JPH10292042A - Polyamide and production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyamide which does not become cloudy in heat treatment, is excellent in clarity, and is soluble in a lower alcohol, etc., by selecting a polyamide comprising units derived from a dicarboxylic acid component mainly comprising 1,6-decanedicarboxylic acid, units derived from a diamine component, and units derived from an aliph. aminocarboxylic acid component and/or units derived from a lactam component. SOLUTION: This polyamide is produced by a two-stage polymn. process comprising the first polymn. step conducted at 160-320 deg.C under 0-50 kgf/cm<2> G to produce a polyamide prepolymer having a number average mol. wt. of 800-5,000 and the second polymn. step conducted at 160-320 deg.C under 10-760 mmHg to produce a polyamide having a number average mol.wt. of 7,000-50,000. 50-100 wt.% of the dicarboxylic acid component is 1,6-decanedicarboxylic acid. An example of the diamine used is 1,4-diaminobutane; that of the aliph. aminocarboxylic acid, ε-aminocaproic acid; and that of the lactam, ε- caprolactam.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polyamide containing a specific dicarboxylic acid as one component. More specifically, the present invention relates to a novel amorphous polyamide containing 1,6-decanedicarboxylic acid having a linear butyl group in a side chain and various diamines as main components, and a method for producing the same.

[Prior art]

[0002] Polyamide is a crystalline polymer having a structure comprising a linear main chain skeleton comprising carbon-carbon bonds and amide groups and hydrogen bonds between amide groups. Polyamide with high crystallinity has excellent rigidity, abrasion resistance, heat resistance, oil resistance, solvent resistance, gas barrier properties, etc., and is widely used in applications such as fibers, films, automobile parts and electric and electronic parts. It is used. On the other hand, a polyamide having a low degree of crystallization or an extremely low crystallization rate and exhibiting substantially no crystallinity is called an amorphous polyamide, and has excellent transparency and solubility in a solvent, and has excellent transparency. It is used for fibers, films, and molded products by taking advantage of its solubility, and for adhesives by taking advantage of its solubility in solvents.

[0003] Nylon 6, Nylon 66, Nylon 12
At room temperature, crystalline polyamides such as are soluble only in specific acidic solvents such as sulfuric acid, formic acid, phenol, cresol, and hexafluoroisopropanol, and can be used to prepare lower alcohols such as methanol and ethanol, dimethylacetamide, and N-methylpyrrolidone. It hardly dissolves in such aprotic organic solvents. Therefore, it is difficult to handle the polyamide in a solution state, which makes it difficult to modify or improve the polyamide by a chemical modification reaction or the like.
Also, when the crystallinity is high, the interaction between the amide group of the polyamide and the hydroxyl group, carboxyl group, amino group, carbonyl group, etc. of other materials due to hydrogen bonding is inhibited, and the coordination ability of the amide group to metal ions Or decrease. For this reason, it has been difficult to expand into the field of functional materials utilizing the inherent polarity of the amide group.
With the sophistication of market needs, application development as a functional material utilizing the inherent properties of polyamide is expected,
There is an increasing demand for amorphous polyamides that suppress crystallization as much as possible.

Hitherto, in order to obtain an amorphous polyamide, crystallization hardly occurs or as a method of delaying the crystallization, a polyamide or a copolyamide having a side chain or a ring structure has been studied. These results have been proposed as various transparent polyamides. For example,
JP-B-49-21115 proposes a transparent polyamide comprising dimethyl terephthalate and trimethylhexanemethylenediamine. This polyamide is slow in crystallization and excellent in transparency, but has low solubility in lower alcohols and the like.

It is known that a polyamide having an amide bond at the 1,3-position of benzene or cyclohexane becomes a transparent and amorphous polyamide. For example, there is a polyamide composed of hexamethylenediamine and isophthalic acid, and a polyamide composed of 1,3-bisaminomethylcyclohexane and adipic acid. These polyamides are transparent in appearance after production, but can be easily crystallized by hot water immersion at 90 to 98 ° C. (hereinafter abbreviated as “hot water treatment”) or methanol immersion at room temperature. Progress is lost. They also have low solubility in lower alcohols and aprotic organic solvents.

It is known that a copolyamide obtained by copolymerizing nylon 6, nylon 66 and / or nylon 12 becomes an amorphous polyamide. However, most of this copolyamide is a differential scanning calorimeter (hereinafter referred to as "D
SC ") measurement shows an endothermic peak based on crystals. Further, even if the appearance is transparent after the production, crystallization easily proceeds by hot water treatment and the transparency is lost. Further, the solubility in an aprotic organic solvent is low.

JP-A-49-36959 discloses that a polyamide comprising hexamethylenediamine and terephthalic acid and a polyamide comprising hexamethylenediamine and isophthalic acid are copolymerized in a specific ratio.
It has been proposed to obtain a transparent copolyamide. This copolyamide is easily crystallized by hot water treatment and loses transparency. Further, the solubility in lower alcohols and aprotic organic solvents is low.

