CH627195A5 - Process for the preparation of stable dispersions - Google Patents

Description

The present invention relates to an improved process group-containing compounds seem unsuitable for the production of finely divided, stable and relatively low-viscosity.

This dispersions of polyisocyanate polyaddition products in the subject of the present invention is thus a process

Compounds containing hydroxyl groups and the use for the in-situ production of stable dispersions of poly-dung of such dispersions as starting components for the isoeyanate polyadducts in hydroxyl groups on-production of polyurethane plastics. send compounds as dispersants by implementation

Diisocyanate poly- addition products dispersed in polyethers or polyesters are known. According to the teaching of DAS 1. using organic polyisocyanates

1,168,075 is used to set diisocyanates with bifunctional primary 2nd primary and / or secondary amino groups and / or

Alcohols in a polyether or polyester (molecular weight of primary hydroxyl compounds and / 500-3000) as a dispersing medium, whereby polyether or ammonia in

Polyester contain at least two (exclusively secondary) hydroxyl- 3. connecting groups having at least one hydroxyl group in the molecule. According to DAS 1 260 142, fertilize

in a polypropylene glycol ether as the dispersant NCO- where the compounds 3) have secondary hydroxyl groups and NH groups-containing compounds “in situ” polyad, if as compounds 2) those with primary hydration. In the processes mentioned, dispersions of xyl groups are used, which is characterized by polyurethanes, polyureas or polyhydrazodicarbonamides, in that the reaction components in the presence of hydroxyl groups in polyvalent, higher molecular weight, more than 4% by weight water, are preferred from 7 to 35% by weight of compounds which, because of their high viscosity as a thickener for textiles, including water, even with less water, particularly preferably 10-25% by weight water, based on the solids content, react, til- or Dyeing aids are recommended. It is preferred according to the invention to use as component 2) polya-

For example, a 10 (20)% polyhydrazodicarbonamide mine and / or hydrazine and / or hydrazide and / or NH3

Use dispersion in a polypropylene glycol ether according to DAS 55.

1 260 142 has a viscosity of over 10,000 (200,000) cP at 25 ° C. Furthermore, it is possible to use proportionally emulsifying and disper- That corresponds to more than 10- (200-) times the viscosity of pure ion-stabilizing substances such as amino , Semicarbazide or dispersant. When trying to use a 40% dispersion containing hydrazide polyether. produce, the reaction mixture, dispersant, d. H. the outer, coherent phase before the polyaddition is complete. The relatively high 60 viscosities of the present invention, which are 1 to 8, preferably 2 to low, solids limits the 6, particularly preferably 2 to 4, primary and / or secondary uses of the process products of external hydroxyl-containing alcohols with a molecular weight, since it is not possible in many fields of application, weights of 62-16,000, preferably 62 to 12,000, especially for their metering, the usual metering devices can be used, preferably 106 to 8000.

the. In the production of polyurethane foams, for 65 There are z. B. low molecular weight alcohols or which such dispersions can be used according to their own older glycols with a molecular weight between 62 and about 400, proposal (DOS 2 423 984), the ether, thioether or ester linkages, if necessary, the viscosities of the starting materials, for example under contain, and on the other hand polyester, polyether, polythioether,

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Polyacetals, polycarbonates and polyester amides with molecular weights of more than 400, as are known per se for the production of polyurethanes.

Suitable low molecular weight dispersants are, in addition to monoalcohols such as sutanol, 2-ethylhexanol, amyl alcohol and ethylene glycol monoethyl ether, and diols or triols, such as triols, which are usually used in polyurethane chemistry as chain extenders or crosslinking agents. B. propylene glycol (1,2) and (1,3), butylene glycol (1,4) and (2,3), hexanediol (1,6), octanediol (1,8), neopentyl glycol, Cyclohexanedimethanol, (1,4-bis-hydroxymethylcyclohexane), 2-methyl-l, 3-propanediol, glycerol, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4 ) or trimethylolethane, especially glycols with a hydrophilic character such as. B. ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol and polyethylene glycols with a molecular weight of up to 400. In addition, however, compounds such as dipropylene glycol, polypropylene glycols with a molecular weight of up to 400, dibutylene glycol, polybutylene glycols with a molecular weight of up to 400 and Castor oil can be used as a dispersant, as can ester diols of the general formulas

H0- (CH2) x-C0-0- (CH2) y-0H and H0- (CH2) X-0-C0-R-C0-0- (CH2) X-0H

in which

R an alkylene or. Arylene residue with 1-10, preferably

2-6 C atoms,

x 2-6 and

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y 3-5 mean

e.g. B. Ö-hydroxybutyl-s-hydroxy-caproic acid ester, co-hydro-xyhexyl-y-hydroxybutyric acid ester, adipic acid bis (ß-hydro-xyethyl) ester and terephthalic acid bis (ß-hydroxyethyl) ester; and diol urethanes of the general formula

H0- (CH2) x-0-C0-NH-R'-NH-C0-0- (CH2) x-0H

in the

R 'is an alkylene, cyeloalkylene or arylene radical with 2-15,

Preferably 2-6, C atoms and x represent a number between 2 and 6,

e.g. B. 1, 6-hexamethylene-bis- (ß-hydroxyethyl urethane) or 4,4'-diphenylmethane-bis- (ô-hydroxybutyl urethane); or also diolureas of the general formula

HO- (CH2) x -N-CO-NH-R "-NH-CO-N- (CH2) x-OH

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R, "

R '"

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in the

R "is an alkylene, cyeloalkylene or arylene radical with 2-15,

preferably 2-9 C atoms,

R '"is H or CH3 and x is 2 or 3,

e.g. B. 4,4'-diphenylmethane-bis- (β-hydroxyethyl urea) 30 or the compound ho-ch2-ch2-nh-co-nh - / h ch ^ h2 "nh ~ c0 ~ nh" ch2 "ch2 ~ 0h

Particularly suitable among the di- and trihydric low-molecular alcohols are those which, if appropriate as a mixture or with the use of higher-molecular alcohols, are liquid at temperatures below 50 ° C.

The high-molecular polyesters that come into question as dispersants are hydroxyl groups. B. Reaction products of polyhydric, preferably dihydric and optionally additionally trihydric alcohols with polyhydric, preferably dihydric, carboxylic acids. Instead of the free polycarboxylic acids, the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures thereof can also be used to produce the polyesters. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic in nature and optionally, e.g. B. by halogen atoms, substituted and / or unsaturated. Examples of these are: succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, trimellitic acid, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, tetrachlorophthalic anhydride, maleficidium maleate, acid malomide, maleic acid malefic acid, endomethylene terehydric acid, endomethylene tereic acid anhydride, endomethylene tereic acid anhydride, endomethylene tereic acid anhydride, endomethylene tereic acid, , optionally in a mixture with monomeric fatty acids, dimethyl terephthalate and bis-gly-terephthalic acid. As polyhydric alcohols such. B. ethylene glycol, propylene glycol (l, 2) and - (, 3), butylene glycol (l, 4) and -2,3), hexanediol- (l, 6), octanediol- (l, 8), Neopentyl glycol, cyclohexanedimethanol, (1,4-bis-hydroxymethylcyclohexane), 2-

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40 methyl-l, 3-propanediol, glycerol, trimethylolpropane, hexane-triol- (l, 2.6), butanetriol- (l, 2.4), trimethylolethane, triethylene glycol, tetraethylene glycol, polyethylene glycols, dipropylene glycol, polypropylene glycols, dibutylene glycol and polybutylene glycols in question. The polyesters can have a proportion of terminal carboxyl groups. Lactone polyester, e.g. B. e-caprolactam or hydroxycarboxylic acids, e.g. B. co-hydroxy caproic acid can be used.

The polyethers of higher molecular weight preferred as dispersants according to the invention can be prepared in a manner known per se by reacting starter compounds with reactive hydrogen atoms with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, tetrahydrofuran or epichlorohydrin or with any mixtures of these alkylene oxides. Those 55 polyethers which predominantly have primary OH groups are often preferred.

Suitable starter compounds with reactive hydrogen atoms are e.g. Water, methanol, ethanol, ethylene glycol, propylene glycol- (l, 2) or- (1,3), butylene glycol- (l, 4) 60 or- (2,3), hexanediol- (l, 6), octanediol- ( l, 8), neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2-methyl-l, 3-propanediol, glycerol, trimethylolpropane, hexanetriol- (1,2,6), butanetriol- (1,2,4), trimethylolethane , Pentaerythritol, mannitol, sorbitol, methyl glycoside, cane sugar, phenol, isononylphenol, Resor-65 a, hydroquinone, 1,2,2-resp. l, l, 3-tris- (hydroxyphenyl) -ethane, ammonia, methylamine, ethylenediamine, tetra- or hexamethylenediamine, diethylenetriamine, ethanolamine, diethanolamine, triethanolamine, aniline, phenylenediamine, 2,4- and 2,6-

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Diaminotoluene and polyphenyl-polymethylene-polyamines, as they are obtained by aniline-formaldehyde condensation. Resin-like materials of the phenol and resol type can also be used as starters.

Also modified by vinyl polymers polyethers such as z. B. by polymerization of styrene and acrylonitrile in the presence of polyethers (US Pat. Nos. 3,383,351,3-304,273,3,523,093,3 110,695, German Pat. No. 1,152,536) are suitable, as are OH-containing polybutadienes.

Among the polythioethers, the condensation products of thiodiglycol with itself and / or with other glycols, dicarboxylic acids, formaldehyde, aminocarboxylic acids or amino alcohols should be mentioned in particular. Depending on the co-components, the products are usually polythio ether, polythio ether ester or polythio ether ester amide.

As polyacetals such. B. from glycols, such as diethylene glycol, triethylene glycol, 4,4'-dioxethoxy-diphenyldi-methylmethane, hexanediol and formaldehyde compounds in question. Suitable polyacetals according to the invention can also be produced, for example, by polymerization of cyclic acetals.

Suitable polycarbonates containing hydroxyl groups are those of the type known per se, which, for. B. by reacting diols such as propanediol (1,3), butanediol (1,4) and / or hexanediol (1,6), diethylene glycol, triethylene glycol or tetraethylene glycol with diaryl carbonates, e.g. B. diphenyl carbonate, or phosgene can be produced.

The polyester amides and polyamides include e.g. B. the predominantly linear condensates obtained from polyvalent saturated and unsaturated carboxylic acids or their anhydrides and polyvalent saturated and unsaturated amino alcohols, diamines, polyamines and their mixtures.

