BRIGHTENING AND SIZING PREPARATION FOR FINISHING VISCOSE

TEXTILE YARN

I. F. Osipenko, I. V. Kulevskaya, N° E. Ivanov, A. N. Bulgakov, A. Ya. Rozenberg, and I. F. Aleksandrovich

UDC 677.044.31

Copolymers of acrylic and methacrylic acids with their esters have a set of properties which offer the possibility of using them widely to finish various yarns. By choosing appropriate monomers in definite proportions, by free-radical copolymerization it is possible to synthesize polymers with the sizing properties which were necessary for a specific form of yarn and method of processing it [i]. Another method of preparing acrylic copolymers is to carry out reactions in the polymer chains. Thus~sizing preparations based on products from the alkaline hydrolysis of polyacrylonitrile [2] and polyacrylamide [3] are known; these are basically polyacrylic acid. However, such sizing preparations have a rather brittle hygroscopic film on the yarn surface. ~

By reactions in the polymer chains we have prepared copolymers containing acrylic ester units. With this objective we have carried out a hydrolysis of copolymers of acrylonitrile, methyl acrylate, and itaconic acid (ANC), in the form of Nitron fibre waste, in an aqueous alcohol solution of sodium hydroxide, with subsequent treatment of the hydrolyzed copolymer with a solution of sulfuric acid in an aliphatic alcohol [4]. Copolymers of similar compo- sition have also been prepared by acid hydrolysis and subsequent esterification with an ali- phatic alcohol [5]. Brightening and sizing preparations (BSP) based on these products ensure an improvement in the ability of viscose textile yarn to be processed; however, the methods for preparing such products are multistage, aggressive agents are used, and a need arises to utilize the wastes, particularly the dilute sulfuric acid.

There are data in the literature about performing the hydrolysis of polyacrylonitrile in aqueous medium at an elevated temperature and pressure without a catalyst or in the pre- sence of a powdered metal [6, 7]. By this method, copolymers were obtained which contained only carboxyl, amide, and carboxylate groups.

We have investigated the possibility of preparing copolymers containing acrylic ester units by high-temperature hydrolysis of an ANC in the presence of aliphatic alcohols and an appropriate catalyst. Hydrolysis of the ANC was carried out in a mixture of water and a lower monohydric aliphatic alcohol at 135-175°C for 6-10 h. As the catalyst we used alu- minum chloride, ferric chloride, copper chloride, or zinc chloride, in an amount of 0.1-0.5% based on weight of the copolymer.

In Fig. i we show the dependence of the overall degree of hydrolysis on reaction time at 135-175°C in the presence of 0.2% AICIs by wt. The hydrolysis process takes place via the stage of forming an insoluble, colorless gel; consequently, no compounds containing a system of conjugated bonds are formed during the course of reaction. The hydrolysis reaction is reversible; the ammonia which accumulates in the system displaces it in the direction of forming acrylamide units.

According to evidence from IR spectroscopy, functional analysis, and elemental analysis, the water-soluble ANC which are obtained as a result of hydrolysis contain acrylic ester, ammonium acrylate, acrylamide, and acrylonitrile units.

On investigating the viscosity characteristics of the ANC obtained, it was found that the relative viscosity of 1% aqueous solutions of the ANC is increased with increase in the carboxylate group content of the copolymer; the relative viscosity of the same solutions containing 100% NaCI by wt. is hardly changed (Fig. 2).

It must be noted that for similar copolymers prepared by free-radical copolymerizatio~ the difference between the viscosities of aqueous and aqueous-salt solutions is far less. Application of solutions of hydrolyzed ANC having a high viscosity as brightening and sizing

Translated from Khimicheskie Volokna, No. 2, pp. 27-28, Mmrch~April, 1988~ Original article submftted November 6, 1987. -

0015-0541/88/2002-0123512.50 © 1988 Plenum Publishing Corporation 123

C, ~o (by mole)

I001

5 I0 f , h

Fig. i

I 1=(~ ~NaCI I0 [ 10

I

- - 0 0

0[~ I 0 10 20

ECOONH4], ~o (molar)

Fig. 2

Fig. i. Dependence of degree of hydrolysis (C) of ANC on reaction time, T, at 130 (i), 150 (2), and 175°C (3) in the presence of AICI3. AICIs concentration, 0.2% by wt.; molar ratio of ethyl alcohol to water, i:i.

Fig. 2. Dependence of nre I of a 1% solution of ANC in water and in 10% aqueous NaCI solution of ammonium carboxylate group content of ANC.

agents is difficult. In the course of our research, it was found that the relative visco- sity of the solution decreases with increase in reaction time, and becomes constant: 2 to

3 for a 1% aqueous solution. This is possibly explained by the fact that the various sec- tions of the starting ANC macromolecule do not enter simultaneously into reaction, because of the heterogeneity of the medium and the higher rate of formation of carboxylate groups as compared with that of ester groups; as a result, blocks of units containing carboxylate anions are formed. The electrostatic repulsion of neighboring anions loosens the tangles of macromolecules, which leads to an increase in the viscosity of the polymer solution, that is, a polyelectrolyte effect takes place.

In the course Of further reaction, part of the carboxylate groups is esterified with the alcohol; the ester groups formed are distributed among the charged units and, by shield- ing their charges, they reduce electrostatic interaction. Thereupon the dimensions of the clusters are reduced and the viscosity is decreased.

