DE2114610A1 - Derivatives of polyhydric alcohols - Google Patents

Description

6700 Ludwigshafen, 24.J.1971 Derivatives of polyhydric alcohols

The invention relates to new derivatives of polyhydric alcohols, - the at least two phosphonic acid groups in the molecule - and at least contain two carbonamide groupings, a process for their preparation and their use for flame retardant finishing of cellulosic! Textile goods.

Numerous compounds have already been used to treat cellulosic! Textile suggested to make this flame retardant To give properties. For example, mixtures of boric acid or ammonium dihydrogen-o-phosphate with borax have been used for treatment used by textiles, but the treatment had to be repeated after each wash.

Substances that are used to produce wash-resistant surface finishes are, for. B. metal oxides in or on the Fibers are knocked down. One has z. B. successive iron (III) oxide and a mixture of tungstic acid and tin (IV) oxide or successively deposited antimony trioxide and titanium dioxide. However, such methods require the use of several baths. Strong acid solutions and other inconvenient Apparatus is therefore very inexpedient. Since there is also a deposition of white metal oxide on the textile surface, considerable difficulties may arise with certain dyeings.

More recent developments consist in applying organic phosphorus compounds to the textile material. B. cellulosic material treated with tetrakishydroxymethylphosphonium chloride in conjunction with an aminoplast. If all components are used in a single bath, however, the amount of phosphonium salt and aminoplast which must be absorbed to produce sufficient flame resistance is undesirably high and causes an increase in the weight of the treated textile material of 20 to 25 %. This massive addition changed

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but the grip of the textile material ^ to a considerable extent. "Many Textiles also have to undergo a special pre-treatment in order to make them sufficiently adsorptive (absorbent) to contain such a large amount of impregnant.

A second method was with tris-aziridin-1-yl-phosphine oxide and tetrakishydroxymethylphosphonium chloride have been suggested. Of the The great disadvantage of using this combination is that aziridinyl phosphorus compounds are very toxic substances and therefore represent an extraordinary source of danger for the operating personnel.

Further developments are in the German Offenlegungsschrift 1 469 28l and 1 594 974 are proposed. Except for these two There are a number of other patent specifications that can be named representative, but "all of them are basically similar Compounds of phosphorus for flame retardant equipment suggest.

These are compounds that are used alone or in admixture with others, and the following general structural scheme exhibit:

0 0
(RO) ₂ P- (CR ¹ ₂ ^ -C-NH-CH ₂ OR "

The substituent R ^w in these compounds is always an H atom, an alkyl radical or an alkenyl radical, which preferably contain 4 to 6 carbon atoms.

These fabrics have undeniably the textile technology in question Brought benefits.

Nevertheless, these connections are not free from disadvantages! The methylol this Carbamoylalkanphosphonsäuredialkylester "are with formaldehyde in balance. The free formaldehyde contained in the equilibrium mixtures leads on the one hand with the equipment to odor nuisance and provides on the other hand with the use of ammonium salt catalysts in the usual condensation temperatures of l40 to 170 ⁰ C a

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Fish odor build-up on the fabric. The proportion of non-methylolated carbamoylalkanephosphonic acid dialkyl ester contained in the equilibrium mixture cannot react with the cellulose fibers and is therefore lost as a flame retardant. In general is therefore the Flammehutζ equipment according to the teaching of the already cited references with methylol and alkoxymethylcarbamoylalkanephosphonic acid dialkyl esters carried out in the presence of aminoplast-forming substances.

However, the combination with these aminoplast formers leads to unwanted tissue stiffening and thus too hard a grip. Around To compensate for this hard handle, the above-mentioned literature references suggest the addition of plasticizers, which in the generally leads to impairment of the flame retardant effect.

A fabric finished in accordance with the previous illustration has all the criteria of a textile product with a flame retardant finish on. But it turned out that the tear resistance of a fabric finished in this way was probably due to the increased use of aminoplast formers did not always meet the desired requirements. In addition, the tissue often had to be after 5 to 6 washing should be re-equipped, since the washing permanence of these compounds does not allow a larger number of washes. That This is because, in order to fully meet the requirements for flame resistance, fabric must contain a minimum amount of flame retardant. If the amount on the fabric drops by just a few percent below a certain visual wave value, the flame retardant finish goes out suddenly and the tissue continues to burn when it becomes inflamed, as if it had never been impregnated.

