JPH0578474A - New polyamide resin - Google Patents

Abstract

PURPOSE:To provide the subject resin having excellent heat-resistance, mechanical properties, etc., and consisting of a specific composition of adipic acid and a mixture of p-xylylenediamine and trans- and cis-1,4-bis(aminomethyl) cyclohexanes. CONSTITUTION:The objective resin useful as engineering plastics, etc., is composed of (A) a constituent unit having a polyamide skeleton of formula I derived from p-xylylenediamine and adipic acid, (B) a constituent unit having a polyamide skeleton of formula II (X1 is trans-1,4-cyclohexane ring residue) derived from trans-1,4-bis(aminomethyl)cyclohexane and adipic acid and (C) a constituent unit having a polyamide skeleton of formula III (X2 is cis-1,4-cyclohexane ring residue) derived from cis-1,4-bis(aminomethyl)cyclohexane and adipic acid. The molar ratio of the constituent units A:(B+C) is 50:50 to 90:10 and that of B:C is 10:90 to 90:10.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention has high heat resistance, good mechanical properties, low water absorption and easy moldability, and is particularly useful for engineering plastics having excellent mechanical properties when wet. The present invention relates to a novel thermoplastic polyamide resin.

[0002]

2. Description of the Related Art Polyamide was used in DuPo in the 1930s.
W. of nt company. H. Since the discovery of Carothers
It has been developed centering on fibers. On the other hand, applications of polyamide resins other than fibers include the industrial parts field, but their development was relatively slow compared to the fiber field. But,
The demand for industrial parts is rapidly expanding, supported by the growth of the electronics / electricity industry, automobile industry, aviation / space industry, etc. in recent years. In particular, the excellent heat resistance, mechanical properties, molding processability, etc. of polyamide resin enable its application to engineering plastics.

Polyamide resins that have been industrialized to date include, for example, Nylon6 and Nyl.
on6.6, Nylon11, Nylon12, Nyl
on 6.10, Nylon MXD-6 and the like.

On the other hand, as various products have been made highly functional and highly integrated, polyamides having higher heat resistance, high strength, low water absorption, easy moldability and excellent mechanical properties when wet. Resins are desired. In particular, polyamide resin has excellent heat resistance, mechanical properties, and moldability, but has high water absorption, and the dimensional change of the molded product during drying and water absorption is large.
There is a serious problem in the molding material that the mechanical strength is significantly reduced when absorbing water.

Nylon 4.6 has recently been industrialized as a polyamide resin aiming at high heat resistance, but it has the drawbacks of high water absorption, large dimensional change, and marked decrease in strength upon water absorption. Further, NylonMXD-6 is known as a low water-absorbing and high-strength polyamide resin, but it has a drawback of insufficient heat resistance. MCX-A (trade name), which is being developed as a high heat resistance and low water absorbing resin, also has a drawback of low strength. As described above, a polyamide resin having the properties of high heat resistance, high strength, low water absorption, easy moldability and excellent mechanical properties when wet has not yet been developed.

Para-xylylenediamine (hereinafter PXD
Called. ) -Based polyamides have been variously studied so far centering on fibers. For example, PXD and meta-xylylenediamine (hereinafter referred to as MXD) and polyamide from an aliphatic dicarboxylic acid (Japanese Patent Publication No. 32-6148), PXD, para-bis (2-aminoethyl) benzene and aliphatic. Polyamide from dicarboxylic acid
-13069 gazette, the same 44-19269 gazette), P.
Polyamide from XD and piperazine and aliphatic dicarboxylic acid (Japanese Patent Publication No. 43-25997), PXD and N
-Polyamides of substituted PXD and aliphatic dicarboxylic acid (Japanese Patent Publication No. 44-19873), polyamides of PXD, hexamethylenediamine, adipic acid and terephthalic acid (Japanese Patent Publication No. 47-33277) and the like. However, there is no example in which a PXD-based polyamide is industrially produced.

