UREA AND URETHANE GROUP CONTAINING ANTI-SETTLING RHEOLOGY CONTROL ADDITIVE

Abstract

The present invention relates to a urea and urethane group containing product comprising one or more species of formula (I) R.sup.1O(CO)NHR.sup.2NH(CO)NHR.sup.3NH[(CO)NHR.sup.4NH(CO)NHR.sup.3NH].sub.n(CO)NHR.sup.2NH(CO)OR.sup.1 (I), wherein R.sup.1 independently represents a non-aromatic hydrocarbyl group having 14 to 30 carbon atoms; R.sup.2 independently represents alkyl-substituted aromatic hydrocarbyl groups having 7 to 12 carbon atoms; R.sup.3 independently represents hydrocarbyl groups having 2 to 36 carbon atoms, which can be interrupted by 1 to 17 ether oxygen atoms in case of aliphatic hydrocarbyl groups; R.sup.4 independently represents hydrocarbyl groups having 2 to 36 carbon atoms; n is an integer from 0 to 200; and wherein on average from 40 mol-% to 100 mol-% of all R.sup.3 and R.sup.4 groups contained in the one or more species of formula (I) are acyclic aliphatic hydrocarbyl groups which, in case of R.sup.3, can be interrupted by 1 to 17 ether oxygen atoms. The invention further relates to a method of manufacturing such product, liquid compositions containing such products and the use of the liquid compositions as rheology control additive, preferably as anti-settling agent. Furthermore, the present invention relates to a process for rheology adjustment, comprising the step of adding such liquid composition to a variety of compositions and formulations.

Claims

1. A urea and urethane group containing product comprising one or more species of formula (I)
R.sup.1O(CO)NHR.sup.2NH(CO)NHR.sup.3NH[(CO)NHR.sup.4NH(CO)NHR.sup.3NH].sub.n(CO)NHR.sup.2NH(CO)OR.sup.1 (I), wherein R.sup.1 independently represent non-aromatic hydrocarbyl groups having 14 to 30 carbon atoms; R.sup.2 independently represent alkyl-substituted aromatic hydrocarbyl groups having 7 to 12 carbon atoms; R.sup.3 independently represent hydrocarbyl groups having 2 to 36 carbon atoms, which can be interrupted by 1 to 17 ether oxygen atoms in case of aliphatic hydrocarbyl groups; R.sup.4 independently represent hydrocarbyl groups having 2 to 36 carbon atoms; n is an integer from 0 to 200; and wherein on average from 40 mol-% to 100 mol-% of all R.sup.3 and R.sup.4 groups contained in the one or more species of formula (I) are acyclic aliphatic hydrocarbyl groups which, in case of R.sup.3, can be interrupted by 1 to 17 ether oxygen atoms.

2. The urea and urethane group containing product according to claim 1, wherein R.sup.1 independently represent branched aliphatic hydrocarbyl groups.

3. The urea and urethane group containing product according to claim 1, wherein R.sup.1 independently represent ethylenically unsaturated aliphatic hydrocarbyl groups.

4. The urea and urethane group containing product according to claim 1, wherein R.sup.1 independent represent an aliphatic hydrocarbyl group contained in an alcohol of formula R.sup.1OH, where the alcohol is liquid at 23 C. and 100 kPa standard pressure.

5. The urea and urethane group containing product according to claim 1, wherein R.sup.1 is an octadecenyl group.

6. The urea and urethane group containing product according claim 1, wherein on average from 50 mol-% to 100 mol % of all R.sup.3 and R.sup.4 groups contained in the one or more species of formula (I) are acyclic aliphatic hydrocarbyl groups which, in case of R.sup.3, can be interrupted by 1 to 17 ether oxygen atoms.

