Ureaurethanes for rheology control

Patent metadata

Field	Value
Publication number	US-10407385-B2
Application number	US-201615577970-A
Country	US
Kind code	B2
Filing date	Jul 22, 2016
Priority date	Jul 27, 2015
Publication date	Sep 10, 2019
Grant date	Sep 10, 2019

Abstract

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

in which at least one of the R 1 or R 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 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 3 is a xylylene radical or a hydrogenated xylylene radical and R 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 antisettling 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.

First claim

The invention claimed is:

1. A urea urethane of the general formula (I)

in which
R 1 is a mono- or polyunsaturated, branched or unbranched alkenyl radical having 12 to 24 carbon atoms,
R 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,
wherein the proportion by weight of the urea urethanes of the formula (I) in which both R 1 and R 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 1 radical is unsaturated is 0% to 90%, based on the totality of the urea urethanes of the formula (I),

and
all n R 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)

and
all n+1 R 4 radicals are independently one or more radicals selected from the structural units (IIIa), (IIIb), (IIIc), (IIId), (IIIe), (IIIf), (IIIg) and (IIIh)

and
n is an integer ≥1, where the upper limit for n arises from the maximum number-average molecular weight M 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 3 and R 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 1 radical is a monounsaturated alkenyl radical having 16 to 20 carbon atoms,
the R 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 3 radicals are independently one or more radicals selected from the structural units (IIa-m) and (IIa-p), and
the n+1 R 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 1 radical is an unbranched octadecenyl radical,
the R 2 radical is a branched or unbranched C 10 -C 14 -alkyl radical or an unbranched octadecenyl radical,
the n R 3 radicals are a radical of the structural unit (IIa-m), and
the n+1 R 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 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 1 and R 2 are a mono- or polyunsaturated, branched or unbranched alkenyl radical having 16 to 20 carbon atoms.

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

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

8. A urea urethane composition comprising one or more urea urethanes of claim 1 .

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 1 —O—(CO)—NH—R 4 —NCO or of the formula R 2 —O—(CO)—NH—R 4 —NCO are prepared from one or more monoalcohols of the formula R 1 OH or R 2 OH, or the formulae R 1 OH and R 2 OH, and one or more diisocyanates of the formula OCN—R 4 —NCO and said monoadduct(s) is/are then reacted
(i) with one or more diamines of the formula H 2 N—R 3 —NH 2 or
(ii) with one or more prepolymers, NH 2 -terminated at both ends, of one or more diamines of the formula H 2 N—R 3 —NH 2 and one or more diisocyanates of the formula OCN—R 4 —NCO or
(iii) with one or more diamines of the formula H 2 N—R 3 —NH 2 and one or more diisocyanates of the formula OCN—R 4 —NCO or
(iv) with one or more prepolymers NH 2 -terminated at both ends or a mixture of one or more diamines of the structure H 2 N—R 3 —NH 2 and one or more prepolymers NH 2 -terminated at both ends, and one or more diisocyanates of the formula OCN—R 4 —NCO;
or
(b) one or more prepolymers, NCO-terminated at both ends, of one or more diisocyanates of the formula OCN—R 4 —NCO and one or more diamines of the formula H 2 N—R 3 —NH 2 is/are prepared, and the prepolymer(s) is/are reacted with one or more monoalcohols of the formulae R 1 OH or R 2 OH, or the formulae R 1 OH and R 2 OH;
and
wherein at least one monoalcohol of the formula R 1 OH 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 1 —O—(CO)—NH—R 4 —NCO or of the formula R 2 —O—(CO)—NH—R 4 —NCO are prepared from one or more monoalcohols of the formula R 1 OH or R 2 OH, or the formulae R 1 OH and R 2 OH, and one or more diisocyanates of the formula OCN—R 4 —NCO and said monoadduct(s) is/are then reacted
(i) with one or more diamines of the formula H 2 N—R 3 —NH 2 or
(ii) with one or more prepolymers, NH 2 -terminated at both ends, of one or more diamines of the formula H 2 N—R 3 —NH 2 and one or more diisocyanates of the formula OCN—R 4 —NCO or
(iii) with one or more diamines of the formula H 2 N—R 3 —NH 2 and one or more diisocyanates of the formula OCN—R 4 —NCO or
(iv) with one or more prepolymers NH 2 -terminated at both ends or a mixture of one or more diamines of the structure H 2 N—R 3 —NH 2 and one or more prepolymers NH 2 -terminated at both ends, and one or more diisocyanates of the formula OCN—R 4 —NCO;
or
(b) one or more prepolymers, NCO-terminated at both ends, of one or more diisocyanates of the formula OCN—R 4 —NCO and one or more diamines of the formula H 2 N—R 3 —NH 2 is/are prepared, and the prepolymer(s) is/are reacted with one or more monoalcohols of the formulae R 1 OH or R 2 OH, or the formulae R 1 OH and R 2 OH;
and then the polar aprotic solvent is removed;
and
wherein at least one monoalcohol of the formula R 1 OH is used in process variants (a) and (b).

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

15. A liquid formulation selected from the group consistin

Assignees

• Byk Chemie Gmbh

Inventors

• Eberhardt Marc
• Nagelsdiek René
• Bühne Sylvia
• Omeis Jürgen
• Schmitt Agnetha

Classifications

• C08G18/7621

  being toluene diisocyanate including isomer mixtures · CPC title

• C09D5/04

  Thixotropic paints · CPC title

• C08G18/675

  Low-molecular-weight compounds · CPC title

• C08L75/16

  having terminal carbon-to-carbon unsaturated bonds · CPC title

• C09D7/45

  Anti-settling agents · CPC title