Urea-group- and/or urethane-group-containing amides as and in rheology control agents, their preparation and their use

Abstract

The invention relates to urea- and/or urethane-substituted amides of the general formula (I) ##STR00001##
The radicals R1, Z1, R2, and Z2 comprise a building block containing urea groups and/or containing urethane groups; the radicals R4, Z4, R5, and Z5 comprise a building block containing amide groups, and E is a carboxylic acid group or salt thereof. The invention also relates to rheology control agents which consist of or comprise the amides of the formula (I). A further subject of the invention is a method for producing the rheology control agents, and the use of the urea- and/or urethane-substituted amides, and also of the rheology control agents, as thickeners, especially in liquid compositions, and also the liquid compositions themselves.

Claims

1. A urea- and/or urethane-substituted amide of the general formula (I) ##STR00006## wherein the radicals R1 independently of one another are selected from the group consisting of hydrogen, if m=1 and Z1 is a covalent bond, and radicals R.sup.a—[O—(C═O).sub.uR.sup.b].sub.v, in which R.sup.a is selected from the group consisting of saturated or unsaturated, linear or branched, aliphatic hydrocarbon radicals having 1 to 40 carbon atoms; aromatic hydrocarbon radicals having 6 to 40 carbon atoms; and araliphatic hydrocarbon radicals having 7 to 40 carbon atoms; u is 0 or 1, v is 0 to 50, the radicals R.sup.b independently of one another are divalent organic radicals which, if u=0, are linear or branched alkylene radicals having 2 to 24 carbon atoms, wherein, if an alkylene radical contains two carbon atoms, said radical may carry a substituent having the formula CH.sub.2—O—(C═O).sub.wR.sup.c, in which w is 0 or 1 and R.sup.c is an organic radical having 2 to 24 carbon atoms; and the radicals R.sup.b, if u=1, are linear or branched alkylene radicals having 3 to 8 carbon atoms; and in the radicals [O—(C═O).sub.uR.sup.b] the value for u in each radical independently is 0 or 1; the radicals R2 independently of one another are divalent organic radicals which are selected from the group consisting of hydrocarbon radicals having 6 to 40 carbon atoms, which optionally contain one or more isocyanurate groups; the radicals R3 independently of one another are (k+1)-valent organic radicals which are selected from the group consisting of saturated or unsaturated, linear or branched, aliphatic hydrocarbon radicals having 2 to 40 carbon atoms, which optionally contain one or more ether oxygen atoms and/or carry one or more hydroxyl groups; aromatic hydrocarbon radicals having 6 to 40 carbon atoms, wherein the aromatic hydrocarbon radicals optionally carry one or more linear or branched alkyl substituents having 1 to 10 carbon atoms; and araliphatic hydrocarbon radicals having 8 to 40 carbon atoms, wherein the aromatic hydrocarbon radicals optionally carry one or more linear or branched alkyl substituents having 1 to 10 carbon atoms; and a radical N—R2-Z1-R1, if Z2 is an NH—(C═O) group, and wherein N in Z2 and Z3 is bonded to the respective carbon atom in NH—(C═O), and m=k=1, the radicals R4 independently of one another are divalent organic radicals which are selected from the group consisting of saturated or unsaturated, linear or branched aliphatic hydrocarbon radicals having 2 to 40 carbon atoms, wherein these are optionally substituted by one or more hydroxyl groups; the radicals R5 independently of one another are divalent organic radicals which are selected from the group consisting of saturated or unsaturated, linear or branched, aliphatic hydrocarbon radicals having 2 to 40 carbon atoms, wherein the hydrocarbon radicals optionally contain ether oxygen atoms and/or tertiary amino groups; araliphatic hydrocarbon radicals having 8 to 40 carbon atoms; and aromatic hydrocarbon radicals having 6 to 40 carbon atoms; the radicals R6 are selected from the group consisting of the aromatic radicals having 6 to 40 carbon atoms and saturated or unsaturated, linear or branched aliphatic hydrocarbon radicals having 4-40 carbons atoms, wherein these are optionally substituted by one or more hydroxyl groups; the radicals E independently of one another are COOH or COO.sup.⊖Z.sup.⊕, wherein Z.sup.⊕ is selected from the group consisting of alkali metal cations, alkaline earth metal cations, NH.sub.4.sup.⊕, heterocyclic cations, and mono- to tetra-organically substituted ammonium ions, wherein when Z.sup.⊕ is an alkaline earth metal cation, Z.sup.⊕ is ½ Z.sup.2⊕, the radicals Z1 independently of one another are a urethane group, a urea group or a covalent bond; the radicals Z2 independently of one another are a urethane group or a urea group, or, if R3 is a radical N—R2-Z1-R1, Z2 is an NH—(C═O) group; the radicals Z3 are an amide group; the radicals Z4 are an amide group; the radicals Z5 independently of one another are an amide group or are an amino group, wherein the amino group may also be in protonated or quaternized form and wherein Z.sup.⊕ in that case is absent; m is 1 to 5; n is 1 to 12; and k is 1 to 5.

2. The urea- and/or urethane-substituted amides as claimed in claim 1, in which at least one of the radicals R1, R2, R3, R4, R5, R6, and E is defined as follows: R1 is selected from the group consisting of (i) linear or branched alkyl or alkenyl radicals having 6 to 24 carbon atoms and (ii) polyether radicals of the formula R.sup.a—[O—R.sup.b].sub.v, in which R.sup.a is a linear or branched alkyl or alkenyl radical having 1 to 18 carbon atoms, R.sup.b is one or more radicals from the group consisting of C.sub.2H.sub.4, C.sub.3H.sub.6 and C.sub.4H.sub.8 and v is an integer from 1 to 25; R2 is selected from the group consisting of ##STR00007## wherein m is 1, Z1 is —O—(C═O)—NH— and Z2 is —NH—(C═O)—O—, and the symbols “*” mark the bonding sites of the respective radical R2 to the radicals Z1 and Z2; R3 is selected from the group consisting of (i) alkylene radicals having 2 to 6 carbon atoms, wherein k is the number 1, and (ii) alkylene radicals having 4 to 6 carbon atoms; R4 is selected from the group consisting of linear or branched alkylene or alkenylene radicals having 4 to 40 carbon atoms; R5 is selected from the group consisting of linear or branched alkylene radicals having 2 to 13 carbon atoms, cycloalkylene radicals having 3 to 13 carbon atoms, and arylalkylene radicals having 7 to 13 carbon atoms; R6 is selected from the group consisting of linear or branched alkylene or alkenylene radicals having 4 to 40 carbon atoms; and E is a COOH group.

