JPH10330446A - Production of solution of segmented polyurethane urea polymer excellent in stability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject stable solution free from the variation of the viscosity of a solution by reacting an intermediate polymer, which has been obtained by reacting a specific polymeric glycol with an organic diisocyanate compound, with an organic monoamine in a specific amount. SOLUTION: This polymer solution is obtained as follows: a polymeric glycol of 600-6000 in a number average molecular weight having hydroxyl groups at both the terminals is made to react with an organic diisocyanate compound (e.g. p,p'-diphenylmethanediisocyanate) in an excess molar quantity to obtain an intermediate polymer having isocyanate groups at both the terminals; the resultant intermediate polymer is made to react with an organic diamine compound to obtain an initial polyurethane urea polymer solution; and the resulting polymer is made to react with an organic monoamine compound (e.g. N,N- diethylamine) after adjusting the quantity of addition of the monoamine compound so that the electroconductivity of the solution will become 60-280 μS/cm after polymerization, to neutralize the excess isocyanate group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a segmented polyurethaneurea polymer solution, and more particularly to a method for producing a segmented polyurethaneurea polymer solution having excellent solution viscosity stability.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a segmented polyurethane urea polymer solution, it has been known to add an organic diamine and an organic monoamine to an intermediate polymer during polymerization to obtain a polymer solution.

Also, Japanese Patent Application Laid-Open No. 2-51518 discloses a method of adding a monoamine to a polymer solution at a specific ratio, but the amount of addition is set within a certain range. Does not sufficiently contribute to the stabilization of the solution viscosity.

[0004]

In the production of a segmented polyurethane urea polymer solution, an intermediate having isocyanate groups at both terminals formed by the reaction of a polymer glycol as a precursor thereof with an excess molar amount of an organic diisocyanate compound. Fluctuations in the isocyanate groups in the polymer cause the amount of residual amine in the final polymer solution to fluctuate, resulting in a decrease in solution viscosity, which is considered to be decomposed by amine, and fluctuate the physical properties of the polymer solution. For this reason, when a yarn is obtained by, for example, dry spinning the polymer solution, a fluctuation in solution viscosity occurs during spinning, and it may be difficult to obtain a yarn having stable physical properties.

The present invention solves the above-mentioned problems of the conventional segmented polyurethane urea polymer solution, and produces a segmented polyurethane urea polymer solution capable of suppressing and stabilizing fluctuations in the solution viscosity of the polymer solution. The purpose is to provide the law.

[0006]

In order to achieve the above object, the method for producing a segmented polyurethane urea polymer solution having excellent stability according to the present invention has a number average molecular weight of 600 to 600.
An initial polyurethaneurea polymer solution obtained by reacting an organic diamine compound with an intermediate polymer having isocyanate groups at both ends obtained by reacting a polymer glycol having hydroxyl groups at both ends with an excess molar amount of an organic diisocyanate compound at 6000 And then reacting an organic monoamine compound to neutralize excess isocyanate groups to obtain a segmented polyurethaneurea polymer solution, thereby producing a segmented polyurethaneurea polymer solution.
An organic monoamine compound is reacted with the initial polyurethaneurea polymer solution so that the electric conductivity of the segmented polyurethaneurea polymer solution is 60 to 280 μS / cm.

The method for producing a segmented polyurethaneurea polymer solution having excellent stability according to the present invention having the above constitution can suppress and stabilize the fluctuation of the solution viscosity of the polymer solution.

In this case, the initial solution viscosity of the polyurethaneurea polymer solution is preferably 4900 poise (30 ° C.) or less.

The method for producing a segmented polyurethane urea polymer solution having the above constitution and excellent stability can particularly stabilize the fluctuation of the solution viscosity of the polymer solution.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of the method for producing a segmented polyurethane urea polymer solution having excellent stability according to the present invention will be described below.

The electric conductivity is continuously detected by an electric conductivity meter in a portion where the polymer solution in the polymerization vessel is flowing. For example, it is performed as follows. Install a pipe / pump to circulate the polymer solution in the polymerization can, circulate the polymer solution out of the tank, and continuously measure the electric conductivity with an electric conductivity meter installed in the line where the polymer solution is returned to the polymerization can. To detect. The amount of the organic monoamine compound added is adjusted so that the value becomes 60 to 280 μS / cm.

When the organic monoamine compound is added, the electric conductivity can be detected and the amount can be automatically controlled. By this method, the polymer solution is stabilized, and the solution viscosity is stabilized.

The polymerization is carried out as follows.

A polymer glycol such as polyester glycol or polyalkylene ether glycol is reacted with an excess molar amount of an organic diisocyanate compound to obtain an intermediate polymer having isocyanate groups at both terminals. After the obtained intermediate polymer is cooled, a solvent is added to obtain an intermediate polymer solution. An organic diamine is added to the intermediate polymer solution to carry out a chain extension reaction to obtain an initial polyurethaneurea polymer solution.

