DE1495749B2 - Process for the preparation of water-soluble or water-swellable surface-active reaction products from polyethylene glycol ethers and isocyanates - Google Patents

Description

R-Y-A-Y-R

Represent 25, in which R is a hydrocarbon radical with

In the German Auslegeschrift 1081225 at least eight carbon atoms, Y the groups of high molecular weight water-soluble polyether urethane pation - NHCO · O - and A a polyethylene through conversion of addition products with glycol ether chain with the recurring structure of a molecular weight of at least 1000 from element - CH ₂ · CH ₂ · O - mean,
an alkylene oxide and, in contrast, only one 30 In contrast to the procedure of the cantilever-reactive hydrogen atom containing document 1 081 225, polyfunctional polybonds with at least 8 carbon atoms are reacted with ethylene glycol ether with isocyanates, and the polyisocyanates are obtained. According to this, the polyhydrophobic radical R is through the link Y, the alkylene glycol ether with a molecular weight of in each case a reactive, for further reactions at least 1000, which contains hydrogen atom enabled by the general formula 35, with the hydro-R ύ Λπ Philen polyethylene glycol ether chain A connected.

^K ~~ ^{ZA UH} From the German patent specification 974 371 it is known

are characterized in which R is a hydrocarbon from polyfunctional polyalkylene glycol ethers and rest with at least 8 carbon atoms, Z the monoisocyanates, such as. B. stearyl isocyanate, as Atoms or atom groups - O -, - S -, 40 emulsifiers usable surface-active additives > N - or - CO · O - and A to produce a polyalkylenation product. But as already in the glycol ether chain with the recurring component. Auslegeschrift 1081225. is set out are on

Emulsifiers produced in this way (see Example 4

R 'R' of patent application F 6215 / 39c) completely unsuitable

I 45 for the production of gasoline-in-water emulsions

- C - C - O - (O / W emulsions), as they are essential components

I I part z. B. used in pigment printing pastes.

R 'R' according to the invention is namely without regard to the

specified very significant limitation of the hydro-

'■ R' = hydrogen or an alkyl radical, with 50 phobic total proportion R to a maximum of 6 weight polyisocyanates implemented. This percentage of the process product is characterized by the manufacture of Manufacturing process of emulsifiers, which are suitable for water-soluble emulsifiers, Manufacture and stabilization of various dis- gators, especially those used for. Manufacturing Persian aqueous systems, such as emulsions or oil-in-water emulsions, are not suitable Suspensions, own.jijj.fet the use of opposite 55 possible. That this limitation is a Isocyanates monofunctional polyalkylene glycol is crucial measure, it shows when ethers, in which the hydrophobic radical R by the 1 mole of a linear polyethylene glycol ether with Link Z, which does not contain a reactive hydrogen atom with a molecular weight of 7000 with 2 moles of stearyl, with the hydrophilic polyalkylene glycol chain A isocyanate is reacted. This product contains connected is. 60 has a total hydrophobic portion R of 6.66

It has now been found that weight percent can be improved. With this product one can Neither do they produce water-soluble or water-swellable surface 5% aqueous solution active reaction products from polyethylene glycol by warming the solution, it finds again and again ethers and isocyanates are obtained if at least one precipitation of the same takes place. The product is out Polyethylene glycol containing two hydroxyl groups for this reason for the intended purpose ethers with a molecular weight of at least not suitable. If, on the other hand, 1 mole of a linear 1000 with monofunctional isocyanates with a polyethylene glycol ether with an average carbon molecular weight of 8060 containing more than eight carbon atoms. Obtained by mixing

3 4

of 80 parts of a polyethylene glycol ether of the molecular weight of the latter at least 3895, at

Molecular weight 7000 with 20 parts of such use of stearyl isocyanate at least 7840

of molecular weight 20,360, with 2 moles of stearyl. If there is a deficit of monoiso-

isocyanate reacted, the addition product contains cyanate worked, so can also polyethylene glycol

a total hydrophobic fraction R of 5.86 Ge 5 ethers with lower molecular weights is used

weight percentage. This product can be made with 5, but working with one is preferred

Dissolve weight percent in water, it is to the NCO / OH ratio of 1.