Of course, according to the invention, as already mentioned above, mixtures of the high and low molecular weight dispersants mentioned can also be used.

Dispersants which do not contain any labile groups (e.g. ester groups) which can be destroyed by hydrolysis or aminolysis during the process according to the invention are preferred according to the invention. Such compounds are expediently only added to the finished dispersion after the polyaddition reaction has ended.

The hydroxyl compounds or their mixtures used as dispersants according to the invention are normally to be selected such that they (in a mixture with the water added according to the invention, optionally OH or preferably NH compounds and optionally an inert solvent) are liquid at the reaction temperature, i.e. be present as a solution or emulsion. The viscosity at the reaction temperature should generally be less than 20,000 cP, preferably less than 5,000 cP, so that the usual stirring and mixing devices can be used.

If inert solvents are also used, then preferably those which can be distilled off as an azeotrope with water, for example benzene and toluene.

According to the invention, polyamines, hydrazines and hydrazides are particularly suitable as components which are reactive toward isocyanates when preparing the dispersions. Suitable polyamines are two and / or polyvalent, primary and / or secondary; aliphatic, araliphatic, cycloaliphatic _ and aromatic amines, e.g. B. ethylenediamine, 1,2- and 1,3-propylenediamine, tetramethylenediamine, hexamethylenediamine, dodecamethylenediamine, trimethyldiaminohexane, N, N'-dimethylethylenediamine, 2,2'-bisaminopropylmethylamine, higher homologues of ethylenediamine, such as diethylenetriamine Triethyl entetramine and tetraethylene pentamine, homologs of propylene

diamines such as diopropylenetriamine, piperazine, N, N'-bisaminoethyl-piperazine, triazine, 4-aminobenzylamine, 4-aminophenylethylamine, l-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 4,4'-diaminodicyclohexylmethane and propane, 1,4-diaminocyclohexane, phenylenediamines, naphthylenediamines, condensates of aniline and formaldehyde, toluenediamines, the bisaminomethylbenzenes and the derivatives of the aromatic amines monoalkylated on one or both nitrogen atoms. The polyamines generally have a molecular weight of 60-10,000, preferably 60-3000, particularly preferably 60-1000.

Hydrazines and, for example, hydrayzine and mono- or N, N'-disubstituted hydrazines may be mentioned, where the substituents can be Q — C6-alkyl groups, cyclohexyl groups or phenyl groups. The hydrazines generally have a molecular weight of 32 to 500. Hydrazine itself is preferably used.

Hydrazides which may be mentioned are, for example, the hydrazides of dibasic or polyvalent carboxylic acids such as carbonic acid, oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, acelainic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, and also the esters of hydrazine monocarboxylic acid with di- or polyhydric alcohols and phenols such as B. ethanediol, propanediol-1, 2, butanediol-1, 2, -l, 3and -1.4, hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and hydrochi-non, and the amides of hydrazine monocarboxylic acids (semi-carbazides ) with e.g. the above-mentioned di- and polyamines. The hydrazides generally have a molecular weight of 90-10,000, preferably 90-3000, particularly preferably 90-1000.

The amines and hydrazines mentioned above are preferably used in the form of their dilute aqueous solutions or - mixed with the dispersant - diluted with the required amount of water.

According to a special variant of the process according to the invention, stable, finely divided and relatively low-viscosity dispersions of reaction products of polyisocyanates, aqueous ammonia and, if appropriate, further amino-functional compounds in polyhydroxyl compounds can also be prepared as dispersants. The previously unknown bis-urea dispersions obtained in this way can then optionally be converted into high-molecular polymethylene ureas by crosslinking with formaldehyde. These polymethylene ureas also usually form finely divided, stable and low-viscosity dispersions in the compounds containing hydroxyl groups and used as dispersants.

In this variant of the process according to the invention, about 0.5 to 1.5, preferably 0.9 to 1.2, particularly preferably 1.0 equivalents of polyisocyanate are generally used per mole of ammonia. If, in addition to ammonia, additional amino-functional compounds are also used, an amount of additional polyisocyanate approximately equivalent to these amino-functional compounds must of course also be used.

The use of aqueous ammonia solution as the starting component over anhydrous ammonia is preferred - on the one hand because of the easier technical applicability of aqueous ammonia and on the other hand because any additional amino-functional compounds which may be used are better distributed in the dispersant as a result of the presence of water. In addition, the polyadduct formed as a solid phase is less prone to agglomeration, which normally increases the stability of the finished dispersions significantly.

It is generally to be regarded as surprising that the bis-ureas (or

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Tris-ureas when using trifunctional isocyanates) form stable dispersions in the compounds containing hydroxyl groups.

If you comparatively bring urea in the form of a. ■ aqueous solution into a polyhydroxy compound and then removes the water by distillation, the urea normally crystallizes in coarse needles. Such a suspension of urea crystals is usually unusable as a starting component for the production of polyurethane plastics.

According to a preferred variant of the process according to the invention, the dispersions of bis-urea (or tris-urea) prepared in situ are mixed with formaldehyde in the presence of catalytic amounts of acids or alkali in a manner known per se (see, for example, DOS 2 324 134) crosslinked to form polymethylene ureas. In general, about 0.2 to 3 moles, preferably 0.4 to 1.5 moles, particularly preferably 0.5 to 0.8 moles, of formaldehyde are used per equivalent of urea groups.

It is usually also possible to use the formaldehyde together with the ammonia solution. This usually results in products with different physical properties than in the post-crosslinking with formaldehyde described above, namely disperse systems which have a microgel-like character. In this variant of the process according to the invention, however, it must be ensured, for example, that all components are either mixed together at the same time or that the polyisocyanate is introduced into the reaction mixture immediately after the mixing of formaldehyde and ammonia solutions in the dispersant, ie. H. essentially before ammonia and formaldehyde have reacted to urotropin.

Of course, it is generally also possible to subsequently crosslink the polyurea or polyurethane and polyhydrazodicarbonamide dispersions prepared according to the invention in an analogous manner with formaldehyde.

As to be used according to the invention. Isocyanate components come into consideration aliphatic, cycloaliphatic, aliphatic, aromatic and heterocyclic polyisocyanates, such as those used for. B. by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136, for example ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, cyclobutane 1,3-diisocyanate, cyclohexane-1,3- and -1,4-diisocyanate and any mixtures of these isomers, l-isocyanato-3,3,5-trimethyl-5-iso-cyanoatomethyl-cyclohexane (DAS 1 202 785, American patent specification 3 401 190), 2,4-and 2,6-hexahydrotoluenediisocyanate and any mixtures of these isomers, hexahydro-1,3- and / or -1,4-phenylene diisocyanate, perhydro-2,4'- and / or-4,4'-diphenylmethane diisocyanate, 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, naphthylene-l, 5-diisocyanate, triphenylme-than-4,4'4 "triisocyanate, polyphenyl-polymethylene-polyisocyanate, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and e.g. in de n British patents 874 430 and 848 671 are described, m- and p-isocyanatophenylsulfonyl isocyanates according to the American patent specification 3,454,606, perchlorinated aryl polyisocyanates, as shown in FIG. B. in German Auslegeschrift 1,157,601 (US Pat. No. 3,277,138), carbodiimide group-containing polyisocyanates as described in German Patent 1,092,007 (US Pat. No. 3,152,162), diisocyanates as described in the American patent 3,492,330 are described, polyisocyanates having allophanate groups, as described, for. B. in the British patent specification 994 890, the Belgian patent specification 761 626 and the published Dutch patent application

627 195

avoidance 7 102 524 are described, isocyanurate-containing polyisocyanates such as z. B. in the American patent specification 3 001 973, in the German patent specifications 1 022 789.1 222 067 and 1 027 394 as well as in the German patent applications! 929 034 and 2 004 048 are described, polyisocyanates containing urethane groups, as shown in FIG. B. in the Belgian patent specification 752 261 or in the American patent specification 3 394 164, acylated urea group-containing polyisocyanates according to the German patent specification 1 230 778, biuret group-containing polyisocyanates, such as. B. in the German patent 1 101 394 (American patents 3 124 605 and 3 201 372) and in the British patent 889 050 described, by telomerization reactions produced polyisocyanates, such as. B. are described in American Patent 3,654,106, ester group-containing polyisocyanates, such as those mentioned, for example, in British Patents 965,474 and 1,072,956, in American Patent 3,567,763 and in German Patent 1,231,688, reaction products of The above-mentioned isocyanates with acetals according to German Patent 1,072,385 and polyisocyanates containing polymeric fatty acid residues according to American Patent 3,455,883.

It is normally also possible to use the distillation residues obtained in the production of isocyanate groups in industrial production, optionally dissolved in one or more of the aforementioned polyisocyanates. Furthermore, it is generally possible to use any mixtures of the aforementioned polyisocyanates.

The technically easily accessible polyisocyanates, e.g. B. the 2,4- and 2,6-tolylene diisocyanate and any mixtures of these isomers ("TDI"), polyphenyl-polymethylene polyisocyanates, such as those produced by aniline-formaldehyde condensation and subsequent phosgenation ("crude MDI") and Polyisocyanates containing carbodiimide groups, urethane groups, allophanate groups, isocyanurate groups, urea groups or biuret groups (“modified polyisocyanates”).

Of course, according to the invention, so-called prepolymers can also be used as the isocyanate component, i.e. reaction products of low and / or higher molecular weight compounds with OH and / or NH groups (e.g. those of the type mentioned above) with an excess of the monomeric polyisocyanates described above.

The inventive method allows z. B. also the proportional or exclusive use of isocyanates or amines, hydrazines or hydrazides, the functionality of which is more than two. It is generally to be regarded as surprising that the reaction according to the invention of such higher-functionality compounds in the dispersant containing hydroxyl groups does not lead to solid or at least very highly viscous reaction products, but also to finely divided, low-viscosity dispersions.

As already mentioned, the polyaddition products prepared by the processes according to the invention and dispersed in compounds containing hydroxyl groups can also be modified by the proportionate use of monofunctional isocyanates, amines, hydrazine derivatives or ammonia.

For example, the average molecular weight of the polyaddition products can be adjusted as desired by incorporating such monofunctional compounds. When using alkanolamines with primary or secondary amino groups, polyureas and polyurea polyhydrazodicarbonamides can be built up which have free hydroxyl groups. The introduction of other groups, such as B. ester groups, longer aliphatic radicals, tertiary amino groups, active double bonds, etc. is possible,

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627 195 6

if appropriately substituted mono- or diamines or and 1.10, it is particularly preferred to use about equivalents

Isocyanates are also used. Quantities.