3. The urea- and/or urethane-substituted amides as claimed in claim 1, in which all radicals R1, R2, R3, R4, R5, R6, and E are defined as follows: R1 is selected from the group consisting of (i) linear or branched alkyl or alkenyl radicals having 6 to 24 carbon atoms and (ii) polyether radicals of the formula R.sup.a—[O—R.sup.b].sub.v, in which R.sup.a is a linear or branched alkyl or alkenyl radical having 1 to 18 carbon atoms, R.sup.b is one or more radicals from the group consisting of C.sub.2H.sub.4, C.sub.3H.sub.6 and C.sub.4H.sub.8 and v is an integer from 1 to 25; R2 is selected from the group consisting of ##STR00008## wherein m is 1, Z1 is —O—(C═O)—NH— and Z2 is —NH—(C═O)—O—, and the symbols “*” mark the bonding sites of the respective radical R2 to the radicals Z1 and Z2; R3 is selected from the group consisting of (i) alkylene radicals having 2 to 6 carbon atoms, wherein k is the number 1, and (ii) alkylene radicals having 4 to 6 carbon atoms; R4 is selected from the group consisting of linear or branched alkylene or alkenylene radicals having 4 to 40 carbon atoms; R5 is selected from the group consisting of linear or branched alkylene radicals having 2 to 13 carbon atoms, cycloalkylene radicals having 3 to 13 carbon atoms, and arylalkylene radicals having 7 to 13 carbon atoms; R6 is selected from the group consisting of linear or branched alkylene or alkenylene radicals having 4 to 40 carbon atoms; and E is a COOH group.

