JPH03180510A - Polyurethane fiber - Google Patents

Abstract

PURPOSE:To obtain the subject fiber useful for deodorant fiber, etc., having high catalytic activity on oxygen-oxidation reaction of mercaptoethanol comprising polyurethane containing specific metallic phthalocyanine in main chain. CONSTITUTION:The aimed fiber is composed of polyurethane containing metallic phthalocyanine expressed by formula I (R is CH2CH2 or expressed by formula II; M is metal atom; x and y are natural numbers) in main chain. Besides, said polyurethane is preferably obtained by following method: for instance, metallic phthalocyanine dicarboxylic acid derivative is used as starting material and at first, chloride derivative is synthesized by using thionyl chloride, then reacted with diol, thus 1,6-hexane diol and 1,6-hexane diisocyanate are heated in dimethylformamide under reflux of nitrogen.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to polyurethane fibers that catalyze the oxygen oxidation reaction of 2-mercaptoethanol and can be used, for example, as deodorizing fibers.

[Conventional technology]

Conventionally, metal phthalocyanines have been widely used as highly fast blue and green pigments and dyes. This metal phthalocyanine is an extremely stable macrocyclic planar ligand metal complex with a tetraazaporphyrin skeleton. In recent years, it has attracted particular attention as a functional material for catalysts, electrons, photo energy conversion, physiological functions, etc., despite its extremely small metal content in a special electronic environment with a large redundant electron system. By combining phthalocyanine with such functions with a polymer, it is possible to impart each of the above functions to the polymer1.
For example, it will become possible to design materials with various functions, such as polymers with catalytic functions, deodorizing polymers, and conductive polymers. JP-A No. 62-104807 discloses a polymeric metal complex in which a metal phthalocyanine derivative is bonded to a polymer compound, and JP-A No. 63-273638 discloses a polyester containing a metal phthalocyanine ring in the main chain. .

[Problem to be solved by the invention]

An object of the present invention is to provide a polyurethane fiber that is effective as a catalyst for the oxygen oxidation reaction of 2-mercaptoethanol.

[Means to solve the problem]

In order to achieve the above object, the present inventors conducted research on the synthesis, properties, functions, and applications of polymers containing metal phthalocyanine, and as a result, the polyurethane resin containing metal phthalocyanine in the main chain was found to be 2-mercaptoethanol. It has been found that this compound has high catalytic activity for the oxygen oxidation reaction. Therefore, in order to widely apply this function to textile products and the like, we attempted to spin (fiberize) a polyurethane resin containing a metal phthalocyanine derivative and completed the present invention. That is, the polyurethane fiber of the first invention of the present invention is. It contains a polyurethane whose main chain contains a metal phthalocyanine whose repeating unit is represented by the formula [ ]. Ru. M is a metal atom. xjS and y are natural numbers. Moreover, the polyurethane fiber of the second invention is as follows. The repeating unit contains polyurethane containing a metal phthalocyanine represented by the formula [2] in the main chain. Ru. M is a metal atom. X and y are natural numbers. The polyurethane containing metal phthalocyanine in the main chain contained in the polyurethane fiber of the first invention is synthesized as follows. Using a metal phthalocyanine dicarboxylic acid derivative as a starting material, a metal phthalocyanine dicarboxylic acid chloride derivative is synthesized using thionyl chloride (SOClal).The synthesis of a metal phthalocyanine dicarboxylic acid is described, for example, in JP-A-63-1989-1.
It is described in No. 273638. The synthesized metal phthalocyanine dihydroxy ester derivative is reacted with a diol (OH-R-0) to remove hydrochloric acid to obtain a metal phthalocyanine dihydroxy ester derivative. Hexanediol (IO-fcL
l--OH) and 1,6-hexane diisocyanate l0CN-fcH*)-NCOI were added, and under a nitrogen stream,
Heat in dimethylformamide iDMFI. Then, the hydroxy group (-OH group) of the metal phthalocyanine dihydroxy ester derivative and the hydroxy group (-OH group) of the diol [0H-R-OH) undergo a polyaddition reaction with the isocyanate group (-NCOI) of 1,6-hexane diisocyanate, respectively. The reaction route is shown below. The polyurethane containing metal phthalocyanine in the main chain contained in the polyurethane fiber of the second invention uses the starting material as metal phthalocyanine tetracarboxylic acid. By replacing it with an acid, it can be synthesized in the same way. The reaction route is shown below. (Left below) The diol (OH-OHI) used is preferably ethylene glycol or p, p'-biphenol, for example. In addition, polyurethane containing metal phthalocyanine in its main chain may contain 10% by weight or more based on the total amount of polyurethane fibers. It is desirable that