The technical problem that arose, therefore, was to look for compounds that

1. enter into a sufficiently strong bond with the fiber without the use of the aminoplast formers mentioned Do not change the grip properties and tear strengths to an undesired extent, and

2. Above all, they are sufficiently wash-permeable so that the laundry can be washed could be repeated any number of times.

3. Finally, on the chemistry side, there should be a process

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be developed that allows such substances in simple way to produce, without that too great a technical effort had to be driven, the one would make such manufacture unprofitable.

The problem has now been solved in a surprising manner with compounds of formula I.

AC-B) _n I,

in which A is the remainder of an n-valent alcohol, η is an integer from 2 to 6 and B is a radical of the formula II

ti

1 2
in which R and R are alkyl radicals with 1 to 4 carbon atoms or a common alkylene radical with 2 to 5 carbon atoms, Tr is a hydrogen atom or an alkyl radical with 1 to J> carbon

4th
substance atoms, R is a hydrogen atom, an alkyl radical having 1 to 2 carbon atoms, a methylol group or an alkoxymethyl group having 1 to 4 carbon atoms.

Technically of particular importance are compounds of the formula I, in the A the remainder of a dihydric alcohol, η thus the number 2

1 2 and B denotes a radical of the formula II in which R and R are identical alkyl radicals with one or two carbon atoms, R ^

4th
Hydrogen and R denotes a hydrogen atom, a methyl group or a methylol group »

Of paramount technical importance are compounds in which A is the remainder of a dihydric alcohol with 2 or 3 carbon atoms, preferably of ethylene glycol.

Examples ^, the substances of paramount technical importance represent according to the invention, are listed below in terms of formulas:

0 0

tf ti

_cu Q ^ 22 ° ° ° - ^

209841 / 1161-

■ 0
dd - 5 - 'O.Z. 21st 14610 9
-P-CH, ο. _oc
/ * itt MXJ / " ¹ TJ / Λ r * XJ P ¹ TJ A / ~ * TJ TJKTr ¹ Ar ⁴ TJ P ¹ TJ Ό ^^
-JOnPiNrI-UnP-U-OrIPUrIp-U-OrIp-IIiNUUOrIpOrIPr 27 417 C ₂ H ₅ O ^
C ₂ H ₅ O ^ 0
> P-CH, O
, CH-CONH-CH ₀ -OCH ₀ CH ₀ O-CH ₀ -HNCO-CH-CH ₀ -P ^
CH, CH ₃ CH O ^ 0 ο ·
, CH ₂ CONH-CH ₂ O-CH-CH ₂ -O-CH ₂ -HNCO-CH ₂ Gh ₂ -P ^ OCH 5 CH ₃ O ^ CH ₃ OCH 3 > P-CH ₂ CH ₂ CON-CH ₂ O-CH ₂ CH ₂ O-CH ₂ -NCOCh ₂ CH ₂ P ^ '""" ⁵
3 3 3 CH ₃ O ^

The process for the preparation of the compounds according to the invention is simple and takes place in such a way that compounds of the formula

_o ^ PH III,

iro

unsaturated acid amides of the formula

H-C = C-CO-NH IV,

Formaldehyde and compounds of the formula

in a stoichiometric ratio in any order can act, where in the formulas III to V A, R,

p -z. H

R, R-% R and η have the meanings according to formula I and II.

You can z. B. a Phosphorigsäuredialky! Ester of the formula III react with one of the unsaturated acid amides of the formula IV, methylolate the compound obtained and then this with one of the mentioned polyhydric alcohols of the formula V in a stoichiometric ratio, d. H. in proportion that all alcoholic groups are affected. But you can also go the other way around, and first z. B. the unsaturated acid amide with formaldehyde methylo-

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lieren, etherifying the methylolated compound directly with the polyhydric alcohol and then this compound with the dialkyl phosphite realize.

In general, the reaction products of unsaturated acid amide, formaldehyde and polyhydric alcohol are already present. Representatives of these compounds are, for example, the so-called glycolamol. In the other case, this can also be done with the dialkyl phosphite Submit converted methylolated unsaturated acid amide, which is then then used with the polyhydric alcohol for implementation got.