4. A method for producing a rheology control agent, comprising (A1) one or more species of the formula (III)
R1-X—H  (III) in which X is O or N(R7), wherein R7 is H, an alkyl radical having 1 to 12 carbon atoms, an aryl radical having 6 to 12 carbon atoms or an alkylaryl radical having 7 to 12 carbon atoms, are reacted with with one or more species of the general formula (IV)
R2(NCO).sub.m+1  (IV); or (A2) one or more diisocyanates containing a uretdione group are reacted with one or more species of the general formula (III)
R1-X—H  (III) whose radicals are defined as under (A1), with retention of the uretdione function and reaction of both isocyanate groups to give corresponding uretdione-functional urethanes and/or uretdione-functional ureas; (B1) one or more species of the general formula (VI)
Y—(O═C)—R4-(C═O)—Y′  (VI) wherein Y and Y′ independently of one another are OR.sup.e or halide, or Y and Y′ are connected to one another and together as Y—Y′ are an oxygen atom, and wherein R.sup.e is hydrogen or is R.sup.d, wherein R.sup.d is a protecting group for a carboxyl group, are reacted with one or more diamines of the general formula (VII)
H.sub.2N—R5-NH.sub.2  (VII) optionally in the presence of one or more species of the general formula (VIII)
(HX).sub.k—R3-NH(R8)  (VIII) wherein X is defined as in formula (III) and in which R8 is H, an alkyl radical having 1 to 12 carbon atoms, which optionally contains one or more ether oxygen atoms and/or carries one or more hydroxyl groups, an aryl radical having 6 to 12 carbon atoms, an alkylaryl radical having 7 to 12 carbon atoms, or a radical —R3′[-Z2-R2-[Z1-R1].sub.m′].sub.k′, and, when a terminal radical —R5-NH2 is formed, this radical is reacted (a) with one or more species of the general formula (VIa)
Y—(O═C)—R6-E′  (VIa) in which E′ is E or COOR.sup.d and, if E′ is (C═O)—Y′, Y and Y′ are defined as in formula (VI), or (b) with one or more species of the general formula (X)
H.sub.2C═C(R.sup.f)-E′  (X) wherein R.sup.f is hydrogen or an alkyl radical having 1 or 2 carbon atoms, in a stoichiometric ratio such that the resulting building block (B1) containing amide groups contains exactly one end group E′; or (B2) one or more amino carboxylic acids of the general formulae (IXa) and/or (IXb)
HOOC—R4-NH.sub.2  (IXa)
and/or
HOOC—R5-NH.sub.2  (IXb) are reacted in a polycondensation reaction in the presence of one or more species of the general formula (VIII)
(HX).sub.k—R3-NH(R8)  (VIII), wherein X is defined as in formula (III) and in which R8 is H, an alkyl radical having 1 to 12 carbon atoms, which optionally contains one or more ether oxygen atoms and/or carries one or more hydroxyl groups, an aryl radical having 6 to 12 carbon atoms, an alkylaryl radical having 7 to 12 carbon atoms, or a radical —R3′[-Z2-R2-[Z1-R1].sub.m′].sub.k′, and the species thus obtained are reacted in turn (a) with one or more species of the general formula (VIa)
Y—(O═C)—R6-E′  (VIa) in which E′ is E or COOR.sup.d and, if E′ is (C═O)—Y′, Y and Y′ are defined as in formula (VI), or (b) with one or more species of the general formula (X)
H.sub.2C═C(R.sup.f)-E′  (X) wherein R.sup.f is hydrogen or an alkyl radical having 1 or 2 carbon atoms, in a stoichiometric ratio such that the resulting building block (B2) containing amide groups contains exactly one end group E′; or (B3) one or more lactams of the general formulae (XIa) and/or (XIb) ##STR00009## wherein at least one radical R7 is hydrogen are reacted by ring-opening polymerization (a) in the presence of one or more species of the general formula (XII)
(HO).sub.k—R3-COOH  (XII) or (b) in the presence of one or more species of the general formula
(HX).sub.k—R3-NH(R8)  (VIII), in which R8 is H, an alkyl radical having 1 to 12 carbon atoms, which optionally contains one or more ether oxygen atoms and/or carries one or more hydroxyl groups, an aryl radical having 6 to 12 carbon atoms, an alkylaryl radical having 7 to 12 carbon atoms, or a radical —R3′[-Z2-R2-[Z1-R1].sub.m′].sub.k′, wherein, in the case (b), the species thus obtained are reacted in turn (c) with one or more species of the general formula (VIa)
Y—(O═C)—R6-E′  (VIa) in which E′ is E or COOR.sup.d and, if E′ is (C═O)—Y′, Y and Y′ are defined as in formula (VI), or (d) with one or more species of the general formula (X)
H.sub.2C═C(R.sup.f)-E′  (X) wherein R.sup.f is hydrogen or an alkyl radical having 1 or 2 carbon atoms, in a stoichiometric ratio such that the resultant building block (B2) containing amide groups contains exactly one end group E′; and wherein subsequently one or more species resulting from (A1) and/or (A2) are reacted with one or more species resulting from (B1), (B2) and/or (B3), and, if E′ is COOR.sup.d, the protective group R.sup.d is eliminated, wherein E′ is converted optionally by salt formation into E, wherein R1 is selected from the group consisting of hydrogen, if m=1 and Z1 is a covalent bond, and radicals R.sup.a—[O—(C═O).sub.uR.sup.b].sub.v, in which R.sup.a is selected from the group consisting of saturated or unsaturated, linear or branched, aliphatic hydrocarbon radicals having 1 to 40 carbon atoms; aromatic hydrocarbon radicals having 6 to 40 carbon atoms; and araliphatic hydrocarbon radicals having 7 to 40 carbon atoms; u is 0 or 1, v is 0 to 50, the radicals Rh independently of one another are divalent organic radicals which, if u=0, are linear or branched alkylene radicals having 2 to 24 carbon atoms, wherein, if an alkylene radical contains two carbon atoms, said radical may carry a substituent having the formula CH.sub.2—O—(C═O).sub.wR.sup.c, in which w is 0 or 1 and R.sup.c is an organic radical having 2 to 24 carbon atoms; and the radicals R.sup.b, if u=1, are linear or branched alkylene radicals having 3 to 8 carbon atoms; and in the radicals [O—(C═O).sub.uR.sup.b] the value for u in each radical independently is 0 or 1; R2 is a divalent organic radical selected from the group consisting of hydrocarbon radicals having 6 to 40 carbon atoms, which optionally contain one or more isocyanurate groups; R3 is a (k+1)-valent organic radical selected from the group consisting of saturated or unsaturated, linear or branched, aliphatic hydrocarbon radicals having 2 to 40 carbon atoms, which optionally contain one or more ether oxygen atoms and/or carry one or more hydroxyl groups; aromatic hydrocarbon radicals having 6 to 40 carbon atoms, wherein the aromatic hydrocarbon radicals optionally carry one or more linear or branched alkyl substituents having 1 to 10 carbon atoms; and araliphatic hydrocarbon radicals having 8 to 40 carbon atoms, wherein the aromatic hydrocarbon radicals optionally carry one or more linear or branched alkyl substituents having 1 to 10 carbon atoms; and a radical N—R2-Z1-R1, if Z2 is an NH—(C═O) group, and wherein N in Z2 and Z3 is bonded to the respective carbon atom in NH—(C═O), and m=k=1; R3′ is a (k′+1)-valent organic radical selected from the group consisting of saturated or unsaturated, linear or branched, aliphatic hydrocarbon radicals having 2 to 40 carbon atoms, which optionally contain one or more ether oxygen atoms and/or carry one or more hydroxyl groups; aromatic hydrocarbon radicals having 6 to 40 carbon atoms, wherein the aromatic hydrocarbon radicals optionally carry one or more linear or branched alkyl substituents having 1 to 10 carbon atoms; and araliphatic hydrocarbon radicals having 8 to 40 carbon atoms, wherein the aromatic hydrocarbon radicals optionally carry one or more linear or branched alkyl substituents having 1 to 10 carbon atoms; and a radical N—R2-Z1-R1, if Z2 is an NH—(C═O) group, and wherein N in Z2 and Z3 is bonded to the respective carbon atom in NH—(C═O); R4 is a divalent organic radical selected from the group consisting of saturated or unsaturated, linear or branched aliphatic hydrocarbon radicals having 2 to 40 carbon atoms, wherein these are optionally substituted by one or more hydroxyl groups; R5 independently is a divalent organic radical selected from the group consisting of saturated or unsaturated, linear or branched, aliphatic hydrocarbon radicals having 2 to 40 carbon atoms, wherein the hydrocarbon radicals optionally contain ether oxygen atoms and/or tertiary amino groups; araliphatic hydrocarbon radicals having 8 to 40 carbon atoms; and aromatic hydrocarbon radicals having 6 to 40 carbon atoms; R6 is selected from the group consisting of the aromatic radicals having 6 to 40 carbon atoms and saturated or unsaturated, linear or branched aliphatic hydrocarbon radicals having 4-40 carbons atoms, wherein these are optionally substituted by one or more hydroxyl groups; E is COOH or COO.sup.⊖Z.sup.⊕, wherein Z.sup.⊕ is selected from the group consisting of alkali metal cations, alkaline earth metal cations, NH.sub.4.sup.⊕, heterocyclic cations, and mono- to tetra-organically substituted ammonium ions, wherein when Z.sup.⊕ is an alkaline earth metal cation, Z.sup.⊕ is ½ Z.sup.2≠, Z1 is a urethane group, a urea group or a covalent bond; Z2 is a urethane group or a urea group, or, if R3 is a radical N—R2-Z1-R1, Z2 is an NH—(C═O) group; Z3 is an amide group; m is 1 to 5; m′ is 1 to 5; k is 1 to 4; k′ is 1 to 4; and k+k′ is 2 to 5; wherein the rheology control agent produced according to the method comprises a urea- and/or urethane-substituted amide of the general formula (I) ##STR00010## wherein the radicals R1 independently of one another are selected from the group consisting of hydrogen, if m=1 and Z1 is a covalent bond, and radicals R.sup.a—[O—(C═O).sub.uR.sup.b].sub.v, in which R.sup.a is selected from the group consisting of saturated or unsaturated, linear or branched, aliphatic hydrocarbon radicals having 1 to 40 carbon atoms; aromatic hydrocarbon radicals having 6 to 40 carbon atoms; and araliphatic hydrocarbon radicals having 7 to 40 carbon atoms; u is 0 or 1, v is 0 to 50, the radicals R.sup.b independently of one another are divalent organic radicals which, if u=0, are linear or branched alkylene radicals having 2 to 24 carbon atoms, wherein, if an alkylene radical contains two carbon atoms, said radical may carry a substituent having the formula CH.sub.2—O—(C═O).sub.wR.sup.c, in which w is 0 or 1 and R.sup.c is an organic radical having 2 to 24 carbon atoms; and the radicals R.sup.b, if u=1, are linear or branched alkylene radicals having 3 to 8 carbon atoms; and in the radicals [O—(C═O).sub.uR.sup.b] the value for u in each radical independently is 0 or 1; the radicals R2 independently of one another are divalent organic radicals which are selected from the group consisting of hydrocarbon radicals having 6 to 40 carbon atoms, which optionally contain one or more isocyanurate groups; the radicals R3 independently of one another are (k+1)-valent organic radicals which are selected from the group consisting of saturated or unsaturated, linear or branched, aliphatic hydrocarbon radicals having 2 to 40 carbon atoms, which optionally contain one or more ether oxygen atoms and/or carry one or more hydroxyl groups; aromatic hydrocarbon radicals having 6 to 40 carbon atoms, wherein the aromatic hydrocarbon radicals optionally carry one or more linear or branched alkyl substituents having 1 to 10 carbon atoms; and araliphatic hydrocarbon radicals having 8 to 40 carbon atoms, wherein the aromatic hydrocarbon radicals optionally carry one or more linear or branched alkyl substituents having 1 to 10 carbon atoms; and a radical N—R2-Z1-R1, if Z2 is an NH—(C═O) group, and wherein N in Z2 and Z3 is bonded to the respective carbon atom in NH—(C═O), and m=k=1, the radicals R4 independently of one another are divalent organic radicals which are selected from the group consisting of saturated or unsaturated, linear or branched aliphatic hydrocarbon radicals having 2 to 40 carbon atoms, wherein these are optionally substituted by one or more hydroxyl groups; the radicals R5 independently of one another are divalent organic radicals which are selected from the group consisting of saturated or unsaturated, linear or branched, aliphatic hydrocarbon radicals having 2 to 40 carbon atoms, wherein the hydrocarbon radicals optionally contain ether oxygen atoms and/or tertiary amino groups; araliphatic hydrocarbon radicals having 8 to 40 carbon atoms; and aromatic hydrocarbon radicals having 6 to 40 carbon atoms; the radicals R6 are selected from the group consisting of the aromatic radicals having 6 to 40 carbon atoms and saturated or unsaturated, linear or branched aliphatic hydrocarbon radicals having 4-40 carbons atoms, wherein these are optionally substituted by one or more hydroxyl groups; the radicals E independently of one another are COOH or COO.sup.⊖Z.sup.⊕, wherein Z.sup.⊕ is selected from the group consisting of alkali metal cations, alkaline earth metal cations, NH.sub.4.sup.⊕, heterocyclic cations, and mono- to tetra-organically substituted ammonium ions, wherein when Z.sup.⊕ is an alkaline earth metal cation, Z.sup.⊕ is ½ Z.sup.2⊕, the radicals Z1 independently of one another are a urethane group, a urea group or a covalent bond; the radicals Z2 independently of one another are a urethane group or a urea group, or, if R3 is a radical N—R2-Z1-R1, Z2 is an NH—(C═O) group; the radicals Z3 are an amide group; the radicals Z4 are an amide group; the radicals Z5 independently of one another are an amide group or are an amino group, wherein the amino group may also be in protonated or quaternized form and wherein Z.sup.⊕ in that case is absent; m is 1 to 5; n is 1 to 12; and k is 1 to 5.