On the other hand, bis (aminomethyl) cyclohexane (hereinafter referred to as BAMC) type polyamides have also been studied so far. For example, polyamide from BAMC and an aliphatic or aromatic dicarboxylic acid (Japanese Patent Publication No.
8-648, U.S. Patent 3,012,994, British Patent 976,094, West Germany 1,49.
5,556), polyamides from BAMC and ε-caprolactam and phthalic acid or an aliphatic dicarboxylic acid (Japanese Patent Publication Nos. 49-2369 and 49-345).
3 and 49-4011), polyamides derived from BAMC and aliphatic diamines and dicarboxylic acids (JP-A-49-55796 and 50-145492), BAMC and ω-aminocarboxylic acids and terephthalates. Polyamides from acids (US Pat. No. 2,985,626), BAMC and polyamides from ω-aminocarboxylic acids and cyclohexane 1,4-dicarboxylic acids (US Pat. No. 2,985,628), BAMC Examples thereof include polyamides derived from fatty acids (US Pat. No. 3,249,629), polyamides derived from BAMC and diamines containing an ether bond (US Pat. No. 2,939,862), and the like.

[0008] In addition, modification of MXD type polyamide using BAMC has also been reported. For example, MX
US Pat. No. 2,91 for the purpose of improving heat resistance by using BAMC as a component of diamine of D-based polyamide
6,476 specification etc. are mentioned. This BAMC-based polyamide is characterized in that the polyamide resin obtained has different properties depending on the BAMC isomer used. 1,2-bis (aminomethyl) cyclohexane (hereinafter referred to as 1,2-BAMC) and 1,3-bis (aminomethyl) cyclohexane (hereinafter referred to as 1,3-B) as structural isomers.
It is called AMC. ), 1,4-bis (aminomethyl) cyclohexane (hereinafter referred to as 1,4-BAMC), and each BAMC has two types of geometric isomers, a trans isomer and a cis isomer. However, there are a total of 6 isomers. However, in order to obtain a polyamide resin having high heat resistance and excellent mechanical properties, 1,4-BAMC is the most superior structural isomer of BAMC, and the trans isomer is a cis isomer as a geometrical isomer. Is known to be better than. At the same time, the transformer body,
It is also known that the thermal characteristics such as the crystal melting point greatly change depending on the composition ratio of the cis isomer [eg, Frank R. Prince et al., Journal of Polymer Science Part A]. -1
(J. Polymer. Sci; Part A-1) 1
0,465 (1972), etc.].

On the other hand, in order to synthesize 1,4-BAMC, reduction of PXD (for example, JP-A-53-79840 and JP-A-54-16452), synthesis of an adduct of butadiene and acrylonitrile, and oxo reaction. , A method obtained via a reductive amination reaction (for example, US Pat. No. 3,0
12, 1994) and the like, but BAMC synthesized by these methods is a mixture of trans isomer and cis isomer (trans / cis (molar ratio); 10/90 to 90/1).
0). Therefore, there is a complication that the ratio of trans form to cis form must be controlled in order to express the desired performance. In particular, in order to obtain 95% or more of trans BAMC as a raw material of polyamide resin that exhibits high heat resistance and excellent mechanical properties, a higher degree of separation /
It required a treatment such as isomerization, which was economically disadvantageous.

The high heat resistance mentioned in this specification means that the polymer has a crystalline melting point of at least 280% or more and 330 ° C.
It means the following. Polyamide resins having a crystalline melting point higher than 330 ° C. are also known, but since they are close to the decomposition temperature of polymers, there is a problem that decomposition / foaming or coloring is accompanied during synthesis or molding. Also, since the molding temperature is high,
It is not preferable as a thermoplastic polyamide resin because of problems such as difficulty in molding with an ordinary molding machine. Low water absorption is generally tested at room temperature to 100 ° C at room temperature using Nylon 6.6 non-filled standard injection molding standard grade (for example, Showa Denko technyl A216) as a comparative material. The value measured under the same condition (for example, ASTM method / JIS method) is at least Nylo.
It is smaller than the value of n6.6. Although the term low hygroscopicity also exists, it is considered to be essentially equivalent to low hygroscopicity only by the difference in the test method. Further, the easy molding process means that ordinary melt molding at 380 ° C. or lower (for example, injection molding, extrusion molding, etc.) is possible. Furthermore, the mechanical properties when wet means that the molded product immediately after molding or when dried is
It means the mechanical properties when placed in water at room temperature to 100 ° C. or in an atmosphere having an arbitrary humidity or in an environment where it may come into contact with water at that temperature for at least 10 hours or more.