Suitable monofunctional isocyanates are e.g. B. Alkyl iso- In the reaction of polyisocyanates with polyamines, cyanates such as methyl, ethyl, isopropyl, isobutyl, hexyl, lau or hydrazines or hydrazides in the presence of hydroxyl

ryl and stearyl isocyanate, chlorhexyl isocyanate, cyclohexyl iso 5 group-containing compounds is the reaction between

cyanate, phenyl isocyanate, tolyl isocyanate, 4-chlorophenyl isocy- see NCO and NH groups usually strongly favored,

anate and di-isopropylphenyl isocyanate. however, depending on the reaction conditions,

As monoamines such. B. alkyl and dialkyl amines with the OH groups of the dispersant on the

Cj-C] 8-alkyl groups, cycloaliphatic amines such as reaction. This reaction usually creates

Cyclohexylamine and homologs, aniline and N-alkylanilines 10 polyurea and / or polyhydrazodicarbonamide chains, the aniline derivatives and alkanols substituted on the benzene nucleus are chemically linked to the mono- or preferably refill used as dispersant, such as ethanolamine, diethanolamine, propanolamine, dipro-polyalcohol are. Such end groups

panolamine, butanolamine and dibutanolamine, as well as diamines presumably dispersing on the solid particles. The one with a tertiary and a primary or secondary amino portion of this participation of the OH groups in the polyaddition

group, like B. N, N-dimethyl-ethylenediamine and N-methyl 15 reaction is particularly mentioned from the temperature control and piperazine. Depends on monofunctional hydrazine derivatives and water content. React too many higher molecular weight

Hydrazides come e.g. B. N, N-dialkylhydrazines, the hydrazide polymolecules with the polyisocyanates, are usually obtained from monocarboxylic acids, hydrazine monocarboxylic acid esters of the highly viscous dispersions. This is apparently the case with the monofunctional alcohols or phenols and semicarbazide procedure according to DAS 1 260 142. On the other hand, such as B. methyl, ethyl, propyl, butyl, hexyl, dodecyl, 20 the proportion of co-reacting polymolecules too low, so

Stearyl, phenyl and cyclohexyl semicarbazide into consideration. for example, there is a risk that the larger particles of

The molecular weight of the dispersions produced according to the invention are not stable, but rather polyaddition products dispersed in sediment in hydroxyl compounds. The process according to the invention is usually permitted by the quantitative ratio between the amount of the NCO / OH reaction and the polyamine Hydrazine or hydrazide, on the one hand, and the polyiso site, on the one hand, which determines finely divided dispersions with eyanat, on the other hand (or arise from the low viscosity which may be desired, but, on the other hand, of monofunctional compounds used). In particular, coarser fractions of the dispersions are still so stable that preference is given to approximately equivalent amounts of isocyanates and they do not normally sediment even after prolonged storage, even at elevated temperature, of OH-functional or preferably NH-functional compounds.

brought into reaction in the hydroxyl-bearing dispersant. (Chains containing primary hydroxyl groups - When using low-viscosity, exclusively extension agents, it is advisable to react with polyethers containing secondary OH groups or medium containing only secondary hydroxyl group-less reactive (aliphatic) isocyanates, the proportion of the pen may have.) It is also possible to work with a limited isocyanate-reacting polyol molecule to achieve a stable excess, but in some cases the NCO / NH polyaddition leads to an increase in dispersion, but products with relatively higher viscosity are obtained because the excess is too small. In these cases, it is expedient to react emulsifying weft on polyiso eyanate with the dispersant. acting and thus increasing the stability of the dispersion, on the other hand, a large excess of low-molecular weight is generally to be included in the polyaddition reaction. Such molecular chain extenders, e.g. amine, substances are e.g. linear polyethers of medium molecular hydrazine or hydrazide, possible without increasing the viscosity, 40 lar weight 300-4000, which are obtained on both or preferably only on polyadducts with reactive end groups and a chain end NCO groups or amino or limited molecular weight. Generally contain hydrazide groups.

becomes an equivalent ratio of polyisocyanate / chain extender. B. possible in minor amounts of isocyanate

between 0.50 and 1.50, preferably between 0.90 adducts of diols of the general formula

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R "'R"'

HO-CH-CH2-N-CH2-CH-OH

CO-NH-R-NH-CO-0-CH2-CH-04-CH2-CH2-X-R1

RIV /

to be used as emulsifying agents, in which 55 disper-

R represents a divalent radical, such as modified polyethers having a yawing action, in addition to those of the isocyanate groups from a diisocyanate of the general formula above, e.g. The addition products of lar weight 112-1000 are also obtained from excess di- and / or polyisocyanates as described above

X stands for oxygen or -NR ", for example, on mono- and / or bifunctional

R 'and R are the same or different and, for monovalent 60 hydroxyl polyethers of average molecular weight 300-4000,

Hydrocarbon residues with 1-12 carbon atoms, which may have been unreacted, free isocyanate by thin layers, have been freed

R '"stands for hydrogen or a monovalent hydrocarbon isocyanate prepolymer but also with the excess free radical having 1-8 carbon atoms, isocyanate is converted to alophanate isocyanates. Furthermore

Rlv a hydrogen atom or -CH3 and 65 it is possible to add the isocyanate end groups

n is an integer from 4-89. Products with excess diamines or hydrazine. B. after

The preparation of such emulsifying diols is DAS 1 122 254 or 1 138 200 in amino or semicarbazide end

e.g. in DOS 2 314 512. to transfer group-containing polyether.

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Also polyether having amino end groups, as z. B. according to the methods of US Pat. No. 3,155,278 or DAS 1 215 373 can be used according to the invention as dispersing agents.

Finally, hydroxyl polyether with phosgene can also be converted into the chloroformic acid esters and then reacted with excess diamine or hydrazine. As already mentioned, such polyethers are preferred as dispersing agents which have an NCO or NH2 grouping only at one chain end.

According to a less preferred variant of the process according to the invention, it is also possible to convert compounds of the type mentioned above with 2 or more primary hydroxyl groups and a molecular weight from 62 to 400 (optionally together with monohydric primary alcohols) with polyisocyanates to give polyurethane dispersions. It must be noted, however, that in this case only dispersants are used which exclusively carry secondary hydroxyl groups and preferably have a molecular weight of more than about 500, so that a selective reaction of the polyisocyanate with the primary hydroxyl compounds is generally ensured .

The amount of water present according to the invention during the polyaddition reaction is generally of decisive importance both in terms of particle size, particle size distribution and the final viscosity of the dispersion. Several factors usually have to be taken into account at the same time: the viscosity and hydrophilicity or hydrophobicity of the dispersant containing alcoholic groups used, the solubility of the emulsifiability of the starting components intended for isocyanate polyaddition, the solids content of the resulting dispersion and the temperature control. In addition, the order and type of addition can be of influence. With increasing water content, as exemplified above, there is a significant increase in viscosity, particularly in the case of hydrophilic, higher molecular weight dispersants. This effect usually increases with the progressive polyaddition in water-diluted alcohol. This limits the maximum amount of water used. In all cases, it is usually necessary to ensure good miscibility of the reaction mixture in the presence of the water during the polyaddition reaction or during the subsequent water distillation. In general, less than 35% by weight, but at least about 7% by weight, of water, based on the total amount of the reaction mixture, will be added (the higher the solids content of the dispersion, the more water should be used). The optimal amount of water is usually to be regarded as that which on the one hand enables the lowest possible viscosity of the dispersions produced according to the invention and on the other hand saves the distillation of unnecessarily large amounts of water. In many cases the preferred amount of water is 10-25% by weight. %, based on the reaction mixture. If strongly hydrophilic alcohols are used, smaller amounts of water, from approx. 4% by weight, can also be used.

In order to achieve the lowest possible final viscosity, it is also advantageous to select the reaction temperature as high as possible, for example at the beginning of the polyaddition reaction, preferably close to the boiling point of the water.

By using boiler stirrers with a reflux condenser, the heat of reaction can be easily removed by refluxing in the strongly exothermic isocyanate reaction. At the same time, adducts that form in the gas phase above the liquid reaction mixture are continuously rinsed “statu nas-cendi” from the water into the liquid phase and are usually finely dispersed.

The dispersant can be mixed with the reaction components in various ways. In the simplest case, the hydroxyl group-containing dispersant, the required amount of water and the NH compound (or the primary hydroxyl compound) are placed in a vessel stirrer, for example, and the mixture is heated to 70-90 ° C., for example, and left The component containing isocyanate groups flows in so rapidly that the reaction mixture boils strongly under reflux. In the production of high-solids dispersions, for example, it is advantageous to introduce the polyisocyanate (mixture) into the lower third of the liquid receiver. In suitable boiler equipment, the reaction temperature can be increased to 105-115 ° C, if necessary, by applying a slight excess pressure. When the isocyanate groups have reacted completely, the water and any inert solvent present are preferably distilled off under reduced pressure and the dispersion is drained off through a sieve. Of course, in many cases the optionally aqueous solution of the NH-20 compound and the polyisocyanate can also flow into the dispersant diluted with water at the same time. However, an excess of isocyanate should normally be avoided here. Part of the heat of reaction can also be consumed by mixing the polyisocyanate at room temperature, for example, with part of the alcohol used as a dispersant immediately before the addition. If it is desired, for example in the case of large-scale production of more than 1000 metric tons, to carry out the process according to the invention continuously, the dispersant, the reaction components and the water can be metered in continuously in continuous mixers. Because of the very strongly exothermic reaction with increasing solids content and thus increasing vapor pressure, the dwell time must expediently be so short that the reaction temperature in the premixer does not exceed 100 ° C. if possible. At dej: Production of a 40% dispersion is e.g. B. The throughput speed is not significantly above 1-3 seconds. The reaction mixture premixed in this way is introduced into a stirring vessel and, after a dwell time of typically 20-30 minutes, is pressed into a vessel 40 for distilling the water.

The water distillation can also be carried out at a later point in time, but the dispersions thus obtained have a higher viscosity.

45 In practice, in order to achieve a particularly low viscosity, preference will usually be given to the discontinuous boiler process and immediate water distillation because of its extraordinary simplicity, safety in the reaction process and reproducibility.