7. A method of manufacturing a urea group containing product, the method comprising: reacting one or more components R.sup.1OH with one or more diisocyanates OCNR.sup.2NCO to form one or more monoisocyanato adducts having the following formula (II)
R.sup.1O(CO)NHR.sup.2NCO (II), and subsequently reacting the one or more monoisocyanato adducts having formula (II) with one or more diamines H.sub.2NR.sup.3NH.sub.2, wherein R.sup.1 represents a non-aromatic hydrocarbyl group having 14 to 30 carbon atoms, R.sup.2 represents an alkyl-substituted aromatic hydrocarbyl group having 7 to 12 carbon atoms, R.sup.3 represents a hydrocarbyl group having 2 to 36 carbon atoms, which can be interrupted by 1 to 17 ether oxygen atoms in case of an aliphatic hydrocarbyl group, wherein on average from 40 mol-% to 100 mol-% of all R.sup.3 groups in the product represent acyclic aliphatic hydrocarbyl groups which can be interrupted by 1 to 17 ether oxygen atoms.

8. A liquid composition comprising the urea and urethane group containing product according to claim 1 and a carrier medium.

9. The liquid composition according to claim 8, wherein the carrier medium includes one or more of an amide, a sulfoxide, and an ionic liquid.

10. The liquid composition according to claim 8, wherein the liquid composition comprises: 5 to 70% by weight of the urea and urethane group containing product, 30 to 95% by weight of one or more of a polar aprotic solvent and an ionic liquid, and 0 to 8% by weight of one or more ionogenic compounds, the amounts of (a), (b) and (c) being based on the total weight of the liquid composition.

11. The liquid composition according to claim 8, further comprising particles.

12-13. (canceled)

14. The liquid composition according to claim 8, wherein the carrier medium comprises one or more liquid hydrocarbons, the liquid composition further comprises one or more insoluble solids in particulate form, and the urea and urethane group containing product is included in an amount of 0.02 to 8.00% by weight, based on the total weight of the liquid composition.

15-16. (canceled)

17. A process for rheology adjustment, the process comprising adding the liquid composition according to claim 8 to one or more of a coating composition, a clear coat composition, a lacquer, a color resist, a plastic formulation, a pigment paste, an effect pigment paste, a sealant formulation, a wire enamel, a cosmetic formulation, a ceramic formulation, an adhesive formulation, a liquid formulation for use in gas and oil production, a liquid composition for the manufacture of electrical components and circuits, a liquid formulation for use in energy storage media, a cleaning agent, a potting compound, a building material formulation, a lubricant, a filling compound, a wax emulsion, a metal-processing product, a metalworking fluid, a liquid composition in the form of a spraying agent, a deposition aid, an ink, a printing ink and an ink jet ink.

18. The urea and urethane group containing product according claim 1, wherein on average from 60 mol-% to 100 mol-% of all R.sup.3 and R.sup.4 groups contained in the one or more species of formula (I) are acyclic aliphatic hydrocarbyl groups.

19. The method of manufacturing a urea group containing product according to claim 7, further comprising forming a mixture comprising the one or more monoisocyanato adducts having formula (II) and one or more diisocyanates OCNR.sup.4NCO, R.sup.4 representing a hydrocarbyl group having 2 to 36 carbon atoms, and reacting the mixture with the one or more diamines H.sub.2NR.sup.3NH.sub.2.

20. The liquid composition according to claim 11, wherein the particles comprise a hydrophilic polymer.

21. The liquid composition according to claim 11, wherein the particles comprise polysaccharides.

22. A drilling fluid comprising a carrier medium and the urea and the urethane group containing product according to claim 1.

23. The drilling fluid according to claim 22, further comprising particles.

24. A coating composition comprising a carrier medium, a film-forming resin, and the urea and urethane group containing product according to claim 1.

Description

EXAMPLES

[0134] Synthesis Examples

TABLE-US-00001 TABLE 1 Explanation of Abbreviations Product name Chemical Composition Supplier TDI T100 2,4-toluylene diisocyanate Covestro AG TDI T80 80/20 mixture of 2,4-toluylene diisocyanate Covestro AG and 2,6-toluylene diisocyanate TDI T65 65/35 mixture of 2,4-toluylene diisocyanate Covestro AG and 2,6-toluylene diisocyanate IPDI isophorone diisocyanate Merck Jeffamine EDR 148 H.sub.2NCH.sub.2CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2NH.sub.2 Huntsman Corp.

