UREAURETHANES FOR RHEOLOGY CONTROL

Abstract

The present invention relates to ureaurethanes of the following formula (I)

##STR00001##

in which at least one of the R.sup.1 or R.sup.2 radicals is a mono- or polyunsaturated, branched or unbranched alkenyl or alkynyl radical having 12 to 24 carbon atoms, n is an integer 1, where the upper limit for n arises from the maximum number average molecular weight M.sub.n of the ureaurethanes of the general formula (I), which is 65 000 g/mol, and which is determined by means of gel permeation chromatography to DIN 55672-2 using a polymethyl methacrylate standard, R.sup.3 is a xylylene radical or a hydrogenated xylylene radical and R.sup.4 is a tolylene radical or various other radicals. The invention also relates to ureaurethane compositions comprising the ureaurethanes of the invention and to the preparation of both. The invention further relates to the use of the ureaurethanes or ureaurethane compositions as rheology control agent and anti-settling agent. The invention further provides liquid formulations from the group consisting of coating compositions, polymer formulations, pigment pastes, sealant formulations, cosmetics, ceramic formulations, drilling fluids, adhesive formulations, potting compounds, construction material formulations, lubricants, spackling compounds, printing inks and other inks, comprising the ureaurethanes and ureaurethane compositions.

Claims

1. A urea urethane of the general formula (I) ##STR00005## in which R.sup.1 is a mono- or polyunsaturated, branched or unbranched alkenyl radical having 12 to 24 carbon atoms, a mono- or polyunsaturated, branched or unbranched alkynyl radical having 12 to 24 carbon atoms or a polyunsaturated hydrocarbyl radical which has 12 to 24 carbon atoms and has at least one carbon-carbon double bond and at least one carbon-carbon triple bond, R.sup.2 is a saturated branched or unbranched alkyl radical having 8 to 24 carbon atoms or a mono- or polyunsaturated, branched or unbranched alkenyl radical having 12 to 24 carbon atoms, a mono- or polyunsaturated, branched or unbranched alkynyl radical having 12 to 24 carbon atoms or a polyunsaturated hydrocarbyl radical which has 12 to 24 carbon atoms and has at least one carbon-carbon double bond and at least one carbon-carbon triple bond, and all n R.sup.3 radicals are independently one or more radicals selected from the structural units (IIa-o), (IIa-m), (IIa-p), (IIb-o), (IIb-m) and (IIb-p) ##STR00006## and all n+1 R.sup.4 radicals are independently one or more radicals selected from the structural units (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg) and (IIIh) ##STR00007## and n is an integer 1, where the upper limit for n arises from the maximum number-average molecular weight M.sub.n of the urea urethanes of the general formula (I) which is 65,000 g/mol and which is determined by means of gel permeation chromatography to DIN 55672-2 using a polymethylmethacrylate standard, and where the bonding sites of the R.sup.3 and R.sup.4 radicals to the adjacent NH groups in the structural units formulae are indicated by the * symbol.

2. The urea urethane as claimed in claim 1, characterized in that the R.sup.1 radical is a monounsaturated alkenyl radical having 16 to 20 carbon atoms, the R.sup.2 radical is a saturated branched alkyl radical having 10 to 16 carbon atoms or a monounsaturated alkenyl radical having 16 to 20 carbon atoms, the n R.sup.3 radicals are independently one or more radicals selected from the structural units (IIa-m) and (IIa-p), and the n+1 R.sup.4 radicals are independently one or more radicals of the structural units (IIIa) and (IIIb).

3. The urea urethane as claimed in claim 1, characterized in that the R.sup.1 radical is an unbranched octadecenyl radical, the R.sup.2 radical is a branched or unbranched C.sub.10-C.sub.14-alkyl radical or an unbranched octadecenyl radical, the n R.sup.3 radicals are a radical of the structural unit (IIa-m), and the n+1 R.sup.4 radicals are independently one or more radicals of the structural units (IIIa) and (IIIb).

4. The urea urethane as claimed in claim 1, characterized in that the structural units (IIIa) and (IIIb) are present in the n+1 R.sup.4 radicals in a molar ratio of 40:60 up to a molar ratio of 100:0.

5. The urea urethane as claimed in claim 1, characterized in that R.sup.1 and R.sup.2 are a mono- or polyunsaturated, branched or unbranched alkenyl radical having 16 to carbon atoms.

