DK151382B - POLYORGANOPHOSPHAZAN WITH CHROMOPHORE GROUPS FOR USE IN COLORING - Google Patents

Description

in 151382

The present invention relates to "h" in 1 unknown ρo 1 vse ~ e t use in dyeing. These polymers are poly (organo-poly; β-α-2enes), which are characterized by the presence of clavomorphic groups. These groups may be covalently bonded to phos-® Phazen polymers. The polymers according to the invention are useful for a variety of purposes, where it is desirable to add color to the known advantageous chemical and physical properties of o py o h ρ s. They can therefore be used as colored films, filters, food dye cases and for a large number of other purposes.

The products -According to the invention may be represented by the formula: x R ~

1 I

- M = P - HJ = P -

15 I I

RR _ r <(I} where X is here a chromophore group selected by the group consisting of those derived from azo, nitro, ketone min, anthraquinone, acridine, triphenylmethane, oxazine, phthalocyanine, indigo and sulfur dyes, R is of the group consisting of methoxy, ethoxy, ρ> ό ρ oxy, butoxy, isobutoxy, trifluoroethoxy, methylamino, ethyl amine, propyl nmi no, butylami.no, phenyl amine and piperidino, and n is a number from 25G to 20,000.

It will be seen that in the formula, the chromophore is covalently bonded to the polymeric skeleton.

the blush illustrates compounds in which the ratio of chromophore groups to organic groups is 1: 3.

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The substituents are selected to impart a desirable property to the final product and to make it as economical as possible. In general, it is desirable to modify the water solubility of the product. This can be easily achieved by selecting a substituent or group of substituents with hydrophobic or hydro-O-35 properties. The most water-soluble polymers can be prepared by choosing a lower alkylamino substituent such as methylamino or ethylamino. The final product is imparted to water resistance using a trifluoroethoxy group.

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Electropositive organic groups which supply electrons to the nitrogen atom of the polymer will increase its basicity and help to stabilize the product. The preferred electron donating groups are those which bind to the polymer through oxygen or nitrogen and include e.g. methoxy, ethoxy, propoxy, butoxy, isobutoxy, methylamino, ethylamino, propylamino, butylamino, phenylamino and piperidino.

It is not essential that all the organic groups are identical. Special properties can be incorporated into the products of the invention by forming them to contain two or more organic groups, e.g. methoxy and methylamino, ethoxy and diethylamino or hutyl am4no and methylamino.

As will be appreciated by those skilled in the art, both acidic and basic chro-X 5 mohore compounds can be used to prepare compounds of Form I by selecting appropriate reaction participants and reaction conditions.

It is clear that the chromophore groups that covalently bind to 2 Π the polymeric substrate are a very large number. These include chromophores from all the usual classi4 cat onions including such dyes as azo, nitro, ketonamine, anthra 9 ion, acridine, free pheny 1 * netha ·, oxa z4 n, phth ε 1 ocya n4 n, into -

Solid and sulfur dyes.

25 ^ and 1 e get special 1e dyed tof fe * ', cited by way of example only, 9 which can be used for the preparation of products of formula I 1 include: cell 1 iton yellow, ce11 iton orange, golden yellow, golden-grange I , celiitcn violet R, oil-orange, para red, cellitazole ^ 1 ", yellow AB, brown V, ce 11 in bright yellow, mart-ns yellow, suramin, s-: dsrv4 c1 et, sudan green, chrysanil ingult, prof avalanche and fuchsin .

special dyes, dsr can be used to make Q nine compounds, e.g. aroidonaphthol brown, 35 2allocyanine, chrysamine in the acid form, benzoic yellow in acid-direct orange, true red, methane yellow, victoria violet, * J ^ ebrich scarlet, orange R and rhodamiη B.

the specially mentioned dyes are illustrated in form in The Chemistry rd Synthetic ryes and Pigments, H.A. Lubs, 151382

Reinhold, 1955. Like Literature, this literature provides ~ ·· £ ζΛ's list of a large number of other chromophore associates. which can be used for the preparation of pods of the invention.