5. A liquid composition comprising one or more urea- and/or urethane-substituted amides as claimed in claim 1.

6. The liquid composition as claimed in claim 5, further comprising one or more polar, aprotic solvents.

7. The liquid composition as claimed in claim 5, wherein the composition is a rheology control agent composition.

8. The liquid composition as claimed in claim 6, wherein it comprises as solvent one or more of N-alkylbutyrolactam, dialkyl sulfoxide, and carboxamide.

9. A rheology control agent composition comprising (i) 5 to 70 wt % of one or more urea- and/or urethane-substituted amides as claimed in claim 1, (ii) 30 to 95 wt % of one or more solvents, and (iii) 0 to 4 wt % of one or more ionogenic compounds.

10. The rheology control agent composition as claimed in claim 9, comprising (i) 10 to 60 wt % of the one or more urea- and/or urethane-substituted amides, (ii) 40 to 90 wt % of one or more polar, aprotic, organic solvents, and (iii) 0 to 3 wt % of one or more ionogenic compounds selected from the group of the halides, pseudohalides, formates, acetates, and nitrates.

11. The liquid composition as claimed in claim 5, wherein the liquid composition comprises 0.1 to 7 wt % of the one or more urea- and/or urethane-substituted amides.

12. The urea- and/or urethane-substituted amides as claimed in claim 1, wherein the radicals [O—(C═O).sub.uR.sup.b] for which u=0 are arranged in one or more blocks.

13. The urea- and/or urethane-substituted amides as claimed in claim 1, wherein the radicals [O—(C═O).sub.uR.sup.b] for which u=1 are arranged in one or more blocks.

14. The urea- and/or urethane-substituted amides as claimed in claim 1, wherein the radicals E independently of one another are COOH or COO.sup.⊖Z.sup.⊕, wherein Z.sup.⊕ is selected from the group consisting of alkali metal cations, NH.sub.4.sup.⊕, heterocyclic cations, mono- to tetra-organically substituted ammonium ions whose organic substituents are selected from the group of alkyl radicals having 1 to 24 carbon atoms, aryl radicals having 6 to 24 carbon atoms, alkylaryl radicals having 7 to 25 carbon atoms, wherein the alkyl radicals, aryl radicals, and alkylaryl radicals optionally carry one or more hydroxyl groups, and alkaline earth metal cations, or wherein Z.sup.⊕ is absent if Z5 is a protonated or quaternized amino group.

