DE2505326A1 - FLAME RESISTANT REGENERATED CELLULOSE - Google Patents

Description

SANDOZ PATENT GMBtI Case 150-3581

7850 Loerrach '_

Regenerated cellulose with a flair-proof finish.

The present invention relates to those with a non-fluffy finish regenerated cellulose, which is characterized / that it is a flame-retardant compound those of the formula

R ^Y R 3 ^ """1 ^J ^ N - P ^X (I)

X R

contains,

where Y is O or S,

^R 3

R ₁ and R ₀ independently of one another -N _v , where

Ra when Y = S, R and R together

also the remainder of the formula -OCH CH Z -OCH ₂ ^ ^ ^CH 2 ^Z '

509834/0968

- λ - Case 150-3581

R independently of one another are hydrogen, methyl or ethyl and if Y = S and R = alkyl, R- also propyl or butyl,

R ₄ cyclohexyl, benzyl, a phenyl radical which is optionally substituted by a bromine atom, 1-3 chlorine atoms and / or 1-3 alkyl or alkoxy radicals with a maximum of 4 carbon atoms, the individual alkyl or alkoxy radical having a maximum of 4 carbon atoms , is substituted, and bears at most 3 substituents, where, when Y = S, R is also an alkyl radical with 1-12 C atoms, or

R. together with the at the same nitrogen atom bonded radical R-, optionally with a further heteroatom to a 5- or 6-membered, saturated heterocyclic ring is connected,

Z is hydrogen, methyl, ethyl or propyl, X is a radical of the formula

r, ' ⁶ * / ^R l
R. or ~ Κ _ς -Ν - P. ^x

^{4 X} R

R ₁ . an alkylene radical with 2-10 carbon atoms, a

Phenylene ring and when R _{ß is} present, R, and R_ hydrogen, or

D j

R ₁ . together with the two neighboring -NR

and -NR _fi groups are a divalent residue of the

Piper azins, - mean.

The present invention also relates to a method for the production of flame retardant regenerated

509834/0968

- 3 - - .. Case 150-3581

Cellulose, which is characterized in that one this precipitates from a solution containing a compound of the above formula (I).

Flame-resistant regenerated cellulose is preferred, which is characterized in that this is a flame-retardant compound of the formula

0 R ¹ • R ¹ (Ia) N - P ^ X ¹ contains where Y or s, from each other -N
, RV ₁ and R ' ₂ ^RI 4 R ¹ 1 ^{and RI} 2
whereby, independent
if Y = S Remainder of the formula together also the

C-CH _n CH

₂ CH ₃

R 'is hydrogen or methyl, where if

Y = S and R- ¹ - = alkyl, R ¹ also ethyl or propyl,

R 'is a phenyl radical, which is optionally by

a, bromine atom in para position _; 1 or 2 chlorine atoms and at most one of them is in the ortho position, and / or an alkyl radical is substituted with 1 or 2 carbon atoms and bears at most 2 substituents, and if Y = S, R ¹ also has an alkyl radical 1-6 carbon atoms or cyclohexyl.,

509834/0 968

Csse 150-3581

χ ·

a remainder of the formula

R 'or

R'-N

R 'is a straight-chain alkylene radical with 2-6

Carbon atoms, a 1,4-phenylene radical, and if

R- is present, b

R ^ and R 'hydrogen or

R 'together with the two adjacent NR ¹ and NR groups represent a divalent radical of piperazine.

If a compound of the formula (I) in which Y is oxygen is used, it is flame-resistant, regenerated cellulose is preferred, which is characterized in that it is used as a flame-proofing compound one of the formula

contains, where R "

R ".

R ", X"

O NH - R "

.N -

(Ib)

NH - R "

a phenyl radical which is optionally substituted by 1 or 2 chlorine atoms, of which at most one is in the ortho position, hydrogen,

509834/0968

- b - Case 150-3581

X "is a remainder of the formulas

R ". Or -R" -N-P 4 5

R 'O NH-R ". I ⁶ II / ⁴

NH-R ". 4

where R "together with the two neighboring ones NR "- and NR 'a divalent residue ob

of piperazine,

mean.

If Y is oxygen, then regenerated cellulose with a flame-retardant finish is preferred, which as a result is characterized in that this is a compound of the formula

P (NH - R "' ₄ ) ₃ (Ic)

contains, '

where R "'is an ortho-, meta- or para-chloropheny1-

rest

means.