Further, JP-A-5-310923 discloses a copolyamide comprising a polyamide comprising hexamethylenediamine and 2,6-naphthalenedicarboxylic acid and a polyamide comprising caprolactam.
No. 1 proposes a copolyamide of a polyamide composed of hexamethylenediamine and 2,6-naphthalenedicarboxylic acid and a polyamide composed of hexamethylenediamine and isophthalic acid as a transparent polyamide. These are transparent in appearance after production,
Without the hot water treatment, D of copolyamide after production
From the SC measurement and the dynamic solid viscoelasticity measurement, an endothermic peak and a change in elastic modulus based on the crystal can be confirmed, and it can be seen that the crystal is crystallized. Further, these copolyamides have low solubility in lower alcohols and aprotic organic solvents. As described above, conventionally, amorphous polyamides that have been proposed are slower in crystallization than nylon 6 or the like, but are easily crystallized by hydrothermal treatment to lose transparency, or have a lower alcohol or aprotic property. The material had almost no solubility in the solvent.

[Problems to be solved by the invention]

It is an object of the present invention to provide a compound which is slow in crystallization, excellent in transparency, and soluble in aprotic organic solvents such as lower alcohols such as methanol and ethanol, dimethylacetamide and N-methylpyrrolidone. To provide a novel amorphous polyamide having the following formula:

[Means for Solving the Problems]

The present inventors have intensively studied a novel method for inhibiting the hydrogen bond interaction between amide groups of a polyamide molecular chain for the purpose of establishing an amorphous polyamide and a method for producing the same. As a result, a polyamide containing a dicarboxylic acid having a branch of a specific length as one component is not easily crystallized by hot water treatment, retains transparency, and is dissolved in a lower alcohol or an aprotic organic solvent. And arrived at the present invention.

That is, the present invention relates to (A) a unit derived from a dicarboxylic acid component in which 50 to 100% by weight of the dicarboxylic acid component is 1,6-decanedicarboxylic acid;
(B) a unit derived from a diamine component, and (C)
0 to 50% by weight of the total amount is a polyamide comprising units derived from an aliphatic aminocarboxylic acid component and / or units derived from a lactam component.

The second invention of the present invention relates to the above polyamide, wherein the number average molecular weight is 80 in the first stage polymerization.
A polyamide prepolymer having a number average molecular weight of 7,000 to 50,000 is produced by preparing a polyamide prepolymer in the range of 0 to 5,000, and increasing the molecular weight of the polyamide prepolymer in the second stage polymerization.
A method for producing the above-mentioned polyamide in the range of 00.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION As the 1,6-decanedicarboxylic acid of the present invention, those produced by oxidative decomposition of cyclohexane or a method using 7-cyanoundecanoic acid as a raw material can be used. It is one of the features of the present invention that a polyamide containing a specific amount of 1,6-decanedicarboxylic acid as a component achieves the object of the present invention. This suggests that 1,6-decanedicarboxylic acid is effectively inhibiting the hydrogen bonding interaction between the amide groups of the polyamide. One of the features of the present invention is that 1,6-decanedicarboxylic acid has been found to be a dicarboxylic acid having good polymerization reactivity and thermal stability and suitable as a raw material for polyamide.

The proportion of 1,6-decanedicarboxylic acid in the dicarboxylic acid component used in the present invention is 50 to 100% by weight, preferably 70 to 100% by weight. When the proportion of 1,6-decanedicarboxylic acid is less than 50% by weight, the transparency of the polyamide immediately after production or immediately after molding is poor, and even when the polyamide is obtained in a transparent appearance, it is easily treated with hot water. Opaque, and its solubility in lower alcohols and aprotic organic solvents is low, which is not preferred.

As the dicarboxylic acid other than 1,6-decanedicarboxylic acid used in the present invention, any of known aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids can be used. Specific examples include butanedioic acid, pentanedioic acid, hexanedioic acid, octanedioic acid, nonandioic acid, decanedioic acid, undecandioic acid, dodecandionic acid, tridecandionic acid, tetradecandionic acid, pentadecandionic acid, and hexadecandionic acid. , 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, and 1,4-naphthalenedicarboxylic acid. These dicarboxylic acids can be used alone or in combination of two or more. Among these, butanedonic acid, 1,3-cyclohexanedicarboxylic acid, and isophthalic acid are easy to handle, have good polymerization reactivity, and can be preferably used.

The diamine used in the present invention includes known diamines, for example, aliphatic alkylene diamines having 4 to 12 carbon atoms, alicyclic diamines and aromatic diamines. Specific examples of the aliphatic alkylenediamine having 4 to 12 carbon atoms include 1,4-diaminobutane, 1,5
-Diaminopentane, 1,6-diaminohexane, 1,
7-diaminoheptane, 1,8-diaminooctane,
1,9-diaminononane, 1,10-diaminononane,
1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotridecane, 1,15-diaminopentadecane,
1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 2,
2,4-, 2,4,4-trimethylhexamethylenediamine and the like can be mentioned. Among them, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane and 2,2,4-, 2,4,4-trimethylhexamethylenediamine are easy to handle and polymerized. It has good reactivity and can be used preferably.

As the alicyclic diamine, any diamine containing a cyclohexane ring can be used. Specific examples include 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, and bis (3-methyl-4-aminocyclohexyl) methane.

