Method for producing rheologically effective urea urethanes in organic salts

Patent metadata

Field	Value
Publication number	US-8956452-B2
Application number	US-200913130349-A
Country	US
Kind code	B2
Filing date	Nov 11, 2009
Priority date	Dec 1, 2008
Publication date	Feb 17, 2015
Grant date	Feb 17, 2015

Abstract

The invention relates to a method for producing a solution comprising urea urethanes and acting as a thixotropic agent, wherein at least two structurally different monohydroxy compounds are converted by an excess of toluoylene diisocyanate, forming monoisocyanate adducts having diamines in an ionic fluid, forming urea urethanes. The invention further relates to the use of the solution for thixotroping coating agents and solutions of urea urethanes in ionic fluids.

First claim

The invention claimed is:

1. A method for producing a solution comprising urea urethanes, wherein the method comprises:
reacting monohydroxy compounds of the general structure R—OH, wherein R is selected from the group consisting of an n-alkyl radical or an iso-alkyl radical of 4 to 22 carbon atoms, an alkenyl radical of 3 to 18 carbon atoms, a cycloalkyl radical, an aralkyl radical, a radical of the formula C m H 2m+1 (O—C n H 2n ) x —, a radical of the formula C m H 2m+1 (OOC—C v H 2v ) x —, and a radical of the formula Z—C 6 H 4 (O—C n H 2n ) x —, wherein m=1-22, n=2-4, x=1-15, v=4 or 5, and Z is an alkyl radical of 1 to 12 carbon atoms, with a 1.5 to 5-fold excess of tolylene diisocyanate,
removing the unconverted tolylene diisocyanate from the reaction mixture, and
reacting the monoisocyanate adducts thus obtained with diamines of the formula H 2 N—R′—NH 2 , wherein R′ is
C o H 2o wherein o= 2 to 12,
(C p H 2p —O) q —C p H 2p wherein p= 2 to 4 and q= 1 to 25,

(wherein R″ and R″′ are each independently CH 3 or H),

or mixtures thereof,
to form urea urethanes, wherein the urea urethanes are produced by reacting at least two structurally different monoisocyanate adducts, which differ in the R radical, with the diamines, and wherein the reaction of the at least two structurally different monoisocyanate adducts with the diamines takes place in an ionic liquid;
wherein:
the ionic liquids have the general formula (I)
[A] n + [Y] n− ,

wherein n is =1 or 2 and
the anion [Y] n− is selected from the group consisting of tetrafluoroborate [BF 4 ] − , tetrachloroborate [BCl 4 ] − , phosphate [PO 4 ] 3− , alkylphosphate [ROPO 3 ] 2− /[ROR′OPO 2 ] − , hexafluorophosphate [PF 6 ] − , hexafluoroantimonate [SbF 6 ] − , hexafluoroarsenate [AsF 6 ] − , tetrachloroaluminate [AlCl 4 ] − , trichlorozincate [ZnCl 3 ] − , dichlorocuprate [CuCl 2 ] − , sulfate [SO 4 ] 2− , alkylsulfate [R′—SO 4 ] − , hydrogen sulfate, carbonate [CO 3 ] 2− , fluorosulfonate, [R′—COO] − , [R′—SO 3 ] − , and [(R′—SO 2 ) 2 N] − , wherein R and R′ are each independently a linear or branched aliphatic or alicyclic alkyl radical containing 1 to 12 carbon atoms, or a C 5 -C 18 -aryl, C 5 -C 18 -aryl-C 1 -C 6 -alkyl or C 1 -C 6 -alkyl-C 5 -C 18 -aryl radical, the hydrogen atoms of which can be wholly or partly replaced by halogen atoms, and the cation [A] + is selected from the group consisting of:

wherein the radicals R1, R2, R3, R4, R5 and R6 are each independently selected from the group consisting of (i) substituted or unsubstituted linear or branched, saturated or unsaturated, aliphatic or alicyclic alkyl groups of 1 to 20 carbon atoms; (ii) heteroaryl or heteroaryl-C 1 -C 6 -alkyl groups having 3 to 8 carbon atoms in the heteroaryl radical and at least one heteroatom selected from the group consisting of N, O, and S, wherein the radical can be substituted with at least one group selected from the group consisting of C 1 -C 6 -alkyl groups and halogen atoms; (iii) substituted or unsubstituted aryl or aryl-C1-C6-alkyl groups having 5 to 12 carbon atoms in the aryl radical; (iv) a group selected from the group consisting of linear or branched aliphatic, cycloaliphatic, and a substituted or unsubstituted aromatic hydrocarbon radical of 2-40 carbon atoms which is interrupted by one or more heteroatoms selected from the group consisting of N and O; and (v) a substituted or unsubstituted linear or branched aliphatic hydrocarbon radical of 2-20 carbon atoms which is interrupted by one or more functionalities selected from the group consisting of —O—C(O)—, —(O)C—O—, —NH—C(O)—, —(O)C—NH—, —(CH 3 )N—C(O)—, —(O)C—N(CH 3 )—, —S(O) 2 —O—, —O—S(O) 2 —, —S(O) 2 —NH—, —NH—S(O) 2 —, —S(O) 2 —N(CH 3 )—, and —N(CH 3 )—S(O) 2 —.