Suitable for the production of oil-in-water emulsions. Compliance with an NCO / OH ratio of 1

Polyethylene glycol ethers are addition products of for the overall reaction is not absolutely necessary,

Ethylene oxide on compounds with at least two io both below and above

the ethylene oxide with reactive water values are still quite within the meaning of the invention

Atoms of matter and products that are effective for the claimed process are obtained. However, in

on their own or in mixtures, provided that the overall balance has an NCO / OH ratio of 1.

they have a molecular weight of at least 1000 - Compliance with the NCO / H ratio of 1 in

point. Other alkylene oxides, such as 1,2-propylene oxide, 15 of the total balance are preferred, with smaller or

1,2- and 2,3-butylene oxide, values higher than this can also be used in the manufacture

the polyethylene glycol ether obtained in subordinate proportions in the context of the invention usable products,

len are also used in their increased When working with hydrophobic monoisocyanates

Use is the water solubility of the process - can monoisocyanates or alcohols, mercaptans,

products no longer available. As starting compounds 20 amines or carboxylic acids with less than 9 carbon atoms

such addition products are polyols which are also used linearly. Through such a reduction

or branched, saturated or unsaturated, and the hydrophobic portion sometimes become desirable

which also include heteroatoms such as sulfur or nitrogen. B.

as well as aromatic or hydroaromatic ring - an improved hydrophilicity achieved,

systems may contain suitable. As examples of 25 The polyethylene glycol ethers are used by the Iso-

Starting compounds are glycols of the general cyanate reaction carefully dehydrated, which z. B.

Formula through a vacuum treatment at elevated temperatures

HO - (CH ₂ ) J ₁ - OH temperatures from 100 to 120 ° C or by treatment

with solvents that boil constantly with water

called, where η is an integer from 1 to 12, 30 form mixtures, can be achieved. Contain 1,2-propylene glycol, 2,2-dimethyl-propanediol-1,3, Oc- the polyethylene glycol ethers from their production her tadecanediol-1,12, glycerine, trimethylolpropane, Rici- nor alkalis or alkali salts of organic acids, nut oil, pentaerythritol , Sorbitol, butene-2-diol-l, 4, octa is usually · also a neutralization with decene-9,10-diol-l, 12, 2,2'-dihydroxydiethyl sulfide, inorganic strong acids such as Hydrochloric acid or N-alkyl diethanolamines, di- (2-hydroxyethyl) oleyl- 35 sulfuric acid, may be necessary to prevent undesired amine, triethanolamine, cyclohexanediol-l ^ terephthalic side reactions in the isocyanate addition reaction acid-di- (2-hydroxyethyl ester), Hydroquinone di - (/ 3-hy- should be avoided. These addition reactions can include hydroxyethyl) ether. Furthermore, polyfunctional, on the other hand, known catalysts for isotional phenols, oxycarboxylic acids, polycarboxylic acids, cyanate reactions can be very effectively influenced in the desired rich amino alcohols with primary or secondary bound 40 device. May be mentioned e.g. B. iron-amino group, primary mono- and polyamines, diacetylacetonate, tin compounds such as dibutyltin amines with primary, primary and secondary or dilaurate, magnesium oxide and tertiary amines,
with secondary amino groups as starter components solvents that are not used to react with isocyanates. capable hydrogen atoms can be

The hydrocarbon radical R with at least 8 carbon atoms can be used. Since the process products are water-

lenstoffatomen is part of an isocyanate. Im soluble, become infinitely miscible with water

For the purposes of the invention are suitable, for. B. Monoisocy solvents such as acetone, tetrahydrofuran, dioxane

anates of the general formula C _n H ₂ ^ ₁ NCO, with and dimethylformamide preferred.

η means an integer greater than 8, Oleyisocyanat, The reaction is expediently in stirred vessels,

/ J-decalyl isocyanate, 4-dicyclohexyl methane isocyanate, 50 kneaders or autoclaves at room temperature or

a-Propyl-a-undecyl-methyl isocyanate, n-decyl ether- elevated temperatures advantageously below one

propyl isocyanate, diphenylmethane-4-isocyanate, 2-Me protective gas atmosphere of nitrogen or carbon

ethyl-4-cyclohexyl-phenyl isocyanate, nonylphenyl isocy- dioxide at atmospheric pressure or higher pressures

anate, p-dodecylphenyl isocyanate. carried out. The course of the reaction is easy

The hydrophobic radical R is followed by determining the isocyanate content alone. Use of a monoisocyanate in the process. Viscosity measurements can also be used as a control If products are introduced, relatively higher molar reaction processes must be used. In this kulare linear or branched polyethylene glycol ether trap, the reaction is interrupted if aqueous can be used to meet the requirement of a viscosity solution of the reaction mixture of the total hydrophobic portion R have not reached a maximum of 60. The response becomes greater than 6 percent by weight. The mixture after reaching this maximum viscosity Molecular weight of the polyethylene glycol ether, which is further heated to higher temperatures than Limit case R equals 6 percent by weight can, of course, depend on the undesired decrease in viscosity to be recorded. Molecular weight of the hydrophobic monoisocyanate. 65 Through the use of small proportions of Are z. B. 2 moles of nonyl isocyanate and 1 mole of antioxidants, such as. B. Di-tertiary butyl linear If polyethylene glycol ether is used, corresponding to p-cresol, these side effects can be effective an NCO / OH ratio of 1, this must be prevented.