6. The urea urethane as claimed in claim 1, characterized in that R.sup.1 is oleyl.

7. The urea urethane as claimed in claim 1, characterized in that R.sup.1R.sup.2.

8. A urea urethane composition comprising one or more urea urethanes of claim 1, characterized in that the proportion by weight of the urea urethanes of the formula (I) in which both R.sup.1 and R.sup.2 radicals are unsaturated is 10% to 100%, based on the totality of the urea urethanes of the formula (I), and the proportion by weight of the urea urethanes of the formula (I) in which only the R.sup.1 radical is unsaturated is 0% to 90%, based on the totality of the urea urethanes of the formula (I).

9. The urea urethane composition as claimed in claim 8, characterized in that it is in liquid form.

10. The urea urethane composition as claimed in claim 8, wherein the urea urethane(s) is/are dissolved in a polar aprotic solvent.

11. The urea urethane composition as claimed in claim 10, wherein the polar aprotic solvent is selected from the group consisting of substituted N-alkylpyrrolidones, unsubstituted N-alkylpyrrolidones, dialkyl sulfoxides, substituted amides, unsubstituted amides and organic salts having a melting point of 80 C.

12. A process for preparing the urea urethane compositions as claimed in claim 8, characterized in that, in the presence of a polar aprotic solvent, (a) one or more monoadducts of the formula R.sup.1O(CO)NHR.sup.4NCO or of the formula R.sup.2O(CO)NHR.sup.4NCO are prepared from one or more monoalcohols of the formula R.sup.1OH and/or R.sup.2OH and one or more diisocyanates of the formula OCNR.sup.4NCO and this/these said monoadduct(s) is/are then reacted (i) with one or more diamines of the formula H.sub.2NR.sup.3NH.sub.2 or (ii) with one or more prepolymers, NH.sub.2-terminated at both ends, of one or more diamines of the formula H.sub.2NR.sup.3NH.sub.2 and one or more diisocyanates of the formula OCNR.sup.4NCO or (iii) with one or more diamines of the formula H.sub.2NR.sup.3NH.sub.2 and one or more diisocyanates of the formula OCNR.sup.4NCO or (iv) with one or more prepolymers NH.sub.2-terminated at both ends or a mixture of one or more diamines of the structure H.sub.2NR.sup.3NH.sub.2 and one or more prepolymers NH.sub.2-terminated at both ends, and one or more diisocyanates of the formula OCNR.sup.4NCO; or (b) one or more prepolymers, NCO-terminated at both ends, of one or more diisocyanates of the formula OCNR.sup.4NCO and one or more diamines of the formula H.sub.2NR.sup.3NH.sub.2 is/are prepared, and the prepolymer(s) is/are reacted with one or more monoalcohols of the formulae R.sup.1OH and/or R.sup.2OH; and wherein at least one monoalcohol of the formula R.sup.1OH is used in process variants (a) and (b).

13. A process for preparing a urea urethane of formula (I) as defined in claim 1, characterized in that in the presence of a polar aprotic solvent, (a) one or more monoadducts of the formula R.sup.1O(CO)NHR.sup.4NCO or of the formula R.sup.2O(CO)NHR.sup.4NCO are prepared from one or more monoalcohols of the formula R.sup.1OH and/or R.sup.2OH and one or more diisocyanates of the formula OCNR.sup.4NCO and said monoadduct(s) is/are then reacted (i) with one or more diamines of the formula H.sub.2NR.sup.3NH or (ii) with one or more prepolymers, NH.sub.2-terminated at both ends, of one or more diamines of the formula H.sub.2NR.sup.3NH.sub.2 and one or more diisocyanates of the formula OCNR.sup.4NCO or (iii) with one or more diamines of the formula H.sub.2NR.sup.3NH.sub.2 and one or more diisocyanates of the formula OCNR.sup.4NCO or (iv) with one or more prepolymers NH-terminated at both ends or a mixture of one or more diamines of the structure H.sub.2NR.sup.3NH.sub.2 and one or more prepolymers NH.sub.2-terminated at both ends, and one or more diisocyanates of the formula OCNR.sup.4NCO; or (b) one or more prepolymers, NCO-terminated at both ends, of one or more diisocyanates of the formula OCNR.sup.4NCO and one or more diamines of the formula H NR.sup.3NH.sub.2 is/are prepared, and the prepolymer(s) is/are reacted with one or more monoalcohols of the formulae R.sup.1OH and/or R.sup.2OH; and then the polar aprotic solvent is removed; and wherein at least one monoalcohol of the formula R.sup.1OH is used in process variants (a) and (b).

14. (canceled)

15. A rheology control agent and/or antisettling agent, characterized in that it comprises one or more urea urethanes of formula (I) as defined in claim 1.