In view of the structures of the above compound 5 combined with the rest of the core 1 of the present description, especially the examples, those skilled in the art will have no difficulty in preparing hundreds of embodiments of the invention.

The following equations illustrate the formula of 11 of typical compounds of the invention are types of Formula I according to the invention. In compounds, compounds I and II are known and prepared by known reactions, and X has the above meanings. while R is tr-; ~

f Τ Ϊ1 O ϊϊ "t -1 O .u- *. / ώ] 1 o p i» i o -h n ty "i rti · ~] O

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Cl Cl \ /

P

A r, Ί 5 Cl N N Cl Cl

\ l 11 / I

p P 2 50 ° S - N = P-

/ \ / \ I

c 1 \ * C1 Cl 10 _n T f XNaII /

-NaCl A / XH

C / -HC1 ν '

C1 X C1 X

, I II

-M = P-N = P- -M -P-N = P-

i i II

Cl Cl Cl Cl 20 \ C.F3CH20Na \ CH3NH2 CH3MH2 B \ \

25 C \ E

t -NaC '- -MCI j-HCl

OCH2CF3 X NHCH3 x NHCH3 X

-N = p-N = P- -N = P N = P- -N = P N = P- OCK2CF3 O C H 2 Cp 3 NHCH3 NMCP3 Μ H C H 3 NHCH3

3 5 zn IV V

Li going A.

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It will be seen from the above reactions that the molecular weights of the! Which polymers depend on the molecular weight of the origin · ?! all pclyphosphases. The most useful compounds according to the invention are those wherein n e · f ^ a? 50 ti! 10,000.

5

Molecular weight ranges slightly for the compounds of the invention vary somewhat with the polymer and the chromophore, but are generally from 100,000 to 4,000.GOG.

The polymers of the invention can be processed using standard polymer processing techniques. They might, for example.

cast as a file to obtain solutions and can be extruded or molded. In order to utilize these methods, it is best to avoid cross-linking during the formation of the polymer because the cross-linked polymers are generally too s 11 v e to be easily processed. However, they * sometimes appear desirable to cross-link the product after it is formed, e.g. by heating, as is the case with curing rubber and other polymers. Crosslinking increases d in while in onstab for 1 in the density of there. polymers.

A very useful technique for crosslinking is to prepare the polymers such that they contain a small number of ethyleneamino groups. Such molecules are readily crosslinked by heating at a fixed point at the time of formation. The cross-linking appears to be by a free radical mechanism by which neighboring polymer chains are linked through tetramethylene groups. In poems prepared for cross-linking, the number of ethers! one imi groups per. repeating rule is generally from 0.0001 to 0.2.

As mentioned above, the polymers of the invention are useful for many different color purposes. They can be molded into fibers, films or numerous molded products.

A particular advantage of the polymers is that they can be used for food dyes which are not adsorbed on and which are fully and safely excreted. This is especially important with coloring agents that are suspected of metabolizing into toxic products when adsorbed. These colored substances can also be incorporated into color-coded coatings t-U pills and other drugs.

Polymers of the invention intended for use as a food grease agent will generally have alkoxy or aryloxy substituents so that resistance to hydrolytic decomposition is increased.

Polymers selected for use as fibers will preferably have a glass transition temperature below 25 ° C and a chain length greater than 10,000 monomeric residues. Since at least the raw degree of microcrystallinity is indistinct in fiber-forming polymers, all the organic groups will be identical to increase molecular orientation.

For optical filters, for optical emulsions and the like, the degree of m-crystal crystallinity must be increased to decrease opal in the ring. As with fibers, the chain length is generally above 1Q0Q monomeric units.

A reaction, such as reaction A in equation A, is usually carried out in a highly polarized manner: o p. "Η g of cast part under safe betinoints at a temperature of -30 to 175 * 0. It is preferred, but is not substantially, to carry out the reaction in an inert atmosphere such as nitrogen.

25 T. .

Typical r-interlayer solution 'j' includes ethers containing up to 8 carbon atoms, esters containing up to 10 ° C carbon atoms, and symmetric and asymmetric ketones containing up to 10 · 10 carbon atoms. - The reaction time is in the range from i0 t-n 600 ** nuts.