[0135] Manufacture of Intermediates A1 to A4:

[0136] Diisocyanates were reacted with mono alcohols according to the procedure described in EP 1188779 to form monoadducts (intermediates), containing one urethane group and one NCO group.

TABLE-US-00002 TABLE 2 Intermediates Intermediate Mono alcohol Diisocyanate A1 (Z)-Octadec-9-enol (oleocetyl alcohol TDI T65 90-95, Mosselman) A2 tridecyl alcohol (Exxal 13, Exon Mobile TDI T65 Chemical) A3 2-Decyltetradecanol (Isofol 24, Sasol TDI T65 Performance Chemicals, Hamburg) A4 (Z)-Octadec-9-enol (oleocetyl alcohol IPDI 90-95, Mosselman)

[0137] Intermediates A1 to A3:

[0138] 2 mol of TDI T65 and 200 ppm benzoyl chloride were weighed into a glass flask equipped with stirrer, reflux condenser and nitrogen inlet and heated to 40 C. Subsequently 1 mol of the mono alcohol (according to the above table 2) was added dropwise to the reaction mixture over a period of 30 min. The reaction mixture was stirred for additional 5 hours at 60 C. A clear, light yellow, liquid crude intermediate containing excessive diisocyanate is obtained. The excessive diisocyanate contained in the crude intermediates obtained, was removed by distillation, whereby intermediates A1 to A3 were obtained.

[0139] Intermediate A4:

[0140] 2 mol of IPDI were weighed into a glass flask equipped with stirrer, reflux condenser and nitrogen inlet and heated to 40 C. Subsequently 1 mol of the mono alcohol (according to the above table 2) was added dropwise to the reaction mixture over a period of 30 min. The reaction mixture was stirred for additional 2 hours at 60 C. A clear, light yellow, liquid crude intermediate containing excessive IPDI is obtained. The excessive IPDI contained in the crude intermediate obtained, was removed by distillation, whereby intermediate A4 was obtained.

Comparative Examples C1 to C12 (Non-Inventive)

[0141] Completeness of the following reactions was evaluated with wet chemical methods by determination of NCO content and amine value.

[0142] Comparative Rheology Additive C1:

[0143] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 4.800 g (0.114 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 4.600 g (0.034 mol) m-xylylene diamine (m-XDA) were added and briefly homogenized. A uniform mixture of 36.400 g (0.076 mol) of adduct A1 and 13.300 g (0.076 mol) TDI T80 was added dropwise to the reaction mixture over a period of 50 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, viscous product was obtained.

[0144] Comparative Rheology Additive C2:

[0145] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.700 g (0.135 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 9.100 g (0.067 mol) m-xylylene diamine were added and briefly homogenized. A uniform mixture of 53.300 g (0.111 mol) of adduct A1 and 1.900 g (0.011 mol) TDI T80 was added dropwise to the reaction mixture over a period of 30 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0146] Comparative Rheology Additive C3:

[0147] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.400 g (0.127 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 8.600 g (0.063 mol) m-xylylenediamine were added and briefly homogenized. A uniform mixture of 55.500 g (0.115 mol) of adduct A1 and 1.000 g (0.006 mol) TDI T80 was added dropwise to the reaction mixture over a period of 30 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0148] Comparative Rheology Additive C4:

[0149] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 8.900 g (0.211 mol) lithium chloride were dissolved in 292.5 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 28.600 g (0.211 mol) m-xyxlene diamine were added and briefly homogenized. A uniform mixture of 101.700 g (0.211 mol) of adduct A1 and 18.300 g (0.105 mol) TDI T80 was added dropwise to the reaction mixture over a period of 30 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0150] Comparative Rheology Additive C5:

[0151] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 3.000 g (0.071 mol) lithium chloride were dissolved in 97.5 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 9.600 g (0.071 mol) m-xylylene diamine were added and briefly homogenized. A uniform mixture of 33.800 g (0.071 mol) of adduct A1 and 6.200 g (0.035 mol) TDI T80 was added dropwise to the reaction mixture over a period of 30 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, highly viscous product was obtained.

