CS196599B1 - Method of substituting an organic cation for alkali metal in sulpho group of modified polyester fibres - Google Patents

Description

The present invention relates to a process for replacing an alkali metal in a sulfo group of modified polyester fibers with an organic cation which provides novel modifying effects.

An important and frequently used modification of fiber forming polyesters is copolyesterification with a monomer containing an alkali salt of sulfo groups. This modification improves the dyeability, obtaining affinity for basic dyes. In combination with a reduction in the molecular weight of the fiber, a reduced tendency to pilling is achieved.

In industrial production, it is not advantageous to produce a larger number of differently modified polymers, but it is an effort to expand the range of fibers as widely as possible based on one method of modification using as many variations and treatments as possible.

Sodium and potassium salts of 5-sulfoisophthalic acid and sodium or potassium salts of sulfoterephthalic acid are most commonly used as modifying monomers containing an alkali salt of sulfo groups. The use of other sulfoacids does not provide advantages nor does it allow the modification effects to be substantially altered. Also, changing the metal forming salt does not provide for modifying the modifying effects. Only alkali metals can be used and from the practical point of view only sodium or potassium are possible.

There are no significant differences in their modifying effects. More than monovalent metals cannot be used, do not give a satisfactory polymer. In summary, variations in the sulfoacid do not give the opportunity to influence the modifying effects. The variation in properties is only possible by varying the content of the modifying component, changing the relative molecular weight of the fiber, and changing the parameters in the division and stagnation.

New possibilities have been sought to modify the modifying effects of the sulfo group. The aim of the work was to find possibilities for attaching suitable radicals to the sulfo group, which will provide new modifying effects that the sulfo group in the modified polyester fibers react with cationic (basic) dyes. Anion is most often chloride. If we organically denote the cation of the dye with the symbol B and the anion with the symbol X, the reaction between the alkali salt of the sulfo group and the cationic dye, which proceeds through the ionic mechanism, can be expressed by the equation:

—SO ₃ Me + B ⁺ X- = -SO ₃ B + MeX

194599

In the search for organic substances which can be attached to the sulfo group by the same mechanisms, but such substances are not cationic dyes, it has been found that compounds which are quaternary nitrogen are reacted with the sulfo group. Such compounds can be represented by the general formula:

wherein R 1 to R ₄ are substituents which may be an aliphatic radical and may also contain heteroatoms in the chain, such type of substituents being, for example, polyglycols. Further, such substituents may also be aromatic radicals such as phenyl or benzyl. In addition, the substituents R 1 -R ₄ may carry other substituents. X is an anion, which may be chloride, bromide, sulfate, it may also be an organic anion such as acetate.

The reaction can be expressed by the equation:

-80 _with Ma +

X * '80.

♦ MaX

The reaction can be carried out in an aqueous medium, preferably at temperatures of 100-130 ° C. At lower temperatures, the reaction slows and the conversion decreases, raising the temperature above the upper limit may lead to a decrease in the molecular weight of the fiber over a longer period of time. The additive carrier accelerates the reaction and also increases the conversion. Fibers containing sulfo groups have an increased susceptibility to hydrolysis, the hydrolysis can be inhibited by the addition of neutrally reacting sodium and potassium salts. The quaternary nitrogen-containing substance itself has been shown to limit hydrolytic degradation, so that the addition of neutral salts is generally not necessary. This is an advantage because the neutral salts slow the reaction slightly. The alkaline environment slows the reaction, acidic supports it.

The fiber treatment described can be carried out in conventional textile finishing machines, especially in dyeing apparatuses. At temperatures above 100 ° C, the reaction must be carried out in autoclaves. The treatment can be combined with coloring.

The progress of the reaction can be monitored by the ash of the fiber. The alkali salt of the sulfo group upon combustion yields sodium sulfate according to the equation:

2-SO ₃ Na = Na ₂ SO ₄ + SO ₂

In the unmated fiber, the ash is practically identical to the sodium sulphate content, in the case of the matt fiber, it is necessary to separately determine either titanium dioxide or sodium sulphate in the ash.

When an organic cation is bonded to the sulfo group via a quaternary nitrogen, such sulfo group does not give ash. Therefore, the loss of sodium sulfate in the ash of the modified fiber is a measure of the conversion of the reaction of the sulfo group with the organic cation.

An advantage of the process according to the invention is that the alkali metal is exchanged in a simple manner in the sulfo group for an organic radical which can give the sulfo group and thus the fiber new properties. In particular, substituents which may be present on the radicals R _{@ 1} --R _{@ 4} may provide novel modification properties.

For such treatments, textile auxiliaries with bacteriocidal, antistatic, flame retardant and the like can be used, for example.