[0011]

The PXD type polyamide has excellent heat resistance, mechanical properties, low water absorption, and chemical stability, but has a high crystal melting point of 330 ° C. or higher, so that it can be used at high temperatures during synthesis and molding. Is required, and it is easy to cause decomposition or deterioration. Various studies have been made to lower the crystal melting point by copolymerization and the like, but there is a problem that the crystal melting point and mechanical properties are significantly lowered when the crystal melting point is lowered too much.

On the other hand, BAMC-based polyamide uses BAMC containing 95% or more of trans isomer, which is complicated to manufacture and expensive, in order to exhibit good performance as a polyamide resin, and the isomer ratio of trans isomer and cis isomer is used. Therefore, there is a problem that the thermal characteristics such as the melting point of the crystal change greatly.

[0013]

As a result of intensive studies to solve the above-mentioned drawbacks of the prior art, the present inventor has found that PXD and economically advantageous transformer 1,4-BAMC and cis 1,4.
-A mixture of BAMC and a polyamide resin obtained from a certain composition range of adipic acid have excellent heat resistance, mechanical properties, low water absorption, easy moldability, and excellent mechanical properties when wet. Therefore, the present invention has been completed. In addition, the present inventors have surprisingly found that in 1,4-BAMC used as a component of a polyamide resin, economically advantageous 1,4-BAMC containing a moderate amount of cis-form that is predicted to reduce the performance is Also has excellent heat resistance,
The present invention was found by providing a polyamide resin having mechanical properties, low water absorption, easy moldability and good mechanical properties when wet.

That is, the present invention provides structural formula (I)

[0015]

[Chemical 4] Structural unit (A) and structural formula (II)

[0016]

[Chemical 5] (In the formula, X ₁ represents a trans 1,4-cyclohexane ring residue.) And the structural unit (B)
I)

[0017]

[Chemical 6] (In the formula, X ₂ represents a cis 1,4-cyclohexane ring residue.) A polyamide resin comprising a structural unit (C) represented by: i) a structural unit (A) and [a structural unit (B ) + Structural unit (C)] in the range of 50:50 to 90:10, and ii) the molar ratio of structural unit (B) to structural unit (C) is 10:
Novel thermoplastic polyamide resin in the range of 90 to 90:10 and having a logarithmic viscosity of 0.4 or more measured in 97% sulfuric acid at a concentration of 1.0 g / dl and a temperature of 30 ° C. Regarding

The structural unit (A) of the novel thermoplastic polyamide resin obtained in the present invention is a polyamide skeleton obtained from PXD and adipic acid, and the structural unit (B) is trans 1,4-BAMC and adipic acid. The polyamide skeleton obtained from and the structural unit (C) is cis-1,4-BAMC
And a polyamide skeleton obtained from adipic acid. [Structural unit (B) + Structural unit (C)] means that the structural unit (B) and the structural unit (C) are added.
It represents a polyamide skeleton obtained from 4-BAMC and adipic acid.

The molar ratio of the structural unit (A) to the structural unit (B) + the structural unit (C) of the novel thermoplastic polyamide resin obtained in the present invention is in the range of 50:50 to 90:10. And more preferably 70:30 to 90:10
The range is. The molar ratio of the structural unit (B) to the structural unit (C) is in the range of 10:90 to 90:10, preferably 25:75 to 90:10, and more preferably 40:60. To 80:20. If this range is schematically expressed using triangular coordinates, it will be a range indicated by hatched lines surrounded by P, Q, R, and S in FIG.

The molar ratio of the structural unit (A) to [the structural unit (B) + the structural unit (C)] exceeds 90:10, or the molar ratio of the structural unit (B) to the structural unit (C) is 90. : 1
If it exceeds 0, the crystallization temperature becomes high, and coloring and foaming during molding occur, which is not preferable. Further, if the molar ratio of the structural unit (B) to the structural unit (C) is 10:90 or less, the heat resistance of the obtained polyamide resin and especially the mechanical properties when wet are deteriorated, which is not preferable.