15. The urea- and/or urethane-substituted amides as claimed in claim 2, wherein the (ii) alkylene radicals having 4 to 6 carbon atoms are substituted by hydroxyl groups, wherein k is the number 1, 2 or 3.

Description

EXAMPLES

(1) Test Methods

(2) Determination of Molecular Weight:

(3) The number-average molecular weight is the numerical average of the molar mass distribution as determined by gel permeation chromatography (GPC). The molar mass distribution was determined in accordance with DIN 55672 Part 1:2007-08. The eluent used was a solution of dibutylamine (1 vol %) in tetrahydrofuran. For the calibration, narrow-distribution polystyrene standards of linear construction, with molecular weights between M.sub.P 1 000 000 and M.sub.P 162 g/mol, were analyzed.

(4) Determination of Amine Number:

(5) The amine number was determined in accordance with DIN 53176:2002-11, using 2-propanol as solvent for the titration. The sample (at least 0.5 g) is weighed to an accuracy of 0.1 mg into an 80 ml beaker and dissolved in 50 ml of 2-propanol. The sample is optionally heated gently until fully dissolved. The sample is placed on a magnetic stirrer and the electrode is immersed completely. The sample is titrated with 0.1 N isopropanolic hydrochloric acid.

(6) Determination of Acid Number:

(7) The acid number was determined in accordance with DIN EN ISO 2114:2002-06, using 2-propanol as solvent for the titration. The sample (at least 0.5 g) is weighed to an accuracy of 0.1 mg into an 80 ml beaker and dissolved in 50 ml of 2-propanol. The sample is optionally heated gently until fully dissolved. The sample is placed on a magnetic stirrer and the electrode is immersed completely. The sample is titrated with 0.1 N ethanolic KOH.

(8) Determination of Hydroxyl Number:

(9) The hydroxyl number of the OH-functional raw materials used for the synthesis of the isocyanate/uretdione adducts was determined in accordance with DIN ISO 4629-1:1998-07. The sample (at least 0.5 g) is weighed to an accuracy of 0.1 mg into an 80 ml weighing bottle with ground lid and dissolved in 4.8 ml of OH number reagent (14.4 g of p-toluenesulfonic acid are dissolved in 360 ml of ethyl acetate and admixed with around 60 ml of acetic anhydride). The reagent is added with a buret or a dispenser. The sample is heated at 50° C. in a water bath or block thermostat for 15 minutes. After cooling to room temperature, the sample is admixed with around 30 ml of a pyridine-water mixture (3:1) to decompose the excess acetic anhydride, and stirred for around 5 minutes. The sample is subsequently titrated with 0.5 N ethanolic KOH.

(10) The hydroxyl number of the polyamide building blocks (“AM”) was determined using a method along the lines of DIN ISO 4629. The sample (at least 0.5 g) is weighed accurately into an 80 ml weighing bottle with ground lid, and dissolved in 20 ml of tetrahydrofuran. Following addition of 10.0 ml of OH number reagent A2 (12.5 g of 4-dimethylaminopyridine are dissolved in around 500 ml of tetrahydrofuran) and 5.0 ml of reagent B (around 25 ml of acetic anhydride are dissolved in around 500 ml of tetrahydrofuran), the sample is stirred on a magnetic stirrer for 30 minutes. Around 2.0 ml of water are added and stirring is repeated for 10 minutes. The sample is subsequently titrated potentiometrically with 0.2 N ethanolic KOH.

(11) Determination of Isocyanate Content:

(12) The isocyanate content was determined in accordance with DIN EN ISO 9369:1997-08. The sample (at least 0.5 g) is weighed to an accuracy of 0.1 mg into an 80 ml of beaker and dissolved in around 5 ml of chlorobenzene (optionally with heating). Following addition of 9.5 ml of 0.2 N dibutylamine solution (in chlorobenzene), the sample is stirred and, after a short reaction time (1 minute) around 30 ml of ethanol are added. The excess dibutylamine is subsequently back-titrated with 0.1 N isopropanolic hydrochloric acid.

(13) TABLE-US-00001 TABLE 1 Raw materials used Raw material tradename Manufacturer Chem. description Pripol 1006 Croda dimer fatty acid Desmodur T100 Bayer MaterialScience 2,4-toluene diisocyanate (Covestro) Desmodur T65 Bayer MaterialScience mixture of 35% of 2,6-toluene (Covestro) diisocyanate and 65% 2,4- toluene diisocyanate Desmodur T80 Bayer MaterialScience mixture of 20% 2,6-toluene (Covestro) diisocyanate and 80% 2,4- toluene diisocyanate Desmodur N3400 Bayer MaterialScience aliphatic polyisocyanate (Covestro) (HDI-uretdione) DBTL Brenntag dibutyltin dilaurate Jeffamin ED-600 Huntsman polyetherdiamine
Preparation of Isocyanate Adducts (AD) as Building Blocks (A) Containing Urea Groups and/or Urethane Groups
Isocyanate Adduct AD1:

(14) At first 90.00 g of a monoadduct in accordance with patent specification EP 1188779 are prepared from a lauryl alcohol and 2,4-toluene diisocyanate. The reaction product is waxlike and has an NCO content of 11.1 wt %.

(15) Isocyanate Adduct AD2:

(16) At first 436.8 g of a monoadduct in accordance with patent specification EP 1188779 are prepared from a polyethylene glycol monomethyl ether having a hydroxyl number of 125 mg KOH/g and a mixture of 35% 2,6-toluene diisocyanate and 65% 2,4-toluene diisocyanate.

(17) Isocyanate Adduct AD3:

(18) 125 g of a monoadduct in accordance with patent specification EP 1188779 are prepared from butylpolyethylene glycol having a hydroxyl number of 270 mg KOH/g and a mixture of 35% 2,6-toluene diisocyanate and 65% 2,4-toluene diisocyanate.