16. A liquid formulation selected from the group consisting of coating compositions, polymer formulations, pigment pastes, sealant formulations, cosmetics, ceramic formulations, drilling fluid solutions, nonaqueous slurries, adhesive formulations, potting compounds, building material formulations, lubricants, spackling compounds, cleaning compositions, printing inks and other inks, characterized in that they comprise one or more urea urethanes of formula (I) as defined in claim 1.

17. The liquid formulation as claimed in claim 16, wherein the proportion of the urea urethane of formula (I) or of the urea urethanes of formula (I) in the overall liquid formulation is 0.1% to 5% by weight.

18. The liquid formulation as claimed in claim 16, characterized in that at least one hydrocarbon selected from the group of the aliphatic, cycloaliphatic, aromatic and araliphatic hydrocarbons is additionally present in the liquid formulation.

19. The liquid formulation as claimed in claim 18, wherein the at least one hydrocarbon is present in the liquid formulation to an extent of at least 10% by weight based on the total weight of the liquid formulation.

20. A rheology control agent and/or antisettling agent, characterized in that it comprises one or more urea urethane compositions as defined in claim 8.

21. A liquid formulation selected from the group consisting of coating compositions, polymer formulations, pigment pastes, sealant formulations, cosmetics, ceramic formulations, drilling fluid solutions, nonaqueous slurries, adhesive formulations, potting compounds, building material formulations, lubricants, spackling compounds, cleaning compositions, printing inks and other inks, characterized in that they comprise one or more urea urethanes compositions as defined in claim 8.

Description

EXAMPLES

[0109] The percentages which follow, unless stated otherwise, are percentages by weight.

[0110] (I) Synthesis of the Rheology Control Agents

COMPARATIVE EXAMPLES

Comparative Example 1 (Analogous to Example 12 of DE-A1-19919482)

[0111] Firstly, a monoadduct is prepared according to patent specification EP 1188779 from tolylene 2,4-diisocyanate (Desmodur T100, Bayer) and lauryl alcohol. In a reaction vessel, 1.65 g (0.04 mol) of LiCl are dissolved in 75.0 g of N-ethylpyrrolidone (BASF) while stirring. Thereafter, 3.55 g (0.026 mol) of meta-xylylenediamine are added and the clear mixture is heated to 60 C. Subsequently, 19.8 g (0.052 mol) of the monoadduct of Desmodur T100 and lauryl alcohol are added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product with a 25% content of urea urethane is obtained.

Comparative Example 2

[0112] Firstly, a monoadduct is prepared according to patent specification EP 1188779 from tolylene 2,4-diisocyanate (Desmodur T100, Bayer) and lauryl alcohol. In a reaction vessel, 1.65 g (0.04 mol) of LiCl are dissolved in 75.0 g of methyl 5-(dimethylamino)-2-methyl-5-oxopentanoate while stirring. Thereafter, 3.55 g (0.026 mol) of meta-xylylenediamine are added and the clear mixture is heated to 60 C. Subsequently, 19.8 g (0.052 mol) of the monoadduct of Desmodur T100 and lauryl alcohol are added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product with a 25% content of urea urethane is obtained.

Comparative Example 3

[0113] As comparative example 3, example 5 from EP 2292675 A1 was prepared.

EXAMPLES

[0114] Firstly, as synthons for the syntheses of the urea urethanes described further down, the following monoadducts are prepared according to patent specification EP 1188779:

[0115] Monoadduct 1 is prepared from a mixture of tolylene 2,4-diisocyanate and tolylene 2,6-diisocyanate (Desmodur T65, Bayer) and (Z)-octadec-9-enol (oleyl alcohol, Merck).

[0116] Monoadduct 2 is prepared from a mixture of tolylene 2,4-diisocyanate and tolylene 2,6-diisocyanate (Desmodur T65, Bayer) and Exxal 13 Tridecyl Alcohol (C.sub.13-rich, C.sub.11-14-alkanol; Exxon Mobil Corporation).

[0117] Monoadduct 3 is prepared from tolylene 2,4-diisocyanate (Desmodur T100, Bayer) and 1-dodecanol (Aldrich).

Example 1

[0118] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 3.0 g (0.07 mol) of LiCl are dissolved in 150.0 g of N-methylpyrrolidone (BASF) while stirring. Thereafter, 6.5 g (0.047 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 24.3 g of monoadduct 1 (0.052 mol) and 16.2 g of monoadduct 2 (0.042 mol) is added dropwise while stirring within 1 hour at such a rate that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture, after the addition has ended, is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 25% content of urea urethane.