The segmented polyurethane urea polymer is obtained by reacting a diamine with an intermediate polymer obtained by reacting a polymer glycol with an excess mole of an organic diisocyanate compound. It is known that an organic monoamine compound is treated so that no active isocyanate groups remain.

If the amount of the organic monoamine compound added at this time is constant regardless of the amount of isocyanate groups remaining in the polymer solution before the addition, the free amine remaining in the final polymer solution The amount fluctuates.

On the other hand, since the final polymer solution is gradually decomposed with amine in the solution, a decrease in the viscosity of the polymer solution which is considered to be a decrease in molecular weight is observed. At this time, if the amine concentration in the polymer solution fluctuates, the viscosity of the polymer solution also fluctuates.

In order to prevent this, it is preferable to carry out the operation so that the amine concentration in the polymer solution after adding the organic monoamine compound is constant, and specifically, 18 to 35 mm / kg of the dissolved polymer. It is desirable to keep it constant within an equivalent range. To achieve this, the method of the present invention is used.

That is, when the organic monoamine compound is added, the electric conductivity of the polymer solution is detected, and the electric conductivity becomes 6%.
By adjusting the addition amount of the organic monoamine compound so as to be 0 to 280 μS / cm, the physical properties of the segmented polyurethane urea polymer solution are stabilized. The electrical conductivity is
Preferably, the adjustment is made to be 80 to 200 μS / cm, more preferably 100 to 180 μS / cm. If the electric conductivity is less than 60 μS / cm, the solution viscosity of the segmented polyurethane urea polymer solution increases with time after polymerization, that is, a so-called thickening tendency is observed, and the fluidity of the polymer solution deteriorates. Further, the electric conductivity of the segmented polyurethane urea polymer solution is 280 μS / c.
If m exceeds m, the viscosity tends to be remarkably lower with the lapse of time, and both are not preferred. When the fluctuation of the solution viscosity of the segmented polyurethane urea polymer solution is on the decrease, it is within a practically acceptable range if the decrease is 1,000 poise or less in one week from immediately after the polymerization, and the decrease is 800 poise or less in one week. Is a preferable state. The tendency that the solution viscosity tends to increase is
Particularly, the spinnability is adversely affected, which is not preferable.

The polymer glycol used in the present invention includes polyester glycol, polyalkylene ether glycol and the like.

Examples of the polyester glycol include those obtained by polycondensing an organic dibasic acid such as succinic acid and adipic acid with an organic glycol such as ethylene glycol, propylene glycol, butanediol or hexanediol. Examples of the polyalkylene ether glycol include polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol. Polymer glycol has a number average molecular weight of 60
0 to 6000, preferably 1000 to 3
000 is preferred.

The organic diisocyanate compound used in the present invention includes p, p'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 1,4
-Phenylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate and the like. Especially,
p, p'-Diphenylmethane diisocyanate is preferred.

Further, the polymer glycol such as polyalkylene ether glycol or polyester glycol and the organic diisocyanate compound are used so that the ratio of the hydroxyl group to the isocyanate group is usually between 1: 1.3 and 1: 2.6. .

As the organic diamine, hydrazine, ethylenediamine, 1,2-propylenediamine, 1,4-
Butylenediamine, 1,6-hexamethylenediamine,
1,3-cyclohexyldiamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodicyclohexylmethane, m-xylylenediamine and its hydrogenated product, p
-Diamines such as xylylenediamine and hydrogenated products thereof, and mixtures thereof.

Among these diamines, ethylenediamine, 1,2-propylenediamine, a mixture thereof and the like are preferred as those giving good physical properties.

The organic monoamine compounds used for stopping the polymerization reaction include N, N-diethylamine,
Secondary aliphatic amines such as N, N-diisopropylamine and N-ethyl-N-isopropylamine are preferred, but primary aliphatic amines such as monoethylamine, monopropylamine and mono-n-butylamine are also used. Can be done.

The inert solvent used in the polymerization reaction includes N, N-dimethylformamide, N, N-dimethylacetamide, N, N, N ', N'-tetramethylurea, N-methylpyrrolidone, dimethyl And polar solvents such as sulfoxide.

An antioxidant, an ultraviolet absorber, a pigment, a tertiary amino compound and the like are added to the obtained polymer solution as required.

The polymer solution thus obtained is formed into an elastic yarn or an elastic film by a usual method. To obtain an elastic yarn, dry spinning is performed and the filaments are converged by a method such as false twisting. An oil agent is applied. Then, it is wound on a bobbin in a winding step. In some cases, the obtained elastic yarn is subjected to a heat treatment in a high-temperature steam bath or the like with the wound cheese, so that the physical properties and the like are sometimes improved.