If Y in the compound of the formula (I) is sulfur, regenerated cellulose with a flame-retardant finish is preferred, which is characterized in that this is a compound of the formula

(Iaa)

contains,,

s 3a

wherein R ¹ and R 'are a radical of the formula -IT

xa za. R '

or together the remainder of the formula 4a

R ¹ 3a S. \ R ¹ la J - ρ χ · a R ¹ 2a

50983A / 0968

- 6 - ■ Case 150-3581

_x / ^CH 3

₂ CH ₃

R 'hydrogen, methyl, where, when R' is methyl or ethyl, R "is also ethyl,

ό 3.

R ¹ methyl, ethyl, a phenyl radical, the given

if by 1 or 2 chlorine atoms, of which

at most one is in the ortho position and / or is substituted by a methyl radical and bears at most 2 substituents, X ^{1 is} a radical of the formulas

et

R. S.R '

, 6a "■ / la.

^R 4a ^or -R'n - ^{N p} v

* ^a 5a \

^Bl 2a

R '1,2-ethylene and

DE

R_ hydrogen or
6a

R 'together with the two neighboring NR ¹ 5a 3a

and NR - groups are a divalent radical oa

of piperazine,
mean.

Flame-resistant regenerated cellulose is preferred, which is characterized in that it a flame retardant compound of the formula

P (NH - R ' _4b ) ₃ (lab)

contains,

wherein R ' _{4h is} a phenyl radical which is optionally replaced by 1 or 2 chlorine atoms, of which at most one is in the ortho position or one

509834/0968

~ 7 - Case 150-3581

Methyl radical is substituted,

means. ·

In the above formulas, R, R ₀ , R and X preferably and independently of one another denote R'-w R ¹ ₂ * ^R 'o or X ¹ . .

For compounds in which Y is oxygen, R, RV mean R, R ¹ , R, R 'and X, X ¹ preferably and independently of one another R ", R" ₂ , R " ₃ and X", respectively. R ₁ , R ^, R ¹ ^, R _37, R ' ₂ , R " ₂ , -N {R ₃ ) X _/ -N (R ^I ₃ ) X ^I and -N (R" ₃ ) X "preferably mean and independently of each other -NH-R ¹ "..

For compounds in which Y is sulfur, R .., R'- ,, R, R ¹ , R, R 'and X, X ^{1 are} preferably and independently of one another ^R ' _la ' ^R ' _2a ' ^R * 3a ^{and X} ' a " ^R l ^{r R} 'l' ^R 'l' .R ₂ , R ' ₂ , R' _2a , -N (R ₃ ) X, -N (R ' ₃ ) X · and -N (R ¹ ^ X ¹ _& preferably and independently of one another denote -NH-R '...

As alkyl radicals, unless otherwise specified ' is, naturally occurring or synthesizable primary, secondary or tertiary, straight-chain or branched in question:

Examples of such primary radicals are methyl, ethyl, Propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, ündecyl, dodecyl, preferably methyl, ethyl, propyl, Butyl.

Examples of alkylene radicals are 1,2 ethylene, 1,3-propylene, tetramethylene, hexamethylene, preferably 1 _f 2-ethylene and hexamethylene. -

Examples of substituted phenyl radicals are 2-, 3- or 4-methylphenyl / 2-, 3- or 4-chlorophenyl1, 3- or 4-bromophenyl, 2,3-, 2,4-, 2,5-, 3,4- or 3,5-dichlorophenyl, 2,4,5-trichlorophenyl, 2,3-, 2,4-, 2,5-, " 2,6-, 3,4-, 3,5-dimethylphenyl, 2,4,5-, 2,4,6-tri-

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- 8 - Case 150-3581

methylphenyl, 2-methyl-4-bromophenyl, 3-methyl-4-bromophenyl, 2-chloro-6-methylphenyl, 3-chloro-2-methylphenyl, 4-chloro-2-methyl-phenyl, 5-chloro-2-methyl-phenyl, 2-, 4-ethylphenyl, 2,4-diaethylphenyl, 2-, 3-, 4-methoxyphenyl, 3-chloro-4-methoxyphenyl, 3-chloro-6-methoxyphenyl, preferably phenyl, 2-methylphenyl, 4-chlorophenyl, 2-chlorophenyl, 3,4- and 2,5-dichlorophenyl. For the radical -N (R) R, the radicals mentioned come for R. in question, where when R. is phenyl or substituted phenyl, R preferably denotes hydrogen. The substitution of the phenyl ring by. Bromine is preferably in the para position.

Examples of heterocyclic rings which correspond to the formula -N (R) R are the piperidino and morpholino rings.

Suitable compounds of the formula (I) include those compounds which are cited in the further cited References are listed.

The conditions for the preparation of the compounds of the formula (I) are not critical.