Example 2

[0119] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 3.3 g (0.078 mol) of LiCl are dissolved in 90.0 g of N-octylpyrrolidone (BASF) while stirring. Thereafter, 7.2 g (0.052 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, 49.5 g (0.104 mol) of monoadduct 1 are added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 40% content of urea urethane.

Example 3

[0120] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 2.8 g (0.066 mol) of LiCl are dissolved in 150.0 g of N-octylpyrrolidone (BASF) while stirring. Thereafter, 6.0 g (0.044 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, 41.2 g (0.088 mol) of monoadduct 1 are added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 25% content of urea urethane.

Example 4

[0121] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 2.8 g (0.066 mol) of LiCl are dissolved in 150.0 g of N-methylpyrrolidone (BASF) while stirring. Thereafter, 6.0 g (0.044 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, 41.2 g (0.088 mol) of monoadduct 1 are added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 25% content of urea urethane.

Example 5

[0122] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 4.5 g (0.105 mol) of LiCl are dissolved in 225.0 g of N-octylpyrrolidone (BASF) while stirring. Thereafter, 9.7 g (0.07 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 36.5 g (0.077 mol) of monoadduct 1 and 24.4 g (0.063 mol) of monoadduct 2 is added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 25% content of urea urethane.

Example 6

[0123] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 5.4 g (0.127 mol) of LiCl are dissolved in 210.0 g of dimethyl sulfoxide (DMSO, Merck) while stirring. Thereafter, 11.7 g (0.085 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 42.0 g (0.089 mol) of monoadduct 1 and 31.0 g (0.081 mol) of monoadduct 2 is added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 30% content of urea urethane.

Example 7

[0124] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 5.3 g (0.126 mol) of LiCl are dissolved in 210.0 g of dimethyl sulfoxide (DMSO, Merck) while stirring. Thereafter, 11.6 g (0.084 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 45.6 g (0.097 mol) of monoadduct 1 and 27.5 g (0.071 mol) of monoadduct 2 is added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 30% content of urea urethane.

Example 8

[0125] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 6.3 g (0.149 mol) of LiCl are dissolved in 195.0 g of dimethyl sulfoxide (DMSO, Merck) while stirring. Thereafter, 13.7 g (0.099 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 46.8 g (0.099 mol) of monoadduct 1 and 38.2 g (0.099 mol) of monoadduct 2 is added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 35% content of urea urethane.

Example 9

[0126] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 6.3 g (0.149 mol) of LiCl are dissolved in 195.0 g of dimethyl sulfoxide (DMSO, Merck) while stirring. Thereafter, 13.5 g (0.098 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 51.1 g (0.108 mol) of monoadduct 1 and 34.1 g (0.089 mol) of monoadduct 2 is added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 35% content of urea urethane.

Example 10

[0127] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 6.2 g (0.146 mol) of LiCl are dissolved in 195.0 g of dimethyl sulfoxide (DMSO, Merck) while stirring. Thereafter, 13.4 g (0.098 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 55.3 g (0.117 mol) of monoadduct 1 and 30.1 g (0.078 mol) of monoadduct 2 is added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 35% content of urea urethane.

Example 11

[0128] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 6.3 g (0.149 mol) of LiCl are dissolved in 245.0 g of dimethyl sulfoxide (DMSO, Merck) while stirring. Thereafter, 13.7 g (0.099 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 46.8 g (0.099 mol) of monoadduct 1 and 38.2 g (0.099 mol) of monoadduct 2 is added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 30% content of urea urethane.

Example 12

[0129] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 6.3 g (0.149 mol) of LiCl are dissolved in 280.0 g of dimethyl sulfoxide (DMSO, Merck) while stirring. Thereafter, 13.7 g (0.099 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 46.8 g (0.099 mol) of monoadduct 1 and 38.2 g (0.099 mol) of monoadduct 2 is added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 27.5% content of urea urethane.

Example 13

[0130] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 6.3 g (0.149 mol) of LiCl are dissolved in 280.0 g of dimethyl sulfoxide (DMSO, Merck) while stirring. Thereafter, 13.5 g (0.098 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 51.1 g (0.108 mol) of monoadduct 1 and 34.1 g (0.089 mol) of monoadduct 2 is added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 27.5% content of urea urethane.

Example 14

[0131] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 6.2 g (0.146 mol) of LiCl are dissolved in 280.0 g of dimethyl sulfoxide (DMSO, Merck) while stirring. Thereafter, 13.4 g (0.098 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 55.3 g (0.117 mol) of monoadduct 1 and 30.1 g (0.078 mol) of monoadduct 2 is added dropwise while stirring within 1 hour, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours. A clear, colorless and fluid product is obtained. The product contains a 27.5% content of urea urethane.