As the aromatic diamine, any diamine containing an aromatic ring can be used. Specific examples include paraxylenediamine, metaxylenediamine, paraphenylenediamine, metaphenylenediamine, and 4,4'-diaminodiphenylmethane. Of these, paraxylenediamine and metaxylenediamine are easy to handle, have good polymerization reactivity, and can be preferably used. These aliphatic alkylenediamines, alicyclic diamines, and aromatic diamines can be used alone or in combination of two or more.

In producing the polyamide of the present invention, 1,6
A dicarboxylic acid and a diamine containing 50 to 100% by weight of decanedicarboxylic acid may be used as they are,
It may be used as a nylon salt synthesized by dissolving and mixing a dicarboxylic acid and a diamine in water or hot water and adjusting the pH. The dicarboxylic acid and the diamine are generally used in a molar ratio in the range of 100/95 to 100/105, preferably in the range of 100/99 to 100/101. Excessively out of this range makes it difficult to obtain a polyamide having a target number average molecular weight (hereinafter abbreviated as “Mn”). The number average molecular weight is a value obtained from the reciprocal of the average value of the terminal amino group concentration and the terminal carboxy group concentration of the obtained polyamide.

Specific examples of the aliphatic aminocarboxylic acid used in the present invention include ε-aminocaproic acid, ω-aminoheptanoic acid, ω-aminononanoic acid, ω-aminoundecanoic acid and ε-aminododecanoic acid. . The lactam is a cyclic amide compound having 4 to 12 carbon atoms, and specific examples include ε-caprolactam and ω-
Enanthractam, ω-undecanelactam, ω-dodecalactam, α-pyrrolidone, δ-methylpyrrolidone, and the like. These aliphatic aminocarboxylic acids and lactams can be used alone or in an appropriate combination of two or more. Among them, ε-aminocaproic acid, ε-aminododecanoic acid and ε-caprolactam are easy to handle, have good polymerization reactivity, and can be preferably used.

The amount of the aliphatic aminocarboxylic acid or lactam used is in the range of 0 to 50% by weight based on the total amount of the polyamide to be produced. When the amount used is more than 50% by weight, the transparency of the polyamide immediately after production or immediately after molding becomes poor, or even when the polyamide can be produced in a transparent state in appearance,
It is not preferable because crystallization is easily caused by the hot water treatment and may become opaque. In addition, the solubility in lower alcohols and aprotic organic solvents may be low, which is not preferable.

For the production of the polyamide of the present invention, a known polyamide production apparatus can be used. As a polymerization method at the time of production, a known method such as melt polymerization or solution polymerization can be used. These polymerization methods can be used alone or in an appropriate combination. Generally, melt polymerization is simple and preferred.

The polymerization can be carried out either batchwise or continuously. Apparatuses to be used include a batch type reaction vessel, a single-tank type or multi-tank type continuous reactor, a tubular continuous reactor, a single-screw kneading extruder, a twin-screw kneading extruder and a multi-screw kneading extruder. A known polymerization reaction device such as a kneading reaction extruder and a horizontal second polymerization tank disclosed in Japanese Patent Publication No. 4-32096 can be used. The polymerization reaction is desirably conducted in a state where the reaction mixture is as uniform as possible. From this point, it is desirable to use a polymerization apparatus having high stirring efficiency.

In the production of the polyamide of the present invention, a dicarboxylic acid and a diamine containing 50 to 100% by weight of 1,6-decanedicarboxylic acid as raw materials, and if necessary, an aliphatic aminocarboxylic acid and a lactam are used as they are. Water was added and the mixture was put into a polymerization tank.
5,000 to 5,000 polyamide prepolymer (hereinafter abbreviated as “prepolymer”), and the prepolymer is highly polymerized in the second stage polymerization to obtain Mn of 7,000 to 50,000.
This is performed by setting it to 0.

When water is used in the present invention, pure water such as ion-exchanged water or distilled water may be used as the water. However, these waters are boiled immediately before use to remove oxygen dissolved in the water. It is preferable to use the degassed water removed. The amount of water used is generally 1 to 100 parts by weight of the total amount of the raw materials.
It is in the range of 150 parts by weight, preferably in the range of 5 to 100 parts by weight. If the amount of water used is too small, the melt viscosity of the polymerization reaction product may increase, or a prepolymer may precipitate during the polymerization reaction. Also, when the amount of water used increases, the number average molecular weight of the obtained prepolymer tends to decrease, the polymerization time in the second stage increases, and the balance between the amino group concentration and the carboxyl group concentration of the terminal group deteriorates. Or

The polymerization temperature in the first stage of polymerizing the prepolymer is generally from 160 to 320 ° C., preferably from 180 to 320 ° C.
It is in the range of 280 ° C, more preferably 180 to 230 ° C. When the polymerization temperature is low, the polymerization rate becomes slow and the polymerization time becomes long. When the polymerization temperature is high, a side reaction or a thermal decomposition reaction easily occurs, and the obtained prepolymer is colored or gelled.