Further, the structural unit (A) and the structural unit (B)
+ Structural unit (C)] in a molar ratio of 70:30 to 90:
When the range is 10, the structural unit (B) and the structural unit (C)
It has excellent heat resistance, mechanical properties, low water absorption, and mechanical properties when wet, almost without depending on the molar ratio of 1, 4, ie, the compositional ratio of geometric isomers of 1,4-BAMC. Therefore, in this case, it is possible to use a large amount of the structural unit (C), that is, the cis isomer, which has been considered to have a low utility value, which is extremely economically advantageous.

The novel thermoplastic polyamide resin obtained in the present invention is one which is dissolved in 97% concentrated sulfuric acid and contains substantially no gel component. The thermoplastic polyamide resin of the present invention has an inherent viscosity (η _inh ) of 0.4 or more, preferably 0.6 or more. When the logarithmic viscosity of the thermoplastic polyamide resin of the present invention is less than 0.4, the strength of the molded product or film is low and it has no practical physical properties.

For the production of the novel thermoplastic polyamide resin obtained in the present invention, the method used in ordinary polyamide synthesis is applied. For example, PXD, adipic acid salt, trans 1,4-BAMC, adipic acid salt, and cis 1,4-B prepared so as to be a polyamide resin having the above composition.
350 ° C under pressure from AMC salt and adipic acid salt or 1,4-BAMC and adipic acid salt whose trans / cis isomer ratio was previously controlled and a certain amount of purified water
The method of synthesizing below, the method of synthesizing under normal pressure using a phenolic solvent as a solvent, and the like can be mentioned.

[0024]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Since the novel thermoplastic polyamide resin obtained by the present invention is extremely difficult to dissolve in a general organic solvent, it is difficult to determine the average molecular weight. Therefore, the logarithmic viscosity measured in concentrated sulfuric acid was used as a measure of the molecular weight. The logarithmic viscosity (η
_inh ) is 30% at a concentration of 0.5 g / dl in 97% concentrated sulfuric acid.
It was measured at ° C and calculated by the following calculation formula.

[0025]

[Equation 1] Here, t ₀ : outflow time of solvent in viscometer t; outflow time of polymer solution in viscometer c; polymer solution concentration, 0.5 g / dl

The physical properties of the polymer were measured as follows.

1) The thermal properties are PERKIN-ELME
DSC measurement was performed using a 7 type series manufactured by R company. About 10 mg of the precisely weighed sample is loaded into a DSC apparatus, heated to 340 ° C. in an inert gas at a temperature rising rate of 20 ° C./minute, and then cooled at a temperature lowering rate of 20 ° C./minute. After repeating this operation twice, the crystalline melting point (T
m), the heat of fusion (ΔHm), and the crystallization temperature (Tc) were measured. Tm represents a melting peak temperature, ΔHm represents a heat of fusion per unit weight obtained from the melting peak, and Tc represents a crystallization peak temperature.

2) Water absorbency was measured at 50 ° C. for the sample after molding.
It was immersed in purified water for 24 hours, and the weight change rate was calculated by the following calculation formula.

[0029]

[Equation 2] However, W ₁ : weight before immersion W ₂ : weight after immersion in water at 50 ° C for 24 hours

3) The mechanical properties of the polymer when dried are 2
CINI MINI MA at a temperature of 85 ° C to 350 ° C
After melt-molding using an X molding machine (MODEL CS-183) and vacuum-drying at 80 ° C. for 24 hours, TENSILON / UTM-1-2500 manufactured by Toyo Baldwin Co., Ltd.
Was used for mechanical strength test measurement.

4) The mechanical properties when wet are:
CINI MINI MA at a temperature of 85 ° C to 350 ° C
After melt molding using an X molding machine (MODEL CS-183), it was immersed in purified water at 50 ° C. for 24 hours and then manufactured by Toyo Baldwin Co., Ltd., TENSILON / UTM-1-25.
00 was used for the mechanical strength test measurement. The dimensional change rate was calculated by immersing the molded sample in purified water at 50 ° C for 24 hours, and calculating the dimensional change rate for each of the resin flow direction (MD) and the perpendicular direction (TD) during molding. I calculated by the formula.