Example 15

[0132] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 4.2 g (0.099 mol) of LiCl are dissolved in 130.0 g of N-octylpyrrolidone (BASF) at 60 C. while stirring. Thereafter, 9.1 g (0.066 mol) of meta-xylylenediamine are added, and the solution turns cloudy after a few seconds. Subsequently, a mixture of 32.1 g of monoadduct 1 (0.066 mol) and 25.5 g of monoadduct 3 (0.066 mol) is added dropwise while stirring within 30 minutes at such a rate that the temperature does not rise above 80 C. During this time, the reaction mixture turns completely clear. To complete the reaction, the reaction mixture, after the addition has ended, is stirred at 80 C. for 3 hours. A clear, yellowish and fluid product is obtained. The product contains 35% urea urethane.

Example 16

[0133] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 4.0 g (0.095 mol) of LiCl are dissolved in 130.0 g of N-octylpyrrolidone (BASF) at 60 C. while stirring. Thereafter, 8.7 g (0.064 mol) of meta-xylylenediamine are added, and the solution turns cloudy after a few seconds. Subsequently, a mixture of 45.0 g of monoadduct 1 (0.095 mol) and 12.2 g of monoadduct 3 (0.032 mol) is added dropwise while stirring within 30 minutes at such a rate that the temperature does not rise above 80 C. During this time, the reaction mixture turns completely clear. To complete the reaction, the reaction mixture, after the addition has ended, is stirred at 80 C. for 3 hours. A clear, yellowish and fluid product is obtained. The product contains 35% urea urethane.

Example 17 (Oligomer/Polymer; M.SUB.n.=3135, M.SUB.w.=3708)

[0134] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 6.0 g (0.142 mol) of LiCl are dissolved in 130.0 g of N-octylpyrrolidone (BASF) at 60 C. while stirring. Thereafter, 9.7 g (0.071 mol) of meta-xylylenediamine are added, and the solution turns cloudy after a few seconds. Subsequently, a mixture of 51.4 g of monoadduct 1 (0.109 mol) and 2.8 g of tolylene diisocyanate (0.016 mol) (Desmodur T80; mixture of tolylene 2,4-diisocyanate and tolylene 2,6-diisocyanate from Bayer) is added dropwise while stirring within 30 minutes at such a rate that the temperature does not rise above 80 C. During this time, the reaction mixture turns completely clear. To complete the reaction, the reaction mixture, after the addition has ended, is stirred at 80 C. for 3 hours. A clear, yellowish and fluid product is obtained. The product contains 35% urea urethane.

Example 18 (Oligomer/Polymer; M.SUB.n.=3317, M.SUB.w.=3967)

[0135] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 6.2 g (0.147 mol) of LiCl are dissolved in 130.0 g of N-octylpyrrolidone (Aldrich) while stirring. Thereafter, 10.0 g (0.073 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 50.1 g (0.105 mol) of monoadduct 1 and 3.6 g (0.021 mol) of tolylene diisocyanate (isomer mixture of tolylene 2,4/2,6-diisocyanate in a ratio of 4:1 from Bayer; Desmodur T80) is added dropwise while stirring within 35 minutes, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours and at 90 C. for another 30 minutes. A clear, yellow and fluid product is obtained. The product contains a 35% content of urea urethane.

Example 19 (Oligomer/Polymer; M.SUB.n.=3377, M.SUB.w.=4102)

[0136] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 6.5 g (0.153 mol) of LiCl are dissolved in 130.0 g of N-octylpyrrolidone (Aldrich) while stirring. Thereafter, 10.4 g (0.077 mol) of meta-xylylenediamine are added and the mixture is heated to 60 C. Subsequently, a mixture of 48.7 g (0.102 mol) of monoadduct 1 and 4.4 g (0.026 mol) of tolylene diisocyanate (isomer mixture of tolylene 2,4/2,6-diisocyanate in a ratio of 4:1 from Bayer; Desmodur T80) is added dropwise while stirring within 35 minutes, such that the temperature does not rise above 80 C. To complete the reaction, the reaction mixture is stirred at 80 C. for 3 hours and at 90 C. for another 30 minutes. A clear, yellow and fluid product is obtained. The product contains a 35% content of urea urethane.