The polymerization pressure in the first stage are atmospheric or pressurized, the general range of 0~50kgf / cm ² G, preferably from 0~30kgf / cm ² G. If the polymerization pressure is lower than normal pressure, the raw materials, particularly the diamine component, may be scattered outside the polymerization system due to evaporation, and in this case, the molar balance with the dicarboxylic acid is lost, and the desired Mn prepolymer may be obtained. It becomes difficult. When the polymerization pressure is high, the Mn of the obtained prepolymer tends to be small, and the polymerization time of the second step may be long, or the balance between the amino group concentration and the carboxyl group concentration of the terminal group may be poor. The pressure in the polymerization tank is determined by the polymerization temperature, the amount of water added to the raw materials, and the amount of water generated in the polymerization (condensation) reaction. The polymerization pressure is adjusted by a pressure control valve or the like directly connected to the polymerization tank.

The polymerization time of the first stage varies depending on the polymerization temperature and the polymerization pressure. Usually, it is in the range of 5 minutes to 10 hours, preferably in the range of 10 minutes to 7 hours, more preferably in the range of 30 minutes to 5 hours. If the polymerization time is too short, the polymerization does not proceed sufficiently, and the number average molecular weight of the prepolymer becomes low.
Further, when the polymerization time is long, side reactions and thermal decomposition reactions are likely to occur, and the resulting prepolymer may be colored or gelled.

The Mn of the prepolymer obtained in the first stage polymerization reaction is in the range of 800 to 5,000, preferably 10 to 5,000.
The range is from 00 to 4,000. When the Mn of the prepolymer is less than 800, the polymerization time in the second stage becomes longer, or the balance between the amino group concentration and the carboxyl group concentration of the terminal group becomes poor, and it becomes difficult to obtain the desired polyamide of Mn. Is not preferred. On the other hand, if it exceeds 5,000, the melt viscosity of the polymerization reaction mixture becomes high, and the polymerization reaction becomes non-uniform.

The polymerization temperature in the second stage is generally the same as or higher than in the first stage. Usually 180-320
° C, preferably a temperature range of 200 to 300 ° C, more preferably a temperature range of 230 to 280 ° C. When the polymerization temperature is low, the polymerization rate becomes slow, the polymerization time becomes long, and it becomes difficult to obtain the target polyamide of Mn. When the polymerization temperature is high, side reactions and thermal decomposition reactions are likely to occur, and the resulting polyamide may be colored or gelled.

The polymerization pressure in the second stage is normal pressure or reduced pressure, and generally ranges from 10 to 760 mmHg.
When the pressure is higher than normal pressure, it is difficult to exhaust water contained in the prepolymer and water produced as a by-product from the polymerization (condensation) reaction of the prepolymer to the outside of the polymerization reaction system, and it is difficult to increase the molecular weight of the prepolymer. Becomes If the polymerization pressure is too low, the decompression equipment for evacuation becomes very costly.

When the polymerization pressure is reduced, at least one vent port is provided in the second-stage polymerization apparatus, and the vent port is connected to a known vacuum equipment such as a Nash pump, a mechanical booster, a steam ejector and forcibly. It is performed by an exhaust method.

The polymerization time in the second step varies depending on the polymerization equipment, polymerization temperature and polymerization pressure used, but is usually from 1 minute to 1 minute.
The range is 10 hours. The Mn of the polyamide of the present invention produced under the above conditions is in the range of 7,000 to 50,000, preferably in the range of 10,000 to 30,000. When Mn is less than 7,000, practical properties such as strength are low, and a polyamide suitable for practical use cannot be obtained. On the other hand, when Mn exceeds 50,000, the viscosity at the time of melting becomes high and melt molding becomes difficult, which is not preferable.

In the method of the present invention, phosphoric acid, phosphorous acid, hypophosphorous acid, or the like may be used in the first or second stage polymerization, if necessary, in order to prevent a polymerization accelerator and deterioration during the polymerization.
Phosphoric compounds such as pyrophosphoric acid, polyphosphoric acid and their alkali metal salts, alkaline earth metal salts or esters can be added. The amount of the phosphorus compound to be added is usually 50 to 50% based on the polyamide to be obtained.
An amount in the range of 3,000 ppm is preferably used. If the amount is out of this range, the polymerization rate is decreased, and the resulting polyamide is colored or gelled, which is not preferable.

For the purpose of controlling the molecular weight of the obtained polyamide and stabilizing the melt viscosity during molding, if necessary, an amine or a carboxylic acid may be used during the polymerization in the first or second step. Can be added. The amine or carboxylic acid to be added is not particularly limited as long as it is monofunctional and / or bifunctional. For example, monoamines such as laurylamine, stearylamine, and benzylamine, 1,6-diaminohexane,
7-diaminoheptane, 1,8-diaminooctane,
1,9-diaminononane, 1,10-diaminononane,
1,11-diaminoundecane, 1,12-diaminododecane, diamines such as meta-xylylenediamine and para-xylylenediamine, monocarboxylic acids such as acetic acid, benzoic acid, lauric acid and stearic acid and butanedioic acid, pentanedioic acid, Dicarboxylic acids such as hexanedioic acid, octanedioic acid, nonandioic acid, decanedioic acid, undecandioic acid, dodecandioic acid, isophthalic acid and terephthalic acid are preferred. The addition amount of these molecular weight regulators varies depending on the reactivity of the molecular weight regulator used and the polymerization conditions, but the Mn of the polyamide finally obtained is 7,000 to 50,000.
Is appropriately determined so as to fall within the range.

