JP3419074B2 - Method for producing polyamide low-order condensate - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a polyamide low-order condensate.

[0002]

2. Description of the Related Art Recently, polyamide resins have been widely used in automobile parts, household electric appliances parts, office parts, industrial parts, textile products, construction materials, miscellaneous goods, etc. Needless to say, heat resistance, heat aging resistance, dimensional stability, and low water absorption are required. Conventionally, a melt polymerization method is widely known as a method for obtaining a general polyamide such as nylon 6 or nylon 66. For example, polyamide resin handbook (Showa 6
3.1.30. (Published by Osamu Fukumoto, published by Nikkan Kogyo Shimbun), etc. However, when a polyamide resin that requires higher mechanical properties, heat resistance, heat aging resistance, dimensional stability, and low water absorption is produced by the melt polymerization method, it becomes impossible to discharge or the melting point of the polymer is Since it is close to the thermal decomposition temperature of, there was a problem of causing decomposition and deterioration.

As a production method for solving these problems, a method of polycondensing a dicarboxylic acid dihalide and a diamine in the presence of a base has been proposed, but the dicarboxylic acid dihalide is expensive and a polyamide is inexpensively produced. I couldn't do that. Also, a method of carrying out a polymerization reaction in a solid state from a nylon salt to a polymer (JP-A-62-205)
No. 27) is also proposed, but there is a problem that the composition of the produced polymer is not stable.

On the other hand, a method of synthesizing a polyamide low-order condensate in the first step and solid-phase polymerizing the low-order condensate in the second step to obtain a polyamide (JP-A-60-163928 and JP-A-61-61). No. 200123), or a method of increasing the degree of polymerization by melt-kneading the low-order condensate in the second stage (Japanese Patent Laid-Open No. 4-123 / 1992).
No. 53825, JP-A-5-230204),
A method of combining solid-phase polymerization and melt-kneading polymerization in the second stage (JP-A-61-228022 and JP-A-5-230).
No. 205) is also proposed.

However, all of these methods require high temperature in order to proceed with the reaction in the step of obtaining the first-order low-order condensate, leading to deterioration or coloring of the low-order condensate to be produced, and finally. However, there is a problem in that the heat stability and heat aging property of the polymer obtained in Example 1 are adversely affected. Furthermore, since the melting point of these low-order condensates varies greatly depending on the molecular weight, it is necessary to control the molecular weight to prevent solidification of the reaction product. Therefore, the reaction system is inevitably at high pressure, and it is necessary to select a reaction vessel that can withstand high temperature and high pressure. Further, in order to take out the low-order condensate obtained at such a high temperature and high pressure, there is disclosed in JP-A 5-2
As disclosed in Japanese Patent No. 30209, 10 kg / cm ²
There was a problem in terms of operability, safety, and economy, such as having to extract it into the atmosphere with a large differential pressure.

On the other hand, a method for obtaining a low-order condensate or polymer from dicarboxylic acid dimethyl ester and diamine is described in Industrial Chemistry Magazine, Vol. 57, p. 212 (1954) and JP-A-60-163928. . However, in the production methods described in these, it is difficult to control the degree of polymerization of the low-order condensate, and further, since water and methanol in the reaction system are distilled off, removal of the produced low-order condensate There was a problem that it would be difficult. Further, there are problems that the reaction does not proceed and the composition becomes unstable when the low-order condensate is made to have a high molecular weight.

[0007]

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a polyamide raw material excellent in mechanical properties, heat resistance, heat aging resistance, solvent resistance, chemical resistance, dimensional stability and low water absorption. To provide a method for producing a polyamide low-order condensate, which is excellent in thermal stability, polymerizability, color tone, and economic efficiency, by synthesizing a secondary condensate at low temperature while controlling the molecular weight and at low pressure. is there.

[0008]

The present invention has been made to solve the above problems, and its gist is (A).
Diamine 10 represented by the following general formula (a)
45 mol%

[0009]

Embedded image ₂ HN—R ¹ —NH ₂ (a)

(In the formula (a), R ¹ represents an alkyl group having 4 or more carbon atoms, a cycloalkyl group or an aryl group which may have a substituent.) (B) The following general formula (b) 10 to 45 mol% of the dicarboxylic acid ester represented by

[0011]

[Chemical 4]

(In the formula (b), R ² and R ⁴ each represent an alkyl group having 3 or less carbon atoms. R ³ is an alkyl group having 2 or more carbon atoms, which may have a substituent, or cycloalkyl. Group, an aryl group) and (c) water 20 to 80 mol
% , The reaction is carried out at 70 to 200 ° C., and most of the charged water is present in the reaction system even at the end of the reaction. Hereinafter, the present invention will be described in detail. The diamine as the component (A) in the present invention is a compound represented by the general formula (a).