If Y is oxygen, the procedure is as described in Houben Weyl, Methods of Organic Chemistry, 4th Edition, Volume 12/11, pages 465-475. The compounds in which R and R _{0 have} the meaning -NC ₀ "^

J- * 4

and Y = O can be, for example, by reacting phosphorus oxychloride with a primary or secondary amine in the presence of an acid-binding agent and optionally in the presence of an inert solvent produce. A corresponding excess of that which takes part in the reaction can be used as the acid-binding agent Amine and / or a tertiary amine such as pyridine can be used. Inert solvents are e.g. benzene,

509834/0968

- - δ - Case 150-358I

Toluene, chlorobenzene and dichlorobenzene / tetrahydrofuran, ■ Diethyl ether. Analogous examples for the production specific compounds are further in the literature, described e.g. in reports of the German chemical Gesellschaft, Volume '28, pages 619-620 (1895) and in Liebig's Annalen der Chemie Volume 326, pages. 251-252 (1903). For example, connections no. 2, 3, 4, 6,7, 8a and 8b, Table 1 according to this scheme. According to the method described in Industrial, and Engineering Chemistry, Process Research and Development Volume 13 Number 1, pages 85-86. (1974) e.g. the connections in the table; 1 No.- 1, 5 and 9 produce.

In some cases it is advantageous to first use phosphorus trichloride in the presence of an acid-binding agent and an inert solvent with one, preferably secondary to implement amine. As. acid-binding agent is used here advantageously a corresponding one Excess of the amine to be reacted. The phosphorous acid triamide obtained then becomes phosphoric acid triamide oxidized. Examples of this method of production can be found, for example, in Zh. obshch.Khim. Volume 43, No. 9, Pages 1900-1903 (1973) or in Journal of the Chemical Society, London, page 4682 (1957).

In this way, Compound No. 8 becomes Table 1 manufactured. In the case of asymmetrical phosphoric acid triamides, the reaction of an amine or amine hydrochloride is used with phosphorus oxychloride first the phosphoric acid

RO monoamide dichloride of the formula 3- ^ » or that

R ₄ - " ^C1 2

Phosphoric acid diamide monochloride of the formula

509834/0 96

- iü -

Case 150-3581

which you can then use with a second amine in Presence of an acid-binding agent to the asymmetric Phosphoric triamide converts. Find examples of this in Liebig's Annalen der-Chemie, Volume 326, pages 129-256 (1903) in reports of the German chemical society 22, pages 2572 - 2579 (1894) and ibid- 2J3, Pages 613 - 620 (1895), as well as in Zh. obshch. Khim. Volume 30, page 3584 (1960). This is how the connections Manufacture No. 10 to 17 of Tables 2 and 3.

50983A / 0968

Case 150-3581

Tabel

P = O sym. Triamide

M.p. ⁰ C

((O) -NHf ₃ P = O

^CH

P = O

((O) -NHf P = O ³

NHf ₃ P = O

Cl
((O) -NHf ₃ P = O

Cl

P = O

0
Cl

Cl

(Cl - / C ^ -NHf P = O

Cl

CH

214-6

242-3

225-6

238-40

239-41

257-9

302-4

136-8

509834/0968

~ 12 Case 150-3581

Table 1 (continued)

Continuation table

No. (Cl- ■ p P = O O M.p. ⁰ C 8a Cl 205-6 (Br - © κ P = 8b 261-2 -NH K - NH H

No. M.p. ⁰ C

((U) - NHJ- P = O 252-4

Tabel

R-

- N

/ 3

unsymm. Triamide

M.p. ⁰ C

0 CH ₃

(<O> -NH> - P -

P -

0 CH ₃ P - Ν— <

509834/0968 191-2

212-3

219-20

Case 15Q-35S1

Tabel

• \ \ Ii N-4- P

I 6 N 6 n // 3

N - P4-N

4/2

Srap .: ⁰ C

O

P-NH-CH ₂ -CH ₂ -NH-P f 238-9

Ii

P -

Il

P f

Cl

-NJI-

S P

Cl

P -

(O) - Cl)

CH_ O O CH_

._ t 3 "^ - ^ ii ι 3_.

(<g) -N - * - P - NN - P-fN- @) 294-5

301-2

294-G

175-6

509834/0968

- 14 - Case 150-3581

The preparation of the compounds of formula (I) in which Y is sulfur takes place according to known Verfahrenr as for example in Houben-Weyl, Methoden der organischen Chemie, 4th edition, Volume 12/11, pages 759-769 and 785-791 is described. .