Further, the polyamide of the present invention may be used, if necessary, in the first or second stage polymerization, as a heat-resistant agent, an antioxidant, a weathering agent, a lubricant, an antistatic agent, a pigment, a dye, an anti-blocking agent. An agent such as an agent can be added in a range that does not impair the physical properties of the polymer.

The polyamide of the present invention can be used as an adhesive or a functional polyamide by taking advantage of its solubility in fibers, films, molded articles and amide group polar or lower alcohols or aprotic organic solvents which require transparency. It can be used for applications such as raw materials for production.

[0038]

EXAMPLES Examples and comparative examples are shown below to specifically explain the effects of the present invention. The measured values shown in the examples and comparative examples were measured by the following methods.

1) Relative Viscosity According to JIS K6810, relative viscosity was measured at a temperature of 25 ° C. using 98 wt% concentrated sulfuric acid as a solvent at a polymer concentration of 1 wt / vol% using an Ubbelohde viscometer.

2) A terminal amino group concentration of about 1 g of a polymer was dissolved in 40 ml of a phenol / methanol mixed solvent (volume ratio: 9/1), and this sample solution was titrated with N / 20 hydrochloric acid using thymol blue as an indicator. .

3) Concentration of terminal carboxyl groups: A sample solution obtained by adding 40 ml of benzyl alcohol to a polymer having a concentration of about 1 g and heating and dissolving in a nitrogen gas atmosphere is
Titration was performed with an N / 20 potassium hydroxide-ethanol solution using phenolphthalein as an indicator.

4) Number average molecular weight The number average molecular weight was determined as the reciprocal of the average of the terminal amino group concentration and the terminal carboxyl group concentration.

5) Glass transition temperature: dried at 40 ° C. for 72 hours under reduced pressure
Using DSC (model DSC-50) manufactured by Shimadzu Corporation,
The measurement was performed at a heating rate of 10 ° C./min in a helium gas atmosphere. The measurement sample was cooled to −50 ° C. with liquid nitrogen, and the inflection point of the heating curve was defined as the glass transition temperature.

6) Melting point: dried under reduced pressure at 40 ° C. for 72 hours as a sample
Using DSC (model DSC-50) manufactured by Shimadzu Corporation,
The temperature was measured under a nitrogen gas atmosphere at a heating rate of 10 ° C./min, and the endothermic peak temperature was defined as the melting point.

7) Evaluation of crystallization About 3 g of a sample dried under reduced pressure at 40 ° C. for 48 hours is 90-98.
The sample was immersed in about 50 cc of hot water at a temperature of 50 ° C. and maintained at the same temperature. When not clouded for more than 1 hour: Crystallization is very slow. If turbid during 30 minutes to less than 1 hour: crystallization is slow. When cloudy during 0 to less than 30 minutes: Crystallization is easy. If cloudy before hot water treatment: Crystallization is fast.

8) Measurement of dynamic viscoelasticity Using a dynamic viscoelasticity measuring apparatus RSAII manufactured by Rheometrics, a film formed by a hot press method was used as a measurement sample.
The temperature dispersion spectrum of dynamic viscoelasticity was measured under the following conditions. Measurement mode: tensile, frequency: 62.7998 rad / s
ec (10 Hz) Temperature range: -150 to 250 ° C, heating step: 3 ° C,
Distortion: 0.05% Dimensions of sample film: width 5 mm, length 35 mm, thickness 0.03 mm Film preparation conditions: The polyamide of the present invention was prepared using a commercially available hot press molding apparatus at a temperature of 180 ° C. and a pressure of 50 kgf /.
It was prepared under the conditions of cm ² G and a retention time of 2.5 minutes. The polyamide of the comparative example was prepared using a commercially available hot press molding machine at a temperature of 26.
It was prepared under the conditions of 0 ° C., a pressure of 100 kgf / cm ² G, and a holding time of 2.5 minutes.

9) Evaluation of Solubility 50 ml of methanol or N, N-dimethylacetamide was added to 1.5 g of the sample polymer, and stirred at room temperature for 2 hours.
After holding for 4 hours, visual judgment was made based on the following criteria. ：: dissolved (transparent and not turbid), ×: not dissolved