In the finished dispersion, of course, that water content can remain which is required for later reactions, for example for the production of polyurethane foams.

The concentration of the polyadducts in the hydroxyl-containing dispersant can vary within wide limits, but is generally between 1 and 60% by weight, especially between 5 and 50% by weight. Depending on their concentration, the dispersions prepared according to the invention generally have viscosities of up to 80,000 cP, preferably up to 60 40,000 cP at 25 ° C. After they have been diluted to 10% by weight. % Solids, the viscosity is generally less than 2500, preferably less than 1500 cP at 25 ° C. It is a particular advantage of the process according to the invention that, in many cases, the dispersions 65 prepared in very high concentration usually have a relatively lower viscosity after dilution with the same dispersant than comparable products which were produced directly with a lower solids content.

50

627 195

In tank stirrers with a reflux condenser, as stated above, despite the strongly exothermic reaction of NCO with NH groups, dispersions with a surprisingly high solids content (up to over 50%) can be produced cost-effectively. Since the dispersions usually have a solids content of about 10% by weight. % are used for the production of polyurethane plastics, there is also the possibility of using such hydroxyl-containing alcohols, for example polyester, in large proportions by weight as a mixed component, which may partially react at the temperatures of the dispersion preparation with water or NH compounds (e.g. B. hydrolysis or aminolysis) would go into. From a finished 40% polyhydrazodicarbonamide dispersion in polyether you get e.g. B. by stirring in the same or 3 times the amount of polyester (see Example 7) a 20- (10)% dispersion with a polyether / polyester weight ratio of 3: 5 (1: 5) and a viscosity that only a little is above or even below the viscosity of the pure polyester. ": *.

Surprisingly, such dispersions in polyol mixtures are usually stable even when the polyether and the polyester cannot be mixed together under otherwise identical conditions. In these cases, the injected polyamide methane apparently acts as an emulsifier, which generally prevents the system from being separated into two phases, even when stored for a long time. This is a further important advantage of the method according to the invention, since such stabilized polyesters / polyether systems can be used to produce novel polyurethane plastics which are not accessible in any other way.

The use of higher molecular weight, hydroxyl group-containing polyethers as dispersants enables, as already mentioned, a particularly economical, "gentle and varied industrial production of dispersions with high solids concentrations, which can possibly serve as a" masterbatch "in the process according to the invention. However, the use of polyethers has For example, there is another advantage: In the large-scale production of polyethers, there are usually aqueous crude polyether intermediate stages with a water content of 8-12% by weight, in which 0.3-1% by weight alkali sulfates are dissolved and additionally 1- 3% by weight of toluene are usually suspended, and such a "crude polyether suspension pen" is first freed from water and toluene by distillation under reduced pressure to a residual content of 0.4-1% by weight, during which the alkali metal sulfates fall and can be isolated using sponge filters.

The sulfate-free polyether containing 0.5-1% by weight of water is largely freed of residual water, for example, by thin layers, so that the water content of the purified commercial polyether goods is less than 0.5% by weight. % is. For the process according to the invention, however, it is generally not necessary to use a highly purified, practically anhydrous polyether. Rather, it is sufficient to use the raw polyether precursors, either the goods before thin-filming, or, what is particularly useful, the «raw polyether suspension» (with about 10%;] water, alkali sulfate and toluene). The water, toluene and sulfate are preferably removed by distillation and filtration after the isocyanate polyaddition has ended by the process according to the invention. j

It has been found that the properties of the polyurethane plastics produced from the dispersions according to the invention can be modified in a technically advantageous manner if, in the process according to the invention, instead of water, for example, a corresponding amount of an aqueous polymer latex, for example an aqueous polyurethane dispersion or the aqueous solution of a ionic polyurethane or a polymer latex or a dispersion of a

Polycondensation product uses. The polymer latex or solution should usually have a solids content of 1 to 60% by weight. %, preferably 5 to 55% by weight, so that the weight ratio between the solid of the polymer latex and the “in situ” polyaddition product between 1:99 and 99: 1, preferably between 10:90 and 90:10, particularly preferably between 25 : 75 and 75:25.

When selecting the known aqueous latices of polymers, polycondensates and polyaddition products or also their mixtures for the process according to the invention, preference should be given to their compatibility with the dispersant carrying alcohol groups. For example, aqueous polyurethane dispersions are particularly widely applicable. In the variant of the process according to the invention described above, both cationic and anionic and nonionic polyurethane dispersions can be used. Aqueous polyurethane dispersions are preferably used which, when dried, provide polyurethane films with elastic properties. These are in particular rubber-elastic or at least impact-resistant polyurethanes or polyureas or polyhydrazodicarbonamides, which have a ball pressure hardness below 1400 kp / m3 (60 seconds according to DIN 53 456), preferably a Shore hardness B of less than 55, particularly preferably a Shore Hardness A of less than 98. For the later production of, for example, polyurethane foams, elastomers or coatings with special properties, dispersions of harder polyurethanes can of course also be used in individual cases.

Aqueous polyurethane dispersions suitable for the process according to the invention can generally be obtained if components which contain ionic or ion-forming groups and, in addition, at least one NCO group or at least one hydrogen atom reacting with icocyanate groups are also used in the production of the polyurethanes .

A summary of the various processes for the production of polyurethane dispersions can be found e.g. B.beiD. Dieterich and H. Reiff “The Applied Macromolecular Chemistry” 26.1972 (pages 85 to 106), D. Dieterich et al in “Angewandte Chemie” 82.1970 (pages 53 to 63) and D. Dieterichetal. J. OilCol. Chem. Assoc. 1970.53 (pages 363 to 379). A comprehensive literature review is also given in these collective papers. With regard to the production of cationic polyurethane dispersions, reference is made, for example, to German Auslegeschrift 1 184 946.1 178 586.1 179 363 and 1 270 276, US Pat. No. 3,686,108, Belgian Patents 653,223,

658 026 and 636 799. Suitable anionic polyurethane dispersions are described, for example, in German Auslegeschrift 1 237 306 and German Offenlegungsschriften 1 495 847.1 570 656 and 1 720 639. Further ionic polyurethane dispersions to be used according to the invention are described, for example, in German Offenlegungsschriften 1 770 068.1 953 345.1 953 348 and 1 953 349, German Auslegeschrift 1 495 745.1 282 962 and 1 694 129 and German Offenlegungsschriften 1 595 687.1 694 148.

1,729,201 and 1,771,068. Nonionic polyurethane dispersions which are suitable according to the invention are produced, for example, by the process of German Offenlegungsschriften 2 141 807.2 314 512.2 314 513 and

2,320,719.

Suitable polymer latices are, for example, those based on natural or synthetic rubber, styrene-butadiene copolymers, neoprene, styrene-acrylonitrile copolymers, polyethylene, chlorosulfonated or chlorinated polyethylene, butadiene-acrylonitrile copolymers, butadiene-methacrylate copolymers, polyacrylic acid copolymers, polyacrylic acid copolymers, polyacrylic acid copolymers PVC and optionally partially saponified ethylene-vinyl acetate copolymers. -

8th

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

9 627 195

Games for such polymer latices are such. B. the US patent with the help of ionic polymers containing polyhydroxyl

2 993 013 or DOS 2 014 385. Connections usually leave foams with

An example of polycondensate dispersions are the counter ion groups, the hydrophilicity of which is increased.

likewise containing amino groups or Phe- Such hydrophilized foams are, for. B. easier

■ -nolplast dispersions mentioned how they can and can be wetted in the German Offenle- 5 (depending on the hydrophilic

supply specification 2 324 134 are described. If necessary, larger quantities of water can be absorbed than conventional

also (nelle products produced with an excess of formaldehyde. They can, for example, also be used as ion exchangers methylolated polycondensate dispersions). Find use.

According to a special embodiment of the present, an interesting advantage of the method according to the invention

The invention can initially be found in a first stage in the hydroxyl, for example, in that the polymers or, for example, ionic polyisocyanate polyadducts, when group-containing dispersants are used

Produce polycondensates directly “in situ” and then let the polyisocyanate polyaddition run from polyester urethane foams to the otherwise necessary in the polyhydroxyl compounds containing lubricants during the manufacture of the reaction vessel. The use of emulsifying aids can be dispensed with

In the described variant of the inventive method. Apparently, the substances introduced into the reaction

While driving, the polyurethanes, polymers or polytene ionic polyurethane molecules are usually used as an internal di-

condensation products or mixtures thereof preferably in detergents.

Used in the form of their aqueous dispersions or solutions. However, a further possible variant of the present invention can also be used in a non-aqueous dispersing agent, for example, in that in the polyhydroxyl compounds

or solvent are presented and the water is added only before the 20th gene dispersed polyisocyanate polyadducts

Polyisocyanate polyaddition reaction (e.g. together with the formaldehyde in the presence of catalytic amounts

NH compounds) are added. Crosslinking acids in a manner known per se. To surprise-

Crosslinked dispersions of this type are also more normal as non-aqueous dispersants or solvents.

in general, particularly suitable are those which are also finely dispersed and stable in storage.

Dispersants are used in in-situ polyaddition. The particular importance of the present invention, that is to say the low molecular weight polyols or the higher molecular weight in general, is that all of the improvements mentioned include polyethers, polyesters, polycarbonates and polyactals with gen or Modifications to the properties of polyurethane hydroxyl groups, as described in the main patent, using the usual raw materials. In special cases it can also be achieved (preferably in compliance with the usual, mostly standardized recipe-boiling below 150 ° C.) organic or organic-aqueous 30 ren.