The product obtained as a result of reaction can be used to prepare BSP without further purification, and there are no manufacturing wastes. A pilot-plant check of the BSP prepared, under the name OVN-6, was performed under artificial fibre plant conditions for the brighten- ing treatment of a lot of 13.3 tex viscose textile yarn, in the amount of 475 kg (864 cakes). Viscose complex yarn which had been treated with a BSP having a copolymer content of i g/ liter in the brightening bath in a finishing assembly with circulation of the working solu- tion had lower breakage and a lower amount of waste in rewinding than that of the control line, where a BSP based on polyvinyl alcohol was used:

Breakage, Waste, Lot B,SP content of bath br~k~r % by wt.

Experimental 1.0 g/lit~ of OVN-6 0,36 1,3 Control 0.4 g/liter of PVA + 0.4 g / 0.42 2,0

liter of preparation 1~

In physico-mechanical properties, the experimental viscose yarn conformed to the require- ments of the All-Union State Standard. Preparation of the finish solutions caused no diffi- culties and did not require installation of any additional equipment.

CONCLUSIONS

A brightening and sizing preparation has been developed which is based on a copolymer having a high content of acrylic ester units, prepared by a one-stage, high-temperature hydro- lysis of an acrylonitrile copolymer in the presence of a mixture of water and an aliphatic alcohol.

124

Use of this preparation (as compared with the use of polyvinyl alcohol) ensures a 15- 25% reduction in breakage and amount of waste in rewinding viscose textile yarn.

LITERATURE CITED

i. P. L. Glubish, Use of Acrylic Acid Polymers and Its Derivatives in the Textile Industry [in Russian], Khimiya, Moscow (1975) o

2. M. P. Mikhailova, F. M. Rozanov, and P. V. Mikhailov, Izv. Vuzov, Ser. "Tekhnol. Tekst. Prom-sti," No. I, 71-75 (1972).

3. P. L. Glubish, Tekst. Prom-st', No. 5, 3-40 (1965). 4. I. F. Osipenko, I. V. Kulevskaya, et al., Izv. Akad. Nauk Bel. SSR, Ser. Khim. Nauk,

No. 4, 112-113 (1982). 5. I. F. OsiPenko, I. V. Kulevskaya, et al., Izv. Akad. Nauk Bel. SSR, Ser. Khim. Nauk,

No. 6, 101-103 (1986). 6. Eo N. Zil'berman, A. A. Starkov, and E. G. Pomerantsev, Vysokomol. Soed., Ser. A, 19,

No. 12, 2714-2718 (1977). 7. S. P. Dorofeev, L. A. Okunev, et al., Izv. Vuzov, Ser. "Khim. Khim. Tekhnol.," 18, No.

7, 1138-1140 (1975).

RESISTANCE OF FIBRES MODIFIED WITH BACTERIA WHICH ARE ALKYLBENZENE-

SULFONATE DEGRADERS TO MICROBIAL DAMAGE

A. B. Lobova, I. I. Shamolina, N. V. Platonova, S. S. Stavskaya, L. A. Taranova, and L. A. Vol'f

UDC 677.4-96.021.12+576.809.53

We have previously shown [I] that bacteria which have been immobilized on a carrier are more active than bacteria which are freely floating. Cells fastened on synthetic fibres have retained viability and degrading power for a year [2].

In the present article we give the results of studies on the immobilization of microe bial cells on activated synthetic fibres and the resistance of these fibres to microbial destruction. The objects of modification were activated polyvinyl alcohol (PVA) and poly- caproamide (PCA) fibres; the modifier was a bacterial culture of P. alcaligenes TR -- a de- grader of the anionic surface-active substance, alkylbenzenesulfonate (ABS) [3].

The strain of P. alcaligenes TR which was used in our studies was cultured on a liquid or agarized medium of the fQllowing composition (in g/liter): Na2HPO4 -- i; NH~NO3 -- i, KCI -- 0.5; and MgCI2 -- 0.i. The only source of carbon arriving from an external medium was the alkylbenzenesulfonate, whose concentration was 200 g/liter.

The PVA fibres selected for immobilizing the bacteria were activated with glutaralde- hyde (GA) by the procedure described in [4]; the free aldehyde group content of these fibres was 1.2% by wt. In another series of experiments, fibres which had been acetalized with GA were subjected to subsequent impregnation with a 3% solution of polyethylenimine (PEI) and to heat treatment at 150°C for 60 min. As concerns the PCA fibres, they were activated by stretching in an adsorption-active medium containing monochloroacetic acid (MCAA). Then amination of the partially hydrolyzed PCA fibre with PEI was carried out by the regime developed for the PVA fibre (however, with the difference that the length of heat-treatment and the temperature, in this case, were 30 min and 100°C). Fibre activated by this method contained 0.36 mmole/g of acid groups and 0.22 mmole/g of basic groups.

Activation of PVA Or PCA fibres by the method indicated above makes it possible to in- crease the content of cells immobilized on them from 0 to 20 mg/g.

Immobilization of cells on the fibres was performed in flow model cleaning units (2 dm s in volume) [5] by feeding to the column a concentrated suspension of the microorganisms at

Translated from Khimicheskie Volokna, No. 2, pp. 29-31, March-April, 1988. Original article submitted June 12, 1987.

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