Example 1 Degassed water at 50 ° C. obtained by boiling high-purity exchanged water
Disperse 200 g of 1,6-decanedicarboxylic acid in 4 g,
While stirring under a nitrogen gas atmosphere, a 35% by weight aqueous solution of 1,6-diaminohexane was added. When the pH reached 8.12, the addition was stopped, and 1,6-diaminohexane and 1,6-diaminohexane were added. An about 35% by weight aqueous solution of a nylon salt composed of decanedicarboxylic acid (hereinafter abbreviated as “6D salt”) was obtained. This aqueous solution was concentrated to about 75% by weight, and 278 g of a 6D salt aqueous solution (0.602 mol as a 6D salt) was placed in a volume of 1 liter equipped with a stirrer, thermometer, pressure gauge, nitrogen inlet, pressure outlet, and polymer outlet. In a pressure vessel. After the pressure vessel was sufficiently purged with nitrogen, the temperature was raised in a closed state under stirring, and the mixture was polymerized at a temperature of 220 ° C. and a pressure of 16 kgf / cm ² G for 3 hours to obtain a prepolymer. Several g of the prepolymer for measuring the number average molecular weight was collected. Number average molecular weight M of prepolymer
n was 2300. Thereafter, the pressure in the pressure vessel is reduced to 1
While maintaining the pressure at 6 kgf / cm ² G, the temperature was raised to 270 ° C. over 1 hour, and then the pressure in the pressure vessel was released at the same temperature over 30 minutes to normal pressure. At normal pressure, 2
While flowing nitrogen gas at a flow rate of 00 ml / min, 27
Polymerization was performed at 0 ° C. and 760 mmHg for 2 hours. Thereafter, stirring was stopped, and the produced polyamide was taken out in a string form from the polymer outlet at the bottom of the pressure vessel, and immediately cooled in a water tank.
A columnar polyamide chip was formed with a pelletizer. This polyamide chip was vacuum dried at 40 ° C. for 72 hours. The obtained polyamide was colorless and transparent. 9
Although hot water treatment was performed at 0 to 98 ° C., it remained transparent after 1 hour, and crystallization was very slow. In the DSC measurement and dynamic viscoelasticity measurement of the obtained polyamide, no melting peak or temperature dispersion spectrum based on crystals was observed. Table 1 shows the results of evaluation of the relative viscosity, terminal amino group concentration, terminal carboxyl group concentration, number average molecular weight, glass transition temperature, and solubility of the obtained polyamide.

Example 2 In a 100 ml glass container equipped with a stirrer and a nitrogen inlet, 6.829 g of metaxylylenediamine (0.
0501 mol) and 1,6-decanedicarboxylic acid.
530 g (0.0501 mol) were charged. After sufficiently replacing the inside of the glass container with nitrogen, the glass container is immersed in a heating medium bath, polymerization is performed at 190 ° C. for 2 hours while flowing nitrogen gas at 50 ml / min with stirring, and then the temperature is raised to 280 ° C. over 1 hour. Subsequently, polymerization was performed at 280 ° C. for 4 hours. The stirring was stopped, the glass container was taken out of the heat medium bath, and naturally cooled to room temperature while flowing nitrogen gas. Then, the glass container was cracked to take out the polyamide, crushed, and then
Dry under reduced pressure for 2 hours. The obtained polyamide was colorless and transparent. The polyamide was subjected to a hot water treatment at 90 to 98 ° C., but remained transparent after 1 hour, and the crystallization was very slow. Also, in the DSC measurement and the dynamic viscoelasticity measurement of the obtained polyamide, no melting peak or temperature dispersion spectrum based on crystals was observed. Table 1 shows the results of evaluation of the relative viscosity, terminal amino group concentration, terminal carboxyl group concentration, number average molecular weight, glass transition temperature, and solubility of the obtained polyamide.

Comparative Example 1 The procedure of Example 2 was repeated, except that 8.718 g (0.0501 mol) of octandionic acid was used instead of 1,6-decanedicarboxylic acid. The resulting polyamide was cloudy and opaque. In the DSC measurement, a melting point was observed. This indicates that the crystallization of the obtained polyamide is fast. Relative viscosity of the obtained polyamide,
Table 1 shows the results of evaluation of the terminal amino group concentration, terminal carboxyl group concentration, number average molecular weight, glass transition temperature, melting point, and solubility.

Comparative Example 2 In a 100 ml glass container equipped with a stirrer and a nitrogen inlet, 8.236 g of 1,6-diaminohexane was added.
(0.071 mol), terephthalic acid 3.486 (0.
021 mol) and 8.30 g of isophthalic acid (0.0
50 mol). After sufficiently replacing the inside of the glass container with nitrogen, the glass container is immersed in a heating medium bath, polymerization is performed at 210 ° C. for 2 hours while flowing nitrogen gas at 50 ml / min with stirring, and then the temperature is raised to 300 ° C. over 1 hour. And then 300
Polymerization was performed at a temperature of 5 ° C. for 5 hours. The stirring was stopped, the glass container was taken out of the heat medium bath, and naturally cooled to room temperature while flowing nitrogen gas. Thereafter, the glass container was cracked to take out the polyamide, pulverized, and dried under reduced pressure at 40 ° C. for 72 hours. The obtained polyamide was colorless and transparent. When this polyamide was subjected to hot water treatment at 90 to 98 ° C., cloudiness started in about 10 minutes and became opaque. This indicates that the degree of crystallization immediately after polymerization is low, but crystallization is easy.
Also, almost no solubility in methanol or N, N-dimethylacetamide was observed.