Solvent (dispersion) be medium, for example an acetone or diluted with water acetone solution or dispersion. The according to the different variants of the

The great advantage of the process according to the invention lies in the fact that dispersions produced by the process can be explained in that, with the aid of the easy-to-carry out polyisocy-

anate polyaddition principle and, due to the extraordinarily 35 hydroxyl compounds in a manner known per se, together with a large abundance of possible reaction components, polyisocyanates of the type mentioned above, if appropriate together

Targeted changes in properties in an optimal way or with unmodified polyhydroxyl compounds or

Improvements in the polyamines, hydrazines or hydrazides of the abovementioned which are accessible according to the invention

Dispersions produced polyurethane plastics by suitable as chain extender and possibly blowing agents, catalytic

nete choice of 'output connections can achieve. 40 generators and other additives to polyurethane plastics

Another variant of the method according to the invention, implemented with improved mechanical properties, is that instead of the aqueous polymer dispersions. Examples include foams, elastomers, homo-

uses aqueous solutions of ionic polyurethanes, such as those called gene and porous coatings and coatings, lacquers and, for example, in the above-mentioned publication of thermoplastically processable polyurethanes. About that

D. Dieterich et al. in Angewandte Chemie 82, 1970, page 45, the process products can also be used as such or after

53-63. Implementation with an excess of polyisocyanate to «modify

Depending on the intended use of the producible polyurethanes »prepolymers for the production of aqueous polyurethane,

thane and the desired modification or improvement 'dispersions by known methods.

their mechanical properties or applicability, for the property improvements which the various starting components, in accordance with the invention, generally select the process products in the polyurides of the process according to the invention produced therefrom. If you want to effect than-plastics (especially improved upsetting a relatively hard, brittle polyurethane type impact-resistant hardness), especially the particle size of the dispersion-modified, you use the aqueous dispersion of a polyaddition products of crucial importance, highly elastic polyurethane, polymer or polycondensation when using polyether dispersions sats. In this way, one can not only greatly reduce the general 55 as a starting material for the production of polyurethane brittleness of the end product, but also foams the diameter of the filler particles far below also the marginal half of the cell web dimensions, which are particularly susceptible to repulsion (20-50 In polyurethane coatings, for example a foam made from them, the particles must preferably be so small that they elasticize, so that even with very thin coats, even coatings

Conversely, of course, one can be obtained after the same 60 gene with a smooth surface.

Principle also a relatively soft polyurethane end product

With the aid of a dispersion of a comparatively hard polyurate, the process according to the invention then gives rise to thans, polymers or polycondensation products, in a modified manner, advantageously dispersions whose particle size is more common. In this way it is possible to optimize the tensile strength of the end product, both in terms of hardness and from 0.01 to 5 µm. In addition, 65 corresponds well.

The following examples illustrate the disperse polyhydrazodicarbonamide particle according to the invention, an improvement process. Unless otherwise noted, figures are given as an indication of the light stability of the process products. To understand parts by weight or percentages by weight.

627 195

example 1

20% polyhydrazodicarbonamide dispersion in trifunctional

nell polyether; identification number

NCO

(100) = 100

NH

Recipe:

80.8 parts by weight of a trimethylolpropane-based polyether made from propylene oxide and ethylene oxide with an OH number of 34 and about 80% primary OH groups (hereinafter referred to as “polyether I”) as a dispersant;

16.9 parts by weight of tolylene diisocyanate (mixture of isomers 2.4-: 2.6- = 80:20; hereinafter referred to as “T 80”);

3.1 parts by weight of hydrazine (99% hydrate, optionally diluted with water).

10th

Water content: see table 1.

5 General mode of operation:

The dispersant, which has been preheated to 70 ° C., and the hydrazine hydrate diluted with water are mixed in a tank stirrer with reflux condenser and heated to 80 ° C. with stirring. Then the diisocyanate mixture is quickly introduced into the Rührke-10 gel. The polyaddition starts immediately with the boiling of the water under reflux. After the addition of diisocyanate, the temperature is reduced to 60-80 ° C. within 20-30 minutes (if necessary by cooling) and the water is distilled off under reduced pressure. Towards the end, the temperature is allowed to rise to 90-120 ° C. until no more water passes over and, if the viscosity permits (Examples 1b and 1c), filter through a 100 μm sieve.

Table 1

% By weight of water, based on the example of reaction-dispersing-solid dispersion viscosity viscosity mixture (one medium (anhydrous) 25 ° C [cp]

sleep Water 20%

la

4.8

6.3

25.2

5.0

268,000

Paste lb

7.9

10.7

42.7

8.5

2,700

finely divided dispersion lc

11.3

16.0

64.0

12.8

2 315 1 350 *

finely divided dispersion

: Diluted to 10% solids by adding polyether I.

Comparative example ld:

If Example 1 is repeated, but without the addition of water, the reaction mixture is pasted under otherwise identical conditions even during the addition of diisocyanate.

Comparative example le:

If Example 1 is repeated with 50% by weight of water in the reaction mixture, the phases are separated; pasting occurs when the water is removed.

. Example 2

40% polyhydrazodicarbonamide dispersion in trifunctional polyether

The recipe is analogous to Example 1, but is set at 40% solids.

With a water content of 20% by weight, based on the reaction mixture including water (that is 41.5 or 62 or 25% by weight, based on dispersant or on solids or on anhydrous dispersion), a very finely divided is obtained Dispersion (0.3-2 (xm) with a viscosity of 12,800 cP / 25 ° C with a residual water content of 0.4% (with additional polyether I diluted to 20 or 10% solids of 1550 or 1050 cP / 25 ° C).

Reaction conditions:

In a modification of the mode of operation of Example 1, the process is carried out in a 5001 stirred kettle and the diisocyanate mixture is introduced into the lower third of the kettle with a low admission pressure and not into the stirred cone.

Comparison test:

Without the addition of water, the reaction mixture is pasted and the stirrer comes to a standstill before the total amount of diisocyanate has been added.

35

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55

60

Example 3

20% modified polyhydrazodicarbonamide dispersion in trifunctional polyether; Key figure = 100

Recipe:

80.0 parts by weight of polyether I;

14.3 parts by weight of T 80 diisocyanate;

3.2 parts by weight of the diol urea ether

HO-CH2-CH2-N-CH2-CH2-OH

C0-NH- (CH2) 6-NHC0-0- (CH2-CH2-0) 45-C4H9

3.5 parts by weight of hydrazine (in the form of 99% hydrazine hydrate; added diluted with water) and a total of 11.9% by weight of water, based on the reaction mixture

(= 16.8%, based on dispersant; 67.4%, based on solid; 13.5%, based on anhydrous end product).

The procedure is analogous to Example 1. However, the diurea ether is first converted with an excess of the diisocyanate (code number 200) at 100 ° C, mixed with the remaining amount of T 80 diisocyanate after cooling and added to the template in this form.

The resulting, very fine-particle polyol dispersion has a viscosity of 2120 cP / 25 ° C with a residual water content of 0.5% by weight.

65

Key figure = 100

Example 3a

Recipe:

80.0 parts by weight of one started on trimethylolpropane

Polyether (Polyether II) from propylene oxide and ethylene

11

627 195

xid (OH number = 35; approx. 70% primary OH groups) 14.3 parts by weight of diisocyanate T 80;

4.4 parts by weight of diethylene glycol;

1.3 parts by weight of hydrazine (as a 99% hydrate; diluted with water added to the template); and a total of 13.7% by weight of water, based on the reaction mixture including water; (= 19.8%, based on dispersant; 73.4%, based on solid matter; 15.9%, based on anhydrous end product).

The procedure is analogous to Example 1, but first a prepolymer is prepared from the diethylene glycol and part of the diisocyanate (code number 200), then the remaining diisocyanate is added and the diluted prepolymer thus obtained is introduced into the reaction mixture.

The viscosity of the resulting finely divided, 20%, essentially water-free dispersion is 2670 cP / 25 ° C.

Example 4

38.3%, OH-functional polyhydrazodicarbonamide polyurea dispersion in a linear polyether.

Code 1

f'NCO \

7

1001 = 100

Key figure 2 NCO

(NCO \

100)

NH + OH /

1001 = 91

Recipe:

61.7 parts by weight of a linear polypropylene glycol with secondary OH groups. (Hereinafter called Polyether III; OH number = 56)

31.0 parts by weight of T 80 diisocyanate;

5.2 parts by weight of hydrazine (as 99% hydrazine hydrate; with

Water diluted added);

2.1 parts by weight of ethanolamine; a total of 22.3% by weight of water, based on the reaction mixture including water (= 46.5%, based on the dispersant; 75.1%, based on the solid; 28.7%, based on the anhydrous dispersion). The procedure is analogous to example 2.

The resulting stable, 0.2% by weight residual water-containing polyether dispersion has a viscosity of 2460 (680 or 510) cP / 25 ° C in 40% strength or when diluted to 20 or 10% with the polyether used.

Example 4a

If the formulation of Example 4 is modified analogously to Example 3, but the reaction product of the diisocyanate with 3% by weight of the dispersant (based on total solids) is used as the prepolymer, the dispersion obtained is even finer than in Example 4 and has excellent flow behavior.

Example 5

40%, highly cross-linked polyurea-polyhydrazodicarbonamide dispersion in trifunctional polyether; Key figure = 100

Recipe:

60.0 parts by weight of polyether I;

31.0 parts by weight of T 80 diisocyanate;

2.9 parts by weight of hydrazine (added as a hydrazine hydrate diluted with water);

6.1 parts by weight of diethylene triamine; a total of 18.9% by weight of water, based on the reaction mixture including water (= 38.9%, based on dispersant; 58.4%, based on solids; 23.3% based on anhydrous

End product).

The stable dispersion produced analogously to Example 1 has 40 (or 20 or 10)% strength and a viscosity of 18,500 (3800 or 2200) cP / 25 ° C.

5

Example 6

20% polyhydrazodicarbonamide dispersion in polyester; Key figure = 100

10 recipe:

80 parts by weight of a polyester made from adipic acid, trimethylolpropane and diethylene glycol (OH number = 56; acid number = 1; hereinafter referred to as polyester ATD); 16.9 parts by weight of T 80 diisocyanate;

15 3.1 parts by weight of hydrazine (added as a hydrazine hydrate diluted with water); a total of 11.3% by weight of water, based on the reaction mixture including water (= 16%, based on the dispersing agent; 64%, based on the solids; 12.8% based on the anhydrous polyester dispersion).

The procedure is analogous to Example 1. A stable dispersion is obtained, the viscosity of which is 35,500 and 24,500 cP / 25 ° C. at 20 or 10% solids content. The pure polyester has a viscosity of 21,400 cP / 25 ° C.

25th

Comparative experiment If no water is added to the initial charge before the diisocyanate is added, so that only the small amount of water from the undiluted hydrazine hydrate is present, the reaction mixture is completely solidified before the addition of the diisocyanate has ended.

30th

35

Example 7

Dispersion in a polyether / polyester mixture If the solids content of the 38.3% dispersion from Example 4 is reduced by stirring in polyester ATD (viscosity 21 400 cP / 25 ° C) to 20 or 10% by weight gives a stable polyether / polyester mixture with a viscosity of 19,800 or 24,200 cP / 25 ° C.

