CH626475A5 - Connecting collar for cables - Google Patents

Description

1

2nd

io

From US Pat. No. 3,767,736 a process for flame retarding textile materials is known, in which methylolated amidophosphates, which have a single amidophosphate residue, are used.

In contrast, in the process according to the invention, 5 reaction products are used which consist of amidophosphates and formaldehyde, ie. H. have been prepared from methylolated amidophosphates as starting products, the reaction products used having at least two amidophosphate residues.

In the known and in the process according to the invention, the amidophosphates, like the reaction products of these amidophosphates, are preferably applied to the textile materials as aqueous preparations. The amidophosphates used in the known method with a single amidophosphate residue have the disadvantage here of insufficient bath stability. After 6 hours, undesirable precipitates occur in the application bath, which; cause poor reproducibility of the flame protection effects in practice, make it impossible to treat large amounts of textiles in the same bath and cause incrustations in the equipment used. In contrast to this, the reaction products with at least two amidophosphate residues used in the process according to the invention have the essential advantage of having excellent bath stability. The stable application baths, which remain clear for over 6 hours, guarantee reproducible flame retardant effects in practice. Even large quantities of textiles can be treated in the same bathroom and there is no wear on the equipment used due to undesirable incrustations.

From US Pat. No. 2,574,515 a process for flame retarding textile materials is known, in which y, / 3-unsaturated or halogenated compounds, which have one or two amidophosphate residues but do not contain alkylene oxy bridge members between two amidophosphate residues, are used.

In contrast, in the process according to the invention, at least two compounds containing amidophosphate residues are used which are halogen-free and saturated. If appropriate, these compounds can also be y, β-unsaturated or halogenated, provided that they have been reacted using diols as reactants. In contrast to the compounds used in the known process, the 4J reaction products thus obtained always contain an alkyleneoxy bridge between the amidophosphate residues.

The reaction products used in the process according to the invention are produced from other starting compounds 50 and therefore have a different chemical composition compared to the compounds used in the known process.

The known compounds have the disadvantage

to have poorer water solubilities than the reaction products according to the invention.

When applying the known compounds for flame retarding z. B. fully synthetic textiles, an unpleasant oily feel of the treated textiles 60 is observed, combined with an increase in their soiling. These disadvantages are largely overcome with the method according to the invention.

The invention thus relates to a process for flame retarding textile materials, characterized in that an amidophosphate reaction product which has at least two amidophosphate residues per molecule and consists of is applied to the textile material

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65

(1) Amidophosphates of the formula r, - c> .0

1 \

p

R1 "0 NU 2

O),

in which R 1 denotes alkyl having 1 to 3 carbon atoms or both Ri together represent alkylene having 2 to 5 carbon atoms,

(2) formaldehyde or a formaldehyde donor,

(3) optionally an aliphatic diol with 2 to 6 carbon atoms,

(4) where appropriate, a monoalkanol having 1 to 3 carbon atoms has been prepared, where, if component (3) has also been used, R in the amidophosphate of the formula (1) additionally means alkenyl or haloalkyl having 2 or 3 carbon atoms, the material then dries and is subjected to a treatment at elevated temperature.

As a rule, the amidophosphate reaction products contain residues of one and the same compound of the formula (1). However, it is also possible for the reaction products to contain residues of more than one compound of the formula (1). This means that the amidophosphate reaction products can be built up from compounds of the formula (1) which are different from one another.

The radicals R in formula (1) are, for. B. for n-propyl, isopropyl, methyl or in particular ethyl.

Furthermore, both Rt together mean branched or unbranched alkylene, such as. B. ethylene, n-propylene, 1-methyl-n-propylene or 2,2-dimethyl-propylene.

Furthermore, if component (3) has been used, R additionally represents 2-chloroethyl, 2-bromoethyl, 2,3-dichloropropyl, preferably allyl or in particular 2,3-dibromopropyl.

Examples of compounds which can be considered as component (1) are the compounds of the formulas ch-j - ch0 - 0 ^ 0

3 2 \

1'

/ \

ch3 - ch2 - 0 nh2

(2.1)

(2.2)

(2.3)

ch2 0

chq ch0 - 0 0

3 \ / 2 \ s c r

/ \ / \

ch3 ch2 - 0 nh2

(2.4)

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3rd

4th

or, if component (3) has been used, additionally the compounds of the formulas

Br!

CH,

CH,

I '

Br or

Br I

CII - CH0-0 0

2 \ p

CII - CI19-0

I z

Br

(2.5)

NILE

CH0 = CH - CH,

C1U «CH - CH,

0

\ ✓

0

0 NH,

(2.6)

Carbon atoms, which preferably have the formula HO-Oi-OH

mentioned.

The compounds which correspond to one of the formulas (2.5), (2.6), preferably (2.4) or in particular (2.1) are preferred.

The amidophosphates used as component (1) are known per se or can be prepared by known methods, for. B. by the action of ammonia gas in organic solutions of the corresponding phosphates in the presence of carbon tetrachloride.

Component (2) is primarily formaldehyde itself, in particular an aqueous formaldehyde solution, but also a formaldehyde-donating agent, such as. B. trioxane or preferably paraformaldehyde.

If component (3) is used, the amidophosphate reaction products generally contain residues of one and the same component (3). However, it is also possible for the reaction products to contain residues of more than one compound of the formula (3), that is to say that the amidophosphate reaction products can, if appropriate, be composed of diols different from one another as component (3).