Example 3 1,3-bisaminomethylcyclohexane 1 was placed in a 160 ml glass container equipped with a stirrer and a nitrogen inlet.
5.419 g (0.1084 mol) and 24.934 g (0.1084 mol) of 1,6-decanedicarboxylic acid were added. After the inside of the glass container was sufficiently purged with nitrogen, the glass container was immersed in a heat medium bath, and polymerization was carried out at 200 ° C. for 2 hours while flowing a nitrogen gas at 50 ml / min with stirring. In order to measure the number average molecular weight of the prepolymer obtained by this polymerization reaction, about 0.5 g was sampled, and then heated to 280 ° C. over 1 hour, followed by polymerization at 280 ° C. for 3 hours. The stirring was stopped, the glass container was taken out of the heat medium bath, and naturally cooled to room temperature while flowing nitrogen gas. Then, the glass container was cracked to take out the polyamide, crushed, and then
Dry under reduced pressure for 2 hours. The number average molecular weight of the prepolymer was 2,800. The obtained polyamide was colorless and transparent. The polyamide was subjected to a hot water treatment at 90 to 98 ° C., but remained transparent after 1 hour, and the crystallization was very slow. Also, in the DSC measurement and the dynamic viscoelasticity measurement, no melting peak or temperature dispersion spectrum based on crystals was observed. Table 1 shows the results of evaluation of the relative viscosity, amino group terminal concentration, carboxyl group terminal concentration, number average molecular weight, glass transition temperature and solubility of the obtained polyamide.

Example 4 Instead of 1,3-bisaminomethylcyclohexane and 1,6-decanedicarboxylic acid, 2,2,4-, 2,4,
16.420 g of 4-trimethylhexamethylenediamine
(0.1037 mol) and 23.835 g (0.1034 mol) of 1,6-decanedicarboxylic acid were used in the same manner as in Example 3. The number average molecular weight of the prepolymer was 3,200. The obtained polyamide was colorless and transparent. The polyamide was subjected to a hot water treatment at 90 to 98 ° C., but remained transparent after 1 hour, and the crystallization was very slow. Also, in the DSC measurement and the dynamic viscoelasticity measurement, no melting peak or temperature dispersion spectrum based on crystals was observed. Table 1 shows the results of evaluation of the relative viscosity, amino group terminal concentration, carboxyl group terminal concentration, number average molecular weight, glass transition temperature, and solubility of the obtained polymer.

Example 5 14.923 g of paraxylylenediamine was placed in a 160 ml glass container equipped with a stirrer and a nitrogen inlet.
(0.1097 mol) and 25.149 g (0.1092 mol) of 1,6-decanedicarboxylic acid. After sufficiently replacing the inside of this glass container with nitrogen, immerse in a heat medium bath,
While stirring and flowing 50 ml / min of nitrogen gas, 20
After polymerization at 0 ° C. for 2 hours, the temperature was raised to 260 ° C. over 1 hour, and subsequently polymerization was performed at 260 ° C. for 1 hour. Further, the temperature was raised to 280 ° C. over 30 minutes, followed by 28
Polymerization was carried out at 0 ° C. for 3 hours. The stirring was stopped, the glass container was taken out of the heat medium bath, and naturally cooled to room temperature while flowing nitrogen gas. Thereafter, the glass container was cracked to take out the polyamide, pulverized, and dried under reduced pressure at 40 ° C. for 72 hours. The obtained polyamide was colorless and transparent. The polyamide was subjected to a hot water treatment at 90 to 98 ° C., but remained transparent after 1 hour, and the crystallization was very slow. Also, in the DSC measurement and the dynamic viscoelasticity measurement of the obtained polyamide, no melting peak or temperature dispersion spectrum based on crystals was observed. Table 1 shows the relative viscosity, amino group terminal concentration, carboxyl group terminal concentration, number average molecular weight, glass transition temperature and solubility of the obtained polyamide.

Example 6 To a 160 ml glass container equipped with a stirrer and a nitrogen inlet, 7.441 g (0.4%) of dodecamethylenediamine was added.
372 mol) and 8.55 of 1,6-decanedicarboxylic acid
7 g (0.0372 mol) and 4.000 g (0.0186 g) of ω-aminododecanoic acid were added. After sufficiently replacing the inside of the glass container with nitrogen, the glass container is immersed in a heating medium bath, polymerization is performed at 200 ° C. for 1 hour while flowing a nitrogen gas at 50 ml / min with stirring, and then the temperature is raised to 280 ° C. over 1 hour. Subsequently, polymerization was performed at 280 ° C. for 4 hours. afterwards,
The stirring was stopped, the glass container was taken out of the heat medium bath, and naturally cooled to room temperature while flowing nitrogen gas. After that, the glass container was cracked to take out the polyamide, crushed,
It was dried under reduced pressure at 0 ° C. for 72 hours. The obtained polyamide was colorless and transparent. The polyamide was subjected to a hot water treatment at 90 to 98 ° C., but remained transparent after 1 hour, and the crystallization was very slow. DSC of the obtained polyamide
In the measurement and the dynamic viscoelasticity measurement, no melting peak or temperature dispersion spectrum based on crystals was observed. Table 1 shows the relative viscosity, amino group terminal concentration, carboxyl group terminal concentration, number average molecular weight, glass transition temperature and solubility of the obtained polyamide.

Comparative Example 3 Dodecamethylenediamine, 1,6-decanedicarboxylic acid and ω-aminododecanoic acid were used in an amount of 3.721 g (0.0186 mol) for dodecamethylenediamine.
l), 4.280 g of 1,6-decanedicarboxylic acid
(0.0186 mol) and ω-aminododecanoic acid were replaced with 12.000 g (0.0558 mol) in the same manner as in Example 6. The obtained polyamide was partly cloudy. This polyamide was subjected to a hot water treatment at 90 to 98 ° C. The whole became cloudy and opaque in about 18 minutes. This polyamide was easy to crystallize. Also, almost no solubility in methanol or N, N-dimethylacetamide was observed.

