JPS5968328A - Production of polyalkylene ether polyamide - Google Patents

Abstract

PURPOSE:To obtain a polyalkylene ether polyamide having a sufficient degree of polymerization and light color, by adding a specified amount of triphenyl phosphite to the polymerization system in carrying out the polymerization of a polyamide-forming monomers. CONSTITUTION:A polyalkylenediamine is prepared by hydrogenating a cyanoethylated product of a polyalkylene ether glycol (e.g., polyethylene or polypropylene glycol). The produced polyalkylenediamine and a carboxylic acid (e.g., adipic or terephthalic acid) are polymerized in the presence of 0.01-10wt%, based on polyalkylenediamine, triphenyl phosphite. In this way, a polyalkylene ether polyamine of a sufficient degree of polymerization can be obtained without retarding the rate of viscosity rise in the course of the polymerization reaction even when the diamine component contains impurities.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing 31 polyj/rurene-1 polyamide.

Borinol 1; Ren-1-del polyamide is antistatic.
There are polymers C useful as R-type polyamides, water-type polyamides, and photosensitive t(l resin groups H).

This polymer is generally produced by hydrogenating the di-7-noethylated product of borinofulkylene]]--fulglylene (hereinafter referred to as the 7-noedylated product). This polyalkylene diamine (3=I L (equimolar silyl/J carboxylic acid, and J on the lifting platform, then another polyamide 1
J is obtained by the polymerization reaction with J. The 1-coupling reaction can be carried out normally without using a catalyst.

However, J5 was involved in the polymerization reaction in the beginning, and the result was a polymerization reaction of 1. L: On the way, C゛ viscosity soil velocity IV decreased and [polymerization degree of poly]? [rukylene]--chirupoly7mil~ was obtained and had a strength of 41 degrees. This is used as the starting material for polymerization.
The diamine component to be used or itself (low polymerization 1a)
It is difficult to purify sufficiently because it has a heavy content of IA (and a molecular weight of +i), and substances with a molecular weight of '5', such as a polyalkylene chloride powder, It is difficult to completely hydrogenate and easily generates impurities, resulting in impurities in the diamine component, such as 11-Cl-12-CHNll2,
CH3-CI-12-1 -ll 2-N-Cl-12(n 1-1 2 G
It was found that the presence of the compound shown in Table 13 in a non-negligible amount was due to C' of J and Rub. In order to prevent this, it is possible to improve the purification of diamines and the hydrogenation reaction, but it is difficult to reduce the impurities present at the ppm@ level when carried out in a single industry. .

Therefore, it is necessary to compensate for the presence of impurities by improving the polymerization method.In addition, even if impurities exist in the polyalkylenediamine component, a decrease in the fermentation rate of the viscous melon during the polymerization reaction may occur. Intensive investigation aimed at establishing a polymerization method that does not require
・At about the same time, a specific compound,
The present invention was achieved by discovering that it is only necessary to add 1 fluoride to 1 heliph.

One major advantage of this is that trinoylene small sphites are used in the polymerization of polyamide-forming L-trium containing at least a diamine and a dicarboxylic acid obtained by hydrogenating a cyanochloride of polyalkylene ether nitride. The above polymerization can be carried out by adding or omitting 0.01 to 1 Qwt% of 0.01 to 1 Qwt% based on the diamine to the polymerization reactions I and b.
J Now Kushi-C is achieved.

More specifically, the method of the present invention will be described in detail. 1. The polyalkylene ether glycol used in the present invention is alkyl! Non 1
- Glycols with chill repeating A 1'/ of 2 or more, and R's of 4 or more, such as PolyL Blengriny J-L, Volip°['Pyrene Glycol, Polybutylene Glycol 1-L, etc. . , ethylene glycol is preferred.

Polyethylene glycol has an average molecular m of 11.0 to 20
,000, more preferably 200 to 6,000.

The polyalkylene ether glyc-1-1+ of the forward bending is cyanoethylated with L acrylonitrile and further hydrogenated to give a polyalkylene diamine.

Here, the purification and hydrogenation of C' and di-7 may be carried out by conventional methods and procedures. The polyalkylene diamine obtained by the hydrogenation reaction may be purified by ion exchange, and the water solution may be purified by distillation using an organic solvent, and then subjected to polymerization. On the other hand, the dicarboxylic acids used in the present invention include adipic acid, levacic acid, azelaic acid, superric acid, and dodecanoic acidic aliphatic dicarboxylic acids;
There are aromatic dicarboxylic acids such as delenotaric acid and isophthalic acid.

Preferably [more aliphatic dicarboxylic acids, even more! lI Mashukuke adipic acid is used.

The above polymerization reaction can be used to form other polyamides, such as ε-lactam, ω-dodecalactano\4, which lactams; Copolymers may also be produced using amine-based dicarboxylic acids such as. Other preferred materials for forming polyamides include salts of 1Ji, ε-)Jb1'lactam, hexamethylene nondiamine, and adipic acid or isophthalic acid.

When using a copolymer as described above, it is preferable that the copolymerization ratio of the polyamide component consisting of polyalkylene diamine and dicarboxylic acid is 99 to 20%.

i~rif-1 nylphostin'i1~ used in the present invention
C-, which is commercially available per se, may also be used.

When the above-mentioned chassis raw material is polymerized in the presence of 1 to linol homeonite, an aqueous solution of boria lundimine and dicarboxylic acid is added to a known polymerization reactor. ~Form and supply with the knob,
At this time, 0.01 to 10 W [% of the diamine is added to the polymerization reaction system and the polymerization is carried out in the usual manner. good.

i ~ Reno] When 0.01 wt% of Ninyl Small Susphine 1 is suspended without swirling, it has the effect of increasing the upper speed of the viscosity (within 1 minute, and conversely, when it exceeds lQwt%, the effect reaches its limit (reaching the viscosity) Te?If the speed is faster than that, yes.