Example 20 (Oligomer/Polymer; M.SUB.n.=5021, M.SUB.w.=7865)

[0137] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 4.8 g (0.114 mol) of LiCl are dissolved in 130.0 g of N-octylpyrrolidone (Aldrich) at 60 C. while stirring. Thereafter, 15.5 g (0.114 mol) of meta-xylylenediamine are added, and the solution turns cloudy after a few seconds. Subsequently, a mixture of 36.4 g of monoadduct 1 (0.076 mol) and 13.3 g of tolylene diisocyanate (0.076 mol) (isomer mixture of tolylene 2,4/2,6-diisocyanate in a ratio of 4:1 from Bayer; Desmodur T80) is added dropwise while stirring within 50 minutes at such a rate that the temperature does not rise above 80 C. During this time, the reaction mixture turns almost completely clear. To complete the reaction, the reaction mixture, after the addition has ended, is stirred at 80 C. for 3 hours. Within this time, the solution turns completely clear, and so a clear, yellow and viscous product is obtained. The product contains 35% urea urethane.

Example 21 (Oligomer/Polymer; M.SUB.n.=3935, M.SUB.w.=5512)

[0138] In a reaction vessel with a stirrer, dropping funnel and nitrogen inlet, 4.0 g (0.094 mol) of LiCl are dissolved in 130.0 g of N-octylpyrrolidone (Aldrich) at 60 C. while stirring. Thereafter, 12.8 g (0.094 mol) of meta-xylylenediamine are added, and the solution turns cloudy after a few seconds. Subsequently, a mixture of 45.0 g of monoadduct 1 (0.094 mol) and 8.2 g of tolylene diisocyanate (0.047 mol) (isomer mixture of tolylene 2,4/2,6-diisocyanate in a ratio of 4:1 from Bayer; Desmodur T80) is added dropwise while stirring within 50 minutes at such a rate that the temperature does not rise above 80 C. During this time, the reaction mixture turns completely clear. To complete the reaction, the reaction mixture, after the addition has ended, is to stirred at 80 C. for 3 hours. A clear, yellow and viscous product is obtained. The product contains 35% urea urethane.

[0139] (II) Performance Testing of the Urea Urethanes Suitable as Rheology Control Agents

[0140] Raw Materials Used

TABLE-US-00001 Name Description Manufacturer Acridic A 188 Nonaqueous dispersion Dainippon Ink & Chemicals, Inc. Acridic A 1300 Nonaqueous dispersion Dainippon Ink & Chemicals, Inc. Bayferrox 130 M Iron oxide red pigment Lanxess Deutschland GmbH Blanc Fixe N Barium sulfate Sachtleben Chemie GmbH Borchinox M 2 2-Butanone oxime Borchers GmbH BYK-052 Defoamer BYK-Chemie GmbH Claytone 3 Sheet silicate BYK Chemie GmbH Disperbyk-108 Wetting and dispersing BYK-Chemie GmbH additive Dowanol PMA Propane-1,2-diol Dow Chemical monoacetate monomethyl Company ether Durcal 5 Calcium carbonate Omya Heucophos ZCP - Zinc/calcium/strontium/ Heubach GmbH plus aluminum orthophosphate silicate hydrate Heucorin RZ Org. corrosion inhibitor Heubach GmbH zinc 5-nitroisophthalate Isomerized C1618 Synthetic olefin Ineos Oligomers Alpha Olefin Micro Talc AT-1 Talc magnesite Mondo Minerals BV Octa Soligen Calcium siccative Borchers GmbH Calcium 10 Octa Soligen Cobalt siccative Borchers GmbH Cobalt 12 Setal A F 26 X Short oil alkyd 60% in Nuplex Resins GmbH xylene Shellsol A Aromatic hydrocarbon Overlack AG mixture Testbenzin Special boiling point spirit Overlack AG K 30 145-200 Tioxide TR 92 Titanium dioxide Huntsman Pigments Worlekyd B Long oil alkyd resin, 90% Worle Chemie GmbH 6301 in dearomat. HC 180-220 Xylene Isomer mixture Overlack AG

[0141] Elucidation of the Rating Scale

TABLE-US-00002 Gel strength: 1 very strong 2 strong 3 moderate 4 very weak 5 no gel Cloudiness 1 clear (compatibility): 2 slightly cloudy 3 cloudy 4 very cloudy 5 extremely cloudy

[0142] Test System 1: Solvent Mixtures

[0143] A 100 mL glass bottle is charged with 50 g of the respective solvent mixture consisting of xylene/n-butanol 90:10 (w/w) and Dowanol PMA/Shellsol A/isobutanol 50:25:25 (w/w/w), and then the respective additive is incorporated while stirring by Dispermat CV (toothed disk d=2.5 cm at 1000 rpm). In all cases, a dosage corresponding to 2% of the urea urethane (based on the total mass of the solvent mixture) was chosen. On completion of addition, stirring is continued for another 1 minute.