The aqueous, more or less strongly rheopexic solutions of the products of the process show a low tendency to foam when they have strong interfacial activity and are therefore eminently suitable for the production of foam-free gasoline-in-water emulsions (O / W emulsions) or as dispersants; their viscosity can be varied within wide limits by the type and amount of the reactants and can, for. B. for 2 ° / ₀ ige aqueous solutions between 10 to 10 000 cP / 25 ° C can be set. Compared to previously known emulsifiers - also compared to those described in Auslegeschrift 1 081 225 - the compounds prepared according to the invention enable the production of emulsions whose inner phase contains 20 to 30% lower amounts of heavy gasoline with a comparable viscosity and the same amounts of emulsifier used. Such emulsions are not only more economical in practice, they give printing technology advantages, especially in pigment printing when using dispersed binders, such as synthetic latices, as a result of the higher water reserve. Furthermore, the substances prepared according to the invention can advantageously be used for dispersing inorganic and organic pigments in water and for preparing non-settling pigment doughs of controllable viscosity. They are also suitable for drilling oil and pesticide emulsions, sizing agents, aqueous finishing and coating compositions for textiles or paper and as dispersants and protective colloids in the preparation of aqueous paints. They can also be used in the production of concrete and screed, where their emulsifying and viscosity behavior has a plasticizing effect. The process products that are no longer soluble in water, but only swellable, are particularly suitable as soil improvers because of their excellent water holding capacity. Since the rheopic viscosity behavior of these substances results in an intensive lubricating effect, they can advantageously be used together with other detergent substances and fillers as face and hand washing soaps.

example

By mixing a linear polyethylene glycol ether with a molecular weight of 7000 (polyether A) with one with a molecular weight of 20,360 (polyether B) in the proportions given in the table, linear polyethers with the given average molecular weights (DM) are produced. 300 parts of each of these polyethers become standard after adding 0.6 ml. Sulfuric acid, Azeotropentwässerung with benzene, addition of 0.017 parts of iron acetylacetonate with said parts of stearyl isocyanate for 1 hour at 100 ⁰ C implemented. The viscosities of the 5% strength aqueous solutions in cP / 25 ° C. show decreasing values corresponding to the lower amount of the stearyl isocyanate used in each case. The products are very suitable for the production of oil-in-water emulsions.

Pole;
A. father
B. DM Stearyl isocyanate viscosity Proportion by weight -C ₁₈ H ₃₇
in percent by weight a 180 120 9 500 18.6 10 300 5.0 b 120 180 11500 15.4 7,970 4.2 C. 90 210 13,000 13.6 4 900 3.7 d 60 240 14 740 12.0 3 380 3.3 e 30th 270 17100 10.35 2,560 2.8 f - 300 20 300 Q Ί
ö, / 2,700 2.4

Claims (1)

1 2 hydrogen residue converts in such amounts that the Claim: coals containing more than eight carbon atoms hydrogen residue not more than 6 percent by weight of the Process for the production of water-soluble or reaction product is. Water-swellable surface-active agent is therefore the subject matter of the present invention Settlement products from polyethylene glycol ethers and a process for the production of water-soluble or in Isocyanates, which are suitable as emulsifiers for the water-swellable surface-active conversion of oil-in-water emulsions products made from polyethylene glycol ethers and isocyanates, and which, in addition to polyethylene glycol ether, are used as emulsifiers for the production of oil-in-water units Hydrocarbon residues with more than 10 emulsions are suitable and those in addition to polyethylene-8 Have carbon atoms, the proportion of glycol ether units being hydrocarbon radicals with more of the hydrocarbon radicals have no more than 6 Ge than 8 carbon atoms, the proportion makes up weight percent of the reaction products, the hydrocarbon residues not more than 6 weight d a characterized in that one makes up percent of the reaction products, the 15 containing at least two hydroxyl groups is characterized in that at least Polyethylene glycol ether of the molecular weight range containing two hydroxyl groups 9,500 to 20,300 in a known manner ether of the molecular weight range 9500 to 20,300 with monofunctional isocyanates with a monofunctional one in a manner known per se Carbon isocyanates containing 8 to 18 carbon atoms and one having 8 to 18 carbon atoms converts hydrogen residue. 20 containing hydrocarbon radical converts. The process products obtained can be z. B. by the general formula