For example, the connections in which R .. and R " together have the meaning, and where Z is the

-OCH ₀ CH.Z.
2 ^ _c / 2-

has the above meaning, by producing 2-chloro -2-thiono-5,5-dialkyl-1,3,2-dioxaphosphorinane

OCH ^ CH Z
Cl- P ^ ^ C ^l

in the presence of an acid-binding agent and in many cases preferably in the presence of an inert solvent, with a primary or secondary amine or diamine. A corresponding excess of the amine to be reacted can be used as the acid-binding agent, or a tertiary amine such as pyridine or triethylamine. Benzene, toluene, tetrahydrofuran or diethyl ether, for example, can be used as inert solvents. Examples of such a method of preparation are described in the literature, for example in Tetrahedron, Volume 20, pages 2781-2795 (1964). For example, the compounds 18, 19, 20, 21, 25, 26, 27, 28, 29 and 30 of Table 4 can be prepared according to this scheme.

In some cases it is advantageous to first use 2-chloro- 5 , 5-dialkyl-l , 3 , 2-dioxaphosphorinane,

509834/0988

- 15 Case 150-3581

Supreme Court
Cl - P ^

OCH _{3 2}

in the presence of an acid-binding agent and in many Cases preferably in the presence of an inert solvent with a primary or secondary amine to re- * to bring action, and then to add sulfur to the intermediate stage obtained. An example of this The method of preparation can be found in Tetrahedron, Volume 23, page 1703 (1967). For example, the connections 22, 23, 24, 26 and 43 of Table 4 according to this scheme

produce. »Ρ

The compounds in which R and R mean -N

and Y = S can be prepared, for example, by reacting thiophosphoryl chloride (PSCl) with a primary or secondary amine in the presence of an acid-binding agent and, in many cases, advantageously in the presence of an inert solvent. Examples of this method of preparation can be found in the literature, for example in the Journal of Organic Chemistry, Volume 24, page 1420 (1959) or in Liebig ¹ s Annalen der Chemie, Volume 326, pages 201-219 (1903). For example, the compounds 31, 32, 34, 35, 36, 37, 38, 41 and 44 of Table 4 can be prepared according to this scheme. In some cases it is again advantageous to first react phosphorus trichloride in the presence of an acid-binding agent and an inert solvent with a preferably secondary amine, and then to add sulfur to the intermediate stage obtained. A corresponding excess of the amine to be reacted is advantageously used as the acid-binding agent.

509834/0968

- 16 - .: Case 150-3581

Examples of this method of preparation can be found, for example, in the chemical reports, volume 28, pages 2205-2211 (1895) or in the Journal of the American Chemical Society, volume 78, pages 976-977 (1956). For example, the compounds 39 and 40 can be prepared according to this scheme. In still other cases it is advantageous to use appropriate amounts of phosphorus pentasulphide, ^p _? ^s c / and amine to react. Using this method, which is described in the Journal of the American Chemical Society, Volume 70, pages 744-746 (1948), the compound 33 of Table 4, for example, can be prepared.

Mixed thiophosphoric acid triamides are prepared by reacting an amine or amine hydrochloride with thiophosphoryl chloride initially thiophosphoric acid monoamide dichloride or thiophosphoric acid diamide chloride, which then with a second Amih in the presence an acid-binding agent to the mixed thiophosphoric acid tri amide. Examples of this method Liebig's Annalen der Chemie, volume 326, pages 201-258 (1903) and volume 625, pages 92 (1959) can be found. For example, compound 42 of Table 4 can be produced according to this scheme.

509834/0968

Case 150-35 31 '

Table 4

Connection no, structure

Melting point (m.p.

or

Boiling point (bp)

CH.

CH.

CH "NH- <O)

CH / CH O _x

/ C ^ P - NH - ^) - Cl

CH CH ₂ O «

CH.

CH

CH.

CH CH

; cC - NH- (OV Cl
Cl

CH

CH ₂ O - NH - <O)
Cl

CH_ .CH ₀ O

³ > C

CH m.p. 163-166 '

M.p. 185-188 "

M.p. 156-159 '

M.p. 134-138 '

M.p. 94-96 °

M.p. 85-88 °

57-60 °

509834/0968

Case 15U-3581

Table 4 (continued)

Connection no.