[0032]

[Equation 3] However, L ₁ : length before immersion L ₂ : length after immersion in water at 50 ° C for 24 hours

5) Infrared absorption spectrum analysis (IR)
It carried out using the Hitachi Ltd. 270-50 type infrared spectrophotometer. NMR spectrum analysis ( ¹³ C-NMR and
⁽¹ H-NMR) was manufactured by JEOL Ltd. GSX400 nuclear magnetic resonance spectrometer, and the measurement was performed using tetramethylsilane (TMS) as an internal standard and a bisulfate solvent or hexafluoroisopropanol.

Example 1 In a glass container equipped with a stirrer, a thermometer and a nitrogen inlet, 9.882 g (0.035 mol) of para-xylylenediamine (PXD) and adipic acid salt, 55% of trans form were prepared.
1,4-Bis (aminomethyl) cyclohexane (1,4-BAMC) consisting of 45% cis isomer, 4.326 g (0.015 mol) of adipic acid salt and 20 ml of meta-cresol were charged and pressurized under nitrogen. -Deaeration was repeated several times to perform sufficient nitrogen replacement. Temperature rising was started under a nitrogen stream while stirring. After reacting at 200 ° C. for 1.5 hours, the temperature was raised to 240 ° C. and the reaction was continued for another hour at this temperature. During this time, most of the produced water and meta-cresol were distilled off. Further raise the temperature to 320 ° C and stop the flow of nitrogen,
The reaction was continued for 20 minutes under a reduced pressure of 5 mmHg or less. After the reaction was completed, the system was cooled to room temperature and the pressure inside the system was returned to normal pressure. 11.9 g (yield 95.3%) of an odorless white polymer was obtained.
The logarithmic viscosity was 1.45. From the IR and NMR analysis, the structure of the obtained polymer was found to be the structure shown in Table 1.

As a result of DSC analysis, a sharp crystal peak was shown, with a crystal melting point (Tm) of 306 ° C. and a heat of fusion of 12 C.
It was a crystalline polyamide with al / g and a crystallization temperature (Tc) of 248 ° C. After melt-molding at 320 to 330 ° C., the performance was evaluated and as a result, it had the following performance. Water absorption 1.9% Dimensional change in TD direction 1.1% Dimensional change in MD direction 0.3% Tensile strength when dried 1,270 kg / cm ² Breaking elongation when dried 10% Bending elasticity when dried rate 38,000kg / cm ² dry flexural strength 1,980kg / cm ² tensile strength 800 kg / cm ² breaking elongation of 10% when wet wet the wet flexural modulus 33,000kg / cm ² of wet Bending strength 1,400kg / cm ²

Example 2 In a 1 L autoclave equipped with a stirrer, a thermometer and a nitrogen inlet, 84.70 g (0.3 mol) of PXD and adipic acid salt, 55% trans isomer and 45% cis isomer were prepared. Four
-BAMC and adipic acid salt 57.68 g (0.2 mol) and purified water 570 ml were charged and pressurized under nitrogen-
Degassing was repeated several times to sufficiently replace nitrogen. After making the system closed, the temperature rise was started while stirring. 185 ° C, 8
Water was distilled off while maintaining kg / cm ² and the reaction was carried out for 3.5 hours. Thereafter, the pressure was returned to normal pressure, and the temperature was further raised to 310 ° C.
After reacting at this temperature for 5 minutes, the pressure inside the system was kept at 3 mmHg or less and the reaction was further performed for 10 minutes. After the reaction was completed, 111.6 g of white polymer (yield 90.0%) was obtained. The logarithmic viscosity was 1.32. IR and ¹³ C-
From the NMR analysis, the structure of the obtained polymer was found to be the structure shown in Table 1.