[0144] Subsequently, the samples are left to stand at room temperature for 1 day and then the gel strength is assessed visually as a measure of the rheological efficacy, and the compatibility of the additive in the system is assessed by the cloudiness.

TABLE-US-00003 Xylene/n-butanol Dowanol MPA/Shellsol 90:10 A/isobutanol 50:25:25 Gel Cloud- Gel Cloud- Product strength iness strength iness Blank sample without 5 1 5 1 additive Comparative example 1 4 3 5 4 Example 1 2 2 3 3 Example 2 3 1 3 1

[0145] It is apparent from the table that comparative example 1 gives a significantly poorer gel strength and is less compatible than inventive examples 1 and 2.

[0146] Test System 2: Acrydic A-188/A-1300 White Paint

[0147] A 100 mL glass bottle is charged with 50 g of Acrydic A-188/A-1300 white paint according to the composition specified below, and then the respective additive is incorporated while stirring by Dispermat CV (toothed disk d=2.5 cm at 1000 rpm). On completion of addition, stirring is continued for another 1 minute. In all cases, a dosage corresponding to 0.25% by weight of the urea urethane (based on the total mass of the formulation) was chosen.

[0148] Subsequently, the samples are left to stand at room temperature for 1 day and then the testing of the sag resistance as a measure of the rheological efficacy was conducted under application conditions.

[0149] For this purpose, the sample is mixed homogeneously by spatula and then applied to contrast charts with a 50-500 m step gap bar applicator and an automatic applicator bench (from BYK-Gardner) at a speed of 5 cm/s. After the application, the contrast charts are directly suspended horizontally for drying. After the drying, the maximum layer thickness in m (wet) at which the paint does not sag, meaning that no runs or blister formation are apparent, is determined. The higher the value for the sag resistance with use of equal amounts of urea urethane, the better the rheological efficacy.

[0150] Formulation of the White Paint:

TABLE-US-00004 Acrydic A-188/A-1300 white paint Acridic A 188 12.7 Tioxide TR 92 22.0 Disperbyk 108 2.5 Testbenzin K 30 12.5 Dispermat, 40 C., 30 min, 8500 rpm, 4 cm toothed disk Acridic A 1300 44.0 Testbenzin K 30 6.3 100.0

[0151] Results:

TABLE-US-00005 Product Sag resistance m (wet) Blank sample without additive 100 Comparative example 2 150 Example 3 200 Example 4 200

[0152] It is apparent in the table that comparative example 2 exhibits poorer rheological efficacy in the form of sag resistance than inventive examples 3 and 4.

[0153] Test System 3: Setal A F 26 X White Paint

[0154] A 100 mL glass bottle is charged with 50 g of Setal A F 26 X white paint according to the composition specified below, and then the respective additive is incorporated while stirring by Dispermat CV (toothed disk d=2.5 cm at 1000 rpm). In all cases, a dosage corresponding to 0.5% by weight of the urea urethane (based on the total mass of the paint formulation) was chosen. On completion of addition, stirring is continued for another 1 minute.

[0155] Subsequently, the samples are left to stand at room temperature for 1 day and the sag resistance is assessed by application as a measure of the rheological efficacy. For this purpose, the sample is mixed homogeneously by spatula and then applied to contrast charts with a 50-500 m step gap bar applicator and an automatic applicator bench (from BYK-Gardner) at a speed of 5 cm/s. After the application, the contrast charts are directly suspended horizontally for drying. After the drying, the maximum layer thickness in m (wet) at which the paint does not sag, meaning that no runs or blister formation are apparent, is determined. The higher the value for the sag resistance with use of equal amounts of the urea urethane, the better the rheological efficacy.

[0156] Formulation of the Setal White Paint:

TABLE-US-00006 Setal A F 26 X 34.5 Shellsol A 7.8 Emulsifying aid* 0.2 BYK-052 0.2 Bayferrox 130 M 6.0 Micro Talc AT-1 7.0 Heucophos ZCP - plus 21.0 Heucorin RZ 0.5 Dispermat, 40 C., 30 min, 8500 rpm, 4 cm toothed disk Setal A F 26 X 8.0 Shellsol A 14.2 Calcium 10 0.3 Cobalt 12 0.2 Borchinox M 2 0.1 100.0 *available from BYK Chemie GmbH

[0157] Results

TABLE-US-00007 Product Sag resistance m (wet) Blank sample without additive 50 Comparative example 2 100 Example 1 200 Example 3 200 Example 5 200

[0158] It is apparent from the table that comparative example 2 enables poorer sag resistance than the products of the invention.