Example 1

Polyethylene terephthalate fiber modified with 2.25 mol% sodium 5-sulfoisophthalic acid was used for the treatments. A textile auxiliary with antistatic properties was used for the treatment, consisting of an oxethylated condensation product of stearic acid with ethanolamine, which was quaternized with methylene chloride. For this textile aid, the abbreviation TPP is used below. 100 g of fiber was treated in 1000 ml of water and autoclaved at 120 ° C. 1 hour with additives of 3 g / l carrier, which is dispersed naphthalene with and without a carrier. The amount of TPP varied. The amount of TPP is given in% relative to the fiber. Conversion was monitored for fiber ash loss. The results were obtained as follows.

Amount of TPP, wt. % Conversion,% without carrier with the transmitter 1 5.6 10.3 2 12.3 16.1 4 17.7 20.9 8 21.5 24.4

The test showed that the modified fiber chemically reacts with theTPP containing quaternary nitrogen in the form of chloride. It also showed that the presence of the transmitter accelerates the reaction and increases the conversion.

Example 2

The assay was carried out in the same manner and with the same products as in Example 1, except that the time course of the reaction was monitored. 8 wt. % TPP, moreover, the conditions were the same as in Example 1. The following results were obtained:

Time, h Conversion% without a carrier with the transmitter 1 21.5 34.4 2.5 35.5 46.5 4 45.6 48.1

Example 3

The procedure was as in Examples 1 and 2, but the reaction was monitored at two temperatures and a varying amount of TPP. Time 1 hour.

The results were obtained as follows:

Amount of TPP, wt. % Conversion% 105 ° C temperature 135 MC 1 8.1 8.6 2 11.1 21.4 4 15.9 34.0 8 17.9 51.4

Example 4

As described in Example 1 using 5 wt. % TPP was treated with a polyester silk modified with sulfo groups. The knit was washed and dried. At the same time, a blank test was carried out in the same manner, in which no antistatic agent was added, otherwise the treatment procedure was the same.

The static charge was measured on the electrostatic static determination apparatus type EP 70, the treated article had no static charge, the blank from the blank showed an electrical pole intensity of 14,400 V / cm.

Example 5

The polyethylene terephthalate fiber, modified with 2.25 mol% of the sodium salt of 5-sulfoisophthalic acid, was treated with the bacteriocidal agent N - (.alpha.-carbetoxypentadecyl) -trimethylammonium bromide:

βΗ, - (θΗ,), - CH-N (CH ") s

C00-0.H,

br

In an autoclave, 1000 ml of water, 3 g / l transmitter as in Example 1, reaction temperature was added to 100 g of fiber.

120 ° C, 1 hour, the amount of bacteriocidal product varied. At the end of the treatment, the contents of the autoclave were cooled and the fiber was washed. The conversion of the reaction was determined by the loss of fiber ash. The results were obtained as follows:

Amount of bacteriocidal product, wt. % Conversion,%

0.5 6.1 1.0 9.1 2.0 32.6 5.0 32.0

The results show that under the conditions used, in about one third of the sulfo groups, the alkali metal has been replaced by a bacteriocidal product.

Example 6

Under the same conditions and the same procedure, the modified fiber was treated with the bacteriocidal agent dimethylayrylbenzylammonium bromide:

'OH, BH, —BH _S ' of \ ^Br '

The results were obtained as follows:

Amount of bacteriocidal product, wt. % Conversion%

0,5 1,9

5.5

41.6

44.4

Example 7

As in Example 6, the fiber was treated with the bacteriocidal agent alkyldimethyltrichlorobenzylammonium chloride:

♦ cr

It was a technical product in which R 1 is an alkyl in which the number of carbons ranged from 14-16. The results were obtained as follows:

Amount of bacteriocidal product, wt. % Conversion,%

0,5 7,5

10.2

38.0

38.4

51.7

Example 8

As in Example 6, the fiber with alkyldimethylphenyleneammonium sulfate was treated at a concentration of 3 wt. %. A conversion of 35% was achieved.

Example 9

Polyethylene terephthalate fiber modified with 2.25 mol% of sodium 5-sulfoisophthalic acid was treated with a commercial wetting agent Syntamin OC. It is a cationic textile composition with a quaternary nitrogen containing acetate as the anion. In an autoclave, 1000 ml of water, 5g Syntamine OC, was added to 100 g of fiber, and the autoclave was heated to 120 ° C for 1 hour. After the treatment was complete, the contents of the autoclave were cooled, and the fiber was washed. The conversion of the reaction was determined by the fiber ash loss. This was

5.2%.

Claims (2)

1. A process for substituting an organic cation for an alkali metal in a sulfo-group of modified polyester fibers, characterized in that the fiber is treated with an aqueous solution of a compound of the general formula at a temperature in the range 60-159 ° C: ./''i + X 'at a concentration of 0.1 to wt. %, wherein X is an inorganic anion, preferably chloride, bromide, sulfate, or an organic anion, preferably acetate, R 1 to R ₄ are the same or different organic substituents, namely alkyls having a carbon number in the main chain of 1 to 30; relative molecular weights up to 600, phenyls or benzyls.