As a result of DSC analysis, a sharp crystal peak was shown, with a crystal melting point (Tm) of 303 ° C. and a heat of fusion of 10 C.
It was a crystalline polyamide with al / g and a crystallization temperature (Tc) of 236 ° C. After melt-molding at 315 to 325 ° C., the performance was evaluated and as a result, it had the following performance. Water absorption rate 2.4% Dimensional change in TD direction 1.0% Dimensional change in MD direction 0.2% Tensile strength when dry 1,200 kg / cm ² Breaking elongation when dry 15% Bending elasticity when dry Rate 35,000 kg / cm ² Bending strength when dry 1,800 kg / cm ² Tensile strength when wet 840 kg / cm ² Breaking elongation when wet 92% Bending elastic modulus when wet 25,000 kg / cm ^{2 When} wet Bending strength 1,350kg / cm ²

Examples 3 to 9 Polyamides were synthesized according to the method of Example 1 or Example 2 except that the charging and polymerization conditions shown in Table 1 were used.
The results of the synthesis are also shown in Tables 1 and 2. Further, the obtained polyamide was melt-molded in the same manner as in Example 1 at a temperature 10 to 20 ° C. higher than the crystal melting point. The performance of the molded product was evaluated. The results are shown in Tables 3 and 4.

Comparative Example 1 P was placed in a glass container equipped with a stirrer, a thermometer and a nitrogen inlet.
A salt of XD and adipic acid 9.882 g (0.035 mol), consisting of trans isomer 95% and cis isomer 5% 1,4-
Bis (aminomethyl) cyclohexane (1,4-BAM
C) and adipic acid salt 4.326 g (0.015 mol)
Then, 20 ml of meta-cresol was charged, and pressurization and deaeration were repeated under nitrogen several times to sufficiently replace nitrogen. Temperature rising was started under a nitrogen stream while stirring. 1. At 200 ° C
After reacting for 5 hours, the temperature was raised to 240 ° C. and further reacted at this temperature for 1 hour. During this time, most of the produced water and meta-cresol were distilled off. The temperature was further raised to 340 ° C., the flow of nitrogen was stopped, and the reaction was continued for 20 minutes under a reduced pressure of 5 mmHg or less. After the reaction was completed, the system was cooled to room temperature and the pressure inside the system was returned to normal pressure. 12.2 g of slightly pale yellow polymer (yield 96.7)
%)was gotten. The logarithmic viscosity was 1.42. IR
And ¹³ C-NMR analysis revealed that the structure of the obtained polymer was the structure shown in Table 2.

As a result of DSC analysis, a sharp crystal peak was shown, with a crystal melting point (Tm) of 331 ° C. and a heat of fusion of 15 C.
It was a crystalline polyamide with al / g and a crystallization temperature (Tc) of 290 ° C. Generation of a gas component was observed during melt molding at 345 to 355 ° C, and the molded product was also foamed or colored. As a result of measuring physical properties, it had the following properties. Water absorption rate 2.0% TD dimensional change rate 1.2% MD dimensional change rate 0.2% Dry tensile strength 700 kg / cm ² Dry elongation at break 3% Bending elastic modulus 27 , 000kg / cm ² dry flexural strength 1,000kg / cm ² wet tensile strength 530 kg / cm ² wet flexural bending strength at elastic modulus 25,000 kg / cm ² wet elongation at break 16% wet during 1,200 kg / cm ²

Comparative Example 2 In a 1 L autoclave equipped with a stirrer, a thermometer and a nitrogen inlet, 134.11 g (0.4) of PXD and adipic acid salt was added.
75 mol), a salt of 1,4-BAMC and adipic acid consisting of 95% of trans isomer and 5% of cis isomer, 7.210 g (0.2.
(025 mol), and 550 ml of purified water were charged, and pressure-deaeration was repeated under nitrogen several times to sufficiently replace nitrogen. After making the system closed, the temperature rise was started while stirring. Two
Water is distilled off while maintaining at 20 ° C and 8 kg / cm ² ,
Reacted for hours. Thereafter, the pressure was returned to normal pressure, and the temperature was further raised to 345 ° C. After reacting at this temperature for 5 minutes, the inside of the system is 3 mm
The pressure was maintained at Hg or less and the reaction was further performed for 10 minutes. After the completion of the reaction, 22.9 g of a slightly pale yellow polymer (yield 93.
1%) was obtained. The logarithmic viscosity was 0.87. I
From the R and ¹³ C-NMR analysis, the structure of the obtained polymer was found to be the structure shown in Table 2. As a result of DSC analysis, it was a crystalline polyamide showing a sharp crystal peak, a melting point (Tm) of 335 ° C, a heat of fusion of 18 Cal / g, and a crystallization temperature (Tc) of 295 ° C. 34
Generation of a gas component was observed during melt molding at 5 to 355 ° C, and the obtained molded product was also foamed or colored. The material was a little brittle as a molded product. The results of performance evaluation are shown in Table 4.