40 On the other hand, a mixture of pure polyether III and polyester ATD (without dispersed solid) separates into two phases after just a few hours.

Example 8

45 20% polyurethane dispersion in polyether with secondary OH groups; Key figure = 100

Recipe:

80.0 parts by weight of polyether III;

11.8 parts by weight of T 80 diisocyanate;

8.2 parts by weight of N-methyldiethanolamine; 7% by weight of water, based on the reaction mixture including water (= 9.4%, based on dispersant; 37.5% based on solid; 7.5%, based on anhydrous dispersion).

Procedure:

Polyether, N-methyldiethanolamine and water are placed in a stirring apparatus at room temperature and the diisocyanate is added slowly with cooling so that the reaction temperature does not exceed 50.degree. 60 minutes after the addition of all of the isocyanate, the water is distilled off under reduced pressure. Towards the end of the distillation, the temperature can be gradually increased to 90 ° C.

The viscosity of the stable 20% dispersion thus obtained is 2210 cP / 25 ° C.

Comparison test:

Under otherwise identical reaction conditions, no

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55

60

65

627 195

12th

Adding water to the reaction mixture creates a dispersion that sediments overnight.

Example 9

20% Polyfiydrazodicarbonamid dispersion in trifunctional 5 nell Polyäthir

Recipe:

80.0 parts by weight of one started on trimethylolpropane

Polyether; from propylene oxide and ethylene oxide (OH number 10 28; approx. 80% primary OH groups);

7.1 parts by weight of tolylene diisocyanate; (Isomer mixture

2.4: 2.6 = $ 5.35);

10.2 parts by weight of 4,4'-diphenylmethane diisocyanate; 2.7 parts by weight of hydrazine (as a 99% hydrate; with water 15

diluted entered); a total of 13.0% by weight of water, based on the reaction mixture including water (=; 18.6%, based on dispersant; 74.5%, based on solids; 14.9%, based on anhydrous end product).

20th

Procedure:

The polyether is used as a raw polyether suspension with a content of 10.5% water and 0.5% alkali sulfate and mixed with the hydrazine hydrate. The polyaddition takes place “in situ” by adding the mixture of the diisocyanates mentioned under the conditions given in Example 1.

The resulting, largely water-free 20% stable dispersion has a viscosity of 4200 cP / 25 ° C or, after being diluted with further (anhydrous) polyether to 10%, of 2100 cP / 25 ° C.

25th

30th

Example 10

The procedure is quite analogous to Example 9, but instead of the pure diphenylmethane diisocyanate, a technical 3j product is used, some of which also contains three and four benzene rings containing polyisocyanates. The viscosity of the 20 or 10% stable dispersion is 3200 or 1900 cP / 25 ° C.

The following examples show possible uses for the dispersion according to the invention.

Example 11

100 parts by weight of the polyhydrazodicarbonamide / polyether dispersion adjusted to 20% solids content according to Example 1c, 3.0 parts by weight of water 0.2 parts by weight of triethylenediamine 0.3 parts by weight of 2-dimethylaminoethanol 0.8 parts by weight of a commercially available polysiloxane foam -

stabilizers (OS 15 from Bayer AG) and 0.22 parts by weight of tin (II) octoate were mixed together. This mixture was mixed with 24.1 parts by weight of tolylene diisocyanate (65% 2.4 and 35%

2,6-isomer) and 12.0 parts by weight of tolylene diisocyanate (80% 2,4- and 20% 2,6-isomer)

stirred intimately at room temperature. After 8-9 seconds a cream-like reaction mixture was formed, the rise time of which was 75 seconds and the setting time of which was 120 seconds.

The foam obtained had the following mechanical properties:

Bulk density; according to DIN 53 420 33 kg / m3

Tensile strength: according to DIN 53 571 160 KPa

Elongation at break / according to DIN 53 571 190%

Compression hardness "; according to DIN 53 577 5.3 KPa

Indentation test according to ASTM D1564-71T H value at 25% deformation (N) 290 H value at 65% deformation (N) 540 RH value at 25% deformation (N) 200

40

45

50

55

60

65

(25% RH value / 25% H value) x 100 70%

65% H value / 25% H value 1.9

Comparison test:

The same recipe was used, but 100 parts by weight of the polyether I used as the dispersant was used instead of the polyhydrazodicarbonamide dispersion. If the same ratio of NCO / OH groups (key figure) is maintained, a foam with the same bulk density is obtained, but which has a compression hardness of only 4.8 KPa according to DIN 53 577.

Example 12

100 parts by weight of the dispersion from Example lc, 5.0 parts by weight of water 0.2 parts by weight of triethylenediamine 0.3 parts by weight of 2-dimethylaminoethanol 1.0 part by weight of polysiloxane foam stabilizer (OS 15 der

Bayer AG) and 0.2 part by weight of tin (II) octoate were mixed together. This mixture was treated with 28.55 parts by weight of tolylene diisocyanate (65% 2.4 and 35%

2,6-isomer) and 28.55 parts by weight of tolylene diisocyanate (80% 2,4- and 20% 2,6-isomer)

stirred at room temperature. After 6-7 seconds a cream-like reaction mixture was formed, the rise time of which was 55 seconds and the setting time of which was 100 seconds.

The foam obtained had the following mechanical properties:

Bulk density according to DIN 53 420 24 kg / m3

Tensile strength according to DIN 53 571 140 KPa

Elongation at break according to DIN 53 571 180%

Compression hardness according to DIN 53 577 4.1 KPa

Indentation test according to ASTM D1564-71T H value with 25% deformation 130 H value with 65% deformation 255 RH value with 25% deformation 95 (25% RH value / 25% H value) X 100 73%

65% H value / 25% H value 2.0

Example 13

100 parts by weight of the dispersion from Example 1c adjusted to a solids content of 10%,

3.0 parts by weight of water 0.1 part by weight of triethylenediamine 0.3 part by weight of 2-dimethylaminoethanol 1.0 part by weight of polysiloxane foam stabilizer (OS 15 der

Bayer AG) and 0.18 part by weight of tin (II) octoate were mixed together. This mixture was mixed with 19.2 parts by weight of tolylene diisocyanate (65% 2.4 and 35%

2,6-isomer) and 19.2 parts by weight of tolylene diisocyanate (80% 2,4- and 20% 2,6-isomer)

stirred intimately at room temperature. After 10 seconds, a cream-like reaction mixture formed, the rise time of which was 102 seconds and the setting time of which was 180 seconds.

The foam obtained had the following mechanical properties:

Bulk density according to DIN 53 420 34 kg / m3

Tensile strength according to DIN 53 571 150 KPa

Elongation at break according to DIN 53 571 200%

Compression hardness according to DIN 53 577 5.1 KPa

Indentation test according to ASTM D1564-7IT H value at 25% deformation 275

13

627 195

H value at 65% deformation 510 RH value at 25% deformation 180 (25% RH value / 25% H value) x 100 65 65% H value / 25% H value 1.9

Example 14

100 parts by weight of the dispersion from Example 1c, 5.0 parts by weight of water 0.1 part by weight of triethylenediamine 0.3 part by weight of 2-dimethylaminoethanol and 1.2 parts by weight of polysiloxane foam stabilizer (OS 15 der

Bayer AG) and 0.2 part by weight of tin (II) octoate were mixed together. This mixture was treated with 28.85 parts by weight of tolylene diisocyanate (65% 2.4 and 35%

2,6-isomer) and 28.85 parts by weight of tolylene diisocyanate (80% 2,4- and 20% 2,6-isomer)

stirred intimately at room temperature. After 8 seconds, a cream-like reaction mixture formed, the rise time of which was 60 seconds and the setting time of which was 100 seconds.

The foam obtained had the following mechanical properties:

Bulk density according to DIN 53 420 23 kg / m3

Tensile strength according to DIN 53 571 140 KPa

Elongation at break according to DIN 53 571 190%

Compression hardness according to DIN 53 577 3.9 KPa

Indentation test according to ASTM D1564-71T H value with 25% deformation 110 H value with 65% deformation 235 RH value with 25% deformation 80 (25% RH value / 25% H value) x 100 72 65% H- Value / 25% H value 1.9

Example 15

100 parts by weight of the stable polyurea-polyhydrazodicarbonamide dispersion (polyester: polyether = 5: 1) adjusted to 10% solids content according to Example 7 4.0 parts by weight of water 0.6 parts by weight of dimethylbenzylamine 0.1 part by weight Parts of Sn (II) octoate and 2.0 parts by weight of a commercially available polysiloxane foam

fabric stabilizer (OS 25 from Bayer AG)

were mixed together. This mixture was mixed with 52.5 parts by weight of T 80 diisocyanate

stirred intimately at room temperature. After 10 seconds, a cream-like reaction mixture formed, the rise time of which was 65 seconds and the setting time of which was 125 seconds.

In contrast to the normally closed-cell, pure polyester foams, the foam obtained has open cells and is suitable, for example, because of its uniform, very fine cell structure. B. as a filter material.

If the example is repeated with a mixture of the pure polyester and polyether without dispersed polyurethane solids in the same mixing ratio, an open-cell foam is obtained, but with much larger cells, the cell membranes of which are still partially present.

The mixture of pure polyester and polyether is, as already mentioned, not stable in storage. It separates into two phases within a short time when standing at room temperature.

Example 16 Homogeneous Polyurethane Sheets a) Preparation of a prepolymer

89.7 parts by weight of the 40% polyether dispersion from Example 2 are reacted at 100-110 ° C. with 10.3 parts by weight of T 80 diisocyanate until the free isocyanate content is 3.0% by weight. The prepolymer obtained in this way has a viscosity of 24,800 cP / 25 ° C. and is stable in storage at room temperature.

b) Production of a polyurethane elastomer

The prepolymer is mixed with 0.2% by weight of tin (II) octoate and applied with the aid of a doctor blade in a layer thickness of 500 μm to a glass plate. After baking at 110-130 ° C (30-60 minutes), a film is obtained which is resistant to organic solvents and has good strength properties.

c) Solvent-free coating

If you mix the same prepolymer with a 5% equivalent excess of ethanolamine in a small volume high-speed stirrer and apply the mixture with a doctor blade 500 µm thick on a release paper using the reverse process, the elastomer that forms solidifies within a few seconds in an infrared channel. A textile substrate is laminated onto the still sticky layer under slight pressure and the polyaddition reaction is brought to an end in a heating duct with the temperature falling from 180 to 120 ° C.