Example 7 In a 160 ml glass container equipped with a stirrer and a nitrogen inlet, 10.180 g of 1,6-diaminohexane was added.
(0.0877 mol), 16.196 g (0.0702 mol) of 1,6-decanedicarboxylic acid, 3.535 g (0.0175 mol) of decandionic acid and 0.03 g of sodium hypophosphite were added. After the inside of the glass container was sufficiently purged with nitrogen, it was immersed in a heat medium bath and stirred for 50 m.
Polymerization was performed at 190 ° C. for 2 hours while flowing a nitrogen gas at 1 / min. Thereafter, the temperature was raised to 260 ° C. over 1 hour, followed by polymerization at 260 ° C. for 4 hours. The stirring was stopped, the glass container was taken out of the heat medium bath, and naturally cooled to room temperature while flowing nitrogen gas. Next, the glass container was cracked to take out the polyamide and pulverized.
Dry under reduced pressure for 2 hours. The obtained polyamide was colorless and transparent. This polyamide was subjected to hot water treatment at 90 to 98 ° C. It remained clear after 1 hour and crystallization was very slow. Further, it was almost dissolved in methanol and N, N-dimethylacetamide.

Example 8 The amounts of 1,6-decanedicarboxylic acid and decandioic acid used were respectively 12.1
To 36 (0.0526 mol), decanedioic acid was 7.
Example 7 except for changing to 091 (0.0351 mol)
Was carried out in the same manner as described above. The obtained polyamide was colorless and transparent. This polyamide was subjected to hot water treatment at 90 to 98 ° C. After about 43 minutes, cloudiness started and gradually became opaque. This polyamide had a slow crystallization.

Example 9 360 g of a 75% by weight aqueous solution of a 6D salt obtained in the same manner as in Example 1 (0.780 mol as a 6D salt) and ε-
30 g (0.265 mol) of caprolactam was stirred with a stirrer,
The mixture was placed in a 1-liter pressure vessel equipped with a thermometer, a pressure gauge, a nitrogen inlet, a pressure relief port, a pressure reducing port, and a polymer outlet. After the inside of the pressure vessel was sufficiently purged with nitrogen, the temperature was raised in a sealed state with stirring, and polymerization was carried out at 220 ° C. under a pressure of 17 kgf / cm ² G for 4 hours. In order to measure the number average molecular weight of the prepolymer obtained by this polymerization reaction, several g were sampled. Next, while maintaining the pressure in the pressure vessel at 17 kgf / cm ² G, the temperature was raised to 275 ° C. over 1 hour, and then the pressure was released to normal pressure over 30 minutes while maintaining the temperature. Thereafter, the pressure was reduced and the polymerization in the pressure vessel was maintained at 500 mmHg at 275 ° C. for 2 hours. afterwards,
After the stirring was stopped and the pressure was returned to normal pressure with nitrogen gas, the produced polymer was taken out in a string form from a polymer outlet at the bottom of the pressure vessel, immediately cooled in a water bath, and then made into a cylindrical polyamide chip with a pelletizer. 40 pieces of this polyamide chip
It dried under reduced pressure at 72 degreeC for 72 hours. The number average molecular weight of the prepolymer was 2,400. The obtained polyamide was colorless and transparent. The polyamide was subjected to a hot water treatment at 90 to 98 ° C., but remained transparent after 1 hour, and the crystallization was very slow. In the DSC measurement and dynamic viscoelasticity measurement of the obtained polyamide, no melting peak or temperature dispersion spectrum based on crystals was observed. Table 1 shows the results of evaluation of the relative viscosity, terminal amino group concentration, terminal carboxyl group concentration, number average molecular weight, glass transition temperature, and solubility of the obtained polymer.

[0060]

[Table 1]

[0061]

The present invention relates to a novel polyamide containing 1,6-decanedicarboxylic acid as an essential component and a method for producing the same. The resulting polyamide does not easily become cloudy by hot water treatment,
It is excellent in transparency and has features such as solubility in lower alcohols and aprotic solvents.

 ────────────────────────────────────────────────── ─── Continued from the front page (72) Inventor Takashi Amane 1-12-12 Nishihonmachi, Ube City, Yamaguchi Prefecture Ube Industries, Ltd. Polymer Research Laboratory

Claims (2)

[Claims] (1) 50 to 100 in the dicarboxylic acid component (A)
A unit derived from a dicarboxylic acid component whose weight% is 1,6-decanedicarboxylic acid; a unit derived from a (B) diamine component; and (C) 0 to 50% by weight of an aliphatic amino based on the total amount. A polyamide composed of units derived from a carboxylic acid component and / or units derived from a lactam component. 2. The method according to claim 1, wherein the number average molecular weight is 800 to 800 in the first stage polymerization.
2. A polyamide prepolymer having a number average molecular weight in the range of 7,000 to 50,000 by preparing a polyamide prepolymer having a molecular weight in the range of 5,000 and increasing the molecular weight in the second stage polymerization. Method for producing polyamide.