Comparative Example 3 A glass container equipped with a stirrer, a thermometer and a nitrogen inlet was charged with P.
XD and adipic acid salt 7.059 g (0.025 mol)
1,4-BAM consisting of 5% trans form and 95% cis form
C. 7.210 g (0.025 mol) and meta-cresol 20 ml were charged, and pressure-deaeration was repeated several times under nitrogen to sufficiently replace nitrogen. Temperature rising was started under a nitrogen stream while stirring. After reacting at 200 ° C. for 1.5 hours, the temperature was raised to 240 ° C. and the reaction was continued for another hour at this temperature. During this time, most of the produced water and meta-cresol were distilled off. Further raise the temperature to 300 ° C and stop the flow of nitrogen,
The reaction was continued for 20 minutes under a reduced pressure of 5 mmHg or less. After the reaction was completed, the system was cooled to room temperature and the pressure inside the system was returned to normal pressure. 11.92 g (yield 96.2%) of an odorless white polymer was obtained. The logarithmic viscosity was 1.35. IR and ¹³ C-
From the NMR analysis, the structure of the obtained polymer was found to be the structure shown in Table 2. In addition, as a result of DSC analysis, a slightly broad crystal peak was observed and the crystal melting point (T
m) 274 ° C, heat of fusion 8 Cal / g, crystallization temperature (Tc)
The polyamide had low heat resistance at 200 ° C. and low crystallinity. After melt molding at 290 to 300 ° C., performance evaluation was performed. The results are shown in Table 4.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

[Table 4]

Example 10 (10-a) 1 L equipped with a stirrer, thermometer, nitrogen inlet
Para-xylylenediamine (PX
D) and adipic acid salt 105.9 g (0.375 mol), trans isomer 75%, cis isomer 25% 1,4
-Bis (aminomethyl) cyclohexane (1,4-BA
MC) and 36.1 g (0.125 mol) of adipic acid salt and 580 ml of purified water were charged, and pressurized under nitrogen.
Degassing was repeated several times to sufficiently replace nitrogen. After making the system closed, the temperature rise was started while stirring. 205 ° C, 1
Water was distilled off while maintaining the rate at 5 kg / cm ² , and the reaction was carried out for 3.5 hours. Thereafter, the pressure was returned to normal pressure, and the temperature was further raised to 325 ° C. After reacting at this temperature for 5 minutes, the pressure inside the system was kept at 3 mmHg or less and the reaction was further performed for 10 minutes. After the reaction was completed, 121.2 g of white polymer (yield 97.1%) was obtained. The logarithmic viscosity was 1.37. IR and
^{From 13} C-NMR analysis, the structure of the obtained polymer was found to be the structure shown in Table 5.

As a result of DSC analysis, a sharp crystal peak was shown, with a crystal melting point (Tm) of 316 ° C. and a heat of fusion of 14 C.
It was a crystalline polyamide with al / g and a crystallization temperature (Tc) of 265 ° C. After melt-molding at 325 to 335 ° C., the performance was evaluated and as a result, it had the following performance. Water absorption 2.1% Dimensional change in TD direction 1.0% Dimensional change in MD direction 0.2% Tensile strength when dry 1,200 kg / cm ² Breaking elongation when dry 11% Bending elasticity when dry rate 37,000kg / cm ² dry flexural strength up to 1,600 kg / cm ² tensile strength 800 kg / cm ² breaking elongation of 10% when wet wet the wet flexural modulus 30,000 / cm ² of wet Bending strength 1,380kg / cm ²