The coated fabric is very resistant to abrasion and organic solvents.

Comparative tests:

If a prepolymer containing 3% free isocyanate groups is prepared from the pure dispersant (polyether I) analogously to Example 16, it is heated with the catalyst under otherwise identical conditions and cooled to room temperature, so that only a transparent, sticky elastomer composition without any structural strength is obtained that cannot be separated from the pad.

The use of ethanolamine leads to a similar, sticky product.

Example 17

Continuous design of the method of Example 1.

The reaction components are continuously conveyed from 2 storage vessels B1 and B2 into a reaction vessel. Storage vessel B1 contains a mixture of 10,000 parts by weight of polyether, 1.612 parts by weight of hydrazine hydrate and 1380 parts by weight of water; Storage vessel B2 contains 2113 parts by weight of T 80 diisocyanate.

The dosing rate per minute is from B1119.90 g, from B2 21.13 g. The total dosage is 141.03 per minute.

How it works:

The mixture, heated to 95 ° C in B1, is coaxially combined with the diisocyanate from B2 kept at 20 ° C in a static mixer from Kenics (diameter 'A inch; 21 elements; volume approx. 3 ml) using a piston pump (residence time 1.3 seconds) and conveyed with a pre-pressure of 2 to 3 bar into an approximately 6 m long reaction tube made of steel. The diameter of the tube is approximately 9 mm; the temperature inside is kept at 130 ± 5 ° C by heating or cooling.

The reaction tube ends in a separation vessel in which the practically water-free dispersion is stirred for a mean residence time of about 4 to 8 minutes at 70 ° C. and a pressure of 20 torr. The separation vessel is connected to a distillation bridge and, via a pump, to another vessel for product acceptance.

The resulting fine-particle, 20% dispersion has a viscosity of 2460 cP at 25 ° C.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

627 195

14

Example 17a

If Example 17 is repeated without the use of water, the reaction mixture already solidifies in the static mixer, so that its delivery into the multiphase flow tube is practically impossible.

t

; ; Example 18

20% POiyhydrazodicarbonamide dispersion in castor oil

Recipe:

80.0 parts by weight of castor oil 16.9 parts by weight of diisocyanate T 80;

3.1 parts by weight of hydrazine (in the form of an aqueous solution of hydrazine hydrate); a total of 11.3 parts by weight of water

The procedure is analogous to Example 1. The viscosity of the 20% dispersion at 25 ° C is 5950 cP.

Example 18a

If Example 18 is repeated with a total water content of the formulation of only 1.8% by weight, based on the total mixture, the reaction product pastes when the water is distilled off and finally becomes rubbery.

Example 19

Modification of a dispersion according to Example 1c with formaldehyde.

The 20% polyhydrazodicarbonamide dispersion from Example 1c is - if necessary even before the distillation of the water - with a 37% aqueous formaldehyde solution (10% by weight formaldehyde, based on the solids content of the dispersion) and a catalytic amount of 85% phosphoric acid added and gradually heated to 80 to 90 ° C. Finally, the water is distilled off under reduced pressure.

The practically formaldehyde-free dispersion has an almost unchanged low viscosity at 25 ° C and can be used to produce polyurethane foams with further improved compression hardness.

Example 20

The procedure described in Example 19 is followed, except that 10% by weight, based on solids, of an aqueous solution of dimethylolurea is used instead of an aqueous formaldehyde solution for the subsequent modification of the polyhydrazodicarbonamide dispersion.

The modification causes only a 5% increase in viscosity of the dispersion of the polyhydrazodicarbonamide.

Example 21

20% hydrazodicarbonamide bis-urea dispersion in polyether III.

Recipe:

80.0 parts by weight of polyether III;

1.1 parts by weight of hydrazine (used as hydrazine hydrate diluted with water);

1.2 parts by weight of ammonia (added as a 25% aqueous solution ^; in total

11.2 parts by weight of water;

17.7 parts by weight of 4,4'-diisocyanatodiphenylmethane

How it works (for examples 17-21)

The dispersing agent and the amino-functional compounds dissolved in water are placed in a stirring apparatus with a reflux condenser at room temperature and the diisocyanate, which has been heated to about 100 ° C., is introduced directly into the liquid phase of the mixture with vigorous stirring. The reaction temperature rises to approx. 65 to 75 ° Can. Then under

10th

reduced pressure removes the water. The resulting 20% fine-particle dispersion has a viscosity of 1920 cP at 25 ° C.

By post-treatment with formaldehyde analogously to Example 19, the dispersion can be modified in a simple manner to a dispersion containing polyethylene urea groups with only a slightly increased viscosity.

Example 22

20% PHD / SAN (polyhydrazodicarbonamide / styrene-acrylonitrile copolymer) dispersion in trifunctional polyether. Solid state ratio PHD: SAN = 1: 1.

Recipe:

15 824.00 parts by weight of a polyether started on trimethylolpropane from propylene oxide and ethylene oxide with the OH number 34 and about 80% primary OH groups (hereinafter referred to as "polyether I") as a dispersant;

20 257.50 parts by weight of a 40% aqueous styrene-acrylonitrile dispersion (styrene: acrylonitrile weight ratio = 72:28; hereinafter referred to as “SAN latex”);

25.25 parts by weight of hydrazine monohydrate (99%); 87.00 parts by weight of tolylene diisocyanate (mixture of isomers

2.4: 2.6 = 80:20; hereinafter referred to as «T80»); Key figure (KZ) =

25th

50

NCO

30th

NH

■ 100 = 100;

35

40

45

55

60

65

Water content 13.7% by weight, based on the reaction mixture (including water).

General mode of operation:

The polyether preheated to 60-70 ° C, the aqueous polymer latex and the hydrazine hydrate are combined in a boiler stirrer with reflux condenser. With the help of an inlet tube, the diisocyanate is introduced directly into the hot mixture at 75 ° C. so quickly that the temperature rises to 85-95 ° C. due to the exothermic polyaddition. Then the pressure can be reduced gradually, the water originating from the polymer latex and the water of hydration being distilled off. Towards the end of the water distillation, the temperature is raised to 100-120 ° C / 20-40 Torr. The practically water-free dispersion is discharged hot through a 100 [xm sieve.

At 25 ° C the viscosities (at 20 and 10% solids content) are 4650 and 1780 cP.

Example 22a

40% PHD / SAN dispersion in polyether I. Solid ratio = 1: 1.

The formulation and procedure are the same as in Example 22; however, using only 309 parts by weight of polyether I and a water content of 24.1% by weight.

The fine-particle dispersion has a viscosity of 68,500 (3,200,1470) cP at 25 ° C 40 (20; 10)% and is suitable in high-percentage form as a “masterbatch” for mixing with polyesters containing hydroxyl groups.

Example 23

20% PHD / SBR (polyhydrazodicarbonamide / polybutadiene) dispersion in polyether I. Solid state ratio PHD / SBR = 1: 1.

Recipe:

824.00 parts by weight of polyether I as dispersant;

15

627 195

229.00 parts by weight of a 45% aqueous polybutadiene latex;

25.25 parts by weight of hydrazine monohydrate (99%); 87.00 parts by weight of diisocyanate "T 80"; KZ = 100; Water content 11.6% by weight.

The procedure is the same as that given in Example 22. The water-free dispersion has a viscosity of 4480 (1880) cP at 25 ° C 20 (10)%.

and the mixture is heated to 95 ° C before starting to introduce the diisocyanate. The distillation of the water under reduced pressure can be started immediately after the addition of diisocyanate.

5 The water-free, stable dispersion has a viscosity of 590 cP at 25 ° C and has a strong Tyndall effect.

Example 24

20% PHD / ABS (head graft polymer) dispersion in branched polyether. Solid state ratio = 1: 1. 824 parts by weight of a polyether started on trimethylolpropane from propylene oxide and ethylene oxide (OH number = 35; approx. 70% primary OH groups; hereinafter referred to as polyether II) as a dispersing agent; 312.00 parts by weight of a 33% aqueous dispersion of 70% by weight of styrene-acrylonitrile copolymer and 30% by weight of graft copolymer of polybutadiene, styrene and acrylonitrile (hereinafter referred to as "ABS dispersion");

25.25 parts by weight of hydrazine monohydrate (99%);

87.00 parts by weight of 2,4-tolylene diisocyanate (hereinafter «T

100 »);

KZ = 100; Water content: 17.5% by weight.

The procedure is the same as that given in Example 22. The 20 (10)%, water-free, stable dispersion has a viscosity of 6900 (1790) cP at 25%.

Example 25

20% PHD / PE (polyethylene) dispersion (solid ratio 1: 1) in polyether II.

The recipe and procedure are identical to Example 24, but 257.5 parts by weight of a 40% strength PE dispersion are used instead of the ABS dispersion. The water content during the diisocyanate polyaddition is 13.7% by weight.

The 20 (10)% dispersion has a viscosity of 8450 (2160) cP at 25 ° C.

Example 26

20% PHD (OH) 2 (hydroxyl-containing polyhydrazodicarbonamide) / PUR elastomer dispersion in polyether III. Solid ratio = 15: 5.

Recipe:

1267 parts by weight of a linear polypropylene glycol with secondary OH groups (hereinafter referred to as “polyether III”), OH number = 56, as the dispersant;

188.6 parts by weight of a 40% anionic, aqueous PUR dispersion composed of a polyester of hexanediol, neopentyl glycol and adipic acid (MW = 1800), 1,6-hexamethylene diisocyanate, ethylenediamine and the diamine sulfonate of the formula _

H2N-CH2-CH2-NH-CH2-CH2-SOP Na®,

(Shore A hardness 60);

50.5 parts by weight of hydrazine monohydrate (99%);

13.0 parts by weight of ethanolamine;

192.5 parts by weight of 2,4-tolylene diisocyanate;

KZ (NC °) • 100 NH

100;

io Example 26a

40% PHD (OH) 2 / PUR dispersion Example 26 is repeated, but using only 475 parts by weight of polyether III and with a water content of 13.9% by weight. •

15 The 40 (20)% dispersion has 4310 (575) cP at 25 ° C.

Example 27

20 20% PHD (OH) 2 / PUR dispersion in branched polyether. Solid ratio = 15: 5.

