DE2219162A1 - EMULSIFIERS BASED ON POLYISOCYANURATE BIURET - Google Patents

Description

The molecules containing all of the following groups were found to be emulsifying. Have properties: Isocyanurate, metal isocyanurate and biuret.

The invention relates generally to the field of isocyanurate-containing organic compounds, and in particular a novel class of emulsifiers.

The relevant state of the art is represented by US-PS 3,072,654, which the use of Calcxumdi (dxchlorisocyanurat) teaches in bleaching and cleaning compounds, see column 1, lines 9 and 32 of this publication. According to U.S. Patent 3,272,813 Chloroisocyanurates bound with potassium in a complex with the formation of ßleichiuassen, see column 16, lines 63 to 70 of this publication. According to US Pat. No. 3,489,696, polyamides are made from isocyanurates !! and polycarboxylic acids prepared using of biuret diisocyanate is mentioned, see column 5, line 62 of this Publication. The publication of Argabright and Phillips in Journal of Heterocyclic Chemistry, 7, 999 (1970) deals with the basic hydrolysis of disubstituted isocyanurates and teaches the formation of relatively simple biurets. Less relevant prior art publications are U.S. Patents 3,150,132, 3,251 Ölü, 3,252,942 and 3,275,630. However, none of the publications according to the stated prior art teach compounds according to the present invention and also does not disclose

209883/1218

BATH ORIGINAL

other use as surface active agents.

The subject matter of the invention relates to a new class of compounds, the is suitable as emulsifiers, e.g. for forming dispersions and emulsions. These connections are identified by the fact that uieseluen contain all of the following groups in a single ilolecule:

Isocyanurate

Λ ι

⁰ ΛΤ O

Ileal isocyanurate "^ ^

Ύ ^N

and biuret (--WHCOHH-CG-NH- and -NHCON-CONH-)

The compounds according to the invention have the general structure according to FIG. 1,
whereby

R = a divalent hydrocarbon or substituted hydrocarbon radical, as explained further below and indicated, for example, in FIG. 2;
X = a metal or hydrogen or quaternary ammonium - which for the purposes of the invention behaves like a metal or a combination thereof. Particularly preferred are hydrogen, quaternary ammonium and metals from the following groups of the periodic table: Ia, Ib, Ha, Hb, IHa, IHb, IVa, IVb ,, Va, Vb, VIa; including metals, such as

- 2 ORIGINAL

2üU883 / 1218

Li ,. Na, K, Rb, Cs, Ca, Ag, Au, Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd,. ilg, H ₁ Al, Sc, Y, La and other rare earth metals, Ac, Ga, In, Tl, Ti, Zr, üf, Ge, Sn, Pb, V, Nb, Ta, Sb, Bi, Cr, Mo, W, Mn, Fe, Ru ₇ Co, jtfi, Rii, Pd, Os, and Ir;

A = a monovalent organic radical from the following iGocyanab (-irco), urethane
Amino (-SMh ₂ ), -WATCH ¹ or -

iGocyanab (-irco), urethane (-NHCO ₂ R ¹ ), urea (-NHCONHR ¹ ),

R ¹ = a monovalent hydrocarbon or substituted hydrocarbon radical, as described below;

iii-a = average number of trisubstituted isocyanurate rings and a positive integer from 0 to about 400, and most preferably from 0 to about 200;

nD = average number of isocyanuric acid and / or isocyanurate salt groups and is an integer value from 1 to about 10,000, more preferably 2 to about 1000 and particularly preferably 3 to about 100.

a = average number of trisubstituted biuret groups, as described below, and a positive integer value from 0 to about 2000, particularly preferably 0 to about 400 and more preferably 1 to about 200.

Jj = average number of disubstituted biuret groups, such as •, fourth below -brushed and an integer fourth from 2 to about 5000 and particularly preferably about 3 to about 1000.

2m + n + l = average number of divalent R groups and an integer value from 2 to about 11,000, more preferably 3 to about 1,100, and particularly preferably 4 to about 140.

m + 2 - average number of Α-groups and an integer value from 2 to about 2000, more preferably 2 to about 400, and especially preferably 2 to about 200;

with no W-to-J bonds and no A-to-N bonds and none A-to-A and no R-to-R bonds exist.

BfMETORIGtNAL

203383/12 1 8

R preferably has 2 to 40, more preferably 2 to 30, and particularly preferably 2 to 18 carbon atoms.

R ¹ v / e is preferably 1 to 40 carbon atoms, more preferably 1 to 20 carbon atoms and particularly preferably 1 to 10 carbon atoms and is, for example, -Cu. , -C ₉ H, -C ^ H ₇ , iC ^ li-,

CH ₃ CH ₃ -C-CH ₂ -,

CH ₃

usv /.