Component (3), which has optionally been used, is an aliphatic diol with 2 to 6

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15

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35

(3)

wherein Q is an optionally halogenated alkylene radical with at most 6 carbon atoms, optionally interrupted by 1 or 2 oxygen atoms or interrupted by 1 or 2 double or triple bonds, and in particular of the formula HO-Q2-OH (4)

45

in which Q2 is an alkylene radical with a maximum of 6 carbon atoms which is optionally substituted by 2 to 4 chlorine or bromine atoms and which is optionally interrupted by 1 or 2 oxygen atoms or by a double or triple bond, 2 or 3 carbon atoms being located between the oxygen atoms.

Examples of such diols are ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-neopentylglycol, 1,6-hexanediol, 2,5-hexanediol, butene -2-diol-1,4, butene-3-diol-1,2, butyne-2-diol-1,4, and hexyne-3-diol-2,5.

Instead of the last-mentioned ethylenically or acetyl-nically unsaturated aliphatic diols, the corresponding halogenated, preferably chlorinated and in particular brominated compounds can also advantageously be used, such as, for. B. butane-dibromo-2,3-diol-1,4, butane-dibromo-3,4-diol-1,2, butane-tetrabromo-2,2,3,3-diol-1,4, 4, 2-bisbromomethylpropanediol-1,3 and hexane-tetrabromo-3,3,4,4-diol-2,5.

Diethylene glycol, 1,2-propanediol, 2,3-dibromobutane-1, 4-diol and in particular ethylene glycol are the focus of interest.

Component (4) is preferably not used. However, products whose free methylol groups are etherified may be desirable. In this case, the etherification component (4) may be monoalkanols such as isopropanol, n-propanol, preferably ethanol or, in particular, methanol.

The phosphorus-containing reaction products used in the process according to the invention generally do not have a uniform structure, but mostly different proportions of higher and lower condensed products. The average molecular weight of the reaction products is usually between 260 and 2400.

Preferred amidophosphate reaction products probably correspond to the formula

P, -N-

1 I

P-0

/ \

0 0

1 I

Ri R1

ch2- (ai) c_I "N

P-0

/ \

0 0

1 I

ìl \ RÏ

1

x

CH2 "(Al) c'-1" N

P = 0 / \ 0 0

R'l R »

-v y-1

(5)

A! and A '] each - (O-Q ^ s-i-O-CHj-,

D] and D '] each hydrogen or -CH2-0-Y !,

Rj, RS and R ", each alkyl with 1 to 3 carbon atoms or both R ,, or R'i or R", together represent alkylene with 2 to 5 carbon atoms,

Oi an optionally halogenated and optionally by 1 or 2 oxygen atoms or by 1 or 2 double 65

or triple bonds interrupted alkylene radical having at most 6 carbon atoms, and

Y is hydrogen or alkyl having 1 to 3 carbon atoms, and wherein s, t, t ', x and y are each 1 or 2, the sum (x + y) being 2 or 3, and, if s is 2, Rl5 R'i and R "! Each can additionally mean alkenyl or haloalkyl having 2 or 3 carbon atoms.

Of particular interest are also amidophosphate reaction products of the likely formula

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6

d, -n-I

P = 0

/ \

0 0

1 I

Ri

R,

cH2- (A2) t-rN

PO

/ \

0 0

1 I

RÌ Ri ch

2 ~ 1 -1 ~

N-

p-0

/ \

0 0

1 I

Rj Kj1

-Di y-1 (6)

A2 and A'2 each have - (0 — Q2) si-0-CH2 ~ and 02 an alkylene radical optionally substituted with 2 to 4 chlorine or bromine atoms and having a maximum of 6 carbon atoms, optionally with 1 or 2 oxygen atoms or with a double or Triple bond is broken, with

15

D "-N-

Z!

p = 0

/ \

0 0

1 I

4c

R,

R,

: H2 "(0" CI! 2) s-rI?

p-0

/ \

0 0

1 !

Ri Ri

D2 or D'2 each hydrogen or -CH2-0-Y2, R2, R'2 and R "2 each alkyl having 1 to 3 carbon atoms or both R2 or R'2 or R" 2 together for alkylene having 2 to 5 Carbon atoms, Y-. Hydrogen,

there are 2 or 3 carbon atoms between the oxygen atoms and Dj, D'i, R], R'i, R "i, s, t, t ', x and y have the meaning given.

However, amidophosphate reaction products of the probable formula are particularly suitable

X

CIV (0-CHo), -N - 2 2 s-1 |

P - 0

/ \

0 0

1 I

R2

R2

-D2

(7)

y-1

35

Is methyl or ethyl and wherein s, x and y are each 1 or 2, the sum (x + y) being 2 or 3.

The phosphorus-containing reaction products of the probable formula have proven to be particularly advantageous

0H3 - CH2 - ox / 0

ch3 - ch2 - 0

0 0 - ch0 - ch.,

\ / 2 3

p

Nil - CH2 - m

/ \

0 - CH2 - CH3

(8.1),

cho - ch0 - 0 0

3 2 \ #

p

CH3 - CH2 - 0

/ \

NH - CH,

0, 0 - CH0 - CH ^

s / 2 3

/ p \

N 0 - CH0 - CH.

ch2oh

* 2

(8.2)

ch "- CH,

ch.

CH,

0

O

\

P

</ NU- ClI2- ° - CH2- N- C »2- Nil

\ 0

0 0

1 I cii0 cii «

, / I z

° \ / °

0

- CH2 - CH.

- CH0 - CH.

ch

3rd

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cn.

(8.3)

3rd

or

Clio - cll0 - 0, 0 0 0-c! Io-ch-i

3 2 \ ^ v / 2 3

P ij A '

/ \H / \

ch3 - cu2 - 0 n-cil2-0-cii2 ~ n ~ cu2-0-ch2-NtI 0-cii2-cii3

/ r \ °

0 0

1 I

cii0 cil

I 2 j 2

(8.4)

cu-

cil ch.