Starting products for the production of the invention Products are dialkyl phosphites which have already been described in German Offenlegungsschrift 1,469,281. It is about here to dialkyl phosphites with 1 to 4 carbon atoms per alkyl radical. In this case, those are preferably used in which the alkyl groups are the same and have 1 or 2 carbon atoms, thus contain methyl or ethyl groups.

In addition, cyclic alkyl phosphites with 2 or 3 carbon atoms are used in the chain.

Further starting products are the unsaturated acid amides. For this purpose, all those as defined in individual can be substituted. The following are to be mentioned: Acrylamide, methyl acrylamide, ethyl acrylamide, propyl and butyl acrylamides, or their on the nitrogen with C, to C, alkyl radicals or derivatives substituted with optionally etherified methylol radicals. The methylol radicals can, for. B. with alkyl groups, containing 1 to 4 carbon atoms, be etherified.

The following should preferably be mentioned here: acrylamide, methacrylamide or N-methylol acrylamide. Technically as particularly meaningful The starting materials are acrylamide and methacrylamide.

The polyvalent ones that represent the real essence of the invention Alcohols, which are used as starting materials in the sense of the invention can be used, are due to alcohols with 2 to max. 6 hydroxyl

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groups in the molecule and contain 2 to β carbon atoms. Here come z. B. glycol, glycerine, propylene glycol, 1,2- and 1,3-butyl glycol, bridged with oxygen atoms polyhydric alcohols such as butyl diglycol and lower polyalkylene oxides with a maximum of 6 carbon atoms, pentits, hexites, sorbitol or spatially branched alcohols such as pentaerythritol are possible. Technically preferred are glycol and 1,3-propylene glycol. Basically but very favorable results are also obtained with sorbitol or pentaerythritol.

The substances according to the invention can in detail, for. B. as follows be produced: You can z. B. a glycolamol of the formula below

CH ₀ = C-Co-N-CH ₀ -A-CH ₀ -N-CO-C = CH ₀ ,

^d » h It; ^dd Xz \ h ^d

R R ^ R ^ R

-χ h

in which A, Rr and R are defined according to formula I, react with a dialkyl phosphite. This implementation goes z. B. in an alkaline medium in the presence of z. B. alcoholates, but also any other basic reacting substances, in a light manner in front of you. Since this reaction belongs to the state of the art, it does not need any further explanation at this point.

However, as already explained more generally above, a compound of the formula below can also be used

η um

^ p-CH ₀ -CH-CO-N-CH ₀ OH,? / ^d 'Ii' R ^d

R ^d 0 R ⁴ R ^

in a manner known per se by reacting dialkyl phosphite one of the unsaturated acid amides, eg. B. acrylamide, and subsequent methylolation with formaldehyde has been obtained ethereal with one of the polyhydric alcohols. The etherification takes place in a manner known per se in the presence of acidic catalysts such as sulfuric acid, boron fluoride etherate and other Lewis acids. The compounds can be optionally methylolated on the nitrogen atoms, and these methylolated compounds with any of the conventional etherifying _m edium etherified "ground _{2098 / [1/1161}

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The substances according to the invention are obtained in each Pall Formula I in excellent yields and excellent purity.

The substances of the formula I can be used very successfully as flame retardants are used for textile goods, primarily for textile goods, natural or regenerated cellulose contains or consists of. Textile material that is particularly suitable for the use of the substances according to the invention is z. B. cotton or regenerated cellulose.

The fabrics finished with the substances according to the invention are now characterized by a very soft handle, excellent Wash permanence and the absence of any odor-causing substances.

Their use in the flame retardant equipment is such. B. in the following way: The textile material to be treated is impregnated with one or more substances of the formula I and then reacted in the presence of at least one acidic and / or potentially acidic catalyst. The substances of the formula I are preferably used in the form of aqueous impregnation baths (liquors). The concentration of substances of the formula I in the liquors is generally between 200 and 600 g / l.

The application takes place in the apparatus customary for aqueous systems in the textile industry. Preferably one serves for the impregnation of a padder. The soaked material is freed one thus in a manner known per se by squeezing off excess impregnation fluid.