R and / or R ¹ can be substituted by groups which do not adversely affect the subsequent field of application of the products or the manufacture of the same. Examples of such non-harmful groups are: -UO ₃ , Cl, F, Br, I, CN, -CO ₂ R ", -CO-R", -0-R ", -SR", NR ₂ "/ -CONR ₂ ", -SO ₃ R, -SO ₂ -, -SO-, phenyl, bjaphthyl, alkyl (1-40 carbon atoms), -PO ₃ R ¹¹ , cyclohexyl, cyclopropyl, polymethylene (e.g. tetramethylene), -OCOR", - NHCOR ", etc., where R" can be hydrogen, a lower alkyl (eg ethyl, hexyl) or aryl (eg monovalent radicals corresponding to the aryl radicals described in FIG. 2) group. The examples for R - see the figure 2 - are to be understood here only as explanatory.

It will be understood that the values for m and η are to be understood on the basis of integer fourths, which are used here for describing a single molecule. In practice there will be mixtures of molecules of the general formula described above. Thus, the average

" ⁴ " 2 0 <A fl fi 3 / 1JM B

BATH OFIIQiNAL

Liehe value of m-a for the mixture from about 1 to about 2000, more preferably about 1 to 400, and particularly preferred amount to about 1 to 200. The average value for n-b can sicn to about 0.5 to 10,000, particularly preferably about 0.5 to 1000 and very particularly preferably about 0.5 ice 100 amount. The value for a can range from about 0 to 2000, more preferably from 0 to 400 and particularly preferably from 2 to 200 amount.

The invention relates to a novel class of emulsifiers, their production and processes for their use. So can e.g. the compounds according to the invention are immiscible in mixtures from water and organic compounds are added, e.g. equal parts by volume of water and a hydrocarbon, and the resulting mixture is formed to form emulsions touched. This result is particularly surprising, because many compounds are only slightly soluble and some are insoluble in any phase.

An exemplary embodiment of the invention is shown in the drawings and will be described in more detail below. Show it:

1 shows the general formula of the products according to the invention;

2 and 3, for example, possible structures of the R groups of the starting materials of the products according to the invention;

4 shows the general formula of the organic starting materials used according to the invention.

Starting products

The starting materials used according to the invention are Salts of polyisocyanuric acids. Which are produced by a metal cyanate and an organic diisocyanate in the presence an aprotic solvent are reacted, whereby isocyanurate groups-containing polyisocyanate metal salts are formed.

ORIGINAL

It has been found that aqueous solutions of these polyisocyanurate salts, see the general formula according to Figure 4, under basic conditions, i.e. a ρ value above 7, for the ßiuretproducts Figure 1 fünren. The product is much less soluble in water than the polyisocyanate salt which is to be reacted. Suitable bases include alkali metal or alkaline earth metal hydroxides.

Re a ktionsmedien: It is used water or mixtures of water and an alcohol, ketone, ester, amide, SuIfoxid, sulfone, etc.

Temperature: If the temperature is not particularly critical, temperatures are preferably in a range of 10 to about 200 ° C, more preferably a range of 15-15O ⁰ C and particularly preferably a range from 2O-12O ° C. The lower limit is generally the freezing point of the solution and the upper limit is generally the boiling point of the solution at the reaction pressure.

Pressure: Although the pressure is not particularly critical, the reaction can be carried out at pressures from 0.5 to 100 atmospheres, with pressures from 0.6 to 50 atmospheres more and from 0.7 to 10 atmospheres being particularly preferred.

Time: The reaction time naturally depends on the original concentration of the starting materials and the temperature. The preferred period of time is from 0.01 to 4500 hours, more preferably from 0.05 to 350 hours and particularly preferably from 0.06 to 200 hours.

The subject of the invention is explained below with reference to a number Embodiments explained.

example 1

h first treatment of the polyisocyanurate salt

183 g are added to a stirred slurry of 82.4 g (1.02 mol) of KOCN in 2000 ml of dimethylformamide (DMF) at 75.degree

■ - 6 - 20 9 883/1218

BATH ORIGINAL

zz ia ι dz

(1.05 moles) tolylene diisocyanate at a rate of 0.35 ml / min, added by means of a syringe pump.

The entire operation is carried out in a nitrogen atmosphere. Following the addition, the reaction mixture is stirred for a further 5 minutes, then, in a large excess, Added dry allethanol and allowed to stand for a further hour translate for a long time to ensure complete quenching. The main product is insoluble in D24F and so easily gets through filtered off once. A very small amount of the product soluble in DMF is released after the solvent has been removed obtained from the filtrate. After vacuum drying at 80 ° C for the purpose Removal of the remaining DMF and methanol, the following yield values and analytical data are obtained:

Product% yield aryl / end groups avg.

Ratio of molecular weight (2m + n + l / m + 2) (minimum)

DMF insoluble * ³ * 96.5 21.2 10,000

DMF soluble lane 1.5 750

(1) corrected for remaining DMF

X2) measured by means of nuclear magnetic resonance spectroscopy

(3) contains 20.9% DMF by solvation.