The molar amount of chloro-oophoric compounds used for the reaction is selected on the basis of the desired ratio of ν'-em oranic groups and chromosomal groups.

Reaction B can be carried out without isolation of the intermediate polymer substituted with chromophore groups by adding the acid substituted salt or the other compound selected for the reaction. Preferably, the addition takes place for a period of from 0.25 to 3 hours while maintaining the temperature from -30 to 150 ° C.

g After the end of ten insertion period, the reaction mixture is allowed to stand at a temperature of 25 to 100 ° C for 3 to 10 hours to complete the reaction.

In general, the amount of trifluoro-substituted compound or equivalent compound used will be at least 10 sufficient to replace the calculated number of chlorine atoms remaining on the polymeric substrate calculated on the amounts of initially polymeric and chromophoric reaction participants.

The SIut product can be recovered (and, if desired, purified) in any convenient manner. Several ways are illustrated in the examples. Reactions C, D and E are all substantially the same. It is convenient to carry out these reactions in the presence of chloride-removing substances such as pyridine or triethylamine. Reactions-20 ns occur under anhydrous conditions.

In the presently preferred process, the reaction is carried out in a solvent which must of course be inert to the reaction. Any of many different solution-2g agents which can dissolve the polymeric starting material in ale can be used. Oises include e.g. aromatic hydrocarbons such as benzene and toluene and cyclic ethers such as dioxane and tetrahydrofuran.

The time and temperature of the reaction will vary within 30 wide intervals depending primarily on the selected reaction participants. The temperature range1 can range from -3? to 35 ° C or even higher and the time from 2 to 43 hours.

A few simple observations go: 'enabling f in g r e e η τ e + 35 to determine the optimum temperature and reaction time for a given set of reaction participants.

The various ways of isolating the final product are illustrated by the examples. Normally, the process 8 varies with the dissolution properties of the product. If it is soluble in the organic solvent in which it is prepared, it can be isolated by evaporation of the solvent or precipitation with a non-dissolving agent1 after removal of the insoluble salt of hydrogen chloride binder by filtration. If both polymer and amine salt are insoluble in the organic reaction medium but soluble in water, the aroine salt can be removed by dialysis using water.

Typical useful organic solvents include aromatic and aliphatic hydrocarbons, ketones and ethers, suitably acetone, benzene or tetrahydrofurar.

The invention is further illustrated by the following examples.

Example 1.

Po1v [(1-Phenylazonaphthalene -? - oxy-1 R in f1 uroethnxy) phosphazenl.

The sodium salt of 1-phenylazo-2-hydroxynaphthalene is prepared with excess sodium hydride in * etrahydrofuran (THF) solution, 20 min, initially under a nitrogen atmosphere for 30 minutes. The color of the solution changes from red-orange to deep red as the salt forms.

A solution of sodium ~ 1-phenyl azonaphtha 1ene-2-oxide (0.38 g, 0.0014 mol) in 250 ml of THF is filtered through a glass frit into a Schlenk-type addition funnel with a positive nitrogen pressure 1 reaction vessel containing a stirred solution of α-poly (dichlorophosphazene) (35.7 g, 0.14 mol) in 1400 ml of THF under a dry nitrogen atmosphere. Addition takes place over 30 30 minutes. After 1 hour reaction, an ethereal solution (250 ml) of sodium trifluoroethoxide (39.8 g, 0.33 mol) is slowly added over 2 hours. The color of the reaction mixture changes from orange-red through brown and then to orange during 36 hours of reaction at 5 ° C. The polymer is recovered by removal of the solvent by recuperated pressure and precipitation in heptane. It is purified by precipitation twice of THF in distilled water and seven times of THF in heptane or benzene (yield 16.2 g, 51%).

9 151382

The corresponding methoxy, ethoxy, butoxy and phenyloxy compounds are prepared in a similar manner.

Analogous compounds of all of the above compounds are prepared by replacing the azo dye with cell 1 itone yellow, golden yellow and golden orange I.

Example 2.