You can then z. B. drying the impregnated fiber material and then heat it preferably in the presence of acidic or potentially acidic catalysts at a temperature up to 200 ⁰ C, at 130 to 170 ⁰ C. In general, the reaction is complete in 1 to 6 minutes under these conditions. ,

Acidic or potentially acidic catalysts are known and used for the purposes of this type of equipment. There come both

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for example inorganic and organic acids such as sulfuric acid, Hydrochloric acid, phosphoric acid, boric acid, oxalic acid and their acidic salts are considered or those, for example by exposure to heat and / or hydrolysis, during their use Can form acids, such as ammonium or amine salts, also Lewis acids, such as magnesium chloride, zinc chloride or Zinc nitrate. Particularly good flame retardant effects are achieved when used achieved by mono- or diammonium phosphateη. the The reaction of the substances of the formula I is, as mentioned, carried out in the presence of these catalysts. This can be achieved by that when the textile material to be finished is impregnated with the new substances, the catalysts, preferably in the form aqueous solutions to this. Preferably, however, the catalysts are added directly to the substances Impregnation bath containing formula I. Catalyst concentrations between 1 and 40 g / l have proven useful for this purpose.

Fabrics that have been made flame-resistant in this way are characterized by excellent properties the handle, the tear resistance and the flame resistance. It can in principle to the fleets together with the substances of the Formula I also include other high-quality finishing agents, for example nitrogen-free hydroxymethyl or alkoxymethyl compounds, polyethylene glycol formals and compounds containing epoxy groups, such as, for example, glycol diglycid ether, can be used. In the end aminoplast-forming substances can also be used, without that, as is the case with the previous flame retardant finishes was the case, the additions of plasticizers are absolutely necessary. Furthermore, the usual hydrophobic, Softening, leveling, wetting and finishing agents can also be used. Water repellants are z. B. aluminum or Paraffin wax emulsions containing zircons, preparations containing silicone or perfluorinated aliphatic compounds. as typical plasticizers are e.g. B. Oxäthylierungsprodukte of higher molecular weight fatty acids, fatty alcohols or fatty acid amides, higher molecular weight Polyglycol ethers and their esters, higher molecular weight fatty acids, fatty alcohol sulfonates, stearyl-N, N-ethylene urea or stearylamidomethylpyridinium chloride. Water-soluble salts of acidic esters can be used as leveling agents.

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basic acids with ethylene oxide or propylene oxide adducts longer-chain alkoxylated raw materials are used. Wetting agents are for example salts of alkylnaphthalenesulfonic acid, the alkali salts of sulfonated dioctyl succinate or addition products of alkylene oxides with fatty alcohols, alkylphenols, pettamines and others.

Cellulose ethers or esters and alginates are used as finishing agents into consideration, also solutions or dispersions of synthetic polymers, eg. B. polyethylene, polyamides, oxyethylated polyamides, Polyvinyl ethers, polyvinyl alcohols ^ polyacrylic acid or their esters and amides as well as of corresponding polymethacrylic compounds, polyvinyl propionate, polyvinylpyrrolidone, of copolymers, ζ. B. of those made of acrylic or methacrylic acid esters and at least 20 percent by weight acrylic and / or methacrylic acid, from vinyl chloride and acrylic acid esters, from butadiene and Styrene or acrylonitriles or from o ^ ß-dichloroethylene, ß-chloroalkylacrylic acid esters or vinyl ß-ethyl ether and acrylic acid amide or the amides of crotonic acid or maleic acid or from N-methylol methacrylic acid amide and other polymerizable compounds. .

After the reaction with the substances of the formula I and, if appropriate, with the aforementioned additives, the textile material has an excellent appearance and very hydrolysis and wash-resistant flame retardant and is also characterized by being completely odorless. Of the Flame protection is in any case without the use of the aforementioned Additives guaranteed. Only special types of use of the fabric can justify the use of the substances mentioned, but without affecting the result of the present Invention to have a noticeable impact.

Special advantages of the new connections on the mentioned The main area of application also consists in the fact that the flame retardant finish has a significantly lower level than in the past Amount of flame retardant and thus also the acidic catalysts mentioned can take place.