2. The method according to claim 1 , wherein initially at least two structurally different alcohols R—OH are mixed and subsequently reacted with a 1.5 to 5-fold excess of tolylene diisocyanate, the unconverted tolylene diisocyanate is removed from the reaction mixture, and the mixture of structurally different monoisocyanate adducts which is obtained in this way is reacted with the diamines in an ionic liquid to form urea urethanes.

3. The method according to claim 1 , wherein initially at least two structurally different alcohols R—OH are separately reacted with a 1.5 to 5-fold excess of tolylene diisocyanate, and the unconverted tolylene diisocyanate is removed from the reaction mixtures, and the structurally different monoisocyanate adducts obtained in this way are mixed with each other and the resulting mixture of structurally different monoisocyanate adducts is reacted with the diamines in an ionic liquid to form urea urethanes.

4. The method according to claim 2 , wherein the molar fraction of the structurally different monoisocyanate adducts in the mixture is between 20 and 80%, wherein the sum total of the molar fractions of the monoisocyanate adducts is 100%.

5. The method according to claim 1 , wherein a solution having a solids content of 5% to 80% by weight is produced.

6. The method according to claim 1 , wherein the molar excess of tolylene diisocyanate is in the range from 2 to 4.

7. The method according to claim 1 , wherein a tolylene diisocyanate isomer mixture having a 2,4-isomer fraction in the range from 50% to 100% by weight is used.

8. The method according to claim 1 , wherein the ionic liquid is liquid at 25° C.

9. A thixotropic coating solution prepared according to the method of claim 1 .

10. A solution in an ionic liquid of the urea urethane defined according to claim 1 .

11. The method according to claim 1 , wherein the ionic liquids have the general formula (I)
[A] n + [Y] n− ,
wherein n is=1 or 2 and
the cation [A] n + is selected from the group consisting of

and mixtures thereof.

12. The method according to claim 11 , wherein the cation [A] n + is selected from the group consisting of

13. The method according to claim 1 , wherein the ionic liquids have the general formula (I)
[A] n + [Y] n− ,
wherein n is=1 or 2 and
the anion [Y] n− is selected from the group consisting of [R ' —SO 4 ] − , [SO 4 ] 2− , hydrogen sulfate, phosphate [PO 4 ] 3− , alkylphosphate [ROPO 3 ] 2− /[ROR′OPO 2 ] − , tosylates, tetrafluroborate [BF 4 ] − , tetrachloroborate [BCl 4 ] − , [R ' —COO] − , and mixtures thereof.

14. The method according to claim 13 wherein the anion [Y] n− is selected from the group consisting of alkyl sulfates, tosylates, and acetates.

15. The method of claim 1 , wherein (i) the linear or branched, saturated or unsaturated, aliphatic or alicyclic alkyl groups of 1 to 20 carbon atoms are substituted with an alkyl group of 1-8 carbon atoms or a halogen atom.

16. The method of claim 1 , wherein (iii) the aryl or the aryl-C 1 -C 6 -alkyl groups having 5 to 12 carbon atoms in the aryl radical is substituted with a C 1 -C 6 -alkyl group or a halogen atom.

17. The method of cla

Assignees

• Orth Ulrich
• Eberhardt Marc
• Omeis Jurgen
• Dams Christian
• Byk Chemie Gmbh

Inventors

• Orth Ulrich
• Eberhardt Marc
• Omeis Jurgen
• Dams Christian

Classifications

• C08G18/2825

  having at least 6 carbon atoms · CPC title

• C07C273/1827

  X being H · CPC title

• C08G18/10

  Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step · CPC title

• C08G18/283

  Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds · CPC title

• C08G18/282

  Alkanols, cycloalkanols or arylalkanols including terpenealcohols · CPC title