[0013]

Embedded image ₂ HN—R ¹ —NH ₂ (a)

In the above formula, R ¹ represents an optionally substituted alkyl group having 4 or more carbon atoms, a cycloalkyl group or an aryl group, preferably R ¹ is an alkyl group having 4 to 20 carbon atoms. Alternatively, it is a cycloalkyl group, more preferably an alkyl group having 4 to 12 carbon atoms or a cycloalkyl group, and particularly preferably a linear alkyl group having 4 to 12 carbon atoms.

Specific examples of the diamine represented by the formula (I) include tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, Linear aliphatic diamines such as dodecamethylenediamine, aliphatic diamines having a substituent such as dimethylhexamethylenediamine, trimethylhexamethylenediamine, phenylenediamines, xylylenediamines, and diamines having an aromatic group , Bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, and the like, diamines having an alicyclic group, and the like, among which linear aliphatic diamines are preferable, and more preferably Hexamethylene diami It is. These diamines may be used alone or in combination of two or more. The ratio of the diamine in the reaction system is 5 to 50 mol%,
Preferably 10 to 45 mol%, particularly preferably 15 to 3
It is 5 mol%. If it is less than 5 mol%, the degree of polymerization of the low-order condensate to be formed becomes too low, or the molecular weight does not increase during post-polymerization, which is not preferable. If it is more than 50 mol%, the system becomes non-uniform, unreacted diamine remains in the system, and the molecular weight does not increase during the post-polymerization, which is not preferable. Component (B) in the present invention
The dicarboxylic acid ester of is a compound represented by the general formula (b).

[0016]

[Chemical 6]

In the above formula, R ² and R ⁴ each have 3 carbon atoms.
The following alkyl groups are shown, and preferably a methyl group.
R ³ represents an optionally substituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, or an aryl group, preferably an alkyl group having 2 to 30 carbon atoms, a cycloalkyl group, an aryl group, and It is preferably an alkyl group having 4 to 12 carbon atoms, a cycloalkyl group or an aryl group, and particularly preferably an alkyl group having 4 to 10 carbon atoms or an aryl group.

Specific examples of the dicarboxylic acid ester represented by the formula (II) include fats such as dimethyl adipate, diethyl adipate, dimethyl pimelate, dimethyl glutarate, dimethyl suberate and dimethyl sebacate. Aromatic dicarboxylic acid esters such as group dicarboxylic acid esters, dimethyl isophthalate, dimethyl terephthalate, dimethyl 2,6-naphthalenedicarboxylic acid, dimethyl 2,7-naphthalenedicarboxylic acid, cyclohexane-1,4 and 1,3-dicarboxylic acid Examples thereof include alicyclic dicarboxylic acid esters such as dimethyl, and among them, aliphatic dicarboxylic acid esters and aromatic dicarboxylic acid esters are preferable, and dimethyl adipate, dimethyl isophthalate, and dimethyl terephthalate are more preferable. List Re particular dimethyl terephthalate is preferred.

These dicarboxylic acid esters may be used alone or in combination of two or more. The proportion of the dicarboxylic acid ester in the reaction system is 5 to 50 mol%
And preferably 10 to 45 mol%, particularly preferably 15 to 35 mol%. If it is less than 5 mol%, the degree of polymerization of the low-order condensate to be formed becomes too low, or the molecular weight does not increase during post-polymerization, which is not preferable.
When it is more than 0 mol%, the system becomes non-uniform, unreacted dicarboxylic acid ester remains in the system, and the molecular weight does not increase during post-polymerization, which is not preferable.

The amount of water charged for producing the polyamide low-order condensate of the present invention is 10 to 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 75 mol%.
Mol%, especially 40 to 70 mol% is preferable. If the amount of water is less than 10 mol%, the system becomes non-uniform and does not become a slurry, making it difficult to extract or leaving unreacted monomers in the system, and as a result, this unreacted monomer is not reacted during the post-polymerization. It is not preferable because the monomer volatilizes and the polymer having the desired composition cannot be obtained, or the molecular weight does not increase.
On the other hand, if it is more than 90 mol%, the degree of polymerization of the low-order condensate to be produced becomes too low, and the molecular weight does not increase during post-polymerization, which is not preferable.