(19) Isocyanate Adduct AD4:

(20) 125 g of a monoadduct in accordance with patent specification EP 1188779 are prepared from a C13-C15 fatty alcohol ethoxylated with 5 mol of ethylene oxide and having a hydroxyl number of 140 mg KOH/g and a mixture of 20% 2,6-toluene diisocyanate and 80% 2,4-toluene diisocyanate. The adduct prepared contains 7.15 wt % NCO.

(21) Isocyanate Adduct AD5:

(22) 200 g of a monoadduct in accordance with patent specification EP 1188779 are prepared from a isotridecyl alcohol and a mixture of 20% 2,6-toluene diisocyanate and 80% 2,4-toluene diisocyanate. The adduct prepared contains 10.7 wt % NCO.

(23) Isocyanate Adduct AD6:

(24) 200 g of a monoadduct in accordance with patent specification EP 1188779 are prepared from butylpolyethylene glycol having a hydroxyl number of 270 mg KOH/g and isophorone diisocyanate. The adduct prepared contains 8.10 wt % NCO.

(25) Uretdione Adduct AD7:

(26) A four-neck flask is provided with stirrer, dropping funnel, thermometer, and reflux condenser. It is charged with 71.42 g (0.14 mol) of a polyethylene glycol monomethyl ether having a hydroxyl number of 113 mg KOH/g, and this initial charge is heated to 80° C. under a nitrogen atmosphere. Then 28.57 g (0.07 mol) of Desmodur N3400 are added by means of a dropping funnel over the course of 10 minutes, and the mixture is homogenized over a period of 10 minutes. Thereafter, 0.01 g of DBTL is added for catalysis of the reaction. After a reaction time of 3 hours at 80° C., a pale, viscous liquid is obtained.

(27) Preparation of Polyamides (AM) as Building Blocks (B) Containing Amide Groups

(28) Polyamide AM1:

(29) A four-neck flask with stirrer, cooler, thermometer, and water separator is charged with 29.64 g of N-ethylpyrrolidone, and 0.07 mol of hexamethylenediamine (10.27 g of an 80% aqueous solution) and 0.035 mol of aminoethanol (2.14 g) are added. The solution is heated to 100° C. and the apparatus is inertized with nitrogen. 0.105 mol (61.95 g) of dimer fatty acid is metered into this solution at 100° C. With water separation, the temperature is raised gradually up to 170° C. and maintained at this temperature until no further water of reaction is distilled over. The reaction is monitored via determination of the amine number of the product prepared. The hydroxyl number is 18.9 mg KOH/g.

(30) Polyamide AM2:

(31) A four-neck flask with stirrer, cooler, thermometer, and water separator is charged with 39.71 g of N-ethylpyrrolidone, and 0.105 mol of hexamethylenediamine (15.40 g of an 80% aqueous solution) and 0.035 mol of aminoethanol (2.14 g) are added. The solution is heated to 100° C. and the apparatus is inertized with nitrogen. 0.14 mol (82.60 g) of dimer fatty acid is metered into this solution at 100° C. With water separation, the temperature is raised gradually up to 170° C. and maintained at this temperature until no further water of reaction is distilled over. The reaction is monitored via determination of the amine number of the product prepared. The hydroxyl number is 14.1 mg KOH/g.

(32) Polyamide AM3:

(33) A four-neck flask with stirrer, cooler, thermometer, and water separator is charged with 30.23 g of N-methylpyrrolidone, and 0.07 mol of m-xylylenediamine (9.59 g) and 0.035 mol of aminoethanol (2.14 g) are added. The solution is heated to 100° C. and the apparatus is inertized with nitrogen. 0.105 mol (61.95 g) of dimer fatty acid is metered into this solution at 100° C. With water separation, the temperature is raised gradually up to 170° C. and maintained at this temperature until no further water of reaction is distilled over. The reaction is monitored via determination of the amine number of the product prepared. The hydroxyl number is 18.9 mg KOH/g.

(34) Polyamide AM4:

(35) A four-neck flask with stirrer, cooler, thermometer, and water separator is charged with 30.42 g of N-methylpyrrolidone, and 0.08 mol of Jeffamine ED-600 (48.48 g), 0.08 mol of aminoethanol (4.89 g), and 0.16 mol (23.38 g) of adipic acid are added. The apparatus is inertized with nitrogen and the mixture is heated with water separation, gradually up to 170° C., and is held at this temperature until no further water of reaction distils over. The reaction is monitored via determination of the amine number of the product prepared. The hydroxyl number is 45.9 mg KOH/g.

(36) Polyamide AM5:

(37) A four-neck flask with stirrer, cooler, thermometer, and water separator is charged with 29.85 g of N-methylpyrrolidone, and 0.07 mol of hexamethylenediamine (10.27 g of an 80% aqueous solution) and 0.035 mol of 1-amino-2-propanol (2.63 g) are added. The solution is heated to 100° C. and the apparatus is inertized with nitrogen. 0.105 mol (61.95 g) of dimer fatty acid is metered into this solution at 100° C. With water separation, the temperature is raised gradually up to 170° C. and maintained at this temperature until no further water of reaction is distilled over. The reaction is monitored via determination of the amine number of the product prepared. The hydroxyl number is 21.4 mg KOH/g.

(38) Polyamide AM6:

(39) A four-neck flask with stirrer, cooler, thermometer, and water separator is charged with 24.65 g of N-octylpyrrolidone, and 0.15 mol of hexamethylenediamine (22.01 g of an 80% aqueous solution) and 0.05 mol of aminoethanol (3.06 g) are added. The solution is heated to 100° C. and the apparatus is inertized with nitrogen. 0.2 mol (40.45 g) of decanedioic acid is added in portions to this solution at 100° C. With water separation, the temperature is raised gradually up to 190° C. and maintained at this temperature until no further water of reaction is distilled over. The reaction is monitored via determination of the amine number of the product prepared. The hydroxyl number is 34.0 mg KOH/g.

(40) Polyamide AM7:

(41) A four-neck flask with stirrer, cooler, thermometer, and water separator is charged with 29.85 g of N-octylpyrrolidone, and 0.07 mol of hexamethylenediamine (10.27 g of an 80% aqueous solution) and 0.035 mol of 1-amino-2-propanol (2.63 g) are added. The solution is heated to 100° C. and the apparatus is inertized with nitrogen. 0.105 mol (61.95 g) of dimer fatty acid is metered into this solution at 100° C. With water separation, the temperature is raised gradually up to 170° C. and maintained at this temperature until no further water of reaction is distilled over. The reaction is monitored via determination of the amine number of the product prepared. The hydroxyl number is 19.6 mg KOH/g.