Structure melting point or boiling point

CH CH

/ CC /

CH CH ₂ CT

- CH

CH

P - NH - η - CH

P - NH - η - CH ⁶

CH

. CH-

CH

CH

° S

-NH-

CH CH

P-NH-n-CH

CH CH CH CHO ⁷ J

CH

CH. CH-O

ρ nIi P

“J, 0CH

S = P (NH- (O)) m.p. 69-7.0 °

Bp 121-123 ° / E, 08 mm Hg

Bp 125-126 ° / 0.05 mm Hg

Bp 193-195 ° / 0.19 mm Hg

Sdp.

mm Hg

M.p. 303-305 '

M.p. 152-154 ^<

50983 % / 0968

Case 150-3581

Table 4 (continued )

Compound No. Structure Melting point or boiling point

S = P (NH - (H))

S = P

S = P (NH- ^ 5)) Cl

= P (NH- (O) - Cl) Cl

S = P (NH- (O) - CH ₃ )

(NH- (O))

S = P (NH- (OVBr)

= P [N m.p. 140-143 '

M.p. 225-226 °

M.p. 12 8-130 '

M.p. 171-174 '

M.p. 185-187 °

M.p. 131-133 '

M.p. 216-217 '

Bp 104 ° / 0.04 mm Hg

138-140 ° / 0.15 mm Hc

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20 -: '·: ";' 'Case 150-3561

Table 4 (continued)

Connection no.

structure

Melting point

or boiling point

S = P (NH - η - C ^ H

6 "13 ' 3

(CH,) _O N - P

CH CHO

^CH

Cl

- NHHto) Cl

Cl

S = P- i

Cl

M.p. 51-51 / 5 '

M.p. 211-212 '

M.p. 170-172 '

M.p. 142-144 '

For the method according to the invention, first Cellulose brought into solution in a manner known per se, e.g. converted into a soluble derivative, for example with tetramine copper (II) hydroxide or according to the xanthate method.

A compound of the formula (I) is added to the cellulose solution thus prepared. The addition can be carried out continuously or discontinuously directly by vigorous stirring of the cellulose solution. But it is also the compounds of formula (I) is first finely disperse them in water and add it as an aqueous dispersion of the cellulose solution. In all cases it can be advantageous to use conventional dispersion stabilizers and

509834/0968

- 21 - Case '150-3531

Add dispersants. But you can also use the flame retardant compounds in a suitable solvent dissolve and admit. The technically important properties of the precipitated regenerated cellulose are apart from the flame retardancy, only insignificantly influenced by the addition of the reaction products. Based on the α-cellulose, for example 5 to 35 percent by weight thereof can be distributed in the cellulose solution. Amounts of 12-25 percent by weight are preferably used. From the cellulose solution that these reaction products contains, the regenerated cellulose is precipitated in a known manner with shaping. as shaping measure comes mainly from the formation of Threads and foils by introducing the cellulose solution into a precipitation bath, using fine nozzles or Slitting, into consideration. You can use the usual in the production of cellulose regenerated threads or films Use felling baths. The flame-retardant reaction products contained in the cellulose solution are largely in the precipitated regenerated cellulose material locked in. In addition to a compound of the formula (I), it is also possible to use other flame-retardant compounds Substances to use. Such compounds are, for example, reaction products of a phosphonitrile chloride with glycols, e.g. Neopentyl glycol or analogous compounds, such as those described, for example, in DOS .2'316'959 are, or cyclodiphosphazanes or thionocyclodiphosphazanes of the general formula

Y
R ₉ -PNR ₈

509834/0968

- 22 - Case 150-3581

where Y is oxygen or sulfur,

R ₀ cyclohexyl, a phenyl radical, the giveno

if by 1-3 chlorine atoms, 1 'bromine atom in the para position and / or 1-3 alkyl or alkoxy radicals with 1 - 4 carbon atoms each with a maximum of 4 carbon atoms and the phenyl radical has a maximum of 3 substituents, or if Y = sulfur , also methyl, Rq is a radical of the formula -NR ₀

Xl

R is hydrogen or an alkyl radical with 1-4 Carbon atoms,

R is an alkyl radical with 1 - 12 carbon atoms, cyclohexyl, a phenyl radical, optionally by 1-3 chlorine atoms, 1 bromine atom in the para position and / or 1-3 alkyl or alkoxy radicals each having 1 - 4 carbon atoms with together a maximum of 4 carbon atoms is substituted and the phenyl radical has a maximum of 3 substituents, or

R. _n and R, - together with the common nitrogen atom, optionally with a further hetero atom, form a saturated 5- or 6-membered heterocyclic ring,

where, if Y is simultaneously oxygen, R - is hydrogen and R _{0 is} phenyl or substituted

——— Q

Phenyl, R ₁₁ only an optionally substituted phenyl radical

mean, like those in Switzerland. Patent Application No. 15814/73 are described.