1267.0 parts by weight of one started on trimethylolpropane

Polyethylene glycol with an OH number of 550 (polyether IV);

25 188.6 parts by weight of a 40% cationic, aqueous, crosslinked PUR dispersion of an adipic acid / phthalic acid / diethylene glycol polyester (MW = 1700), approximately equal parts of tolylene and hexamethylene diisocyanate, N-methyldiethanolamine, Diethylene triamine and

30 dimethyl sulfate as quaternizing agent (Shore A hardness 85);

50.5 parts by weight of hydrazine monohydrate (99%);

13.0 parts by weight of ethanolamine;

192.5 parts by weight of tolylene diisocyanate [mixture of isomers (2.4: 2.6 = 4: 1)];

35

KZ (™ ° -) NH

100 = 100;

40

Water content: 11.8% by weight / NCO

-) • 100 = 91.

Water content: 11.8% by weight;

KZ (NC °) • 100 = 91.

NH + OH

How it works:

The dispersant, the aqueous PU dispersion and the NH compound are introduced as described in Example 22

KZ (

NH + OH ^

45 The finely divided 20% dispersion produced as in Example 26 has a viscosity at 25 ° C. of 2100 cP.

Example 28

10% aromatic BHS (bis urea) dispersion in tri-50 functional polyether.

Recipe:

936 parts by weight of a polyether started on trimethylolpropane from propylene oxide and ethylene oxide with the OH number 34 55 and about 80% primary OH groups (hereinafter referred to as polyether I) as a dispersing agent; 68 parts by weight of a 25% aqueous ammonia solution; 87 parts by weight of tolylene diisocyanate (mixture of isomers 2.4-: 2.6- = 80:20; hereinafter referred to as “T 80”) .; 60 Water content: 4.7% by weight, based on the reaction mixture including water.

Operation and reaction conditions:

The dispersant and the aqueous ammonia solution are initially introduced at room temperature (18 to 25 ° C.) in a boiler stirrer with reflux condenser and the diisocyanate T 80 is introduced directly into the liquid phase of the mixture with stirring, so that the temperature is exothermic due to the exothermic

627 195

16

found polyaddition reaction increases to 50 to 70 ° C. After the addition of isocyanate has ended, distillation of the water under reduced pressure can begin immediately. The hot, water-free dispersion is discharged through a 100 μm sieve. | j 5 At 25 ° C the dispersion has a viscosity of 2560 cP.

• 'I

; iy, - Example 28a Example 28 is repeated under the above conditions using the same starting components, but with a water content of 10 wt .-% in the reaction mixture and using such an amount of polyether I that a 20% Dispersion arises. The 20% water-free dispersion thus obtained has a viscosity of 7430 cP at 25 ° C immediately after preparation. At 15

Storage at room temperature for a longer period of time gradually increases the viscosity of the 20% dispersion. However, it can be reduced to its original value by stirring for 5 minutes at room temperature. After dilution with additional polyether I to a 10% solids content, the dispersion 20 has a viscosity of 2050 cP / 25 ° C. The viscosity of this 10% dispersion remains constant even after long storage.

Recipe:

808 parts by weight of polyether II;

136 parts by weight of 25% aqueous ammonia solution; 10 parts by weight of water;

168 parts by weight of 1,6-hexamethylene diisocyanate;

Water content: 10 percent by weight.

The dispersion is prepared analogously to Example 28. At 25 ° C., the 20 (15.10)% anhydrous dispersion has a viscosity of 9800 (1750, 1040) cP.

Example 33

20% aromatic BHS dispersion in monoethylene glycol. Recipe:

416 parts by weight of monoethylene glycol;

68 parts by weight of 25% aqueous ammonia solution; 87 parts by weight of T 80 diisocyanate;

Water content: 8.9 percent by weight.

The dispersion is prepared as described in Example 28. As the following table shows, the viscosity of the anhydrous dispersion is very much dependent on both the solids content and the temperature.

Example 29

20% aromatic BHS dispersion in a linear polyether.

Recipe:

416 parts by weight of a linear propylene glycol (OH number 56; hereinafter referred to as polyether II) as a dispersant; 68 parts by weight of 25% aqueous ammonia solution; 87 parts by weight of T 80 diisocyanate;

Water content: 8.9 percent by weight.

The procedure is the same as in Example 28. The 20% dispersion has a viscosity of 1930 cP at 25 ° C, which does not change even after prolonged storage.

25th

30th

Solid content

(% By weight)

20th

20th

17.5

17.5

35

40

45

50

Example 30

20% aromatic BHS dispersion in a linear polyether.

Recipe:

1136 parts by weight of polyether II; 136 parts by weight 25% aqueous ammonia solution;

56 parts by weight of water;

250 parts by weight of diisocyanate D 44;

Water content: 10 percent by weight.

The reaction conditions are the same as given in Example 28. The finely divided 20% dispersion has a viscosity of 1960 cP at 25 ° C.

Example 31

20.9% PMHS (polymethylene urea) dispersion in linear polyether.

If the BHS dispersion of Example 30 is optionally left with distilling off the water, an amount of aqueous formalin solution such that a formaldehyde molecule is present for every 2 urea groups at 70 to 95 ° C. in the presence of a catalytic solution for one hour Applying the amount of 85% phosphoric acid, a polymethylene urea dispersion is obtained which is anhydrous at 25 ° C. and has a solids content of 20.9 (10)% and a viscosity of 2860 (1680) cP.

55

temperature

(° C)

25th

50

50

40

Viscosity (cP)

highly viscous paste

270

150

175

65

Example 32

20% aliphatic BBB dispersion in a linear polyether.

Example 34

20% aromatic BHS dispersion in monoethylene glycol. Example 31 is repeated, but using 1136 parts by weight of monoethylene glycol instead of polyether II.

The viscosity of the fine-particle stable dispersion (depending on the solids content) at 25 ° C is:

Solids content (% by weight) 20 17.5 15 10

Viscosity (cP) 1200 700 200 71

Example 35

20% BHS / S AN dispersion in a linear polyether. Solid ratio 1: 1.

Recipe:

1136 parts by weight of polyether II;

355 parts by weight of a 40% aqueous styrene-acrylonitrile dispersion (styrene: acrylonitrile weight ratio = 72:28), hereinafter referred to as “SAN latex”;

68 parts by weight of a 25% aqueous ammonia solution; 125 parts by weight of 4,4'-diisocyanatodiphenylmethane; Water content: 15.7 percent by weight.

How it works:

The dispersing agent, the SAN latex and the aqueous ammonia solution are mixed at room temperature in a stirring apparatus with a distillation attachment and the diisocyanate D 44 heated to 80-100 ° C is slowly passed directly into the liquid receiver and, if necessary, the reaction temperature is raised to 60-70 ° using a heat exchanger C brought until free isocyanate can no longer be detected. The water is distilled off under reduced pressure.

The viscosity of the 20 (10)% water-free dispersion is 4200 (1680) cP at 25 ° C.

Example 35a

PMHS (polymethylene urea) / SAN dispersion from the PHS / SAN dispersion of Example 35.

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627 195

If the 20% dispersion described in Example 35 (if necessary even before the water distillation) is mixed with the equivalent amount of an aqueous formaldehyde solution calculated for the urea groups and a catalytic amount of 85% phosphoric acid is added, the mixture is added for 60-90 minutes 70-100 ° C the condensation reaction to the aromatic polymethylene urea.

The 20.3%, water-free, stable PMHS / SAN dispersion thus obtained has a viscosity of 4440 cP at 25 ° C.

Example 36

20% PHS / ABS dispersion in linear polyether. Solid ratio 1: 1.

The recipe and procedure are identical to Example 35, but 430 parts by weight of a 33% aqueous ABS dispersion (70% by weight styrene-acrylonitrile copolymer and 30% by weight graft copolymer made from polybutadiene, styrene and acrylonitrile) are used . The water content is 19.3% by weight.

The 20 (10)% dispersion has a viscosity of 3480 (1450) cP at 25 ° C.

Example 36a

10 20.3% PMHS / ABS dispersion.

If the urea groups formed by polyisocyanate polyaddition in the dispersion of Example 36 are condensed with formaldehyde analogously to Example 35a, a finely divided dispersion having a viscosity of 3610 cP / 25 ° C. is obtained.

Claims (5)

627 195 2 PATENT CLAIMS 2500 cP if the predominantly used high pressure machines are used. (1) with organic polyisocyanates, if you continuously in the polyaddition reaction 1. Process for the «in situ» production of stable dispersions- According to a further older proposal (DOS 2 513 815) of polyisocyanate polyadducts in hydroxyl- it is possible to use largely water-free, relatively low-viscosity group-containing compounds as dispersants using 5 dispersions of polyureas and / or polyhydrazodicar conversion of bonamides in hydroxyl-containing polyethers. 2. The method according to claim 1, characterized in that group-containing compounds and a larger amount in component 2 additionally formaldehyde is also present. Carries out water and the water after the polyaddition (2) primary and / or secondary amino groups and / or flow mixers. The process has the post-primary compounds having hydroxyl groups and / or that a relatively complex metering and mixing technique is necessary or ammonia in 10, which is unprofitable for normal production batches; also 3. The method according to claim 1, characterized in that 20 tion removed by distillation. after the reaction, the water is removed. A water content of 10.15 or 20% by weight (based on (3) at least one hydroxyl group-containing compound can fertilize the solids concentration in some cases, whereby the compounds 3 secondary hydroxyl groups have considerable difficulties in removing the heat of reaction if, as compounds 2, those with primary hydroxyl causes. groups are used, characterized in that it has now surprisingly been found that stable the reaction components in the presence of more than 4 15 dispersions with the desired low viscosity also in wt .-% water, based on the reaction mixture including simple stirring apparatus can be implemented if lent water. the polyaddition “in situ” in a mixture of hydroxyl 4. The method according to claim 1, characterized in that the total amount of polyether and water) increases, for example, as component 2, at least difunctional amines and / or as the viscosity of a polyalkylene ether glycol at 25 ° C on hydrazines and / or hydrazides and / or NH3 used 2; 4, 8 or more than 50 times the original value (3500,. 7300 or more than 50 000 cP). If the water 5. Use of the hold obtainable according to claims 1 to 4 in many cases segregates the initially formed dispersions of polyisocyanate polyadducts in solution or emulsion with phase separation. Both the compounds containing strong hydroxyl groups as an initial increase in viscosity and the segregation had to be the specialist component for the production of polyurethane plastics. the use of water, which could also interfere as an additional reaction partner in the isocyanate polyaddition reaction, for the technical production of low-viscosity polyisocyanate polyaddition products in hydroxyl