(42) Polyamide AM8:

(43) A four-neck flask with stirrer, cooler, thermometer, and water separator is charged with 30.23 g of N-octylpyrrolidone, and 0.07 mol of m-xylylenediamine (9.59 g) and 0.035 mol of aminoethanol (2.14 g) are added. The solution is heated to 100° C. and the apparatus is inertized with nitrogen. 0.105 mol (61.95 g) of dimer fatty acid is metered into this solution at 100° C. With water separation, the temperature is raised gradually up to 170° C. and maintained at this temperature until no further water of reaction is distilled over. The reaction is monitored via determination of the amine number of the product prepared. The hydroxyl number is 17.1 mg KOH/g.

(44) Polyamide AM9:

(45) A four-neck flask with stirrer, cooler, thermometer, and water separator is charged with 30.42 g of N-octylpyrrolidone, and 0.08 mol of Jeffamine ED-600 (48.48 g), 0.08 mol of aminoethanol (4.89 g), and 0.16 mol (23.38 g) of adipic acid are added. The apparatus is inertized with nitrogen and the mixture is heated with water separation, gradually up to 170° C., and is held at this temperature until no further water of reaction distils over. The reaction is monitored via determination of the amine number of the product prepared. The hydroxyl number is 39.9 mg KOH/g.

(46) Polyamide AM10:

(47) A four-neck flask with stirrer, cooler, thermometer, and water separator is charged with 29.64 g of N-methylpyrrolidone, and 0.07 mol of hexamethylenediamine (10.27 g of an 80% aqueous solution) and 0.035 mol of aminoethanol (2.14 g) are added. The solution is heated to 100° C. and the apparatus is inertized with nitrogen. 0.105 mol (61.95 g) of dimer fatty acid is metered into this solution at 100° C. With water separation, the temperature is raised gradually up to 170° C. and maintained at this temperature until no further water of reaction is distilled over. The reaction is monitored via determination of the amine number of the product prepared. The hydroxyl number is 18.9 mg KOH/g.

(48) Polyamide AM11:

(49) A four-neck flask with stirrer, cooler, thermometer, and water separator is charged with 33.9 g of N-ethylpyrrolidone, and 0.08 mol of butanediamine (7.05 g) and 0.04 mol of tris(hydroxymethyl)aminomethane (4.84 g) are added. The solution is heated to 100° C. and the apparatus is inertized with nitrogen. Subsequently 0.12 mol (70.8 g) of dimer fatty acid is metered into this solution at 100° C. With water separation, the temperature is raised gradually up to 170° C. and maintained at this temperature until no further water of reaction is distilled over. The reaction is monitored via determination of the amine number of the product prepared. The hydroxyl number is 46.7 mg KOH/g.

(50) Polyamide AM12:

(51) A four-neck flask with stirrer, cooler, thermometer, and water separator is charged with 167.48 g of N-ethylpyrrolidone, and 0.26 mol of hexamethylenediamine (37.75 g of an 80% aqueous solution) is added. The solution is heated to 100° C. and the apparatus is inertized with nitrogen. Subsequently 0.24 mol (141.6 g) of dimer fatty acid is metered into this solution at 100° C. With water separation, the temperature is raised gradually up to 160° C. and the reaction is discontinued when the amine number reaches 18.2 mg KOH/g. The acid number of the product prepared is 18.2 mg KOH/g.

(52) Polyamide AM13:

(53) The polyamide was prepared from 0.132 mol of hexamethylenediamine (19.17 g of an 80% aqueous solution) and 0.12 mol (70.8 g) of dimer fatty acid in accordance with patent specification DE 10 2006 010 721 A1. The amine number of the product is 18.2 mg KOH/g, the acid number 15.2 mg KOH/g.

(54) Preparation of the Rheology Control Agents of the Invention

Example B1

(55) In a four-neck flask with stirrer, condenser, and thermometer, 64.68 g of N-methylpyrrolidone and 29.7 g of the polyamide solution AM10 prepared (corresponding to 20.79 g (0.01 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 3.74 g (0.01 mol) of the synthesized isocyanatourethane AD1, heated to around 50° C., are metered in with a pipette. The temperature is raised to 60° C. and maintained for 2.5 hours. The product obtained is amber in color and of high viscosity.

Example B2

(56) In a four-neck flask with stirrer, condenser, dropping funnel, and thermometer, 996.3 g of N-ethylpyrrolidone and 450.0 g of the polyamide solution AM1 prepared (corresponding to 315 g (0.15 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 61.21 g (0.15 mol) of the synthesized isocyanatourethane AD3 are added by means of the dropping funnel in a period of 20 minutes. The temperature is raised to 60° C. and maintained for 2.5 hours. The product obtained is amber in color and of high viscosity (the number average M.sub.n determined by gel permeation chromatography is 2387 g/mol).

Example B3

(57) In a four-neck flask with stirrer, condenser, and thermometer, 71.46 g of N-ethylpyrrolidone and 29.70 g of the polyamide solution AM1 prepared (corresponding to 20.79 g (0.01 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 6.00 g (0.01 mol) of the synthesized isocyanatourethane AD2 are metered in by means of a pipette in a period of 5 minutes. The temperature is raised to 60° C. and maintained for 3 hours. The product obtained is amber in color and of high viscosity (the number average M.sub.n determined by gel permeation chromatography is 2340 g/mol).

Example B4

(58) In a four-neck flask with stirrer, condenser, and thermometer, 65.25 g of N-ethylpyrrolidone and 29.70 g of the polyamide solution AM1 prepared (corresponding to 20.79 g (0.01 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 3.93 g (0.01 mol) of the synthesized isocyanatourethane AD5 are added by means of a pipette. The temperature is raised to 60° C. and maintained for 2.5 hours. The product obtained is amber in color and of high viscosity (the number average M.sub.n determined by gel permeation chromatography is 2390 g/mol).