The proportion of these additional components can vary within wide limits and can be up to 90% of the total

509834/0968

- 23 - Case 150-3581

amount of the flame retardant composition present, It is preferable to use 10-70%, in particular 15-60% of the reaction product between Phosphonii.tr ilchlorid and glycol or a cyclodiphosphazane or thionocyclodiphosphazane based on the total amount the present flame retardant combination, the latter corresponds to the quantities already given above.

In the following examples the parts mean weight r parts, the percentages percentages by weight. ,

Manufacture of flame retardant regenerated Cellulose

Example 1 -

In 200 parts of a xanthate-based cellulose solution, which contains 18 parts of α-cellulose, 18 parts of a 20% aqueous dispersion of the flame retardant Active ingredient No. 5 Table 1 stirred in. Such a dispersion is made in the following way: 15 parts of compound no. 5 are made with 3.75 parts a dispersant based on sodium naphthalene, sulfonate and 56.25 parts of water in the presence of 75 parts of quartzite beads for 4 hours sand-milled, working with cooling with ice at a number of revolutions of 1500 revolutions per minute. After detaching of the quartzite beads by filtration, 67 parts of a dispersion containing 20% of active ingredient are obtained. The above cellulose solution described, provided with a flame-retardant active ingredient, is produced by a conventional spinning process pressed through nozzles into a precipitation bath, which contains the following substances per liter: '

125 g sulfuric acid, 240 g sodium sulfate (anhydrous)

509834/0968

- 24 '- ■' Case 150-3581

and 12 g zinc sulfate (anhydrous). The fiber obtained was sufficiently rewashed and made into knitted fabrics. The knitted fabrics were tested for their flame resistance by the method of Fenimore and Martin (cf. Modem Plastics, November 1966) by determining the oxygen limit value (LOI value).

In an analogous manner to prepare the flame-retardant regenerated cellulose, which contains as active ingredient the compound f lammwidrigeri Nos. 1, 2 _f 4, 6, 7, 8, 8a, 8b, 9, 14 or Tables 1-3 or a combination thereof .

Example 2

The procedure is as in Example 1, but used as a flame-retardant active ingredient the compound Nr. 33 of Table In an analogous manner to prepare the flame-retardant regenerated cellulose containing as active ingredient one or more of the compounds of formula no. 18, 19, 20 _# 21, 22, 30, 31, 32, 34, 35, 36, 37, 38, 42, 43 and 44 from Table 4.

example

In 200 parts of a xanthate-based cellulose solution containing 18 parts ^ -cellulose, 3.6 parts of the flairan-adverse active ingredient of the formula 39 are stirred into and the mixture is processed into knitted fabrics in a manner analogous to that in Example 1.

In an analogous manner, regenerated cellulose with a flame retardant finish / which contains the compounds of the formulas 26, 27, 28, 29 and 40 of the table as active ingredients is prepared .

509834/0968

- 25 -, ■:. ■ Case '150-3581

example

In 200 parts of a cellulose solution based on xanthate, which contain 18 parts of JL cellulose, there are 7.2 parts a 50% solution of the flame-retardant active ingredient of the formula 24 of Table 4 in trichlorethylene and the mixture is processed into knitted fabrics in the same way as described in Example 1. .

In an analogous manner, regenerated cellulose with a flame-retardant finish is prepared, which contains the compounds as active ingredients of the formulas 23, 25, 41 of Table 4, a 40-50% solution in dichloroethane being used.

Example 5

In 200 parts of a cellulose solution based on xanthate, which contains 18 parts of c'l-cellulose, are successively 9 parts of a 20% strength aqueous dispersion of the flame-retardant active ingredient No. 5 in Table 1 and 5.1 parts a 35% aqueous dispersion of the reaction product of oligomeric phosphonitrile chlorides and 2,2-Dimethylrl, 3-propanediol stirred in. The production of the dispersion of the flame-retardant active ingredient no. 5 is described in Example 1. The preparation of the dispersion the mixture of reaction products of oligomeric phosphonitrile chlorides and 2,2-dimethyl-propanediol happens in a manner known per se, e.g. as described in Example 4 of DOS 2,316,959. The procedure for the production and testing of the corresponding flame-resistant cellulose is analogous to the example

50983A / 0968

- 26 - Case 150-3581

Example 6

In 200 parts of a xanthate-based cellulose solution, which contain 18 parts, ^ .- cellulose, are sequentially 9 parts of a 20% strength aqueous dispersion of the flame-retardant active ingredient No. 5 in Table 1 and 9 parts a 20% aqueous dispersion of 2,4-dianilino-1,3-cyclodiphosphazane stirred in. The preparation of the dispersion of anti-flain agent no. 5 is in Example 1 described.

