DE1594915A1 - Process for making fiber material made of cellulose flame-resistant - Google Patents

Description

Process for making fiber material flame resistant

The present invention relates to a method for flame retardant finishing of cellulose fiber material using certain phosphoramides and chloromethylphosphonamides.

The amides, especially the dialkyl amides and the 1,2-alkylene amides of phosphoric acid and of alkyl and haloalkyl phosphonic acids are general as agents for the flame-proofing of fiber material known from cellulose.

With the help of these agents, which are generally fixed on the fiber material by heating, the combustibility can be reduced reduce the fiber material considerably, but mostly only with the impairment of other desired properties, For example, the embrittlement and the tendency to Yellowing of textiles finished in this way, as well as the poor wash resistance of some of these known plasma protection finishes. This is especially true for the connections with the previous

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and
best / most wash-resistant flame retardant effects, namely tris-N-aziridinylphosphine oxide (phosphoric acid trisethylene amide, APO) and chloromethylphosphonic acid bisethylene amide (APCl)

CH ClCH ₉ - (O) P / ^

APO APCl

which are also very toxic in the unchanged, i.e. not fixed, state. The use of other phosphorus and phosphonamides however, including the non-toxic compounds phosphoric acid trismethylamide and chloromethylphosphonic acid bismethylamide the flame retardant effects are good, but not washable.

The present invention was therefore based on the object of developing new flame retardants for fiber materials To enrich cellulose, its use with optimal and wash-resistant flame retardant effect with the least possible disadvantageous Side effects is connected.

It has been found that cellulose fiber materials can be used with phosphoramides or chloromethylphosphonamides is known to be washable with excellent results

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Can be made flame-retardant if you use mixtures of compounds used, which are defined by the general formulas I or II,

CH ₂ /2-n

I II

where m all values from 2.7 to 1.0 and η all values from 1.8 to 1.0 and with these indices being the average Frequency of the methylamido and ethyleneamido groups in weighable amounts of the trivalent compound I or the divalent compound II corresponds.

Mixtures of compounds I and II (hereinafter referred to as compounds for the sake of simplicity) can be obtained in a known manner, preferably by reacting 1 mole of phosphorus oxychloride or chloromethylphosphone dichloride with m or η moles of methylamine and 3-m or 2-n mol ethyleneimine in an indifferent organic solvent at temperatures between about -40 and 40 ⁰ C. this is, the solvent, such as methylene chloride, benzene, dioxane, tetrahydrofuran or ether is recommended to submit and the Beaktionspartner simultaneously at equal speeds in the ratio of the molar composition

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of the products of the process herein. To bind the at the reaction released hydrogen chloride is a corresponding one molar excess of methylamine, ammonia or a tertiary amine also to be used. Both methylammonium chloride and the Hydrogen chlorides of the tertiary amines as well as ammonium chloride are insoluble in the solvents mentioned and can use them be filtered off. The solution is then - expediently under reduced pressure - evaporated, after which the process products remain as colorless, syrupy liquids. It recommends that they remain unchanged for a longer period of time to dilute them, for example with water, dioxane or dimethylformamide.

To finish the cellulose fiber material, the new agents are advantageously used in 5 to 50% aqueous solution (percentages by weight as below), the amount being measured so that the fiber material is about 5 to 50, depending on the desired strength of the flame retardant effect. takes up preferably 10 to 30 $ s of its dry weight. After drying, the impregnated fiber material is fixed to the means then thereto, by about 2 to 20 minutes heating at about 100 to 200, preferably 150 to 170 ⁰ C. Subsequently, the thus finished fiber material for removing unfixed means as usual with diluted aqueous alkali hydroxide or alkali carbonate solutions.

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The means I and II, which can also be used together, are with all other agents for textile finishing, especially with the most varied of aminoplast-forming monomers, oligomers and polymeric compounds compatible and can be used together with these. Otherwise you can for the method according to the invention use all procedures and devices that are otherwise used for the equipment used by fiber materials.

Cellulose fiber materials include cotton, linen, sisal, Hemp, regenerated cellulose and wood wool in the form of threads, fibers, tangled fibers such as wadding and fleeces or in the form of flat structures like textiles and papers of all kinds. These materials can also be used with others, e.g. those made of wool, Silk, polyester, polyamide or polyacrylonitrile be mixed, with the overall flame retardant effect, however, on the whole Corresponds to the proportion of cellulose.

example 1

A cotton fabric was impregnated with a 30% aqueous solution of a compound I ¹ , characterized by m = 2, in such a way that the amount of ^{finishing agent fixed on the fabric at 160 to 170 °} C. was about 22% of the dry weight of the fabric fraud.

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The flame resistance values achieved in accordance with DIN 53 096 and the wash resistance of the finish are in table 1 compiled.