[0152] Comparative Rheology Additive C6:

[0153] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 6.000 g (0.141 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 9.500 g (0.070 mol) m-xylylene diamine were added and briefly homogenized. A uniform mixture of 51.700 g (0.108 mol) of adduct A1 and 2.800 g (0.016 mol) TDI T80 was added dropwise to the reaction mixture over a period of 30 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0154] Comparative Rheology Additive C7:

[0155] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 3.000 g (0.071 mol) lithium chloride were dissolved in 97.5 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 9.600 g (0.071 mol) m-xylylene diamine were added and briefly homogenized. A uniform mixture of 33.800 g (0.071 mol) of adduct A1 and 6.200 g (0.035 mol) TDI T80 was added dropwise to the reaction mixture over a period of 30 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0156] Comparative Rheology Additive C8:

[0157] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.200 g (0.053 mol) lithium chloride were dissolved in 63.4 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 3.600 g (0.026 mol) m-xylylene diamine were added and briefly homogenized. A uniform mixture of 28.100 g (0.070 mol) of adduct A4 and 0.200 g (0.035 mol) TDI T80 was added dropwise to the reaction mixture over a period of 10 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0158] Comparative Rheology Additive C9:

[0159] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.300 g (0.055 mol) lithium chloride were dissolved in 66.0 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 3.700 g (0.028 mol) m-xylylene diamine were added and briefly homogenized. A uniform mixture of 29.300 g (0.052 mol) of adduct A4 and 0.200 g (0.001 mol) hexamethylene diisocyanate (HDI) was added dropwise to the reaction mixture over a period of 10 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0160] Comparative Rheology Additive C10:

[0161] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.300 g (0.055 mol) lithium chloride were dissolved in 61.8 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 3.700 g (0.027 mol) 1,3-diaminopropane were added and briefly homogenized. A uniform mixture of 28.800 g (0.051 mol) of adduct A4 and 0.200 g (0.001 mol) TDI T80 was added dropwise to the reaction mixture over a period of 10 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0162] Comparative Rheology Additive C11:

[0163] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 2.400 g (0.057 mol) lithium chloride were dissolved in 65.3 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 2.100 g (0.029 mol) 1,3-diaminopropane were added and briefly homogenized. A uniform mixture of 30.400 g (0.054 mol) of adduct A4 and 0.200 g (0.001 mol) hexamethylene diisocyanate was added dropwise to the reaction mixture over a period of 10 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0164] Comparative Rheology Additive C12:

[0165] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.760 g (0.136 mol) lithium chloride were dissolved in 122.6 g N-butyl butyrolactam while stirring over a period of 30 min at 60 C., whereby a clear solution was obtained. Subsequently 7.900 g (0.068 mol) hexamethylenediamine were added and briefly homogenized. Subsequently 52.360 g (0.136 mol) of adduct A2 were added dropwise to the reaction mixture over a period of 20 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

Examples E1 to E16 (According to the Invention)

[0166] Completeness of the following reactions was evaluated with wet chemical methods by determination of NCO content and the amine value.

[0167] Rheology Additive According to the Invention E1:

[0168] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.300 g (0.125 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 5.600 g (0.064 mol) 1,4-diaminobutane were added and briefly homogenized. A uniform mixture of 58.600 g (0.120 mol) of adduct A1 and 0.500 g (0.003 mol) TDI T80 was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 4.5 hours at 80 C. A clear, yellow, liquid product was obtained.

[0169] Rheology Additive According to the Invention E2:

[0170] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.200 g (0.123 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 7.200 g (0.062 mol) 1,6-diaminohexane were added and briefly homogenized. A uniform mixture of 57.100 g (0.117 mol) of adduct A1 and 0.500 g (0.003 mol) TDI T80 was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 1.5 hours at 100 C. A clear, yellow, liquid product was obtained.

[0171] Rheology Additive According to the Invention E3:

[0172] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.000 g (0.118 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 6.900 g (0.059 mol) 1,6-diaminobutane were added and briefly homogenized. Subsequently 58.000 g (0.119 mol) of adduct A1 was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 4.5 hours at 80 C., 2 hours at 100 C. and 1 hour at 120 C. A clear, yellow, liquid product was obtained.