In the present invention, 5 to 50 mol% of the component (A) diamine, 5 to 50 mol% of the component (B) dicarboxylic acid ester and 10 to 90 mol% of the component (C) water are polymerized. Charged in the system, reacted at a temperature of 70 to 200 ° C., and even at the end of the reaction, most of the charged component (C) water, usually 60% or more, preferably 80% or more, more preferably 90% or more. Must be present in the reaction system. The number average molecular weight of the polyamide low-order condensate at the end of the reaction is usually about 200 to 3000.
That is, the present invention makes it possible to control the molecular weight of a polyamide low-order condensate by adjusting the amount of water, and to manufacture a low-order condensate having a desired molecular weight. The number average molecular weight Mn of the finally obtained low-order condensate can be represented by the following formula (c).

[0022]

[Equation 2]

In the formula, [B] is mol% when the dicarboxylic acid ester represented by the formula (b) is charged, [H ₂ O] is mol% when water is charged, k is 100 ≦ k ≦ 600, Preferably 200 ≦ k ≦ 500, particularly preferably 300 ≦ k ≦ 50.
Represents a constant of 0. When producing the polyamide low-order condensate of the present invention, the mol% of the diamine represented by the formula (a) at the time of charging
[A], mol% of the dicarboxylic acid ester represented by the formula (b) when charged [B], and mol% of water when charged [H ₂
O], the molar ratio of [A] / [B] is not particularly limited as long as it is within the above range, but is preferably 0.6 to 1.5, more preferably 0.9 to 1. 0.1, and particularly preferably 0.95 to 1.05. Also,
The molar ratio of ([A] + [B]) / [H ₂ O] is not particularly limited as long as it is within the above range, but is preferably 2
0/80 to 80/20, more preferably 30 /
70-75 / 25, particularly preferably 40 / 60-70 / 3
It is 0.

There are no particular restrictions on the method of charging the raw materials and the order of charging when producing the polyamide low-order condensate of the present invention. The reaction temperature is suitably 70 to 200 ° C, preferably 90 to 180 ° C, more preferably 100 to 150 ° C. If the temperature is lower than 70 ° C., the reaction proceeds slowly, which is not practical, and if the temperature is higher than 200 ° C., thermal deterioration or coloring of the low-order condensate occurs, which is not preferable.

The polyamide low-order condensate of the present invention is produced.
The reaction pressure at that time depends on the reaction temperature, but is usually atmospheric pressure to
5 kg / cm², Preferably normal pressure to 3 kg / cm²so,
Can be done under an inert atmosphere, such as under a nitrogen atmosphere
More preferable. 5 kg / cm ²Withdrawal at higher pressure
Is difficult and requires special equipment.
No

The reaction time for producing the polyamide low-order condensate of the present invention is usually 0.5 to 10 hours, preferably 1
~ 5 hours. Further, in order to improve the fluidity and moldability of the polymer finally obtained, the aliphatic ω represented by the following general formula (d) at the time of producing the low-order condensate of the present invention is
-Amino acid and / or a lactam represented by the following general formula (e) may be added.

[0027]

[Chemical 7]

In the formulas (d) and (e), n represents an integer of 3 to 20, preferably 5 to 11. Specific examples of the ω-amino acid represented by the general formula (d) include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Among them, 6-aminocaproic acid is preferable. Specific examples of the lactam represented by the general formula (e) include butyllactam, pivalolalactam, caprolactam, capryllactam, enanthlactam, undecanolactam, dodecanolactam, and the like, with caprolactam being preferred. These ω-amino acids and /
Alternatively, one type of lactam may be used, or two or more types may be combined. The proportion of the ω-amino acid and / or lactam in the reaction system is 0 to 10 mol%, preferably 0 to 5 mol%, and more preferably 0 to 3 mol%. When it is more than 10 mol%, the mechanical properties, heat resistance and low water absorption of the polymer finally produced are impaired. Furthermore, for the purpose of improving the fluidity and thermal stability of the polymer finally obtained, a monocarboxylic acid ester or a monocarboxylic acid represented by the following general formula (f) is produced during the production of the low-order condensate of the present invention. Acid may be added.