At the same time, there is a much shorter reaction time,

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which, together with the aforementioned properties, contributes to the greatest possible protection of the tissue.

The parts and percentages given in the examples are weight units. The parts by weight relate to parts of space like the kilogram to the liter.

example 1

To a mixture of 1320 parts of dimethyl phosphite and 1368 parts of glycolamol, 150 parts of a 30% sodium methylate solution are added dropwise with stirring at 70 to 80 ° C. After about 50 parts of the sodium methylate solution have been added, the addition reaction begins. The temperature can be regulated with a cooling bath. The reaction mixture is ^{heated at 70 °} C. for 40 minutes and then cooled to room temperature, the product crystallizing. 2500 parts are obtained. This corresponds to a yield of 93 % of theory. The melting point of the product recrystallized from acetone / methanol is 126 to 128 ° C.

H, C0. 0 0 s

^ P-CH ₂ CH ₂ CONHCH ₂ OCH ₂ CH ₂ OCH ₂ CH ₂ -P ₂ HNCOCH

C ₁₄ H ₃₀ N ₂ O ₁₀ P ₂ C. 5 MG = 448 N 8 % O 7 % P. 7 % Analysis: 37, 5 H 5, 2 % - 13, 82: found 37, % 6.9 % 6, 37, 13, ber. % 6.7 % Example 2

In a stirred apparatus, the mixture of 724 parts, 2-Carbamoyläthan-phosphorsäuredimethylester, 300 parts of formaldehyde solution 40 # and βθ parts 25 $ aqueous sodium hydroxide solution heated for two hours under stirring at 50 ⁰ C. The reaction mixture is then evaporated to about 870 parts under reduced pressure. The syrupy residue is mixed with 124 parts of ethylene glycol and 20 parts

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len phthalic acid are added and the mixture is heated at 50 ° C. for 3 hours. After the mixture has been neutralized with sodium hydroxide solution, it is cooled to room temperature. After standing for one day, the reaction product crystallizes. Crude yield: 790 g = 88 % of theory. The crude product can be recrystallized from a mixture of acetone with methanol. The data of the paper chromatogram and the mixed melting point agree with the product prepared according to Example 1.

Example 3

2 pp

P-CH ₀ CH ₀ CONH-CH ₀ -OCH ₀ CHO-CH ₀ -HNCOCH ₀ CH ₀ P

d. d. d. d \ d. d. egg

CH ₃ O CH,

905 parts Carbamoyläthanphosphansäuredimethylester (5 moles), 575 parts of 40 $ strength Pormaldehydlösung and 10 parts of a lO ^ strength sodium hydroxide solution are heated in a stirred apparatus for 3 hours at 50 ⁰ C. After 1βθ parts of water have been evaporated off under reduced pressure, 190 parts of 1,2-propylene glycol and 14 parts of 45% sulfuric acid are added. The reaction mixture is heated at 60 ° C. for k hours. The water of reaction formed is then distilled off under reduced pressure. This is followed by neutralization with dilute sodium hydroxide solution at room temperature. After standing for one day, the reaction product crystallizes. 900 parts = 78 % of theory are obtained.

Example 4

-CH ₂ CH ₂ CO NH-CH ₂ -0 (CH ₂ ) _{il •} O-CH _{2 -HNCOCH 2} CH ₂ -P

CH, 0

In a stirred apparatus, the mixture of 1055 parts of N-Methylolcarbamoyläthanphosphonsäuredimethylester, 225 parts is 1,4-butanediol and 25 parts of phthalic acid is heated for 3 hours at ⁰ C to 65 βθ. After neutralization with sodium hydroxide solution, the reaction product crystallizes out after standing for a short time at the room temperature. 860 parts = 72 % of theory were obtained.

2 O 9 8 A 1/1 1 6 1 bad or! G «mÄ? "

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Example 5

25 parts of a 30 $ strength methanolic sodium methylate solution are added dropwise with stirring at 80 bis 90 ⁰ C to a mixture of 228 parts and 276 parts Glykolamol diethyl phosphite. admitted. The reaction temperature of 85 ° C can be regulated by cooling. The mixture is then heated at 80 ° C. for a further 1 hour. 475 parts are obtained. Yield: 94 % of theory.