[0173] Rheology Additive According to the Invention E4:

[0174] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.400 g (0.127 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 5.600 g (0.064 mol) 1,4-diaminobutane were added and briefly homogenized. A uniform mixture of 58.500 g (0.121 mol) of adduct A1 and 0.500 g (0.003 mol) hexamethylene diisocyanate was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0175] Rheology Additive According to the Invention E5:

[0176] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.400 g (0.127 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 5.600 g (0.064 mol) 1,4-diaminobutane were added and briefly homogenized. A uniform mixture of 58.400 g (0.121 mol) of adduct A1 and 0.500 g (0.003 mol) isophorone diisocyanate was added dropwise to the reaction mixture over a period of 20 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0177] Rheology Additive According to the Invention E6:

[0178] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.300 g (0.125 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 7.200 g (0.062 mol) 1,6-diaminohexane were added and briefly homogenized. A uniform mixture of 57.000 g (0.118 mol) of adduct A1 and 0.500 g (0.003 mol) hexamethylene diisocyanate was added dropwise to the reaction mixture over a period of 15 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0179] Rheology Additive According to the Invention E7:

[0180] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.200 g (0.123 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 7.200 g (0.062 mol) 1,6-diaminohexane were added and briefly homogenized. A uniform mixture of 56.900 g (0.118 mol) of adduct A1 and 0.700 g (0.003 mol) isophorone diisocyanate was added dropwise to the reaction mixture over a period of 15 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0181] Rheology Additive According to the Invention E8:

[0182] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 3.100 g (0.073 mol) lithium chloride were dissolved in 97.5 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 6.400 g (0.073 mol) 1,4-diaminobutane were added and briefly homogenized. A uniform mixture of 35.000 g (0.073 mol) of adduct A1 and 8.100 g (0.036 mol) isophorone diisocyanate was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0183] Rheology Additive According to the Invention E9:

[0184] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.600 g (0.131 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 5.800 g (0.066 mol) 1,4-diaminobutane were added and briefly homogenized. A uniform mixture of 57.600 g (0.119 mol) of adduct A1 and 1.000 g (0.006 mol) hexamethylene diisocyanate was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0185] Rheology Additive According to the Invention E10:

[0186] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.500 g (0.131 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 5.800 g (0.065 mol) 1,4-diaminobutane were added and briefly homogenized. A uniform mixture of 57.400 g (0.118 mol) of adduct A1 and 1.300 g (0.006 mol) isophorone diisocyanate was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0187] Rheology Additive According to the Invention E11:

[0188] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.500 g (0.130 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 4.700 g (0.065 mol) 1,3-diaminopropane were added and briefly homogenized. A uniform mixture of 59.300 g (0.123 mol) of adduct A1 and 0.500 g (0.003 mol) hexamethylene diisocyanate was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0189] Rheology Additive According to the Invention E12:

[0190] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.100 g (0.121 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 8.900 g (0.060 mol) Jeffamine EDR 148 were added and briefly homogenized. A uniform mixture of 55.500 g (0.115 mol) of adduct A1 and 0.500 g (0.003 mol) hexamethylene diisocyanate was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0191] Rheology Additive According to the Invention E13:

[0192] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.000 g (0.117 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 8.600 g (0.058 mol) Jeffamine EDR 148 were added and briefly homogenized. Subsequently 56.400 g (0.117 mol) of adduct A1 was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0193] Rheology Additive According to the Invention E14:

[0194] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 5.100 g (0.121 mol) lithium chloride were dissolved in 130 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 8.900 g (0.060 mol) Jeffamine EDR 148 were added and briefly homogenized. A uniform mixture of 55.400 g (0.115 mol) of adduct A1 and 0.600 g (0.003 mol) isophorone diisocyanate was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0195] Rheology Additive According to the Invention E15:

[0196] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 23.900 g (0.563 mol) lithium chloride were dissolved in 557.1 g N-butyl butyrolactam while stirring over a period of 30 min, whereby a clear solution was obtained. Subsequently 24.800 g (0.281 mol) 1,4-diaminobutane were added and briefly homogenized. A uniform mixture of 247.00 g (0.512 mol) of adduct A1 and 4.300 g (0.026 mol) hexamethylene diisocyanate was added dropwise to the reaction mixture over a period of 25 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

[0197] Rheology Additive According to the Invention E16:

[0198] In a glass flask with stirrer, reflux condenser and nitrogen inlet, 6.825 g lithium chloride were dissolved in 233.24 g N-butyl butyrolactam while stirring over a period of 30 min at 60 C., whereby a clear solution was obtained. Subsequently 5.970 g (0.081 mol) 1,3-diaminopropane were added and briefly homogenized. A uniform mixture of 112.150 g (0.210 mol) of adduct A3 and 0.650 g (0.004 mol) hexamethylene diisocyanate was added dropwise to the reaction mixture over a period of 30 min. The reaction mixture was stirred for additional 3 hours at 80 C. A clear, yellow, liquid product was obtained.

TABLE-US-00003 TABLE 3A Starting compounds for Producing Comparative Rheology Additives (used amounts in mol and (gram)) H.sub.2NR.sup.3NH.sub.2 Intermediate OCNF.sup.4NCO Additives D1 D2 D3 A1 A2 A4 TDI T80 HDI C1 0.034 0.076 0.076 (4.600) (36.400) (13.300) C2 0.067 0.111 0.011 (9.100) (53.300) (1.900) C3 0.063 0.115 0.006 (8.600) (55.000) (1.000) C4 0.211 0.211 0.105 (28.600) (101.700) (18.300) C5 0.071 0.071 0.035 (9.600) (33.800) (6.200) C6 0.070 0.108 0.016 (9.500) (51.700) (2.800) C7 0.071 0.071 0.035 (9.600) (33.800) (6.200) C8 0.026 0.070 0.001 (3.600) (28.100) (0.200) C9 0.028 0.052 0.001 (3.700) (29.300) (0.200) C10 0.027 0.051 0.001 (3.700) (28.800) (0.200) C11 0.029 0.054 0.001 (2.100) (30.400) (0.200) C12 0.068 0.136 (7.900) (52.360) D1: m-XDA; D2: 1,3-diaminopropane; D3: 1,6-diaminohexane

TABLE-US-00004 TABLE 3B Starting Compounds for Producing Inventive Rheology Additives (used amounts in mol and (gram)) H.sub.2NR.sup.3NH.sub.2 Intermediate OCNF.sup.4NCO Additives D2 D3 D5 D6 A1 A3 HDI TDI T80 IPDI E1 0.064 0.120 0.003 (5.600) (58.600) (0.500) E2 0.062 0.117 0.003 (7.200) (57.100) (0.500) E3 0.059 0.119 (6.900) (58.000) E4 0.064 0.121 0.003 (5.600) (58.500) (0.500) E5 0.064 0.121 0.003 (5.600) (58.400) (0.500) E6 0.062 0.118 0.003 (7.200) (57.000) (0.500) E7 0.062 0.118 0.003 (7.200) (56.900) (0.700) E8 0.073 0.073 0.036 (6.400) (35.000) (8.100) E9 0.066 0.119 0.006 (5.800) (57.600) (1.000) E10 0.065 0.118 0.006 (5.800) (57.400) (1.300) E11 0.065 0.123 0.003 (4.700) (59.300) (0.500) E12 0.060 0.115 0.003 (8.900) (55.500) (0.500) E13 0.058 0.117 (8.600) (56.400) E14 0.060 0.115 0.003 (8.900) (55.400) (0.600) E15 0.281 0.512 0.026 (24.800) (247.00) (4.300) E16 0.081 0.210 0.004 (5.970) (112.150) (0.650) D2: 1,3-diaminopropane; D3: 1,6-diaminohexane; D5: Jeffamine EDR 148; D6: 1,4-diaminobutane