[0030]

The present invention will be described more specifically in the following examples. These examples illustrate the present invention, and the present invention is not limited to these examples. In the examples, parts indicate weight.

(Example 1) 9000 parts of polytetramethylene ether glycol having a number average molecular weight of 1800,
2125 parts of 4'-diphenylmethane diisocyanate was charged into a polymerization vessel and heated to 70 ° C while stirring.

After heating for 100 minutes, 17000 parts of N, N-dimethylacetamide was added, and the reaction mixture was dissolved with cooling to obtain an intermediate polymer solution. Then, the temperature of the intermediate polymer solution was maintained at about 12 ° C.

Here, 160 parts of ethylenediamine, 1,
A solution prepared by dissolving 49 parts of 2-propylenediamine in 3800 parts of N, N-dimethylacetamide was gradually added with stirring.

After the solution viscosity reached 3050 poise (30 ° C.), the addition of the diamine solution was stopped to obtain an initial polyurethaneurea polymer solution. Next, 100 parts of N, N-diethylamine was supplied to an electric conductivity meter in a polymerization vessel using a pump, and 100 parts of N, N-diethylamine was measured while the electric conductivity was measured by refluxing from the outlet to the reactor.
The solution dissolved in the part was gradually added. Electric conductivity is 1
When the pressure reached 50 μS / cm, the supply of the N, N-diethylamine solution was stopped, and the mixture was further stirred for 15 minutes.

The polymer solution thus obtained is
It had a solution viscosity of 2760 poise at 0 ° C.

The polymer solution was allowed to stand at 40 ° C., and the change in the solution viscosity was measured. After one day, 2610 poise (30 ° C.), two days after 2700 poise (30 ° C.), and four days after 2590 poise (30 ° C.) 7 days later 2500 poise (3
(0 ° C.), which was stable with only a slight tendency to decrease.

The storage stability of the polymer solution thus obtained was excellent, and no problems with the passage of time were observed in the subsequent spinning step and the like.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1 to obtain a polymer solution. Further, an N, N-diethylamine solution was supplied until the electric conductivity reached 300 μS / cm, and the mixture was further stirred for 15 minutes.

The obtained polymer solution was 2990 at 30 ° C.
Poise had a viscosity.

The polymer solution was allowed to stand at 40 ° C., and the change in the solution viscosity was measured. The result was 2540 poise (30 ° C.) after 1 day, 2390 poise (30 ° C.) after 2 days, and 2240 poise (30 ° C.) after 4 days. 7 days later, 1000 poise (3
0 ° C.), the solution viscosity was greatly reduced.

Example 2 Polymerization was carried out in the same manner as in Example 1.
At that time, the supply of the N, N-diethylamine solution to be added was adjusted so that the electric conductivity was different, and the polymer solutions A to D were adjusted. Then, the change in the solution viscosity was measured. Table 1 shows the results.

Electric conductivity is from 60 μS / cm to 250 μS
The polymer solutions B, C, and D in the range of S / cm were stable, with the solution viscosity tending to slightly decrease over time. On the other hand, the polymer solution D having a viscosity of less than 60 μS / cm has an increased and fluctuating solution viscosity, and is not preferable because of lacking spinning stability.

[0043]

[Table 1]

[0044]

According to the method of the present invention for producing a segmented polyurethane urea polymer solution having excellent stability, the segmented polyurethane urea polymer solution can be kept in a stable state by suppressing the fluctuation of the solution viscosity of the solution. Obtainable.

In particular, when the chain extension reaction is performed so that the solution viscosity of the initial polyurethaneurea polymer solution is 4900 poise or less, the solution viscosity of the obtained segmented polyurethaneurea polymer solution becomes particularly stable.

Claims (2)

[Claims] 1. An intermediate polymer having isocyanate groups at both ends obtained by reacting a polymer glycol having hydroxyl groups at both ends with a number average molecular weight of 600 to 6000 with an excess molar amount of an organic diisocyanate compound, and an organic diamine A method for producing a segmented polyurethane urea polymer solution in which a compound is reacted to obtain an initial polyurethane urea polymer solution, and then an organic monoamine compound is reacted to neutralize excess isocyanate groups to obtain a segmented polyurethane urea polymer solution. In the above, the electric conductivity of the segmented polyurethane urea polymer solution is from 60 to 28.
A method for producing a segmented polyurethane urea polymer solution having excellent stability, comprising adding an organic monoamine compound to an initial polyurethane urea polymer solution so as to have a concentration of 0 μS / cm. 2. A method for producing a segmented polyurethane urea polymer solution having excellent stability, wherein the solution viscosity of the initial polyurethane urea polymer solution is 4900 poise (30 ° C.) or less.