test Pieces of Molded Polyamide Composition and Evaluation of Physical Properties]

The polyamide composition was crushed by a crusher (passed through 32 mesh) and dried at 100 ° C. and 1 mmHg for 12 hours. This polyamide composition was hot-pressed at a temperature of 20 ° C. higher than the melting point of the polyamide under a pressure of 100 kg / cm ^{2 in} a nitrogen atmosphere using a press molding machine, and then cold-pressed at a temperature of 20 ° C. to 2-4 mm. A thick compression molded plate was prepared. These molded plates were cut into test pieces having the dimensions shown in Table 1, then left for 96 hours in an atmosphere having a temperature of 23 ° C. and a relative humidity of 65%, and then subjected to each test. The heat aging resistance was evaluated by the flexural strength after the flexural test piece was stored in an air oven at 250 ° C. for 2 days and its retention rate with respect to the initial value.

In addition, the glass fiber compounded molding is 60 parts by weight of pulverized and dried polyamide and 40 parts by weight of glass fiber (average length 6 mm, manufactured by Nitto Boseki Co., Ltd., CS 6PE-231) and a predetermined stability. The agent is fed to a single-screw extruder (L / D = 28, 20 mm diameter) and mixed to obtain a strand-shaped polyamide composition of about 6 mm, which is used in the same manner as in the case of not blending the glass fiber described above. And press-molded to produce a test piece.

Example 1 123.6 g (0.744 mol) of terephthalic acid, 52.9 g of isophthalic acid
(0.318 mol), benzoic acid 1.22 g (0.01 mol), hexamethylenediamine 123.4 g (1.06 mol), sodium hypophosphite monohydrate 0.2254 g (0.00212 mol) and ion-exchanged water 33 g were charged in a 1-volume autoclave, After sufficiently purging with nitrogen, the temperature was raised to 280 ° C. for 2 hours with stirring. Furthermore, after allowing the reaction to proceed at 280 ° C for 1 hour in a sealed state, stirring was stopped and the differential pressure from the bottom of the autoclave was 10 kg / cm ²
The reaction mixture was taken out at. This in nitrogen at 100 ℃, 100
Dried overnight at mmHg.

Use this oligomer for twin-screw extruder (Screen diameter 30mm, L / D
= 42, barrel temperature (℃) 30/260/280/340/340/340/320/3
20/320/320, 4th and 6th zone are open to the atmosphere vent, rotation speed is 80 rpm, oligomer supply rate is 2 kg / hour, exhaust gas is nitrogen purge) to proceed polycondensation to obtain high molecular weight polyamide composition. It was Table 2 shows the properties of the polyamide composition thus obtained and the physical properties of molded test pieces obtained from this composition.

Example 2 In Example 1, instead of 1.22 g of benzoic acid, aniline
A polyamide composition was produced in the same manner as in Example 1 except that 0.93 g (0.01 mol) was used. Table 2 shows the properties of the polyamide thus obtained and the physical properties of the molded test piece obtained from this composition.

(Production of concentrated sulfuric acid insoluble polyamide) Example 3 The polyamide composition obtained in Example 1 was treated at 280 ° C and 1 mmHg.
Solid-state polymerization was carried out for 4 hours under stirring under the conditions of (1) to increase the molecular weight to obtain a concentrated sulfuric acid-insoluble polyamide composition. Table 2 shows the properties of the polyamide thus obtained and the physical properties of the molded test piece obtained from this composition.

Example 4 In Example 1, 129.6 g of hexamethylenediamine (1.
An oligomer was obtained in the same manner as in Example 1 except that 12 mol) was used, and the oligomer was made to have a high molecular weight in the same manner as in Example 3 to obtain a concentrated sulfuric acid-insoluble polyamide composition. Table 2 shows the properties of the polyamide thus obtained and the physical properties of the molded test piece obtained from this composition.