H ₅ C ₂ O '

CH ₂ NHCOCH ₂ CH ₂ -

^c l8 ^H 38 ^N 2 ° 10 ^P 2 ^MW = 504

Analysis: CHN found 42.4 % 7.2 % 5.15 %

calc. 42.8 % 7.5 % 5.56 %.

Example 6

300 parts of the compound of the formula below

^ -CH ₂ CH ₂ CONH-CH ₂ -OCH ₂ CH ₂ O-Ch ₂ -HNCOCH ₂ CH ₂ P:

CH, 0 OCH,

and 15 parts of monoammonophosphate are made up to one liter with water. Cotton twill with a weight per square meter of 170 g is treated with this solution on a padder at room temperature in such a way that a liquor pick-up of 100 % results. It is then dried at 100 ^° C. The dry fabric is then subjected to a treatment at 165 ^° C. for 5 minutes. After 24 hours of storage in a normal climate, a fiber add-on of flame retardant of $ 21, based on the dry weight of the textile goods, is determined. Is then treated with an aqueous solution of soda # 0.2 for two minutes at 70 ⁰ C. After rinsing and acid washing with diluted acetic acid and neutral rinsing is dried. The finished and treated cotton fabric is flame retardant.

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The test according to DIN 53 906 provides the following result:

- ■ untreated
deltes
tissue tissue
after
Soda laundry tissue
Laundry,
House shark
1 h according to Mascn
95 ° C, 1.5
tswaschmit
5 h in cooking
g / l
tel +)
7 h. Test duration
(lake) 6th 6th 6th 6th 6th Burn time
(lake) 21st 0 0 0 0 Glow duration
(lake) 65 0 0 0 0 Tear length
(mm)
at 50 g Be
burden durenge
burns 80 98 99 114

+) Commercially available household detergents, e.g. B. the agent known under the brand name ®DIXAN from Procter & Gamble
® reg. trademark

Example 7

A cotton twill with a m ² weight of 170 g is in an aqueous liquor containing 325 parts of the following compound

k °

P-CHgCHgCON-CHg-OCHgCHgO-CHg-HNCOCHgCHg-P:

CHgOH

-OH

and 17 parts of monoammonophosphate per liter of solution, treated on a padder so that a liquor pick-up of about 90 % results. The fabric is ^{dried at 110 °} C. and treated in a tenter ^{at 165 ° C. for 5 minutes.} The fiber application, based on the dry weight of the textile material, is 22 % after storage for 24 hours in a normal climate. Then it is washed with a 0.2 $ strength soda solution for 2 minutes at 70 ^° C. After the neutral rinsing, drying is carried out again.

The fabric finished in this way is flame-retardant in accordance with DIN 53 906.

0 9 8 41/1161

O.Z. 27 417

untreated
deltes
tissue tissue
after
Soda laundry tissue
Laundry,
1 h after Masch
95 ° C, 1.5
5 h in cooking
g / 1 Dixan
7 h Test duration
(sec) 6th β 6 ' 6th 6th Burn time
(sec) 21st 0 0 0 1 Glow duration
(sec) 65 0 0 0 0 Tear length
(mm) at 50 g
load by
burned 75 102 110 118

Example 8

350 parts of the compound with the formula

CH ^ O,

0 ti

CH ₂ CON-CH ₂ -OCH ₂ Ch ₂ O-CH ₂ - ^ - COCH ₂ CH ₂ P.

CH ₂ OH

CH ₂ OH

OCH.

OCH,

and 18 parts of monoammonophosphate are dissolved in water and made up to one liter of solution. With this solution, cotton poplin fabric, which has been washed thoroughly after dyeing and is absorbent, is treated on a padder at room temperature in such a way that a liquor pick-up of 80 % results. The weight per square meter of the cotton poplin is 350 g. Is then dried at 100 ° C and includes a heat-setting (5 minutes, 165 ⁰ C, tenter) to. The fiber application, based on the dry weight of the textile material, is 23 % after "air conditioning" for 24 hours. After treatment with an aqueous 0.2 # sodium carbonate solution (2 minutes, 70 ° C., washing machine), it is washed neutral and dried.