Table 1

not equipped with equipped I ¹ (m = 2)

Amount Q of on the paser
fixed agent Soda boil washes
⁰¹¹ <β _soda) - by 22-6 Q after, three
according to DIN 54 jsecl Ä by 15.496 Burn time B E [cm] burns 0 Tear length burns 8.9

These effects are as good as when using the much more toxic APO (m = 0).

Compound I ¹ was prepared from the appropriate molar quantities of phosphorus oxychloride, methylamine, ethyleneimine New York Convention ammonia (as acid acceptor) in the course of 2 to 3 hours at -40 to + 3O ⁰ C in methylene chloride. The elemental analysis of the salt-free, pure syrup-like product corresponded to the molar ratio of the reactants within the error limits.

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Example 2

A cotton fabric was so impregnated with a 23 or 30 * iigen aqueous solution of a compound I ", characterized by m = 1.8, that the amount of the finishing agent ^{fixed on the fabric at 150 to 170 0} C was about 15 or . $ 20 of the dry weight of the fabric ".

The flame resistance values achieved in accordance with DIN 53 096 and the wash resistance of the finish are in table 2 compiled.

Table 2

not equipped with
equipped I "(m = 1.8) blows away. 15 * not equipped with
equipped I "(m = 1.8) 20 * Q * t blows away 13.5 * ■ - 16 * *
^Q soda I. 0 - O B * n, α blows away 10.0 E * blows away

*) Meaning cf. Table 1

These effects are as good as using the essential more toxic APO (τη = 0).

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The compound I ″ was prepared in the same way as the compound I ^{1 as described in Example 1.}

Example 5

A cotton fabric was so impregnated with a 23 or strength aqueous solution of a compound I ¹ ″, characterized by m = 1.5, that the amount of the finishing agent fixed on the fabric ^{at 160 to 170 ° C. was about 15 or} Was $ 18 the dry weight of the fabric.

The flame resistance values achieved in accordance with DIN 53 096 and the wash resistance of the finish are shown in Table 3.

Table 3

not equipped with not equipped with equipped I "'(m = 1.5) equipped I ·" (m = 1.5)

*
^Q soda burns by 13, 1 - by H, • B * burns by 0 burns by 0 4th E * 10, burns 8th,

*) For meaning see table 1

These effects are as good as when using the much more toxic APO (m = 0).

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The compound I '"was prepared as described in Example 1 as the compound I ^1,

Example 4

A cotton fabric was impregnated with a 25% aqueous solution of a compound II ', characterized by η = Ί, in such a way that the amount of finishing agent ^{fixed on the fabric at 155 to 170 0 was} about 18% of the dry weight of the fabric.

The values for flame resistance and washing resistance of the finish achieved in accordance with DIN 53 096 are summarized in Table 4.
Table 4 Charging height IcmJ

rlicht equipped with j equipped "II '(n = 1)

I.
Tear length, cm
without laundry *) > 30 7th "Wash b" with
Water at 60 ° C - 8th 1 time "whites c"
Soap / soda - 9 3 times hot wash
Soap / soda - 11

These effects are as good as when using the much more toxic APCl (n = 0).

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The compound II 'was prepared as described in Example 1 as the compound I'.

Example 5

A cotton fabric was impregnated in the! "Else with a 24 # aqueous solution of a compound II", characterized by η = 1.4 ", that the amount of fixed at 160 to 17O ⁰ C on the fabric finishing agent about 18 $ of the dry weight of the fabric.

In addition, the fabric was finished in a similar manner in a further experiment with the addition of 4 $ hexamethoxymethylmelamine (III).

The flame resistance values achieved in accordance with DIN 53 096 and wash resistance of the finish are summarized in Table 5.

Table 5

not equipped with I856 equipped with 1 armed II »(n = 1.4) II" (n-1.4) and III

E * after
3 boil washes burns through 11 8 DIN 54011

*) For meaning see table 1

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These effects are as good as when using the essential more toxic APCl (n = 0).

The compound II ″ was prepared as described in Example 1 in the same way as the compound I ^1.

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Claims (1)

1B94915 Claim Process for making fiber material made of cellulose flame-resistant with the aid of phosphoramides or chloromethylphosphonamides in a manner known per se, characterized in that mixtures of compounds which are defined by the general formulas I and II are used for this purpose -NH-GH, ΟΡ-ί ^ν / Cl-CH ₂ - (O) P- I II where m all values from 2.7 to 1.0 and η all values from 1.8 to 1.0 and with these indices the average frequency of methylamido and ethyleneamido groups in weighable Corresponds to amounts of the trivalent compounds I or the divalent compounds II. BADISCHE ANILIN- & SODA-FABRIK AG 909835/1396