[Examples] Examples of the present invention will be described in detail below. Example 1 (Example of the first invention) 20 ml of thionyl chloride was added to 2.00 g of cobalt phthalocyanine dicarboxylic acid well ground in a mortar, and 110 g of thionyl chloride was added.
After completion of the 0 reaction, which was heated and refluxed at °C for 12 hours, the mixture was allowed to cool and then evaporated under reduced pressure to dryness. Petroleum ether was added to this solid product, solid matter was filtered out using a glass filter, and then dried under reduced pressure to obtain cobalt phthalocyanine dicarboxylic acid chloride. To this was added 44.72 g of ethylene glycol and heated at 110° C. for 15 hours while stirring with a magnetic stirrer. After completion of the reaction, the mixture was allowed to cool and evaporated under reduced pressure to dryness. Acetone was added to this solid product, solid matter was filtered out using a glass filter, and then dried under reduced pressure.
I got g. 1.6-
Hexanediol 1.17g (9,9xlO-”mol)
and 1,6-hexane diisocyanate 1.82a11.
1xlo-" mole) was added and heated and stirred at 110°C for 12 hours in dimethylformamide [DMF] under a nitrogen stream, and then heated and stirred at 140°C for 3 hours. After completion of the reaction, the contents were left to cool to room temperature. The substance solidified into a gel-like state, so it was reheated and poured into water as a hot solution to form a precipitate. After stirring for about 30 minutes, the solid was filtered with a glass filter.The filtered solid was things in methanol
After stirring for 8 hours, it was filtered through a glass filter and dried under reduced pressure to obtain a polyurethane containing cobalt phthalocyanine in the main chain represented by formula [l] (-CH*CHa-).
87g was obtained. Polyurethane fibers are manufactured as follows. The polyurethane containing cobalt phthalocyanine in the main chain synthesized above is dissolved in dimethylacetamide (DMACl. The solution is mixed with a 0 MAc solution of polyurethane for spinning (manufactured by Nisshinbo #I, stock solution for spinning, molecular weight approximately 200,000). ,
A polyurethane solution is prepared in which the weight ratio of polyurethane containing cobalt phthalocyanine in its main chain to polyurethane for spinning is 1:9. This solution was spun at 50°C using a wet spinning device.
The polyurethane fibers were spun into hot water at 50° C. from a spinneret with a diameter of 0.4 mm at a spinning speed of 0.5 m/min to produce polyurethane fibers. Example 2 (Example of the first invention) A polyurethane fiber containing polyurethane containing type 1 cyanine in the main chain was produced in the same manner as in Example 1, except that p, p''-biphenol was used instead of ethylene glycol. Example 3 (Example of the second invention) In the same manner as in Example 1 except that cobalt phthalocyanine tetracarboxylic acid was used instead of cobalt phthalocyanine dicarboxylic acid, a polyurethane containing formula [2]% formula % in the main chain was prepared. Example 4 (Example of the second invention) In the same manner as in Example 3 except that p, p'-biphenol was used instead of ethylene glycol, formula [2] was added to the main chain. Polyurethane fibers containing polyurethane were produced. Using the polyurethane fibers produced in Examples 1 to 4,
An oxygen oxidation reaction of mercaptoethanol tnoco and cozs was performed, and the oxygen consumption concentration accompanying this reaction was measured. A Warburg pressure gauge is used for measurement. Put the polyurethane fibers produced in each example together with 1 ml of water into the main chamber side of a sliding-type reaction container, and add 1 ml of the polyurethane fibers to the side chamber side of the reaction container.
55 mol/j 2-mercaptoethanol aqueous solution 1 m
Enter g. The 2-mercaptoethanol aqueous solution was adjusted to pH=7.0 with potassium hydroxide, and the concentration was determined by iodometric titration. After placing the reaction container in a constant temperature bath and keeping the temperature constant, pour the 2-mercaptoethanol aqueous solution from the side chamber into the main chamber.
Stir and mix at 36 rpm, U consumed every certain time
The preparation was read with a manometer. Further, only 2-mercaptoethanol was placed in the reaction vessel, and the amount of oxygen consumed by natural oxidation of 2-mercaptoethanol under the same conditions as above was determined, and the previously read value was corrected to determine the oxygen consumption concentration. Table 1 shows the amount of polyurethane fiber in each example used in the measurement. Table 1 Figures 1 and 2 show the oxygen consumption concentration of each example (no!
/11 shows the change over time. In addition, the polyurethane containing cobalt phthalocyanine in the main chain synthesized during the production of the polyurethane of each example was activated using the Arrhenius method based on the reaction rate constant of the rate-limiting process obtained at 15 to 35 °C. I asked for energy. The phthalocyanine concentration here is i, oxt
o-' (constant at s + ol/jl. Table 2 shows activation parameters in the reaction of each example (reaction rate Vmax, Michaelis constant 81 reaction rate constant ks
, activation enkleby ΔH2, activation enthalpy ΔS
t). Table 2 [Operations and Effects of the Invention] As explained in detail above, the polyurethane fiber of the present invention contains polyurethane containing metal phthalocyanine in its main chain, and is capable of oxidizing 2-mercaptoethanol with oxygen. It is effective as a catalyst. Moreover, this polyurethane fiber can be formed into various shapes that effectively exhibit catalytic action, such as a woven fabric, and used as a deodorizing fiber.

[Brief explanation of drawings]

FIG. 1 and FIG. 2 are diagrams showing the results of a performance test of the catalytic action of the polyurethane fiber of the present invention.

Claims (1)

[Claims] 1. The repeating unit is a general formula, ▲ there are mathematical formulas, chemical formulas, tables, etc. ▼ [1] [In the formula, -R- is -CH_2CH_2- or ▲ mathematical formula,
Chemical formulas, tables, etc. are available ▼M is a metal atom, x and y are natural numbers] A polyurethane fiber containing polyurethane containing metal phthalocyanine in its main chain. 2. The repeating unit is a general formula, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [2] [In the formula, -R- is -CH_2CH_2- or ▲ Mathematical formula,
Chemical formulas, tables, etc. are available ▼M is a metal atom, x and y are natural numbers] A polyurethane fiber containing polyurethane containing metal phthalocyanine in its main chain.