Example 2 Manufacture of polyisocyanurate biuret

The polyisocyanurate product obtained according to Example 1 and insoluble in DMF is dissolved in water to form a 10% strength by weight solution. An equal volume of 8% is added to this solution aqueous NaOH added. After standing for 4 hours at 25 ° C., the hydrolysis is practically complete. The intended product is a water-insoluble solid in the form of a colloidal suspension.

Aliquots of this suspension are used for testing without further purification applied.

_ 7 _ 209 883/1? 18

BATH ORIGINAL Example 3

The following is the useful application of the polyisocyanurate biuret proven as an emulsifier.

In a 10 ml of n-heptane and 9 ml of water - deionized and 2 ml of the crude suspension according to Example 2 are added to the measuring cylinder containing distilled. By shaking it results a stable emulsion that has a volume of approximately 16 ml.

Example 4

In a manner similar to Example 3, 10 ml of n-heptane, 10 ml of water and 0.5 ml of the suspension obtained according to Example 2 are converted into an emulsion comprising about 11 ml by shaking, which remains stable.

209883/1218

ο -

Claims (7)

Claims vj. Emulsifier, characterized in that the same Contains isocyanurate, metal isocyanurate and biuret groups and corresponds to the general structure of the formula according to FIG. 1, whereby R = a divalent carbon or substituted one Hydrogen radical having 2 to about 40 carbon atoms; X = selected from the group consisting of metals, hydrogen or quaternary ammonium radicals; A = a monovalent organic radical selected from the Group consisting of -iSiCO, -NHCO ₂ R ¹ , -NHCONHR ¹ , -NH ₂ , -NHR ¹ and -NR ', where R ¹ = a monovalent hydrocarbon radical or substituted hydrocarbon radical with 1 to about 40 carbon atoms, m-a = the average number of trisubstituted isocyanurate rings per molecule and an integer from 0 to about 400; n-b = the average number of isocyanuric acid and / or Isocyanurate salt groups and an integer value from 1 to about 10,000; a = the average number of tri-substituted biuret groups ; b = the average number of disubstituted biurfet groups; 2m + n + 1 = the average number of divalent R groups and an integer value from 2 to about 11,000; m + 2 = the average number of Α groups and an integer Value from 2 to about 2,000, with no N-to-N bonds and there are no A-to-N bonds, no A-to-A bonds, and no R-to-R bonds. 2098 8 3/1218 2. Emulsifier according to claim 1, characterized in that R is selected from the group of organic radicals according to FIG 2 is selected. 3. Emulsifier according to claim 1, characterized in that X is selected from the group consisting of hydrogen, quaternary ammonium radicals and metal radicals which are selected from the following groups of the Periodic Table: Ia, Ib, Ha, Hb, IHa, IHb, IVa, IVb, Va, Vb, VIa; including metals such as Li, Na, K, Rb, Cs, Ca, Ag, Au, Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg, B, Al, Sc, Y, La and others rare earth metals, such as Ac, Ga, In, Tl, Ti, Zr, Hf, Ge, Sn, Pb, V, lib, Ta, Sb, Bi, Cr, Mo, ri, Mn, Fe, Ru, Co, Ni, Rh, Pd, Os, and Ir. 4. Emulsifier according to claim 1, characterized in that that m-a is an integer value from 0 to about 200, n-b is an integer value from 3 to about 100, a is an integer Fourth from 1 to about 200, b is an integer value from 3 to about 1000, and 2m + n + 1 is an integer value from 4 to about 140 and m + 2 is an integer value from about 2 to about 200. 5. Emulsifier according to claim 1, characterized in that R is selected from the group of organic radicals, as explained in Figure 2 and the substituted descendants thereof, which are selected from the group consisting of -IiO, Cl, F, Br, I, CN, -CO ₂ R ¹ , -CO-R ", -0-R", -SR ", NR ₂ ", -CONR ^, -SO ₃ R, -SO ₂ -, -SO-, phenyl, Jstaphthyl, Alkyl, - 1 to 40 carbon atoms -, -PO-.R ", cyclohexyl, cyclopropyl, polymethylene (e.g. tetramethylene), -OCOR", -NHCOR ", etc. are selected, where R" is hydrogen or a lower alkyl group (e.g. ethyl -, hexyl or ary! Group). - 10 - 209883/1218 6. Emulsifier according to claim 1, characterized in that R ¹ Ibis has 10 carbon atoms and is selected from the group -CH ₃ , -C ₂ H ₅ , -C ₃ H ₇ , XC ₃ H ₇ , <r ^H 3 CH ₃ 2 2 y ^ j / ^CH 2 7. Process for the preparation of both water and at least one organic liquid which is immiscible with water Emulsions, characterized in that the water and the organic compound form a compound according to claim 1 is added. - 11 - 209883/1218 BAP ORIGINAL