[0029]

[Chemical 8]

In the formula, R ⁵ represents H or an optionally substituted alkyl group having 1 to 20 carbon atoms, a cycloalkyl group or an aryl group, preferably a straight chain having 1 to 10 carbon atoms. It is an alkyl group or an aryl group, and especially has 1 to 1 carbon atoms.
A linear alkyl group of 5 is preferred. R ⁶ represents H or an alkyl group having 3 or less carbon atoms, preferably H or a methyl group, and particularly preferably a methyl group.

Specific examples of the monocarboxylic acid ester or monocarboxylic acid represented by the formula (f) include methyl formate, methyl acetate, ethyl acetate, propyl acetate, phenyl acetate, methyl propionate and methyl butyrate.
Fatty acid esters such as methyl dodecanoate and methyl stearate, formic acid, acetic acid, propionic acid, butyric acid, dodecanoic acid,
Fatty acids such as stearic acid, aromatic carboxylic acid esters such as methyl benzoate, ethyl benzoate, phenyl benzoate, methyl toluate, methyl naphthoate, and aromatic carboxylic acids such as benzoic acid, toluic acid, naphthoic acid, and the like. Among them, fatty acid ester or fatty acid is preferable, acetic acid ester or acetic acid is more preferable, and methyl acetate is particularly preferable. These monocarboxylic acid esters and / or monocarboxylic acids may be used alone or in combination of two or more. The proportion of the monocarboxylic acid ester or monocarboxylic acid in the reaction system is 0 to 5 mol%, preferably 0 to 2 mol%, and particularly preferably 0 to 0.6 mol%. If it exceeds 5 mol%, the molecular weight will not be sufficiently increased during the post-polymerization.

During the production of the low-order condensate of the present invention, other conventional components such as heat stabilizers, light stabilizers, UV absorbers,
A small amount of antioxidants, antistatic agents, preservatives, adhesion promoters, colorants, crystallization promoters, lubricants, bactericides, plasticizers, release agents, thickeners and the like can be added. According to the method for producing a low-order condensate of the present invention, it is not necessary to distill off water in the reaction system, and thus the produced low-order condensate can be easily taken out. The low-order condensate produced by the present invention can be increased in polymerization degree by a known method, preferably a method of increasing the polymerization degree in a solid state, a melt kneader, a continuous kneader, or the like in a molten state. Examples thereof include a method of increasing the degree of heat treatment, a method of combining these methods, and the like, and a polyamide resin can be produced using these methods.

[0033]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples unless it exceeds the gist thereof. The polyamide low-order condensate of the present invention was analyzed and evaluated by the following methods. (1) Accurately weigh 0.1 to 2 g of the terminal amino group sample, and add 50 ml of phenol.
After being dissolved in the solution, an automatic titrator (Mitsubishi Kasei Co., Ltd., G
T-05) was used for titration with 0.1 N hydrochloric acid, and the calculation was performed. (2) 0.1 to 2 g of a terminal carboxyl group sample was accurately weighed and dissolved in 50 ml of benzyl alcohol, and then an automatic titrator (GT-05 manufactured by Mitsubishi Kasei Co., Ltd.) or a normal burette type titrator was used. It was calculated by titrating with 0.1 N sodium hydroxide. (3) Dissolve 5 to 10 mg of a terminal ester group, a terminal monocarboxylic acid, a composition analysis, and an unreacted analysis sample in concentrated sulfuric acid, and give a resonance frequency of 27
It was calculated from the intensity of each absorption peak by 0 H ¹ H NMR (manufactured by JEOL Ltd.). After evaporating the filtrate, the unreacted product was analyzed by NMR in the same manner. (4) Number average molecular weight The number average molecular weight was calculated according to the following formula from the total number of terminals obtained by the methods of (1), (2) and (3).

[0034]

[Equation 3]

(5) Relative viscosity (η _re1 ) The sample was dissolved in concentrated sulfuric acid to a concentration of 1 g / dl, the drop time was measured at 25 ° C. with an Ubbelohde viscous tube, and calculated according to the following formula.

[0036]

[Equation 4]

(6) Melting point (Tm) 16 ° C. using DSC (TA-2000) manufactured by DuPont
It was measured at a temperature rising rate of / min.