[0199] Application Examples and Testing

TABLE-US-00005 TABLE 4 Raw Materials Product name Chemical Composition Manufacturer XP-07 Base Synthetic paraffin base oil Halliburton, SIP Ltd. LVT 200 Low viscosity base oil Deep South Chemical Inc. Guar Gum Guar Gum Eurotech Int. Sp. Z.z.z. 5300 Celpol R Polyanionic cellulose CP Kelco Oil Field Group (PAC)

TABLE-US-00006 TABLE 5 Test Systems (TS) Test Systems (Reference Systems without Additive) Amounts in parts by weight TS1-0 TS2-0 TS3-0 TS4-0 Oil LVT 200 65 65 Component XP-07 Base 65 65 Particle Guar gum 5300 65 65 Component Celpol R 65 65

[0200] Additivation of Test Systems TS1, TS2, TS3 and TS4

[0201] The suspensions of the particle component in the oil component were prepared according to the formulations given in Table 5. 65 g of the oil component were weighed into a 250-ml glass flask and 65 g of the particle component were then added. Thereafter, the comparative and inventive rheology control additives (C1 to C12 and E1 to E16, respectively), were added as obtained in the above Experimental Section to obtain test systems containing 0.5 wt.-% and 0.25 wt.-% of the respective rheology additive based on solid ingredients (which comprises the urea and urethane group containing product and lithium chloride), respectively. The mixture was homogenized with the spatula for 1 minute. The dispersion was obtain using the shaker apparatus Natalie from Andalok for a period of 20 min. After shaking, a part of the homogeneous sample was transferred into 100 ml of rolled edge snap-on glasses and stored at 22 C. for one week. The filling height in the snap-on glass was 10 cm. After one week, the homogeneity of the samples was assessed by determining the syneresis in percent of the total height. The higher the value for the syneresis, the more of the particle component deposited in the sample, i.e. the worse was the stability/homogeneity of the suspension.

[0202] The results are shown in the following Tables 6 (TS1), 7 (TS2), 8 (TS3) and 9 (TS4).

TABLE-US-00007 TABLE 6 Test System TS1 Syneresis @ dosage of @ dosage of TS1-# Rheology Additive 0.5 wt.-% 0.25 wt.-% 0 Reference (no additive) 36 36 1 C1 36 2 C2 12 3 C3 12 4 C4 16 18 5 C5 12 6 C6 12 7 C7 12 8 C8 40 60 9 C9 40 40 10 C10 40 35 11 C11 40 40 12 C12 15 13 E1 1 8 14 E2 2 3 15 E3 5 7 16 E4 0 4 17 E5 0 18 E6 2 4 19 E7 1 6 20 E8 0 21 E9 0 22 E10 0 23 E11 5 24 E13 10 25 E14 2 26 E15 5 27 E16 10

[0203] Some rheology control additives were tested only at the higher dosage of 0.5 wt.-% active ingredient, while other rheology control additives were only tested at the lower dosage of 0.25 wt.-%. However, some rheology control additives were also tested at both dosages.

[0204] It was surprisingly found that inventive rheology additives E1 to E11 and E13 to E16 provided a highly improved anti-settling behavior to the inventive test systems TS1-13 to TS1-27 which contain Guar Gum particles dispersed in a low viscosity base oil, compared to comparative rheology additives C1 to C12 in non-inventive test systems TS1-1 to TS1-12. In some cases, the test systems containing non-inventive rheology additives (C8 to C11) showed even worse anti-settling behavior compared to the reference test system TS1-0. Even at the lower dosage of 0.25 wt.-% of active ingredient, the inventive rheology additives performed very well.

TABLE-US-00008 TABLE 7 Test System TS2 Syneresis @ dosage @ dosage TS2-# Rheology Additive 0.5 wt.-% 0.25 wt.-% 0 Reference (no additive) 24 24 1 C1 31 2 C2 24 3 C3 12 4 C4 18 5 C5 12 6 C6 12 7 C7 12 8 C8 30 40 9 C9 35 40 10 C10 35 45 11 C11 35 40 12 E1 4 8 13 E2 2 5 14 E3 3 5 15 E4 0 1 16 E5 0 3 17 E6 0 5 18 E7 0 2 19 E8 5 20 E9 0 8 21 E10 5 22 E11 0 4 23 E12 0 24 E13 0 2 25 E14 0 2 26 E15 0

[0205] Some rheology control additives were tested only at the higher dosage of 0.5 wt.-% active ingredient, while other rheology control additives were only tested at the lower dosage of 0.25 wt.-%. However, some rheology control additives were also tested at both dosages.