Example 5 In Example 2, 114.7 g (0.70 mol) of terephthalic acid,
An oligomer was obtained in the same manner as in Example 2 except that 61.7 g (0.37 mol) of isophthalic acid was used. The oligomer was polymerized in the same manner as in Example 3 to obtain a concentrated sulfuric acid-insoluble polyamide composition. Table 2 shows the properties of the polyamide thus obtained and the physical properties of the molded test piece obtained from this composition.

Example 6 232 g (1.40 mol) of terephthalic acid, 1.10-diaminodecane
241 g (1.4 mol), sodium hypophosphite monohydrate 0.297 g (0.0
028 mol) and 10 l of ion-exchanged water were charged into a 10 l reactor equipped with a stir bar, a thermometer and a reflux condenser, and reacted under a nitrogen atmosphere at a temperature of 95 to 100 ° C. for 1 hour. After the reaction was completed, the transparent solution was air-cooled, and the precipitated nylon salt was collected by suction filtration and dried at 100 ° C. and 100 mmHg to obtain 450 g of terephthalic acid-1,10-diaminodecane nylon salt.

450 g (1.33 mol) of this nylon salt was charged into a 1-volume reactor, the inside of the reaction vessel was replaced with nitrogen, the temperature was gradually raised in a nitrogen stream, and after reaching 300 ° C, the reaction was carried out for 1.5 hours to produce Water was taken out of the system to obtain 390 g of an oligomer composed of terephthalic acid-1,10-diaminodecane. The [η] measured in concentrated sulfuric acid at 30 ° C was 0.45 dl / g.

After crushing this polyamide with a crusher (passing through 32 mesh) and drying for 12 hours at 80 ° C. and 50 mmHg,
Solid-state polymerization was carried out for 10 hours at 300 ° C. and 0.7 mmHg to obtain a polyamide composed of terephthalic acid-1,10-diaminodecane. Table 2 shows the properties of the polyamide thus obtained and the physical properties of the molded test piece obtained from this composition.

Example 7 A composition was prepared by mixing 60 parts by weight of the polyamide synthesized by the method of Example 2 with 40 parts by weight of glass fiber (average length 6 mm, manufactured by Nitto Boseki Co., Ltd. CS6PE-231).
This physical property was evaluated. The results are shown in Table 2.

Comparative Examples 1 to 3 Polyamides were produced by the method described in Example 1 except that benzoic acid or aniline was used in the amount shown in Table 2 instead of 1.22 g of benzoic acid in Example 1. . The results are shown in Table 2.

Comparative Example 4 A polyamide was produced by the method described in Example 1, except that 1.22 g of benzoic acid was used instead of 1.22 g of benzoic acid and 6.74 g of sodium hypophosphite monohydrate was used. . The results are shown in Table 2.

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Claims (2)

[Claims] 1. A (a) (a) terephthalic acid component unit is 60
To 100 mol% and aromatic dicarboxylic acid component units other than terephthalic acid component units in the range of 0 to 40 mol%, and (b) aliphatic having 6 to 18 carbon atoms. An alkylenediamine component unit having a melting point of 309 ° C. or higher, and (B) 0.01 to 5 mol% of an aromatic monocarboxylic acid or an aromatic monocarboxylic acid with respect to the aliphatic alkylenediamine component constituting the polyamide. Amine, 0.01-5 mol%
A polyamic acid composition for engineering, comprising: 2. The (a) terephthalic acid component unit is 60 to 100.
An aromatic dicarboxylic acid component unit in the range of mol% and an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit in the range of 0 to 40 mol%; and (b) an aliphatic alkylenediamine having 6 to 18 carbon atoms. (C) 0.01-5 mol% of aromatic monocarboxylic acid or aromatic monocarboxylic acid with respect to the aliphatic alkylenediamine component constituting the polyamide when producing a polyamide having a melting point of 309 ° C. or higher. Primary amine and 0.01-5 mol%
The method for producing a polyamide composition for engineering, which comprises polycondensing an aliphatic alkylenediamine component in the coexistence with the hypophosphite, or polycondensing a nylon salt or an oligomer thereof.