[0159] Test System 4: Worleekyd B6301 Binder

[0160] A 100 mL glass bottle is charged with 50 g of Worleekyd B6301 binder, and then the respective additive is incorporated while stirring by Dispermat CV (toothed disk d=2.5 cm at 1000 rpm). In all cases, a dosage corresponding to 1.0% by weight of the urea urethane (based on the total mass of the paint formulation) was chosen. On completion of addition, stirring is continued for another 1 minute.

[0161] Subsequently, the samples are left to stand at room temperature for 1 day and the sag resistance is assessed by application as a measure of the rheological efficacy. For this purpose, the sample is mixed homogeneously by spatula and then applied to contrast charts with a 50-500 m step gap bar applicator and an automatic applicator bench (from BYK-Gardner) at a speed of 5 cm/s. After the application, the contrast charts are directly suspended horizontally for drying. After the drying, the maximum layer thickness in m (wet) at which the paint does not sag, meaning that no runs or blister formation are apparent, is determined. The higher the value for the sag resistance with use of the same active substance, the better the rheological efficacy.

TABLE-US-00008 Product Sag resistance m (wet) Blank sample without additive <50 Comparative example 1 50 Comparative example 2 100 Example 6 500 Example 7 500 Example 8 600 Example 9 550 Example 10 550 Example 11 350 Example 12 350 Example 13 400 Example 14 350

[0162] It is apparent from the table that comparative examples 1 and 2 enable poorer sag resistance than the inventive examples.

[0163] Test System 5: Oil-Based Drilling Mud

[0164] Firstly, 400 g of drilling mud are produced according to the formulation specified by means of a Hamilton Beach mixer, GM20 type, HMD200-CE model (manufacturer: Hamilton Beach; setting: level 1).

[0165] The mud is divided into 100 g samples and the respective additive is incorporated with an Ultra-Turrax stirrer (manufacturer: IKA-Werke GmbH, model T 45) at 6000 rpm for 5 min (the blank sample is sheared analogously). In all cases, a dosage corresponding to 0.5% by weight of the urea urethane (based on the total mass of the drilling mud) was chosen.

[0166] For the separation characteristics, 60 g of drilling mud in each case were dispensed into 50 mL snap-lid bottles and stored at room temperature for 4 weeks. Thereafter, the separation (syneresis formation) in % is evaluated, based on the total fill height in the snap-lid bottle, as a measure of the rheological efficacy. The lower the height of the separated phase, the better the rheological efficacy of the additive and the better it can consequently be used to counter the separation of the components.

[0167] For selected examples, the remaining 40 g of the drilling mud are dispensed into 50 mL glass bottles. After standing at RT for 16 h, the viscosity is measured in a temperature-dependent manner by Physica MCR-301 rheometer (manufacturer: Anton Paar GmbH) at the three temperatures of 4 C., 25 C. and 66 C. under shear rate control at the shear rates of 10, 150, 300, 500 and 1000 l/s with a DPP30 plate-plate geometry and a 0.5 mm measurement gap.

[0168] Oil-Based Drilling Mud:

TABLE-US-00009 Component Weight/g Mixing/min Isomerized C1618 Alpha Olefin 25.0 Claytone 3 0.2 10 Durcal 5 0.5 10 Emulsifying aid* 1.8 10 CaCl.sub.2 solution, 25% in water 18.5 10 Blanc Fixe N 54.0 10 100.0 *available from BYK Chemie GmbH

[0169] Results: Separation

TABLE-US-00010 Dosage, % by wt. Separation (syneresis) % Product of urea urethane after 4 weeks at RT Blank sample without 36 additive Comparative example 1 0.5 27 Comparative example 3 0.5 44 Example 2 0.5 9 Example 15 0.5 4 Example 16 0.5 3 Example 17 0.5 1 Example 18 0.5 1 Example 19 0.5 1 Example 20 0.5 4 Example 21 0.5 2

[0170] It is apparent from the table that the products of the invention according to examples 2 and 15 to 21 are able to better stabilize the system again separation than comparative examples 1 and 3 or the blank sample.

[0171] Results: Viscosity Measurement

TABLE-US-00011 Viscosity/mPas at shear rate 1/s Product Temperature/ C. 10 150 300 500 1000 Blank sample 4.4 797 178 133 114 92 without additive 25 272 79 62 55 46 66 62 19 16 14 12 Comparative 4.4 831 218 171 152 130 example 1 25 305 101 83 76 67 66 183 49 39 34 28 Example 2 4.4 2953 460 308 247 182 25 1987 289 189 149 108 66 1176 177 117 100 73

[0172] It is apparent from the table that comparative example 1 enables only a smaller increase in viscosity compared to the inventive product from example 2.