Preferably it is 0.05 to 5 wt%, more preferably -2 wt% C to O5'1.

The silicone strength of the polymerization reaction system may be maintained at elevated stage C under elevated pressure, normal pressure, or reduced pressure.

When the i-compensation is completed, polyalky1non- is removed from the heavy reactor.
+---5 Lubolino! The midge is taken out of the river and made into a belt or GEL strip and once pelletized. 13
The collected parts 1 to 1 are used depending on their purpose. .

According to the method disclosed in Tree 5, there are impurities accompanying the polyall:11 nondino'mine in the polymerization reaction system for forming polyj'mide using the diamine as a raw material [and the rate of increase in viscosity decreases]. It also has an additional effect on improving the color tone of polyamide obtained by IUI.

Next, the present invention will be explained in detail with reference to Examples.

In addition, the relative viscosity and color tone in the following examples are the values measured by the following method.

(Relative viscosity) Test onion (1wt in 7Qwt% hydrate []ral)
What is the concentration of t#l? This is the value measured at 25°C using Os 1 ~ Wald viscosity it.

Based on the measurement method of JIS-L-1074 (1965).

Example 1 Polyethylene glycol with an average molecular weight of FF 1600 was converted into cyano-1-del by 1-cri[]-di-lyl in the presence of an alkali catalyst, and a hydrogenation reaction (J became polyethylene
Synthesize len glycol diamine, [U4'1.
By removing 16 cyamine and adipic acid and reacting with salt, a 5 Qwt% aqueous solution of poly1f-dilene glycol dianium j7 dibe I was made into 1
20 parts by weight, 24 parts by weight of 85 wt% aqueous solution of ε-caprolactam, 40 parts by weight of 5Qwt% aqueous solution of l' 0.1 part by weight (
0.2W (1%) based on the above-mentioned siamin was added, and heating was started by flowing 0.5f/1 pile + C/nitrogen into the polymerization reactor. 1W from the time the internal temperature reaches 200'C
Hit? The vehicle was heated at an internal temperature of 240°C for a predetermined 1.5 minutes.

The heavy content was discharged in a conventional manner to obtain a product polymer.

The relative viscosity and color tone of the obtained polymer were measured, and the reaction time (time after the liquid temperature reached 240'C; the same applies hereinafter) and 11
The relationship between the relative viscosity and color tone of the formed polymer is shown as a curve △ in Figure 1.2.

Example 2 Eleven polymerization reactions were carried out in the same manner as in Example 1, except that 1~Linostoyl small sulfite I~ was added (IL was 0.2 parts by weight (Q based on the diamine, 4 wt%)) The results are shown as curve B in Figure 1.2.

Example 3 The addition amount of trinoenylphosnoai 1 to 1.0 parts by weight (
Example 1 except that 2wt% based on diamine
The results of a polymerization reaction carried out in the same manner as above are shown as curve 0 in Figure 1.2.

Comparative example 1 '1.2 The curve]) and -(shown in the figure).

Examples 1 to 3 and Comparative Example 1 (curve A in Figure 1.2)
It is clear from ~D) that the polyalkylene beads obtained by Ming's method are I.
The relative viscosity is extremely large compared to the case where ~Refair Small Snow Eye 1~ is not added to the liquid.
The color tone (Y11 straight) is stable at 1 generation and 1.L:.

Example 4 Using a PolyFf resin with i1L1 molecular weight of 4000, Example 1 Reproduction method C1 and Poly■ Dilene Grey1-Lucifin2 "Kumajbe 1 ~ 5Qw
94 weight M parts of t% aqueous solution, 85 w of ε-turnip 11 cytam
t% aqueous solution! :) 9 parts by weight and 6 parts by weight of a 50 wt% aqueous solution of hexylamide diammonium isophthalate i-, and 0.02 parts by weight of C trifluor 1-1-1 (diamine 'a' 7YG) as an additive. '? - 0.εN5wt%) of ilZ mixture iW 'd'j, was continuously supplied to the polymerization group,
111) At a temperature of 20 hours, a polymer with a relative viscosity of 2.10 was obtained under normal pressure.

This polymer was dissolved fA'l', in the form
' 2 /I5) 'Match the batting for 5 minutes with C (-J Natsu ηt
l 1. The viscosity of the x polymer is 2.78) 5
．． .

Comparative Example 2 The polymerization reaction was carried out in the same manner as in Example 4, except that 1.1% of the phosphorus acid was added to 1. It was as low as .03.

The relative viscosity of the polymer was as low as 2.18 and l
ζ.

[Brief explanation of the drawing]

Figure 1: What is the relationship between polymerization time and phase viscosity?
FIG. 2 is a graph showing the relationship between chassis time and color tone (Yl). Song N'A△21~Rino Do Niru Ko Sunononoi I-0,2)
vt%l, +3: 0. /
I"tlC:2 n j): Iishi

Claims (1)

[Claims] A polyamide 1 containing at least a diamine and a dicarboxylic acid obtained by hydrogenating a cyanoyl-1-lene ether glycol is polymerized. At this time, 0.01-10 wt % of 1 heliphatide I and 2 were added to the polymerization reaction system based on the diamine. (Manufacture of polyalkylene-on-derbolyamide characterized by polymerization of the following method) "J method."