Example 1 0.43 mol of hexamethylenediamine (HMDA) (5
0.0 g), dimethyl adipate (DMA) 0.21 mol (36.6 g), dimethyl terephthalate (DMT)
0.21 mol (40.8 g), H ₂ O 0.57 mol (1
0.3 g) was charged into a 0.5 L separable flask equipped with a reflux condenser, and after sufficiently purging with nitrogen, the mixture was stirred on a 140 ° C. oil bath under a nitrogen atmosphere at atmospheric pressure. The reaction system became cloudy immediately after the start of heating, but methanol gradually evolved as the reaction progressed, and became transparent and uniform. As the reaction proceeded further, the system gradually began to become cloudy. During this time, the internal temperature was 120 to 130 ° C. After heating for 2 hours, the heating was stopped, and the slurry-like product was filtered off with a 4G glass filter.
It was vacuum dried at 100 ° C. for one day. ¹ H NMR of the filtrate
No unreacted substance was detected when analyzed by. The powdery low-order condensate obtained was white without any coloring, and as a result of analysis, the number average molecular weight was 700. When this low-order condensate was heated from 140 ° C. to 230 ° C. in a nitrogen atmosphere at atmospheric pressure over 5 hours and then solid-state polymerized at 230 ° C. for 3 hours, η _{re 1} = 2. A polyamide of 3 was obtained. When this polyamide was analyzed by ¹ H NMR, it had the same composition as that charged.

Example 2 A polyamide low-order condensate was obtained in the same manner as in Example 1 except that the amount of H ₂ O charged was 3.33 mol (60.0 g). As in Example 1, no unreacted product was detected in the filtrate, and the low-order condensate of the obtained fine powder was white without any coloration. As a result of analysis, the number average molecular weight was 240.
When this low-order condensate was _subjected to solid-phase polymerization in the same manner as in Example 1, a polyamide with η _re1 = 2.4 was obtained.

Example 3 HMDA 1 mol (116.2 g), DMA 0.5 mol (87.1 g), DMT 0.5 mol (97.1)
g) and 3 mol of H ₂ O (54.0 g) were charged into an autoclave, and after nitrogen replacement was sufficiently performed, the autoclave was sealed and the internal temperature was set to 1
The mixture was stirred while controlling the temperature to 20 ° C. During this time, the internal pressure was 0 to 1.6 kg / cm ² . After 3 hours, the heating was stopped and the content in the form of a slurry was taken out, separated by a centrifuge, and vacuum dried at 100 ° C. for one day. No unreacted material was detected in the separated liquid. The powdery low-order condensate obtained was white with no coloration as in Example 1, and as a result of analysis, the number average molecular weight was 420. When this low-order condensate was _subjected to solid-phase polymerization in the same manner as in Example 1, a polyamide with η _re1 = 2.4 was obtained.

Example 4 HMDA 1 mol (116.2 g), DMA 0.5 mol (87.1 g), DMT 0.5 mol (97.1)
g) and 0.5 mol of H ₂ O (9.0 g) were charged into an autoclave, and a polyamide low-order condensate was obtained in the same manner as in Example 3. The low-order condensate obtained was white with no coloration as in Example 1, and as a result of analysis, the number average molecular weight was 1480.
Met. When this low-order condensate was _subjected to solid-phase polymerization in the same manner as in Example 1, a polyamide with η _re1 = 2.5 was obtained.

Example 5 A polyamide low-order condensate was obtained in the same manner as in Example 3 except that the internal temperature of the autoclave was set to 100 ° C. Internal pressure is 0
Was about 1.2 kg / cm ² . The low-order condensate obtained was white with no coloration as in Example 1, and as a result of analysis, the number average molecular weight was 410. This low-order condensate was used in Example 1.
Solid phase polymerization was carried out in the same manner as in _Example 1, but η _re1 = 2.
A polyamide of 3 was obtained.

Example 6 HMDA 1 mol (116.2 g), dimethyl isophthalate (DMI) 0.25 mol (48.5 g), DMT
0.75 mol (145.6 g), H ₂ O 3 mol (5
4.0 g) was charged into an autoclave and a polyamide low-order condensate was obtained in the same manner as in Example 3. The low-order condensate obtained was white with no coloration as in Example 1, and as a result of analysis, the number average molecular weight was 430. When this low-order condensate was _subjected to solid-phase polymerization in the same manner as in Example 1, η _re1
A polyamide of = 2.3 was obtained.