According to DIN 53 906 the following values result:

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Ό.Ζ. 27 417

untreated
deltes
tissue tissue
after
Soda laundry tissue
Laundry,
1 h after Masch
95 ° C, 1.5
5 h in cooking
g / 1 Dixan
7 h Test duration
(sec) 10. 10 10 10 10 Burn time
(sec) 35 0 0 0 0 Glow duration
(sec) 75 0 0 0 0 Tear length
(mm) at 50 g
load by
burned 60 65 80 81

Example 9

320 parts of the compound

t!

: P-CH,

OCE

are dissolved in about 500 parts of water. Add 20 parts of 85% phosphoric acid, stir well and make up to one liter. Cotton twill weighing 170 g per square meter is impregnated with this solution on a padder so that a liquor pick-up of 100 % results. Then it is dried at 100 ° C. The dry fabric is then subjected to a treatment at 150 ^° C. for 4 minutes. After storage for 2 hours in a normal climate, a fiber add-on of flame retardant of 22 based on the dry weight of the textile material was determined. It is then treated with an aqueous 0.4 # soda solution for 2 minutes at 70 ° C. Rinse neutral and dry again. After "air conditioning", the following values are found in accordance with DIN 53 906;

2 0 9 8 Λ 1/1 1S1

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O.Z. 27 417

untreated
deltes
tissue tissue
after
Soda laundry tissue
Laundry,
1 h after Masch
95 ° C, 1.5
5 h in cooking
g / 1 Dixan
7 h Test duration
(sec) 6th 6th 6th 6th 6 ' Burn time
(sec) 21st 0 0 0 0 Glow duration
(sec) 65 0 0 0 0 Tear length
(mm) at 50 g
load by
burned 80 110 120 128

209841/1 161

Claims (1)

Claims 1. Compounds of formula I in the A the remainder of an n-valent alcohol, η a whole Number from 2 to 6 and B is a radical of the formula II -CH ₀ -NC-CH ₀ -P 1 <2
in which R and R are alkyl radicals with 1 to 4 carbon atoms or a common alkylene radical with 2 to 3 carbon atoms, r5 is a hydrogen atom or an alkyl radical with 1 to 3 carbon atoms, R is a hydrogen atom, an alkyl radical with 1 to 2 carbon atoms, a methylol group or an alkoxymethyl ! group with 1 to 4 carbon atoms. 2. Compounds of formula I according to claim 1, in which A denotes Remainder of a dihydric alcohol, η thus the number 2 and B 1 2 denotes a radical of the formula II in which R and R denote identical alkyl radicals with one or two carbon atoms, B denotes hydrogen and R denotes a hydrogen atom, a methyl group or a methylol group. 3. CH, 0. i? -C-CH ₂ CH ₂ -C-CH ₂ -HNCo-CH ₂ -P- ^ ^0CH 3 4. C ₂ H ₅ O ί? ί? / ^0C 2 ^H 5 C ₂ H ₅ O OC ₂ H ₅ 5. CH ^ O 0 0 ^ -P-CH ₂ Ch-CONH-CH ₂ -OCH ₂ CH ₂ O-CH ₂ -HNCO-CH-CH ₂ -P ^ CH ₃ CH ₃ β. CH ₃ O 0 '0 .0CH ₃ ^> P-CH CH CONH-CH ₀ O-CH-CH ₀ -O-CH ₀ -HNCO-Ch ₀ CH ₀ -PQ CH, 0 ^ ^{22 2} ' ^{2 2 22} ^ 0CH, 3 OH ₃ ^ 2098-1 / 1161 "" ¹⁹ ~ - 19 - O.Z. 27 417 7. OH-O. O 'o 8. Process for the preparation of compounds according to Claims 1 to 7, characterized in that compounds of the formula R ¹ O. S
₂ "> PH III, unsaturated acid amides of the formula HR ⁴ H-C = C-CO-NH IV, r3
Formaldehyde and compounds of the formula A (H) _n V, can act on one another in a stoichiometric ratio in any order, with in the formulas III to V 1 2 "5 4
A, R, R, R, R and η di < according to claim 1 have. 1 2 "5 A, R, R, R, R ^ and η are the meanings of formulas I and II 9 · Use of compounds according to claims 1 to 7 Flame retardant finishing of cellulosic textiles. Badische Anilin- & Soda-Fabrik AG 209841/11