The dispersion of 2,4-dianilino-l _r 3-cyclodiphosphazane is prepared in a manner known per se. The procedure for the production and testing of the corresponding flame-resistant cellulose is analogous to the example

509834/0968

Claims (1)

- 27 - Case 150-3581 P aten tans check before {| l.) Flameproof regenerated cellulose, thereby marked / that this as a flame retardant compound one of the formula R, « ^ R ₁
XR ₂ contains, where YO or S, _o / 3. R and R ₀ independently of one another -N-, where R A if Y = S, R and R ₀ together ⁴ and the radical of the formula -OCH ₀ ^ CH ₀ Z
2 - ^ _c s- I R_ independently of one another hydrogen, methyl or AethyI _x and if Y = S and R. = alkyl, R also propyl or butyl , R. Cyclohexyl, benzyl, a phenyl radical, which optionally by a bromine atom, 1-3 chlorine atom and / or 1-3 alkyl or alkoxy radicals with a total of at most 4 carbon atoms, the individual alkyl or alkoxy radical has at most 4 carbon atoms, is substituted, and at most Bears 3 substituents, where, when Y- S-, "R. also an alkyl radical with 1-12 carbon atoms, or R together with the radical R bonded to the same nitrogen atom, optionally with one further heteroatom to form a 5- or 6-membered, saturated heterocyclic ring 509834/0968 - 28 - I Case 150-3531 connected is, Z is hydrogen, methyl, ethyl or propyl, X is a radical of the formula ^R fi ^Y / ^R l I O M / 1 R. or -R _c -N - P 4 5 ^R 2 R _{5 is} an alkyl radical with 2-10 carbon atoms, a phenylene ring and when R is present, R ,, and R_ hydrogen or ο j R _c together with the two neighboring -NR and -NR groups are a divalent radical of the piperazine
mean. 2. Flameproof regenerated cellulose according to claim 1, characterized in that this is a flame-retardant compound of the formula οι Υ pt ■> - p ' ^X (la) X ¹ ^ R « ₂ contains , where Y 0 or S _f R ¹ ^ and R ' ₂ independently of one another -N where, if Y = S, R 'and R' ^R ' ⁴ / ^RI 3 together also the rest of the formula ~ 0-CH _o CH ₀ 2/3 y \ f - -0-CH ₂ CH ₃ R ' _{3 is} hydrogen or methyl, where if ■ Y = S and R ' ₄ = alkyl, R' ₃ also ethyl or 509834/0968 - 29 - ^: ' ^: Case 150-35 & 1 Propyl, R ^{1 is} a phenyl radical which is optionally substituted by a bromine atom in the para position, 1 or 2 chlorine atoms and at most one of them is in the ortho position, and / or an alkyl radical with 1 or 2 carbon atoms and has a maximum of 2 substituents, and if Y = S, R * is also an alkyl radical with 1-6 carbon atoms or cyclohexyl X ^{1 is} a radical of the formula ^R α ^YR 'i I ^b H X ^L
R 'or -R ^! -N - P ^Xr1 2 R 'is a straight-chain alkylene radical with 2-6 Carbon atoms, a 1,4-phenylene radical, and if R * is present, R, and R 'hydrogen or " D j R ¹ together with the two adjacent NR ¹ and NR groups form a divalent radical of piperazine
mean. 3. Flameproof regenerated cellulose according to claims 1 and 2, characterized in that this as a flame-retardant compound is one of the formula R "0 NH-R ¹ '3" / 4 ^ N-P '- (Ib) X "NH-R ¹ ' 4 " contains,. · 509834/0968 Case 150-3581 where R " R ". X" a phenyl radical, which optionally by 1 or 2 chlorine atoms are substituted, of which at most one is in the ortho position, Hydrogen, a remainder of the formulas R 'O NH-R "ι 6" / R "or -R" -NP 4 ο \ NH-R ". 4 where R ¹ 'together with the two neighboring NR "- and Nr' are a divalent radical j D of piperazine, mean. 4. Flameproof regenerated cellulose according to the Claims 1-3, characterized in that this is a compound of the formula Il P (NH - R '" ₄ ) (Ic) contains, 'wherein'R "' is an ortho-, meta- or para-chlorophenyl- means. rest: ~ 509834/096 8 - 31 - Case 150-3581 5. Flameproof regenerated cellulose according to the Claims 1 and 2, characterized in that this is a compound of the formula R 'SR' 3a "/ la .. · - .. .N - P. (Iaa) ^X 'a ^XRI 2a contains, t> i s 3a wherein R ¹ , and R \ is a radical of the formula -N. , la 2a R ¹ or together the remainder of the formula 4a -O-CH- CH. CH ₃ R 'hydrogen, methyl where, when R ¹ , methyl, or ethyl, R' also ethyl, R 'methyl, ethyl is a phenyl radical, which optionally by 1 or 2 chlorine atoms of which at most one is in the ortho position and / or a methyl radical · is substituted, and carries a maximum of 2 substituents, ■ X ¹ Ct a rest of the formulas R. I.