Example 7 1 mol of HMDA (116.2 g), 0.5 mol of DMA (87.1 g), 0.5 mol of DMT (97.1)
g), 0.1 mol of ε-caprolactam (CL) (11.
3 g) and 3 mol of H ₂ O (54.0 g) were charged into an autoclave, and a polyamide low-order condensate was obtained in the same manner as in Example 3. The low-order condensate obtained was white with no coloration as in Example 1, and as a result of analysis, the number average molecular weight was 390. When this low-order condensate was _subjected to solid-phase polymerization in the same manner as in Example 1, a polyamide with η _re1 = 2.2 was obtained.

Example 8 HMDA 1 mol (116.2 g), DMA 0.5 mol (87.1 g), DMT 0.5 mol (97.1)
g), methyl acetate 0.02 mol (1.5 g), H ₂ O
3 mol (54.0 g) was charged into an autoclave and a polyamide low-order condensate was obtained in the same manner as in Example 3. The low-order condensate obtained was white with no coloration as in Example 1, and as a result of analysis, the number average molecular weight was 390. When this low-order condensate was _subjected to solid-phase polymerization in the same manner as in Example 1, a polyamide with η _re1 = 2.2 was obtained.

Example 9 1 mol of HMDA (116.2 g), DMA 0.45
Mol (78.4 g), DMT 0.45 mol (87.4 g)
g) and 3 mol of H ₂ O (54.0 g) were charged in an autoclave, and a polyamide low-order condensate was obtained in the same manner as in Example 3. The low-order condensate obtained was white with no coloration as in Example 1, and as a result of analysis, the number average molecular weight was 350.

Example 10 0.9 mol of HMDA (104.6 g), DMA 0.
5 mol (87.1 g), DMT 0.5 mol (97.1)
g) and 3 mol of H ₂ O (54.0 g) were charged in an autoclave, and a polyamide low-order condensate was obtained in the same manner as in Example 3. The low-order condensate obtained was white with no coloration as in Example 1, and as a result of analysis, the number average molecular weight was 380. An equal amount of this low-order condensate and the low-order condensate obtained in Example 7 were mixed, and a vent type twin-screw extruder (screw diameter 30 mm, barrel length to screw diameter ratio (L / D)) was used.
_{Polycondensation} proceeded at 32.5, barrel temperature 350 ° C.) to obtain a polyamide with η _re1 = 2.0.

Comparative Example 1 HMDA 0.3 mol (34.9 g), DMA 0.1
5 mol (26.1 g), DMT 0.15 mol (29.
1 g) and 9.4 mol (169.2 g) of H ₂ O were charged into an autoclave, and an attempt was made to synthesize a polyamide low-order condensate in the same manner as in Example 3. When the product was analyzed,
The number average molecular weight was 140 and almost no condensation occurred. This product was _subjected to solid phase polymerization in the same manner as in Example 1, but the degree of polymerization hardly _increased at η _re1 = 1.1.

Comparative Example 2 HMDA 0.72 mol (83.6 g), DMA 0.
36 mol (62.7 g), DMT 0.36 mol (6
9.9 g) and 0.06 mol (1.1 g) of H ₂ O were charged into an autoclave, and an attempt was made to synthesize a polyamide low-order condensate in the same manner as in Example 3. When the product was analyzed, it had a number average molecular weight of 150 and almost no condensation occurred. A large amount of unreacted carboxylic acid ester remained in the system. This product was _subjected to solid-phase polymerization in the same manner as in Example 1, but the degree of polymerization hardly _increased at η _re1 = 1.3.

Comparative Example 3 HMDA 0.045 mol (5.2 g), DMA 0.
45 mol (78.4 g), DMT 0.45 mol (8
7.4 g) and 0.56 mol (10.0 g) of H ₂ O were charged into an autoclave, and an attempt was made to synthesize a polyamide low-order condensate in the same manner as in Example 3. When the product was analyzed, the number average molecular weight was 140 and almost no condensation occurred. This product was _subjected to solid phase polymerization in the same manner as in Example 1, but the degree of polymerization hardly _increased at η _re1 = 1.1.

Comparative Example 4 0.72 mol of HMDA (83.6 g), DMA 0.
36 mol (62.7 g), DMT 0.36 mol (6
9.9 g) and 0.16 mol (1.1 g) of H ₂ O were charged into an autoclave and the internal temperature was set to 230 ° C. The synthesis of a polyamide low-order condensate was tried in the same manner as in Example 3. At this time, the internal pressure reached 20 kg / cm ² . Also,
Three hours after the internal temperature reached 230 ° C., the contents solidified and could not be extracted.