Next, two different types of polyamide resin (10-) were prepared in the same manner as in the above synthetic method except that the molar ratio of 1,4-BAMC trans isomer and cis isomer was changed as shown in Table 5.
b, 10-c) was obtained. The results are shown in Tables 5 and 6.
From the results, it was found that a polyamide resin having high heat resistance, high strength, low water absorption, easy moldability, and excellent mechanical properties when wet independent of the isomer molar ratio of 1,4-BAMC was obtained. It was

Example 11 (11-a) 12.0 g (0.0) of PXD and adipic acid salt was placed in a glass container equipped with a stirrer, a thermometer and a nitrogen inlet.
425 mol), 1,4-BAMC consisting of 75% trans isomer and 25% cis isomer, and 2.16 g (0.
(0075 mol) and 20 ml of meta-cresol were charged, and pressure-deaeration was repeated several times under nitrogen to sufficiently replace nitrogen. Temperature rising was started under a nitrogen stream while stirring. After reacting at 200 ° C. for 1.5 hours, the temperature was raised to 240 ° C. and the reaction was continued for another hour at this temperature. During this time, most of the produced water and meta-cresol were distilled off. Further 330
The temperature was raised to ℃ and the flow of nitrogen was stopped, and the reaction was continued for 20 minutes under a reduced pressure of 5 mmHg or less. After the reaction was completed, the system was cooled to room temperature and the pressure inside the system was returned to normal pressure. Odorless white polymer 11.
9 g (yield 95.3%) was obtained. The logarithmic viscosity is 1.
It was 27. From the IR and ¹³ C-NMR analysis, the structure of the obtained polymer was found to be the structure shown in Table 5.

As a result of DSC analysis, a sharp crystal peak was shown, and the crystal melting point (Tm) was 320 ° C. and the heat of fusion was 16 C.
It was a crystalline polyamide with al / g and a crystallization temperature (Tc) of 270 ° C. After melt-molding at 330 to 340 ° C., the performance was evaluated and as a result, it had the following performance. Water absorption rate 2.0% TD dimensional change rate 1.0% MD dimensional change rate 0.2% Dry tensile strength 1,350kg / cm ² Dry elongation at break 15% Bending elasticity rate 37,000kg / cm ² dry flexural strength 1,650kg / cm ² tensile strength 800 kg / cm ² breaking elongation of 10% when wet wet the wet flexural modulus 32,000kg / cm ² of wet Bending strength 1,400kg / cm ²

Next, two more kinds (11-b, 11-c) were prepared in the same manner as in the above synthetic method except that the molar ratio of 1,4-BAMC trans isomer and cis isomer was changed as shown in Table 5. ) Was obtained. The results are shown in Tables 5 and 6.
From the results, it was found that a polyamide resin having high heat resistance, high strength, low water absorption, easy moldability, and excellent mechanical properties when wet independent of the isomer molar ratio of 1,4-BAMC was obtained. It was

[0053]

[Table 5]

[0054]

[Table 6]

[0055]

As is clear from the examples, the novel thermoplastic polyamide resin of the present invention is a resin having excellent high heat resistance, low water absorption, high strength and easy molding process, and is an engineering plastic. It is industrially useful as a device.

[Brief description of drawings]

FIG. 1 is a triangular diagram showing composition ratios of a structural unit (A), a structural unit (B) and a structural unit (C) in a thermoplastic resin of the present invention.

Claims (2)

[Claims] 1. A structural formula (I): Structural unit (A) represented by and structural formula (II) (In the formula, X ₁ represents a trans 1,4-cyclohexane ring residue.) And the structural unit (B)
I) [Chemical 3] (In the formula, X ₂ represents a cis 1,4-cyclohexane ring residue.) A polyamide resin comprising a structural unit (C) represented by: i) a structural unit (A) and [a structural unit (B ) + Structural unit (C)] in the range of 50:50 to 90:10, and ii) the molar ratio of structural unit (B) to structural unit (C) is 10:
Novel thermoplastic polyamide resin in the range of 90 to 90:10 and having a logarithmic viscosity of 0.4 or more measured in 97% sulfuric acid at a concentration of 1.0 g / dl and a temperature of 30 ° C. .. 2. The molar ratio of the structural unit (A) to [the structural unit (B) + the structural unit (C)] is 70:30 to 90:10.
The novel thermoplastic polyamide resin according to claim 1, which is in the range of.