la I 6a ^Rl 4a or ^R1 5a - ^N - 2 a R '1,2-ethylene and R_ hydrogen or
- 6a R 'together with the two adjacent NR ¹ _.- 5a 3a and NR groups a divalent radical oa ·. of piperazine,. mean. 50983 A / 0968 Case 150-3581 Flameproof regenerated cellulose according to the Claims 1, 2 and 5, characterized in that this is a flame-proofing compound of the formula P (NH-R ' _4b ) ₃ (lab) contains,
wherein R ¹ a phenyl radical, optionally by 1 or 2 chlorine atoms, v / o of itself at most one is in the ortho position or a methyl radical is substituted, means. 7. Flameproof regenerated cellulose according to claims 1-4, characterized in that this one compound of the formula 0 = P - ( HU- (Q) -Cl ) contains. 8. Flameproof regenerated cellulose according to claims 1-4, characterized in that this one compound of the formula Cl O = P -f NH- (OS) ο contains. 509834/0968 - 33 - i '«Case 150-3581 9. Flameproof regenerated cellulose according to claims 1 - 4, characterized in that this a compound of the formula O = P ~ f NH- (O) J ₃ CH ₃ contains. 10. Flameproof regenerated cellulose according to the Claims 1-4, characterized in that this one compound of the formula Cl o = ρ ~ t m-fijy ei) contains. 11. Flameproof regenerated cellulose according to claims 1, 2, 5 and 6, characterized in that that this is a compound of the formula S = P contains. 12. Flameproof regenerated cellulose according to claims 1, 2, 5 and 6, characterized in that that this is a compound of the formula Cl S = P (NH-ZoV- Cl) ,, contains. . ' 509834/0968 - 34 - Case 150-3581 13. Regenerated cellulose with a non-resistant finish, according to claims 1, 2, 5 and 6, characterized in that it is a compound of the formula S = P - £ Cl contains. 14. Flameproof regenerated cellulose, according to claims 1, 2, 5 and "6, characterized in that that this is a compound of the formula S = P -f NH- <O> - CH ₃ ) contains. 15. Flameproof regenerated cellulose, according to claims 1, 2, 5 and 6, characterized in that that this is a compound of the formula S = P (NH- <O>) ₃ contains. 16. Flameproof, regenerated cellulose according to claims 1-15, characterized in that this in addition to a compound of the formula (I) also 10-90%, preferably 10-70% and in particular 15-60% of a reaction product of phosphonitrile chloride and Neopentyl 509834/0968 - 35 - C-ise 150-3581 glycol, based on the total amount of contains flame retardant substance. 17. Flameproof, regenerated cellulose according to claims 1-15, characterized in that this in addition to a compound of the formula (I) also 10-90% _# preferably 10- * 70% and in particular 15-60% 2.4 Dianilino-1,3-cyclodiphosphazane, based on the total amount of flame-retardant substance present. 18. Flameproof, regenerated cellulose according to patent claims 1-17, characterized in that this contains 5-35 percent by weight of the flame-retardant compound, based on α-cellulose. 19. Flameproof, regenerated cellulose according to the Claims 1-17, characterized in that these 12-25 percent by weight of the flame retardant Compound, based on α-cellulose, contains. 20. Flameproof, regenerated xanthate cellulose according to claims 1-19. · 21. Process for the production of flame retardant, regenerated cellulose, characterized in that ■ -man this precipitates from a solution, which is a compound of formula (I) as a flame-retardant substance the claims 1-20 contains. 22. The method according to claim 21, characterized in that that one precipitates out of a solution, the 5-35 percent by weight of the flame retardant substance, based on 509834/0968 Case 15C-3581 α-cellulose / contains. 23. The method according to claim 21, characterized in that one precipitates from a solution that is 12-25 percent by weight the flame-proofing compound, based on α-cellulose. 24. The method according to claims 21-23, characterized in that one from a cellulose xanthate solution fails. SANDOZ-PATENT-GMBH 3700 / SI / VS 509834/0968