Comparative Example 5 1 mol (116.2 g) of HMDA, 0.5 mol (87.1 g) of DMA, 0.5 mol (97.1) of DMT.
g) and 3 mol of H ₂ O (54.0 g) were charged into an autoclave, and after nitrogen replacement was sufficiently performed, the autoclave was sealed and the internal temperature was set to 1
The mixture was stirred while controlling the temperature to 20 ° C. During this time, the internal pressure was 0 to 1.6 kg / cm ² . After 3 hours, the heat medium temperature was set to 140 ° C. and H ₂ O and methanol were distilled off. As a result, the contents solidified and it became impossible to extract. Furthermore, when the temperature of the heating medium was raised to 350 ° C. over 6 hours, the distillate was distilled off and the contents were extracted, and it turned brown. The molar ratio of the raw materials used in Examples 1 to 10 and Comparative Examples 1 to 5, reaction temperature, reaction pressure, the number average molecular weight of the obtained low-order condensate, the melting point, the value of k, and the relative viscosity of the polyamide obtained by post-polymerization. Is shown in Table-1.

[0053]

[Table 1]

[0054]

According to the method of the present invention, since it is possible to produce a polyamide low-order condensate at low temperature and low pressure while controlling the molecular weight, the production safety and operability can be improved as compared with the conventional production method. Further, the obtained low-order condensate is excellent in thermal stability, polymerization reactivity, color tone, economical efficiency and the like. Furthermore, the polyamide resin produced by using the low-order condensate produced by the method of the present invention as a raw material can be easily molded by various molding methods such as injection molding, extrusion molding and compression molding, and has mechanical properties and heat resistance. It has excellent heat aging resistance, dimensional stability, low water absorption, solvent resistance, chemical resistance, color tone, etc.

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-57-80426 (JP, A) JP-A-61-228022 (JP, A) JP-A-60-163928 (JP, A) JP-A-5- 230205 (JP, A) JP-A-61-176628 (JP, A) JP-B-44-11908 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 69/00-69 / 36

Claims (8)

(57) [Claims] 1. (A) 10 to 45 mol% of a diamine represented by the following general formula (a): embedded image ₂ HN—R ¹ —NH ₂ (a) (wherein R ¹ is a substituent An alkyl group having 4 or more carbon atoms, a cycloalkyl group, or an aryl group, which may have). (B) 10 to 45 mol% of a dicarboxylic acid ester represented by the following general formula (b): (In the formula (b), R ² and R ⁴ each represent an alkyl group having 3 or less carbon atoms. R ³ is an optionally substituted alkyl group having 2 or more carbon atoms, a cycloalkyl group, or aryl. Group) and (c) 20 to 80 mol% of water is charged, and
A method for producing a polyamide low-order condensate, which comprises reacting at 0 to 200 ° C. and allowing most of the charged water to be present in the reaction system even at the end of the reaction. 2. The method for producing a polyamide low-order condensate according to claim 1, wherein the number average molecular weight Mn of the polyamide low-order condensate at the end of the reaction satisfies the following formula (c). [Equation 1] (In the formula, [B] is mol% when the dicarboxylic acid ester represented by the formula (b) is charged, [H ₂ O] is mol% when water is charged, and k is a constant of 100 ≦ k ≦ 600. Show.) 3. When the mol% of the diamine of the formula (a) when charged is [A] and the mol% of the dicarboxylic acid ester of the formula (b) when charged is [B], [A] ] /
The method for producing a polyamide low-order condensate according to claim 1 or 2, wherein [B] is in the range of 0.6 to 1.5. 4. The amount of the diamine represented by the formula (a) when charged is [A], the amount of the dicarboxylic acid ester represented by the formula (b) is [B], and when the water is charged. 4. When the mol% is [H ₂ O], ([A] + [B]) / [H ₂ O] is in the range of 20/80 to 80/20. A method for producing a polyamide low-order condensate according to claim 1. 5. The method for producing a polyamide low-order condensate according to claim 1, wherein R ² and R ⁴ in the general formula (b) are each a methyl group. 6. The method for producing a polyamide low-order condensate according to claim 5, wherein dimethyl terephthalate is used as the component (B). 7. The method for producing a polyamide low-order condensate according to claim 1, wherein the component (A) is hexamethylenediamine and the component (B) is dimethyl ester. 8. Any solid by-phase polymerization of the obtained polyamide low condensate by the method according to the claims 1-7
A method for producing a polyamide resin , comprising: