DE2404203A1 - PROCESS FOR THE PRODUCTION OF CONDENSED POLYMER PHOSPHAZEN AND THEIR USE FOR THE FLAME RESTORATION OF TEXTILE MATERIAL FROM REGENERATED CELLULOSE - Google Patents

Description

"Process for the production of condensed polymeric phosphazenes and their use for making textiles from regenerated cellulose flame resistant ^w

Priority: January 29, 1973, V.St.A., No. 327 301

The invention relates to a method for the production of condensed polymeric phosphazenes and their use for making textiles made of regenerated cellulose flame resistant.

For various areas of application of textile goods it is necessary Cellulose fiber ^! and reduced flammability yarns to manufacture. When producing rayon using the viscose method, the addition of various flame retardants is beneficial to viscose prior to the spinning process a number of problems arise due to the particular chemistry of the viscose process are conditional. The flame retardant must be stable and inert to the strongly alkaline viscose and also to the acidic regeneration bath into which the viscose is extruded. During spinning and further processing stages

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-The flame / agent must not be extracted for protection. Also may the added flame retardant does not interfere with the spinning process, e.g. by clogging the spinnerets.

From U.S. Patents 3,455,713, 3,505,087, and 3,532,526 It is known that rayon can be made permanently flame-resistant by using an essentially water-insoluble, liquid Phosphorus nitride polyesters dispersed in rayon. The known Flame retardants impair the properties of the rayon fiber not sustainable, and flame retardant is retained during the spinning process in such quantities that the Flame resistance of rayon is increased. However, there is a need for more effective flame retardants and for flame retardants that an improved retention capacity in the fiber during the spinning process and subsequent washing of the Have textile goods and the retention of sufficient flame resistance with a lower content of the flame retardant allow.

The object of the invention is therefore to create improved flame retardants for textiles made from regenerated cellulose, soft affect the physical properties of the finished textile material only slightly, even in small amounts effective, are sam and in this way reduce manufacturing costs. Of the The term textile material includes, inter alia, threads, fibers, yarns, knitted fabrics, woven fabrics and nonwoven material.

The invention relates to a process for the preparation of condensed polymeric phosphazenes, which is marked thereby

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1 net is that one

(a) one by a metal alkoxide and / or an alcohol with each 1 to 12 carbon atoms partially esterified phosphorus nitride chloride with

(B) a tertiary amine from the group of mono- or polynuclear heterocyclic aromatic amines, aliphatic amines of the general formula I.

R ₁ R ₂ R ₃ N (I)

in which R ₁ , R ₂ and R ^ are identical or different alkyl or alkenyl radicals with 1 to 10 carbon atoms,

aromatic amines or aralkylamines of the general formula II.

R ₄ R ₅ R ₆ N (II)

in which Rg is an aryl radical and R ₄ and Rc are identical or different alkyl and alkenyl radicals having 1 to 10 carbon atoms, the tertiary amine containing no active hydrogen atoms, at temperatures of at least 20 ^° C. being reacted.

In the process according to the invention, a condensed polymeric phosphazene ester of higher molecular weight and higher viscosity is obtained by reacting a partial ester of phosphorus nitride chloride with a tertiary amine, such as pyridine, at temperatures of at least 20 ^° C. with elimination of a chlorine-containing by-product. The phosphorus nitride chloride partial ester is obtained by reacting of phosphorus nitride chloride with a metal alkoxide or an alcohol, each having 1 to 12 carbon atoms.Suitable metal cations are, for example, sodium and potassium

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Tridchloride can consist of 100 percent of a linear polymer or 100 percent of a cyclic polymer or a mixture consist of linear and cyclic polymers. Generally the partial ester will contain from about 1 to 15 percent by weight, i.

1 to 15 parts by weight of chlorine, based on 100 parts by weight of the Partial esters, and preferably 3 to 10 percent by weight not converted chlorine, based on the weight of the partial ester.

The phosphorus nitride chloride polymers have the general formula III

(III)

in which η has a value of at least 3 and an integer up to can mean about 9 for cyclic polymers and up to about 15 to 20 or even more for linear polymers, which can have an average molecular weight of about 1,100 to 1,500. the partially chlorinated esters can be prepared by reacting these phosphorus nitride polymers with an alcohol or a metal alkoxide each having 1 to 12 carbon atoms contain. In this way, partially chlorinated esters can be produced, which are either cyclic or linear, and which have the general formula IV:

25 / X

(IV)

4 0 9 8 3 1/1111

_Γ 2 AU 4 2 03 -ι

in which η has the aforementioned meaning and X and Y are the same or represent different substituents and mean chlorine and -OR groups, in which R is an aliphatic, cycloaliphatic, means aromatic or heterocyclic hydrocarbon radical. The aliphatic radical can be straight or ver ~ be branched and contain 1 to 12 carbon atoms. Of the R group preferably denotes an alkyl or alkenyl group having 2 to 6 carbon atoms; is particularly preferred n-propyl group. The cycloaliphatic radicals have 4 to 6 carbon atoms and the aromatic radicals 6 to 10 carbon atoms. The radical R can be substituted by halogen atoms or amino groups or contain ether functions.

Two embodiments are available for carrying out the method according to the invention. In the first embodiment of the partial esters of phosphonitrilic chloride with a tertiary amine at temperatures of about 5O ⁰ C to 220 ⁰ C, preferably implemented in a range of about 50 ⁰ C to 150 ⁰ C. New condensed polymeric phosphazenes of increased molecular weight and increased viscosity are obtained. The duration of the reaction depends on the temperature and can be from a few minutes to 30 hours or more. After removing the tertiary amine and the chlorine-containing by-product, a viscous polymeric phosphazene remains, the viscosity of which generally allows pumping. According to the second embodiment, the partial ester can be prepared in situ by reacting a phosphorus _{nitride chloride with a C 1} -C ₁₂ -AlkOhOl in the presence of a tertiary amine and at temperatures of about 20 ° C to 150 ° C. In this way you get the new _j

U 0 3 S 3 1/1 1 1 1

condensed phosphazenes. The condensed phosphazenes prepared according to the invention are generally pumpable liquids of relatively high viscosity. Very highly viscous or semi-solid process products can be processed with solvents or with Lower molecular weight phosphazenes can be diluted to facilitate incorporation into the rayon.

The preparation of the partial ester can be carried out by reacting the Phosphorus nitride chloride with a metal alkoxide or an alcohol in the presence of an acid acceptor such as a tertiary amine or a carbonate such as sodium carbonate or potassium carbonate. During the esterification by adding the Phosphorus nitride chloride with stirring to form a solution or slurry of the metal alkoxide becomes a stoichiometric deficit of the alkoxide is used to produce the partial ester, which contains about 1 to 15 percent of the remaining unreacted Contains chlorine. In the process, the metal alkoxide can also preferably be added to the phosphorus nitride chloride in the reverse manner v / earth. In this embodiment, the remaining, unreacted chlorine is more uniform over the molecules of the Partialesters distributed. This is due to the progressive decrease in the reactivity of the chlorine atoms when these are substituted in the phosphorus nitride chloride. The esterification is preferably carried out in an inert solvent or Diluent running and the esterification reaction will generally carried out at the reflux temperature of the reaction medium from the solvent and / or diluent consists. The process for the preparation of the partial ester can of course also be carried out continuously, _j

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by continuously adding the appropriate amounts of phosphorus nitride chloride and metal alkoxide are fed to the reactor.

The condensation of the partial ester in the presence of the tertiary amine is preferably carried out by heating under reduced pressure _} preferably at 5 to 400 torr. This lets

of

the removal of the chlorine-containing by-product and / or remainder Manage solvents or thinners more easily, which are used in the esterification. The condensation of the partial esters under reduced pressure takes place rapidly. The process product is only faintly colored and there are residues of solvents and other low-boiling impurities in the reaction mixture remain, can be easily removed.

There are no special devices for the preparation of the condensed polymeric phosphazenes by the process according to the invention necessary. A conventional reactor with devices for measuring, stirring, heating, cooling and refluxing is sufficient and distilling is equipped. After removing the remaining bound chlorine to the desired level is the tertiary amine by appropriate measures, such as vacuum distillation; removed. Chlorinated compounds released during the reaction can be released Hydrocarbons react with the tertiary amine to form quaternary ammonium salts. This can be done without being detrimental Effect remain in the process product. However, these compounds can be removed by washing out with water.

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The tertiary amines used according to the process should be free of active hydrogen atoms, i.e. they should not contain primary or secondary amino groups, but they can contain more than one tertiary nitrogen atom. Also should they will be free of hydroxyl groups. Specific examples of suitable tertiary amines are pyridine, α-, ß- and γ-picoline, 5-ethyl-2- picoline, trimethylpyridine and vinylpyridine, bicyclic heterocyclic compounds such as quinuclidine, quinoline, isoquinoline and methylquinoline, triethylamine, tripropylamine, Tributylamine, trioctylamine, N-methyl-N-ethylpropylamine, Ν, Ν-diethylpropylaiain, dirnethylaniline, diethylaniline, diethylo-toluidine and triethyleiiamine and like tertiary amines. Particularly suitable and preferred in the process according to the invention are pyridine or mono-, di- or tri-C- ^ g-alkylsubstitu-

15 ated pyridines or mixtures thereof.

The amount of the tertiary amine used in the process of the present invention can be in a relatively broad range - in general, at least 1 percent by weight, based on the weight of the partial ester, is used. So at least about 1 part by weight of the amine is used per 100 parts by weight of the ester. There is no upper limit to the proportion of the tertiary amine used, since it has been found that a large excess does not adversely affect the reaction. If the preferred tertiary amines mentioned, for example pyridine, are used, at least 25 percent by weight and in particular 50 to 75 percent by weight of the amine, based on the weight of the partial ester, are used.

larger amine oil can also be used without any adverse effect

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_Q 24ÜA203-1

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1 use shares.

The condensed produced by the process of the invention polymeric phosphazenes, when dispersed in regenerated cellulose, impart regenerated cellulose to this (Rayon) high flame resistance. They also show improved retention in the thread during the spinning process and Tx im later washing of the textile material made from the threads.

The proportion of dispersing in the regenerated cellulose Flame retardant depends on the desired flame retardant Effect and the desired properties of the textile. The proportion is generally 10 to AO percent by weight and preferably 15 to 25 percent by weight, based on the

15 weight of the cellulose thread.

The flame retardants produced according to the invention can be incorporated into the threads of regenerated cellulose in a manner known per se be incorporated. Since the viscose process is preferred, the flame retardant is used in cellulose-containing spinning solutions incorporated, spun into threads and the cellulose regenerated. Also the copper oxide-ammonia method and the method the saponification of cellulose esters for the production of the threads from regenerated cellulose are used, this Fa-

25 containing the incorporated flame retardant.

The condensed polymeric phosphazenes according to the invention are preferably incorporated into a viscose solution, and the viscose is in the form of one or more threads in a coagulating_j

4 09831/1 1.1 1

- ίο -

and regenerating medium. The threads obtained are aftertreated in a manner known per se. In this way continuous filaments, fibers, yarns and staple fibers are obtained. These can be processed into any kind of textile structure

5 where flame resistance is desired.

The examples illustrate the invention.

example 1

A mixture of 334 g (14.5 mol) of sodium in 5.2 liters of xylene is mixed with 1205 ml (16.1 mol) of n-propanol ^{at a temperature of 102 to 118 ° C. over the course of one hour. The mixture is stirred at 110 °} C. for a further 30 minutes to complete the reaction. The mixture is then added to a reaction vessel containing a 30 weight percent solution of 928 grams (16 equivalents) of 91 percent cyclic phosphorus nitride chloride in chlorobenzene. The addition is carried out over 1 hour at temperatures up to 130 ⁰ C. The reaction mixture is then heated under reflux for 2 1/2 hours while distilling off a mixture of 2.4 liters of n-propanol and xylene at temperatures up to 138 ⁰ C. The refluxing is continued for a further 24 hours at 134 ° C. After washing out and concentrating, 1200 g of an ester are obtained. Analysis values are given under Product (A) in Table I.

500 g of the product (A) are reacted with stirring with 250 g of pyridine for 5 1/2 hours at 100 ^° C. under nitrogen. The reaction product is concentrated at 85 ° C./0.3 torr. In this way 450 g of a reaction product are obtained which _j

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is listed under product (B) of Table I. 60 g of product (B) are dissolved in 100 ml of chlorobenzene and 100 ml a saturated aqueous sodium bicarbonate solution. After the chlorobenzene solution has been separated off and then dried and concentrated at 85 ° C./0.3 torr, the product (C) is obtained. Table I shows the corresponding analytical values for products (A), (B) and (C). The remainder of the Elementarana-Iyse is oxygen and traces of impurities.

Table I.

C H N P Cl

¹⁵ Molecular weight, acid number, refractive index, 24 ° C

Viscosity (Centistoke at 25 ⁰ C)

Example 2 A 12 liter reaction vessel is charged with 1160 g (20 equivalents) of cyclic phosphorus nitride chloride in chlorobenzene (30 percent solution). 3.2 liters (46 mol) of pyridine are added to the solution while stirring. 2 liters (26.7 mol) of n-propanol are then added dropwise at a reaction ^{temperature of 30 to 32 °} C. over the course of 41/2 hours. The reaction mixture is then stirred at 30 ° C. for 18 hours. The separated pyridine hydrochloride is then filtered off. The filtrate is mixed with 1 liter of an aqueous solution from-_j

4 0 9 8 31/1111

product product product (A) (C) 40.39 40.87 40.25 8.02 7.66 7.80 9.03 9.71 9.64 19.63 20.06 21.02 4.29 1.29 0.50 733 1162 1299 5.0 4.6 3.5 1.4642 1.4735 1.4705 ϊ at 125 5000 5000

2AÜA203 π

washed containing 150 g of NaHCO 3 and 40 g of NaOH. To separate the layers, sodium chloride is added to this mixture. The organic solution is dried over sodium sulfate, filtered and evaporated at 85 ° C./0.3 torr. Yield 1170 g of a liquid product having the following analytical values: C 37.39 refractive index, 25 ⁰ C 1.4730

H "6.92, acid number 10.9

N 9.57 viscosity (centistokes at 6400

25 ⁰ C)

P 20.99 molecular weight 1110

Cl 1.99

Example 3, *. ι -n _he ,

manufactured

. The retention and flame-retardant properties of the condensed polymeric phosphazene designated according to Example 1 / and with product (B) v / earth tested in rayon, which was produced from a thread-forming aqueous viscose containing 8.6 percent by weight of cellulose, 6.2 percent by weight of sodium hydroxide and, based on the weight of the cellulose, 33.0 weight percent sulfurization! carbon and having a spinning viscosity of 6000 centipoises at 18 ⁰ C. The phosphorus-containing flame retardant is fed into the viscose flow at the calculated rate (based on the concentration of cellulose), which is then fed into a high-shear mixer. The flame retardant is dispersed in the viscose to form fine droplets with a diameter of about 1 to 10 μ.

The viscose is spun in a conventional aqueous spinning bath containing 7.5 percent by weight of sulfuric acid and 3.7 percent by weight of zinc sulfate and contains 11.0 weight percent sodium sulfate. The Bad _J

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¹ - 13 -

temperature is 35 ^° C. During the spinning process, the threads are wet drawn to about 129 percent of their original length. Yarns with a thread denier of 1.5 denier are obtained. The thread bundle is cut into staple fibers 38 mm in length, which are passed through an ash bath, desulfurization bath, bleach bath, acid bath, dechlorination bath and a bath containing a plasticizer for post-treatment. The staple fibers are then spun into yarns, dried, wound up and knitted into circular structures that weigh about 144 to 174 g / m 2. The. Yarns made of regenerated cellulose produced in this way consist of single threads which contain fine liquid particles of the flame retardant distributed in the cellulose matrix.

The rayon threads are processed into fabrics and checked for their flame resistance and their retention capacity of the phosphazenes was investigated. The results of the fiber analyzes after spinning and after 50 washes are summarized in Table II. The information of the retention capacity are given in each case in percent, based on the weight of the cellulose. The value of restraint are calculated from the analysis of the phosphorus content in the fiber or in the textile material. Furthermore, the Percentage of the flame retardant or retention capacity, based on the amount of originally present in the viscose solution

25 existing cellulose, calculated.

The "Vertical Strip Test" is used to examine the flame resistance carried out according to the test standard AATCC 34-1960. A swatch with the dimensions 7.6 χ 20.3 cm is in a U-shaped j

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attached to the frame, which in turn is arranged in an open chamber, the open end of the fabric tube pointing downwards. The fabric is lit with a Tirrell burner that is fed with butane. A 38.1 mm long flame is placed at the bottom of the swatch so that 19.05 mm of the flame extends into the swatch. The flame contact is 3 seconds. The charring length and the caching time are determined. A char length greater than 17.78 cm is considered a failure in the 3 second test. All fabric samples are dried in an oven for 3 hours at 105 ^° C. and cooled in a desiccator before use.

Comparative example A.

For comparison purposes, a fabric sample according to the example is used 3 containing a flame retardant described in US Pat. No. 3,445,713 and from a liquid mixture of di-n-propyl phosphorus nitride polymers with a proportion of 65 percent by weight of a trimer, 15 percent by weight of a tetramer and etv / a 15 to 20 percent by weight of a higher cyclic polymers and less than 5 percent by weight of a linear one Polymers is made. The results of the "vertical strip test" and retention are also summarized in Table II.

The results show that the condensed polymeric phosphazenes prepared in accordance with the present invention have superior flame resistance impart even with small additions of the flame retardant. Above all, the flame retardancy remains even after 50 washes

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were still going, while the flame retardant of the comparative example the "vertical strip test" after 50 washes no longer exists, even if there are relatively high additives in the

Fabric sample can be incorporated. 5

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Table II

- 16 -

CD CO CO CO

Fabric-i flame retardant
pr'obe I medium
j
j!
ί ι
I] Weight percent j
the flame retardant j Il 36.5 i
Fiber analysis according to! Fiber analysis according to
, spinning: 50 V / s oscillate: phosphorus
salary,
Wt .-? O in
the fiber Weight of the retention phosphorus retention
FlarQK- assets; salary in assets,
protection in % (loading ■ the material, weight,
tels, related I related to sample i (related
pulled on cellulose); (Wt .-%) j on cellu-
Cellulose > loose) I.
92.5 j
j 30.5 83.6 j '4.07 83.0 j 1 product (B)
j I manufactured
ί ί according to the example
ί "1 means in Yis-!
kose (related to
on weight
of cellulose ¹ I ί ■!
Comparative j 45.0
example A j 3.06 17.9 74.9 j 2.85
i! 3.88 x 23.9; 77.9 '3.50 88.1 34.2! 75.8; 3.57
! ! ■ i 68.6 23.9
! 4.70 ^1st ι
¹ 2 ί »j 30.7 ι
3 5

S3

S3 O

Table II - continued

- 17 -

CO OO CO

Remaining test sample j retention after spinning and Washes

Vertical strip test (3 sec.)

Initial sample

after 50 washes

; Sales ^; Afterburning
! length, cm j sec. slope, cm

CD 68, 6th 6, 60 O 3, 04 5 3. 69 4th 3, 81 - O 4, 06 ■
0 5 52, 1 5, 15th ⁰ 25, 40 14th

r 24CM203-1

Also the process products, which are produced according to Example 2 and the product (C) according to Example 1 also show excellent retention and very good flame-retardant properties when they are used in regrind

5 cellulose are incorporated.

Example 4

100 parts by weight of the partial ester (A) prepared according to Example 1 are stirred ^{with 50 parts by weight of α-picoline at 100 ° C. for 5 hours.} A viscous condensed polymeric phosphazene with excellent flame-proofing properties is obtained.

Example 5 “ · -u *. ,

Weight ^

Example 4 is made using 75 files triethylenediamine repeated. It also becomes a condensed polymeric phosphazene with excellent flame retardant properties obtain.

20 examples

Weight- ^

Example 4 is repeated using 60 parts / parts of quinoline. A product with excellent flame retardant properties is also obtained.

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Claims (9)

1 'claims 1. Process for the preparation of condensed polymers Phosphazenes characterized by (a) one partially esterified by a metal alkoxide and / or an alcohol each having 1 to 12 carbon atoms Phosphorus nitride chloride with ■ (B) a tertiary amine from the group of mono- or polynuclear heterocyclic aromatic / imines »aliphatic Amines of the general formula I R ₁ R ₂ R ₃ N (I) _; . ■ in which R ^, R ₂ and R-, identical or different alkyl or alkenyl radicals with 1 to 10 carbon atoms, aromatic amines or aralkylamines of the general formula II R ₄ R ₅ R ₆ K (II) in Rg an aryl radical and R ₄ and R, - mean identical or different alkyl and alkenyl radicals with 1 to 10 carbon atoms, the tertiary amine containing no active hydrogen atoms, at temperatures of at least 20 ° C for implementation. 2. The method according to claim 1, characterized in that a partial ester with 1 to 15 percent by weight of unreacted Chlorine, based on the weight of the partial ester, is used. 409831/1111 3. The method according to claim 1, characterized in that a propyl ester is used as the partial ester. 4. The method according to claim 1, characterized in that the tertiary amine is pyridine or a mono-, di- or tri-Cj_g ^ alkyl-substituted pyridine or a mixture thereof is used. 5. The method according to claim 1 and 4, characterized in that at least 25 percent by weight of the tertiary amine, based based on the weight of the partial ester. 6. The method according to claim 1 and 4, characterized in that one carries out the reaction with the tertiary amine at temperatures of about 50 to 15O ⁰ C. 7. The method according to claim 1, characterized in that a partial ester is used by adding a metal alkoxide to which phosphorus nitride chloride has been produced. 8. The method according to claim 1, characterized in that a partial ester is used, which in situ by reacting the Phosphorus nitride chloride has been prepared with an alcohol having 1 to 12 carbon atoms in the presence of the tertiary amine is. '. 9. Use of the condensed produced according to claim 1 to 8 polymeric phosphazenes for making textiles flame resistant made of regenerated cellulose. L --J 409831/1 1 1 1