»CH0

k / 2

r ch.,

\

ch,

0 0 0 0

sV

0 nh-Cil2--0-Cn2-NH 0 - cu ch0 ch.

2 \ / 3 c

ch.,

(3.5)

or, if component (3) has been used, the likely formula ch, -cho-0 .0 3 2 x /

/ P \

cii3-ch2-0 nh-ch2-0-ch2-ch2-0-ch2-nh or cho-ch0-0 0 3 2 n /

p ov o-ch0-c: i7 \ / 2 3

0-ch2 "ch3

0

(9.1)

ch3-c: h2 - o

/ \

nh- ch ,, - ü - chch ,, - 0 ch., - n-- ch0 -0-ch ,, - ch0- 0 - ch., - nh

* /

V / \

0-CH9-CH3

2nd

* 2 I

p-0

c / vo

I I

ch "ch, I

2nd

0-CH2-CJf3

(9.2)

'2

CH., CH.

3rd

proven.

The R-substituted amidophosphate radicals in the formulas (5) to (7) are methylolated with a methylene carbon atom originating from formaldehyde to a nitrogen atom of another dialkylamidophosphate radical or with a -0-CH2 radical to a nitrogen atom of another dialkylamidophosphate radical is bound, the -0-CH2 radical originating from the methylol group of the methylolated dialkylamidophosphate radical.

If component (3) has been used, the amidophosphate radicals substituted with R are those having a methylene carbon atom derived from formaldehyde via a -O-alkylene radical derived from diol and a -0-CH2 radical to a nitrogen atom of a further dialkylamidophosphate radical, the methylolated is bound, the —O — CH2 residue being part of the methylol group of the methylolated dialkylamido phosphate.

Depending on the value of x and y in formulas (5) to (7), they are reaction products with 2 or 3 amidophosphate residues and 0 to 2 methylol groups, which may be partially or completely etherified.

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55

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The amidophosphate reaction products used in the process according to the invention can be prepared by customary methods known per se. Appropriately, the procedure is such that 1 or 2 moles of the component

(1) reacted with 1 mol of component (2); the reaction products thus obtained are optionally post-methylolated with component (2); or optionally etherified with component (3) and then optionally with the component

(2) post methylolated; and the post-methylolated products are optionally etherified with component (4).

The reaction with component (2) or the post-methylolation with component (2) can advantageously take place at 20 to 80 ° C., preferably at 20 ° C. or at 50 to 60 ° C. Especially at 50 to 60 ° C, this reaction can optionally be carried out in the presence of a basic catalyst, both strong bases such as sodium hydroxide or potassium hydroxide and weak bases such as sodium acetate, magnesium carbonate or magnesium oxide being considered. In particular, the reaction of 2 moles of component (1) with 1 mole of component (2) can preferably be carried out at 20 ° C. without a catalyst,

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whereby 1 mole of an amidophosphate reaction product can be obtained which contains 2 amidophosphate residues.

The degree of methylolation can be followed in the course of the reaction by determining the bound formaldehyde.

In a preferred method, the amidophosphate reaction products used in the process according to the invention can be prepared by first methylolating 1 mol of component (1) with 1 mol of component (2) and then at least at 20 to 120 ° C., if appropriate in the presence an inert, organic water-insoluble solvent and optionally condensed with the use of an acid catalyst.

The methylolated amidophosphate obtained first condenses with itself to amidophosphates containing two or three amidophosphate residues. This condensation reaction can preferably be carried out at 50 to 80 ° C. But it can also be done at 20 ° C, z. B. in the preferably aqueous application bath.

In general, the acid catalyst can optionally be carried out without the use of solvent, ie. H. when carrying out the reaction in an aqueous medium. As acid catalysts come strong inorganic acids, such as. As phosphoric acid, hydrochloric acid, sulfuric acid, also acidic inorganic salts, such as. B. magnesium chloride, ferric chloride, zinc nitrate or in particular strong organic acids, such as. B. p-toluenesulfonic acid or in particular phthalic acid.

Suitable organic inert solvents or solvent mixtures, which may also be used, are especially those solvents which are immiscible with water and which form an azeotrope with water. Especially aromatic hydrocarbons, such as. B. benzene, toluene, o-, m-, p-xylene or a mixture thereof, or also xylene-toluene, xylene-benzenecol or xylene-decahydronaphthalene mixtures are suitable. When such solvents are used, the reaction can generally be carried out at the boiling point of the solvent or solvent mixture, the water formed by the reaction being able to be removed azeotropically from the reaction mixture.

The etherification to be carried out with component (3), if appropriate, can expediently take place at 20 to 80 ° C., in particular at 50 to 60 ° C., in the presence of an acidic catalyst. The acidic catalysts which can be used are the same inorganic acids, inorganic salts and organic acids as mentioned above.

Post-etherified amidophosphate reaction products can optionally be obtained by completely or partially etherifying the methylol groups with component (4), this etherification to be carried out optionally at 20 to 80 ° C., preferably at 50 to 60 ° C., in an acidic medium.

Organic textile materials which are made flame-resistant by the process according to the invention are, in particular, cellulose-containing textile materials,

the cellulose or the cellulose fraction of the textile material, e.g. B. of linen, rayon, rayon, preferably regenerated cellulose, e.g. B. viscose or in particular cotton. In addition to pure cellulose fibers, textile fiber mixtures such as polyacrylonitrile cellulose, polyamide cellulose or in particular polyester cellulose can also be used. These textile materials are textiles in any processing stage, such as threads, yarns, bobbins, nonwovens, knitted fabrics, fabrics or finished garments.

The amidophosphate reaction products, which have been produced with the use of component (3) and which contain chlorine and in particular bromine atoms, are used in the process according to the invention primarily for flame retarding fully synthetic fiber materials, such as. B. polyacrylonitrile, acrylonitrile copolymers, polyamide and in particular polyester.

In the case of the acrylonitrile copolymers, the acrylonitrile fraction is expediently at least 50 percent by weight and preferably at least 85 percent by weight of the copolymer. These are mainly mixed polymers, for the production of which other vinyl compounds, such as. B. vinyl chloride, vinylidene chloride, methyl acrylates, acrylamide or styrene sulfonic acids have been used as comonomers.

As polyamide fibers come e.g. B. from poly-2-capro-lactam, polyhexylmethylene diamine adipate or poly-o) -amino-undecanoic acid into consideration.

The preferred polyester fibers are derived primarily from terephthalic acid, e.g. B. from poly (äthylengIycolterephtha-lat) or poly (1, 4-cyclohexylenedimethylene terephthalate) from. Polyester fibers are used e.g. As described in U.S. Patents 2,465,319 or 2,901,446.

When flame retarding fully synthetic textile materials with halogenated, in particular brominated amidophosphate reaction products, these are applied to the fully synthetic fiber materials as organic solutions or in particular as aqueous solutions, emulsions or suspensions, whereupon the textile material is dried and a heat treatment at 175 to 220 ° C, preferably 190 to 210 ° C is subjected.

Suitable organic solvents here are aliphatic alcohols, ketones or esters with at most 4 carbon atoms, aromatic or cycloaliphatic hydrocarbons or chlorinated aliphatic hydrocarbons with 1 to 7 carbon atoms. Of particular interest are ethanol, methanol and trichlorethylene.

The dispersants customary in the dye and textile industry can be added to the aqueous emulsions or suspensions, such as. B. lignin sulfonates, aromatic sulfonic acids, saturated aliphatic, substituted with longer alkyl radicals dicarboxylic acids, Konderisationspro-products of aromatic sulfonamides and formaldehyde, alkylphenol-ethylene oxide adducts, fatty acid, fatty amine or fatty alcohol-ethylene oxide adducts, sulfated, substituted fatty acid amides or sulfonated benzide imidides.

However, cellulose-containing textile materials in particular are preferably made flame-resistant with the amidophosphate reaction products according to the invention, at least one amidophosphate reaction product and optionally an oxygen-containing and / or nitrogen-containing polyfunctional compound being applied to these textile materials, the materials thereupon dried and a treatment at elevated temperature submits.

The amidophosphate reaction products and the polyfunctional compound are expediently applied in the form of an aqueous preparation. As a rule, the pH of the aqueous preparations is 5.0 to 7.5 and in particular 6.0 to 7.0. At pH values from 5.0 to 6.0, as already mentioned, the reaction of the amidophosphate with methylolated, polyfunctional compounds, in particular with aminoplast precondensates, can be carried out in situ, ie. H. in the aqueous preparation immediately before it is applied to the textile materials. If necessary, the preparations with inorganic acids, such as. As hydrochloric acid, sulfuric acid, preferably phosphoric acid or with inorganic bases, such as. B. an aqueous potassium or in particular sodium hydroxide solution to the preferred pH of 6.0 to 7.0.

An addition of buffer substances, such as. B. sodium bicarbonate, di- and trisodium phosphate or triethanolamine can also be advantageous.

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45

50

35

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65

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The preparations can also accelerate curing so-called latent acid catalysts such. B. ammonium chloride, ammonium dihydrogen orthophosphate, magnesium chloride, zinc nitrate and others, in particular 2-amino-2-methyl-1-propanol hydrochloride.

In addition to the amidophosphate reaction products and, where appropriate, the additives necessary for adjusting the pH and the latent acidic catalysts, the preparations for flame retardant expediently also contain at least one polyfunctional oxygen and / or nitrogen-containing compound in order to achieve a washable flame retardant finish. This is e.g. B. polyfunctional epoxides, especially at 20 ° C liquid epoxy with at least two epoxy groups, which are preferably derived from polyhydric phenols, to polyalkylene polyamines or in particular to aminoplast precondensates.

Aminoplast precondensates are generally addition products of formaldehyde with methylolatable nitrogen compounds. The following can be mentioned as methylolatable nitrogen compounds:

1,3,5-aminotriazines such as N-substituted melamines, e.g. B. N-butyl melamine, N-trihalomethyl melamine, triazone and guanamine, z. B. Benzoguanamine, Acetoguanamine or Diguanamine.

The following are also suitable: cyanamide, acrylamide, alkylurea or arylurea and thioureas, alkyleneureas or diureas. e.g. B. urea, thiourea, urones,

12

Ethylene urea, propylene urea, acetylene diurea or in particular 4,5-dihydroxyimidazolidone-2 and derivatives thereof, e.g. B. 4,5-di-5-hydroxyimidazolidone-2 substituted in the 4-position on the hydroxyl group with the radical -CH2CH2-CO-NH-CH2OH. The methylolver compounds of a urea, an ethyleneurea or in particular melamine are preferably used. Valuable products generally deliver as high as possible, but in particular also low methylolated compounds, e.g. B. etherified or io unetherified methylol melamines, such as di- or trimethylol melamine or its corresponding ether. Suitable aminoplast precondensates are predominantly monomolecular as well as higher precondensed aminoplasts.

The ethers of these aminoplast precondensates can also be used together with the amidophosphate reaction products. Z are advantageous. B. the ether of alkanols such as methanol, ethanol, n-propanol, isopropanol, n-butanol or pentanols. However, it is useful if these aminoplast precondensates are water-soluble, such as. B. 20 of the pentamethylol melamine dimethyl ether or the trimethylol melamine dimethyl ether.

As a further, in some cases advantageous additive, a softening agent, e.g. B. an aqueous polysiloxane or polyethylene emulsion or Äthylencopoly-25 merisat emulsion to mention or in particular softening agents, as described in Belgian Patent 808 621, for. B. the imidazole of the formula

N II

H35C17 'C

CH ,,

1U

© CH ,,

./V

CHoCH „-NH-C0-C, -, H ..

'2V' "2

17 35

H-C-SO, © 3 4

(10)

or highly etherified melamine-formaldehyde condensation products modified with fatty acid alkanolamides.

The addition of wetting agents such. B. condensation products of alkylated phenols with ethylene oxide can be advantageous.

The amount of amidophosphate reaction products in the aqueous preparations is expediently such that 10 to 289? is applied. It must be taken into account here that the commercially available textile materials made from native or regenerated cellulose can absorb between 50 and 120% of an aqueous preparation.

The amount of the additive that may be used to adjust the pH from 6.0 to 7.0 depends on the selected value and the type of additive.

If you add other additives to the preparation, such as a latent acid catalyst, a softening agent and / or a wetting agent of the type specified, this is advantageously done in small amounts, e.g. B. 1 to 10%, based on the amount of the phosphorus-containing reaction product.

In a preferred embodiment, the aqueous preparations for flame retarding cellulose-containing textile materials contain 100 to 400, preferably 150 to 300 g / 1 of at least one amidophosphate reaction product according to the invention, 50 to 300, preferably 100 to 200 g / 1 of at least one polyfunctional compound, in particular an aminoplast precondensate and 0 to 80, preferably 2 to 40 g / 1 of at least one of the additives mentioned above.

The preparations are now applied to the cellulose-containing 45 fiber materials, which can be carried out in a manner known per se. It is preferable to work with piece goods and impregnate them on a foulard of the usual type, which is fed with the preparation at room temperature.

50 The textile material impregnated in this way must now be dried, which is conveniently done at temperatures up to 100 ° C. Then it is a dry heat treatment at temperatures above 100 ° C, z. B. between 130 and 200 ° C and preferably between 150 and 180 ° C, under-55, the duration of which can be shorter, the higher the temperature. This heating time is, for example, 2 to 6 minutes at temperatures of 150 to 180 ° C.

If amidophosphate reaction products are used which have been methylolated and optionally post-etherified 60, the methylol or, if appropriate, the methylol ether residues are cleaved in this process, so that water or, if appropriate, an alcohol is formed.

In this case, it has been shown that these volatile fission products have to be removed continuously from the material so that the desired effect can occur to the full extent. The devices in which the heat treatment is carried out must be selected accordingly. Apparatuses are well suited for which

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maintenance of the prescribed temperature, fresh air is continuously supplied and the air laden with the volatile substances produced is removed.

Such devices, e.g. B. so-called turbo fixers or nozzle fixers are known. 5

Rinsing with an acid-binding agent, preferably with aqueous sodium carbonate solution, e.g. B. at 40 ° C to boiling temperature and for 3 to 10 minutes, is useful in a strongly acidic reaction medium.

The flame retardants obtained by the present process have the advantage, as already indicated, of

to be largely retained even after multiple washing or chemical cleaning. This also applies to short runs, i.e. H. with small amounts of phosphorus on the finished material. is

In addition, the flame retardant finishes obtained do not cause an intolerable reduction in the textile mechanical properties of the treated material. This applies in particular to the handle of the finished textile materials. In particular, the tear resistance of the finished textile materials is largely retained even after chlorine treatment with a hypochlorite solution, the chlorine-bleached materials subsequently being subjected to heat treatment. Furthermore, the finished textiles remain shrink-proof even after repeated washing. 25th

Another advantage of the method according to the invention is that when flame retarding textile materials with amidophosphate reaction products the treated material does not yellow. The good stability over several hours of the aqueous preparations used in the process and containing the amidophosphate reaction product is also particularly advantageous.

The percentages and parts in the following examples are units by weight unless otherwise stated. Volumetric parts behave in parts by weight like ml to g. 35

Manufacturing instructions for intermediates that have a single amidophosphate residue per molecule

A. 612 parts of diethylamidophosphate (4 mol) and 367 parts of a 36% aqueous formaldehyde solution (4.4 mol) are dissolved at 20 ° C. and adjusted to pH 10 to 11 by adding a total of 8.2 parts of a 30-day aqueous sodium hydroxide solution. The methylolation is carried out at 20 to 30 ° C. and at pH 10 to 11 for 3 hours. An approximately 90% methylolation is determined by determining the free formaldehyde content of a reaction sample. The water is then removed from the reaction mixture at 50 ° C. under vacuum.

725 parts (99% of theory) of a yellowish, viscous liquid are obtained as the methylolation product. The methylated product corresponds to the likely formula c2u5 ° \

P - Nile • CII, OH (101)

C 11 0 "

L2 5 0

AS

B. 165 parts of neopentylamido phosphate (1 mol) and 90.4 parts of a 36.5% aqueous formaldehyde solution (1.1 mol) are dissolved at 20 ° C and by adding a total of 23 parts of a 30% aqueous sodium hydroxide solution to pH 8 , 5 to 9.0. The methylolation is carried out for 15 minutes at 60 ° C. and at pH 8.5 to 9.0. By determining the free formaldehyde content of a reaction sample, an approximately 83% methylol

60

65

tion determined. The water is then removed from the reaction mixture at 60 ° C. under vacuum.

195 parts (99% of theory) of a white, viscous syrup are obtained as methylolation product. The methylated product corresponds to the likely formula h.c ch0 - 0

3 2 \

c p - nh - ch., oh

/ \ / II 2

H3c ch2 - 0 i

(102)

Manufacturing instructions for reaction products that have at least two amidophosphate residues per molecule

C. 153 parts (1 mole) of diethylamidophosphate are dissolved in 41.6 parts of a 36% aqueous formaldehyde solution (0.5 mole) and left to stand at 20 ° C. for 48 hours. The water of the formaldehyde solution and the water formed during the reaction are then removed in vacuo at 60 ° C. 159 parts (~ 100% of theory) of a colorless, semi-solid product are obtained. This contains a compound as the main component, that of the probable formula

CoIlt-0

2 5 \

C2H5

O/!

oc2h5

P-nh-ch0-hn-p

2 || \

b OC2H5

(103)

0

corresponds, which is confirmed by the following elementary analysis:

Calculated: Found:

C 33.97 C 32.3

H H

7.6 7.8

N N

8.8 8.6

19.47% 18.8%

40 Gel permeation chromatography (GPC) gives the following composition:

approx. 17% of a reaction product with a molecular weight of approx. 650 and 4 phosphorus atoms,

approx. 19% of a reaction product with a molecular weight of approx. 480 and 3 phosphorus atoms,

approx. 45% of a reaction product with a molecular weight of approx. 320 and 2 phosphorus atoms, approx. 19% diethylamidophosphate.

50 D. 79.5 parts (0.25 mol) of the compound described in Example 1 are dissolved in 20.8 parts (0.25 mol) of a 36% aqueous formaldehyde solution at 20 ° C. The solution is adjusted to pH 10 to 10.5 by adding a 30% aqueous sodium hydroxide solution, the temperature rising temporarily to approximately 40 ° C. The solution is then cooled again to 20 ° C. and kept at this temperature for a further 3 hours at a temperature of 9.5 to 10.5 with the temporary addition of the sodium hydroxide solution. A total of 7.7 parts of the 30% aqueous sodium hydroxide solution are required to maintain the pH. Examination of a reaction mixture sample for its content of free formaldehyde shows that 94% of the formaldehyde used is now bound. 105 parts of an opaque, viscous solution which had a phosphorus content of 13.8% and an active substance content of 80.5% were obtained as the methylated reaction product.

The product obtained contains as a main component a compound which has the likely formula

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16

CoHr0

2 ■> \

V - N - CH., / Il | L

p H n l, 2 5 0 CHo0H

HN - P

OC, .Hr / l j

>

ÓN ° C2HS

(104)

corresponds, which is confirmed by the following elementary analysis:

Calculated: C 34.5 H 7.53 N 8.04 P 17.8% Found: C 33.4 H 7.5 N 7.9 P 17.5%

E. 183 parts (1 mol) of the intermediate product obtained according to preparation instruction A and 160 parts of benzene are heated to boiling temperature (78 ° C). The water formed by the etherification is removed azeotropically and collected separately. The reaction is complete after about 5 hours, a total of 8 parts of water being separated off. The ben-io zol is removed from the reaction mixture under vacuum at about 50 to 60 ° C.

176 parts of a viscous, slightly yellowish liquid are obtained, which consists of a mixture of at least two reaction products, which correspond to the two probable formulas:

C2H5 ° OC2H5

XP-NH-CHO-0-CH0-NH-P / II 2 2 II \

CoHcO J! I OC2H

(105)

'2 5

0

C ^ H.O f-

2 5 s. / ^ ->

r-NH-CHo-0-CHo-N-CHo0CHo-HN-P / II 2 2.2 2

(106)

C2H5 ° E

P '= 0 / \ 0 0

O OC2H5

H5C2

C2H5

The formulas (105) and (106) are confirmed by the following elementary analysis:

Calculated for formula (105):

C 34.7 H 7.5 N 7.9 P 17.0%

Calculated for formula (106):

C 35.36 H 7.42 N 7.73 P 17.1%

Found for the mixture of formula (105) and (106): C 34.5 H 7.53 N 8.04 P 17.8% The separation of the mixture obtained by means of GPC gives the following composition:

approx. 2% of a reaction product with a molecular weight of approx. 740 and 4 phosphorus atoms,

approx. 6% of a reaction product with a molecular weight of approx. 320 and 4 phosphorus atoms,

approx. 15% of a reaction product with a molecular weight of approx. 540 and 3 phosphorus atoms,

approx. 37% of a reaction product with a molecular weight of approx. 350 and 2 phosphorus atoms,

approx. 5% of a reaction product with a molecular weight of approx. 210 and 1 phosphorus atom,

approx. 19% of a reaction product with a molecular weight of approx. 180 and 1 phosphorus atom, approx. 6% diethylamidophosphate.

F. 183 parts (1 mol) of the intermediate product obtained according to preparation instruction A are etherified in the presence of 5 parts of phthalic acid for 3 hours at 50 ° C. The reaction mixture is then cooled to 20 ° C., neutralized to pH 6.5 to 7.0 with 8 parts of a 30% aqueous sodium hydroxide solution, and the resulting fine suspension is poured into 200 parts of acetone. After filtering off the precipitated sodium phthalate, the filtrate is freed from acetone and water under vacuum at approx. 50 ° C.

This gives 172 parts of a colorless, clear liquid which consists of a mixture of at least two of the reaction products listed in Example 3. 40 The probable formulas (105) and (106) are confirmed by the following elementary analyzes:

Calculated for formula (105):

C 34.7 H 7.5 N 7.9 P 17.0%

Calculated for formula (106):

45 C 35.36 H 7.42 N 7.73 P 17.1%

Found for the mixture of formula (105) and (106): C 34.3 H 7.6 N 7.8 P 17.0%

The separation of the mixture obtained by means of GPC gives the following composition:

50 approx. 8% of a reaction product with a molecular weight of approx. 740 and 4 phosphorus atoms,

approx. 6% of a reaction product with a molecular weight of approx. 320 and 4 phosphorus atoms,

approx. 18% of a reaction product with a molecular weight of approx. 540 and 3 phosphorus atoms,

approx. 38% of a reaction product with a molecular weight of approx. 350 and 2 phosphorus atoms,

about 14% of a reaction product with a molecular weight of about 210 and 1 phosphorus atom,

60 approx. 9% of a reaction product with a molecular weight of approx. 180 and 1 phosphorus atom, approx. 7% diethyl amido phosphate.

G. 69.6 parts (0.2 mol) of the compounds obtained according to Example 3 are dissolved in 16.6 parts of a 36% aqueous formaldehyde solution (0.2 mol) at 20 ° C. The solution is adjusted to pH 10.0 to 10.5 by adding a 30% aqueous sodium hydroxide solution with stirring, and methylolated for 3 hours at 20 to 30 ° C., with

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temporary addition of the sodium hydroxide solution the pH is maintained at 10.0 to 10.5. A total of 7 parts of the sodium hydroxide solution are required. By testing a reaction mixture sample for its free formaldehyde content, a 69-70% methylolation is determined, which cannot be increased even by a further 3-hour treatment.

The methylolated reaction product obtained is 88.5 parts of a colorless, clear, viscous solution which has a phosphorus content of 14.0% and an active substance content of 85.4%.

The product obtained consists of a mixture of at least two compounds which correspond to the partially methylolated form of the two probable formulas in Example 3.

10th

C2 "5 °

C2H 0

\

H. 183 parts (1 mol) of the product obtained according to preparation instruction A and 31 parts of ethylene glycol (0.5 mol) are etherified in the presence of 5 parts of phthalic acid at 50 to 55 ° C. for 3 hours. The reaction mixture is then cooled to 20 ° C., neutralized to pH 6.5 to 7 with 8 parts of a 30% aqueous sodium hydroxide solution and the fine suspension formed is poured into 120 parts of acetone. After filtering off the precipitated sodium phthalate, the filtrate is freed from acetone and water under vacuum at approx. 50 ° C.

199 parts of a colorless, clear, low-viscosity liquid are obtained, which consists of a mixture of at least two reaction products which correspond to the two likely formulas:

/ OC2H5

/ II

P-NI-CHo-0-CHoCHo-0-ClIo-HN-P

2 2 2 2 il N

(107)

0

0

OC2H5

ColItrO

'2 5

Y

0C, .H. / l J

P-III-Clio-0-CHoCHo-0 ~ CHo-N-CHo-0-CHoCH „-0-CH0-NH-P / i, 1 2 Z l | l room

C2n50 »1 OC., H

/ \

oc2H5

Collr0 l 5

0v ~ 2 "5 (108)

The formulas (107) and (108) are confirmed by the following elementary analysis:

Calculated for formula (107):

C 36.74 H 7.71 N 7.14 P 15.8%

Calculated for formula (108):

C 38.04 H 7.66 N 6.65 P 14.7%.

Found for the mixture of formula (107) and (108): C 36.3 H 7.8 N 6.9 P 15.0%

I. 175 parts (1 mol) of the intermediate product obtained according to preparation instruction B are in the presence of

35

40

45

5 parts of phthalic acid etherified at 50 to 60 ° C for 3 hours. The reaction mixture is then cooled to 20 ° C., neutralized to pH 6.5 to 7.0 with 8.5 parts of a 30% aqueous sodium hydroxide solution, and the viscous reaction mixture is diluted with 500 parts of acetone. The resulting fine suspension is filtered off from the precipitated sodium phthalate and the filtrate is freed from acetone and water under vacuum at approx. 50 ° C.

This gives 156 parts of a product as a colorless, brittle mass which is hard at 20 ° C., and as a main component a compound which has the probable formula

CH-, CH-0 0 - CHr,

3 \ / 2 \ / 2

C P-NH-CHo-0-CH "-HN-P

/ \ / h 2 2 CH3 CH20 «R 0 - CH,

CH-,

(109)

which is confirmed by the following elementary analysis:

Calculated: C 38.7 H 7.05 N 7.5 P 16.65% Found: C 40.0 H 7.2 N 7.0 P 14.8%

The following Table 1 shows the absorption bands 55 in the infrared absorption spectra of the reaction product mixtures which were obtained in accordance with the preparation instructions C to I.

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Table 1

Manufacturing instructions C D E F

H

3650 m 3630 w 3590 m 3550 w 3460 m 3400 ms 3380 m 3340 s 3020 w 2960 s 2920 m 2880 m 2850 m 1590 w 1530 w 1495 w 1460 wm 1430 w 1405 w 1380 wm 1360 m 1315 w 1280 wm 1230 s 1180s 1150 wm 1115 m 1080 s 1040 s 1010s 995 s 960 ms 940 m 920 w 905 w 870 s 860 w 840 w 615 ww = weak absorption m = medium absorption s = strong absorption

example 1

A cotton fabric (basis weight: 150 g / m 2) is padded with the aqueous liquor A having the composition given in Table 2 below. The fleet intake is 80%. It is dried for 30 minutes at 80 ° C. and then cured for 4 V2 minutes at 160 ° C. A part of the fabric is then in 5 minutes in a solution containing 4 g of anhydrous sodium carbonate and 1 g of a reaction product from 1 mol in 1 liter of water Contains 4-nonylphenol and 9 moles of ethylene oxide, washed at 95 ° C, rinsed and dried.

Another part of this fabric is now washed up to 40 times for 60 minutes in a solution at 95 ° C, which contains 5 g / 1 detergent according to SNV 198 861.

10th

35

The individual fabric pieces are then checked for their flame resistance (vertical test according to DIN 53906). The results of this test are also summarized in Table 2 below.

In addition, the grip of the fabric is checked after washing and rated with grades according to the following grip scale:

0 unchanged

1 track stiffer than 0

2 somewhat stiffer than 0

3 stiff

4 very stiff

Table 2

15

untreated

Treated with fleet A

20th

23

30th

35

Components in g / 1 product according to preparation instructions C (p content: 19.5%) di-trimethylolmelamine reaction product from 1 mol of 4-nonylphenol and 9 mol of ethylene oxide 2-amino-2-methyl-1-propanol hydrochloride

Hexamethylolmelamine penta-

methyl ether stearic acid

alkanolamide reaction product

30%

g phosphorus / kg tissue pH value of the bath degree of fixation in%

Flame resistance BZ = burning time in seconds. EL = tear length in cm

160 150 2

40 20

After washing

After 20 washes

After 40 washes

BZ EL BZ EL BZ EL

45

Handle burns burns

0

25th

5.6 70

0

10.5 0

12.5

0

13.5

1

65

Example 2

Analogously to that described in Example 1, a cotton fabric with the liquors A to E having the composition given in Table 3 below is made flame-resistant and tested.

In addition to assessing the handle, the Scorch test according to AATCC 92-1967 is also carried out, in which the damage caused by retained chlorine is determined. For this purpose, the tissues are treated with a sodium hypochlorite solution and rinsed. Some of the fabrics are then locally heated in the warp direction on a hot plate. The tensile strength of the chlorine-treated fabrics on the one hand and of both the chlorine-treated and heated fabrics on the other hand is then determined as a percentage of the tensile strength of the untreated fabrics.

The results are summarized in Table 3 below:

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Table 3

Unbe

Fleet name

acts

A

B

c

D

E

Components in g / 1

Product according to regulation D (P content 13.8%)

227

Product according to regulation E (P content 17.8%)

176

Product according to regulation F (P content 17.8%)

175

Product according to regulation G (P content 14.0%)

224

Product according to regulation H (P content 15.8%)

198

2-amino-2-methyl-1-propanol hydrochloride

40

40

40

40

40

Reaction product from 1 mol of 4-nonylphenol

and 9 moles of ethylene oxide

2nd

2nd

2nd

2nd

2nd

Di-trimethylol melamine

150

150

150

150

150

Hexamethylolmelamine pentamethyl ether

Stearic acid-alkanolamide reaction

product 30%

20th

20th

20th

20th

20th

g phosphorus / kg tissue

25th

25th

25th

25th

25th

pH of the bath

6.8

6.8

6.8

6.8

6.8

Degree of fixation in%

74

81

88

84

81

Flame resistance

BZ = burning time in seconds

EL = tear length in cm

After washing BZ

burns

0

0

0

0

0

EL

12.5

13

12.5

11.5

11.5

After 20 washes BZ EL

burns

0

12.5

0

12th

0

10.5

0

11.5

0

11

After 40 washes BZ

burns

0

0

0

0

0

EL

14.5

12

11.5

12.5

11.5

Handle

1

1

1

l '/ 2

1

Scorch test:

Tear resistance chlorinated / untreated

traded fabric%

99.6

98.3

95.0

101.0

101.0

99.0

Tear resistance chlorine and heat resistant

treated / unhindered Fabric%

101.2

93.8

95.1

101.0

100.0

95.5

Example 3

Analogously to that described in Example 1, a cotton fabric is made flame-resistant with the liquor A of the composition given in Table 4 below and tested for its flame resistance.

The results are summarized in Table 4 below:

Table 4

Table 4 (continued)

Untreated

Components in g / 1 product according to preparation instructions I (P content: 14.3%) di-trimethylolmelamine reaction product from 1 mol of 4-nonylphenol and 9 mol of ethylene oxide 2-amino-2-methyl-l-propanol hydrochloride g phosphorus / kg Tissue pH of the bath Degree of fixation in%

305 150 2

40 35

44

Treated with fleet A

55

Untreated

Flame resistance 50 BZ = burning time in seconds EL = tear length in cm

Before washing

After washing

After 1 wash

BZ EL BZ EL BZ EL

burns burns burns

60

65

Treated with fleet A

0

8.5 0

11.5 0

12.5

Example 4

Analogously to that described in Example 1, a fabric made from regenerated cellulose is made flame-resistant with the liquor A having the composition given in Table 5 below, but is only washed and washed at 60 ° C.

The flame resistance test was carried out as indicated in Example 1.

The results are summarized in Table 5 below:

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Table 5

Untreated

Treated with fleet A

Components in g / 1 product according to preparation instructions I (P content: 14.3%) di-trimethylolmelamine reaction product from 1 mol of 4-nonylphenol and 9 mol of ethylene oxide 2-amino-2-methyl-l-propanol hydrochloride g phosphorus / kg Tissue pH of the bath Degree of fixation in%

Flame resistance BZ = burning time in seconds. EL = tear length in cm

Before washing

After washing

After 1 wash

BZ EL BZ EL BZ EL

burns burns burns

305 150 2

40 35

6 60

0 8 0

7

8th

13.5