[0206] It was surprisingly found that inventive rheology additives E1 to E15 provided a highly improved anti-settling behavior to the inventive test systems TS2-12 to TS2-26 which contain carboxylated cellulose particles (Celpol R) dispersed in a low viscosity base oil, compared to comparative rheology additives C1 to C11 in non-inventive test systems TS2-1 to TS2-11. In some cases, the test systems containing non-inventive rheology additives (C8 to C11) showed even worse anti-settling behavior compared to the reference test system TS2-0. Even at the lower dosage of 0.25 wt.-% of active ingredient, the inventive rheology additives performed very well.

TABLE-US-00009 TABLE 8 Test System TS3 Syneresis @ dosage @ dosage TS3-# Rheology Additive 0.5 wt.-% 0.25 wt.-% 0 Reference (no additive) 36 36 1 C1 40 2 C2 24 3 C3 24 4 C4 30 5 C5 36 6 C6 24 7 C7 36 8 C8 35 35 9 C9 35 35 10 C10 40 35 11 C11 35 35 12 C12 25 13 E1 3 14 E2 11 17 15 E3 10 20 16 E4 3 20 17 E5 8 20 18 E6 8 20 19 E7 10 20 E9 5 21 E11 2 20 22 E12 5 20 23 E13 15 24 E14 15 25 E15 0 15 26 E16 20

[0207] Some rheology control additives were tested only at the higher dosage of 0.5 wt.-% active ingredient, while other rheology control additives were only tested at the lower dosage of 0.25 wt.-%. However, some rheology control additives were also tested at both dosages.

[0208] It was surprisingly found that inventive rheology additives provided a highly improved anti-settling behavior to the inventive test systems TS3-13 to TS3-26 which contain Guar Gum particles dispersed in synthetic paraffin base oil, compared to comparative rheology additives C1 to C12 in non-inventive test systems TS3-1 to TS3-12. In most cases the test systems containing non-inventive rheology additives showed even worse anti-settling behavior compared to the reference test system TS3-0. Even at the lower dosage of 0.25 wt.-% of active ingredient, the inventive rheology additives performed well.

TABLE-US-00010 TABLE 9 Test System TS4 Syneresis @ dosage @ dosage TS4-# Rheology Additive 0.5 wt.-% 0.25 wt.-% 0 Reference (no additive) 24 24 1 C1 43 2 C2 36 3 C3 36 4 C4 26 33 5 C5 24 6 C6 24 7 C7 24 8 C8 40 40 9 C9 35 45 10 C10 45 40 11 C11 40 40 12 E1 3 18 13 E2 5 13 14 E3 4 10 15 E4 2 14 16 E5 4 20 17 E6 13 15 18 E7 3 14 19 E8 10 20 E9 5 15 21 E10 20 22 E11 0 15 23 E12 5 10 24 E13 5 10 25 E14 15 15 26 E15 5 20

[0209] Some rheology control additives were tested only at the higher dosage of 0.5 wt.-% active ingredient, while other rheology control additives were only tested at the lower dosage of 0.25 wt.-%. However, some rheology control additives were also tested at both dosages.

[0210] It was surprisingly found that inventive rheology additives provided a highly improved anti-settling behavior to the inventive test systems TS4-12 to TS3-26 which contain carboxylated cellulose particles (Celpol R) dispersed in synthetic paraffin base oil, compared to comparative rheology additives C1 to C11 in non-inventive test systems TS4-1 to TS4-11. In most cases the test systems containing non-inventive rheology additives showed even worse anti-settling behavior compared to the reference test system TS4-0. Even at the lower dosage of 0.25 wt.-% of active ingredient, the inventive rheology additives performed well.