Poly (1-phenviazonaphthalene-2-oxy-methylamino) phosphazenl.

10

A solution of sodium 1-phenyl-azonaphthalene-2-oxide (0.24 g, 1 x 10 -3 mol) in 200 mL of THF is pressure filtered under nitrogen in a stirred solution of poly (dichlorophosphazene) (11.2 g, , 01 mol) in 700 ml of THF. The total addition time is 35 minutes. After another 90 minutes reaction time, the mixture is transferred to an addition funnel and added dropwise over 3 hours to a stirred solution of methylamine (43 ml, 0.96 mol) in 500 ml of THF at 0 ° C. Atmospheric humidity is kept strictly excluded. After a further 42 hours of reaction, the solvent 2q is removed at reduced pressure and the polymer is isolated by precipitation in heptane. Purification is effected by dialysis in water for 4S hours, centrifugerino for 30 minutes at 1,000 rpm or, minute and several times precipitation of aqueous 95¾ ethanol in THF or Hepatane until free dye spectroscopic 2g is no longer detected. in the precipitation medium. Yield 3.4 g, 30.0 - ¾. The polymeric has an orange color. It forms hygroscopic, sharper films which were soluble in water, methanol or ethanol but poorly soluble in sopropanol.

The corresponding ethyl am in no, p ropy1 am in no οα d i e thvi am i nc fo ^ b in η -30 ratios are similarly prepared.

A polymer with mixed organic groups is prepared using an equimolar mixture of methylamine and butylamine.

3g Analogous compounds of all the above compounds are prepared by replacing the dye with oil orange, para red and mart in pale yellow.

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Example 3

PolV Γ (p-pheny "azoani 1 ino-methyl arm" no) phosohazenl.

A solution of p-phenyl azoani 1 in (0.34 g, 0.0017 mol) and S, S 5 ml of triethyl amiη in 50 ml of benzene is allowed to react with poly (di-chlorophosphazene) (II) (20 g, 0.17 mol) under a dry nitrogen atmosphere for 35 minutes. The mixture is then added dropwise to a solution of methylamine (91.8 ml, 2.06 mol) in 700 nT THE at 0 ° C under a nitrogen atmosphere. At this stage a color change from orange-brown to clear yellow occurs and a fine is formed

precipitate. After another 48 hours of reaction, first at 0 ° C

and later at 25 ° C, the product is isolated and purified by dialysis in water for 5 days. Subsequent etching for 8 hours from methanol in benzene ensures removal of all the non-covalently bound dye. Yield 4.3 g, 23.4%. G.P.C. analysis in methanol or aqueous R 5% methanol showed e> Mp values near 1.1 x 10 6. UV visible spectroscopy of solutions of 0.0205 g polymer in 10 ml aqueous 95% ethanol showed (assuming an average chain length of 15,000 repetitive units) that approx. 6 dyes were added to each polymer chain. Pure polymers form yellow or green brittle hygroscope films that are soluble in water, methanol or ethanol, but only slightly soluble in isopropanol.

The corresponding ethylamino, propylamine and buty 1 am in rof orbi nde1 · -25 ser are prepared in a similar manner.

0e analogous compounds of all the above are prepared by replacing the dye with cell 1 iton orange, ceHitonvoiet R, cellitazole ST, yellow AB, sudanvoi light and chrysaniline.

Example 4

Polvr (l-phenvlazo -? - naphthlamino-methylamino) phosphazenl.

A solution of 1-phenylazc-2-napthylamine in (0.5 g, 2 x 10 3 mol) in 250 ml of glyme is slowly added over 45 minutes to a rapidly stirred solution of poly (dichlorophosphazene) (15, 7

g, 0.15 mol) in 1500 ml of THF under an atmosphere of dry nitrogen. After 2 hours of reaction, the stirred mixture is treated at 0 ° C

1.51382 11 with a large excess of methylamine added as a cooled liquid by means of a condenser with dry ice. The reaction temperature is allowed to rise to 25 ° C over 4 hours and the mixture is then dialyzed to remove hydrochloride salts. The resulting polymer is then isolated by freeze-drying.

The corresponding diethylamino, propylamino and buty 1 amino compounds are similarly prepared except that the polymer is isolated as a film by casting from a solution.

The analogous compounds of all the above are prepared by replacing the chromophore group with the chromophore group derived from cell li tonorange, ce11 in tazol ST, yellow AB, brown V, au-ramin, sudanvoil or sudan green.

Example 5.

Polyfn-phenylazo-4-p-oxophenvlazonaphthalen-ethoxy) phospha2en1.

The sodium salt is prepared from 1-phenylazo-4- (p-hydroxyphenylazo) naphthalene (0.25 g, 7.1 x 10-4 mol) with excess sodium hydride in hot benzene-THF mixture. This mixture is then added to a solution of poly (dichlorophosphazene) (15.7 g, 0.14 mol) in a benzene-THF mixture (1500 ml) and the reaction is allowed to proceed at 50 ° C for 1 hour. To this solution is added an excess of sodium t hox id, and mixtures are stirred at 25 ° C for 25 hours The polymer is recovered by precipitation from ethane1 1 water.

The corresponding compound in which half of the ethoxy groups is replaced by methoxy groups is similarly prepared by using a mixture of l-l of sodium methoxide and sodium in urethoxy d.

Example 6

The sodium salt of p-nitrophenol (0.8 g, 5 x 10 mol) is prepared by treating p-m'trophenol with aqueous sodium hydroxide solution followed by vigorous drying. A suspension solution of this material in THF (200 ml) is added to a stirring solution. pure solution of the poly (dichlorophosphazene) (11.2 g, 0.01 mol) in 700 ml of THF. After the mixture is stirred for 7 hours, an excess of 3f of butylamine is added and stirring is continued for 24 hours.

The yellow polymer is precipitated by precipitation in water.

5

The analogous methyl amino and dimethylamino compounds are similarly prepared.

The analogous compound of all of the above is prepared by replacing there, chrom ofore group with the chrom ofore group 10 derived from martin yellow.

Example 7

Polypiperidinophosphase with chromophore derived from 3,4-dlamino- ... arthraqu 'ror-.

1 o -----

A solution suspension of 1,4-diaminoanthraquinone (0.24 g, 5 x 1C-3 mol, sudan violet) in 300 ml of THF is added to a stirred solution of poly (dichlorophosphazene) (11.2 g, 0.01 mol) in 600 ml of benzene. After 1 hour reaction time at 50 ° C, the mixture is treated with piperidine. The piperidine hydrochloride was filtered off and the colored polymer was precipitated in ethanol and redissolved in benzene for casting as a film.

The analogous sudan green compound is similarly prepared from the sodium salt of the chromophore.

Example S.

The polyphosphazene with chromophore derived from c'nrysaniline substituted with trifluroethylamino and triethylamino groups.

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A solution of 3-amino-9-β-aminophenylacridine (chrysaniline) (0.27 g, 1 x 10 "3 mol) in 300 ml of a 50:50 mixture of toluene and diglyme is added to a solution of poly ( dichlorophosphazene) (15.7 g, 0.14 mol) in 2000 ml of benzene After stirring for 3 hours at 35 ° C, the mixture is treated with an excess of 50:50 mixture of trifluoroethylamide and triethylamine and stirred at 30 ° C for 24 hours. molecules of amine hydrochloride salt are filtered off and the solution evaporated to form a yellow film.

Claims (1)

3 3 151382 Patent claims. Polyorganophosphazane for use in dyeing, is known to have the general formula 5? i --- Μ = P - W = P - Ί IRR n {I} 10 where X is a chromophore group selected by the group consisting of those derived from azo, nitro, ketonam in, an + h raqui non , acridine, triphenylmethane, oxazine, phthalocyanine, i nd in go ^ de and so on 1 f rves t of fe, R is of the group consisting of methoxy, ethoxy-xy, propoxy, butoxy, in sobutoxy, tri fluoroethoxy, methyl am in no, ethylamino, propylamino, butylamino, phenylamino and piperidine, and n is a number from 250 to 20,000.