Example B5

(59) In a four-neck flask with stirrer, condenser, and thermometer, 64.68 g of N-methylpyrrolidone and 29.7 g of the polyamide solution AM3 prepared (corresponding to 20.79 g (0.01 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 3.74 g (0.01 mol) of the synthesized isocyanatourethane AD1, warmed to around 50° C., are metered in by means of a pipette in a period of 5 minutes. The temperature is raised to 60° C. and maintained for 2.5 hours. The product obtained is amber in color and of high viscosity (the number average M.sub.n determined by gel permeation chromatography is 2230 g/mol).

Example B6

(60) In a four-neck flask with stirrer, condenser, and thermometer, 64.88 g of N-methylpyrrolidone and 26.2 g of the polyamide solution AM5 prepared (corresponding to 18.34 g (0.01 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 5.90 g (0.01 mol) of the synthesized isocyanatourethane AD4 are metered in by means of a pipette in a period of 5 minutes. The temperature is raised to 60° C. and maintained for 2.5 hours. The product obtained is amber in color and of high viscosity (the number average M.sub.n determined by gel permeation chromatography is 2265 g/mol).

Example B7

(61) In a four-neck flask with stirrer, condenser, and thermometer, 62.72 g of N-methylpyrrolidone, 26.21 g of the polyamide solution AM10 prepared (corresponding to 18.35 g (0.01 mol) of polyamide) and 5.18 g (0.01 mol) of the synthesized isocyanatourethane AD6 are weighed out and the apparatus is inertized with nitrogen. With stirring, the mixture is heated to 60° C. and this temperature range is maintained for 3 hours. The resulting product is amber in color and of high viscosity (the number average M.sub.n determined by gel permeation chromatography is 2301 g/mol).

Example B8

(62) In a four-neck flask with stirrer, condenser, and thermometer, 69.82 g of N-methylpyrrolidone and 25.32 g of the polyamide solution AM4 prepared (corresponding to 17.72 g (0.02 mol) of polyamide) are heated to 40° C., placed under nitrogen, and admixed with 5.0 g of a commercial zeolite in order to remove the residual water of reaction present in the amide. During this procedure, the mixture becomes cloudy. With stirring, 8.08 g (0.02 mol) of the synthesized isocyanatourethane AD3 are metered in with a pipette in a period of 5 minutes. The temperature is raised to 60° C. and maintained for 3 hours. The product obtained is amber in color and of high viscosity (the number average M.sub.n determined by gel permeation chromatography is 1481 g/mol).

Example B9

(63) In a four-neck flask with stirrer, condenser, and thermometer, 47.7 g of N-octylpyrrolidone and 16.5 g of the polyamide solution AM6 prepared (corresponding to 11.55 g (0.01 mol) of polyamide) are weighed out, the apparatus is inertized with nitrogen, and the mixture is heated to 180° C. to form a homogeneous solution. With stirring, 6.0 g (0.01 mol) of the synthesized isocyanatourethane AD2 are metered in with a pipette in a period of 5 minutes. The temperature is maintained for 2.5 hours. The reaction product obtained is dark brown and of high viscosity.

Example B10

(64) In a four-neck flask with stirrer, condenser, and thermometer, 80.02 g of N-ethylpyrrolidone and 39.54 g of the polyamide solution AM2 prepared (corresponding to 27.68 g (0.01 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 2.95 g (0.01 mol) of the stearyl isocyanate, heated to around 45° C., are metered in with a pipette in a period of 5 minutes. 100 ppm of DBTL are added for catalysis of the reaction. The temperature is raised to 100° C. and maintained for 3 hours. The product obtained is yellowish, of high viscosity, and slightly cloudy.

Example B11

(65) In a four-neck flask with stirrer, condenser, and thermometer, 30.21 g of N-octylpyrrolidone, 40.05 g of N-formylmorpholine and 32.8 g of the polyamide solution AM8 prepared (corresponding to 22.96 g (0.01 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 3.74 g (0.01 mol) of the synthesized isocyanatourethane AD1, heated to around 50° C., are metered in with a pipette in a period of 5 minutes. The temperature is raised to 60° C. and maintained for 2.5 hours. The product obtained is yellowish and liquid (the number average M.sub.n determined by gel permeation chromatography is 2521 g/mol).

Example B12

(66) In a four-neck flask with stirrer, condenser, and thermometer, 30.3 g of N-octylpyrrolidone, 38.88 g of N-formylmorpholine and 28.6 g of the polyamide solution AM7 prepared (corresponding to 20.02 g (0.01 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 5.9 g (0.01 mol) of the synthesized isocyanatourethane AD4 are metered in with a pipette in a period of 5 minutes. The temperature is raised to 60° C. and maintained for 3 hours. The product obtained is amber in color and of high viscosity (the number average M.sub.n determined by gel permeation chromatography is 2486 g/mol).

Example B13

(67) In a four-neck flask with stirrer, condenser, and thermometer, 33.21 g of N-octylpyrrolidone, 41.65 g of N-formylmorpholine and 28.12 g of the polyamide solution AM9 prepared (corresponding to 19.68 g (0.02 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 8.08 g (0.02 mol) of the synthesized isocyanatourethane AD3 are metered in with a pipette in a period of 5 minutes. The temperature is raised to 60° C. and maintained for 3 hours. The product obtained is amber in color and liquid (the number average M.sub.n determined by gel permeation chromatography is 1603 g/mol).

Example B14

(68) In a four-neck flask with stirrer, condenser, and thermometer, 646.8 g of N-ethylpyrrolidone, and 297.0 g of the polyamide solution AM1 prepared (corresponding to 207.9 g (0.1 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 37.4 g (0.1 mol) of the synthesized isocyanatourethane AD1, heated to around 50° C., are metered in with a pipette. The temperature is raised to 60° C. and maintained for 2.5 hours. The product obtained is amber in color and of high viscosity (the number average M.sub.n determined by gel permeation chromatography is 2468 g/mol).

Example B15

(69) A four-neck flask with stirrer, condenser, and thermometer is charged with 64.68 g of N-ethylpyrrolidone and 3.74 g (0.01 mol) of the synthesized isocyanatourethane AD1 at a temperature of 40° C., and the apparatus is inertized with nitrogen. With stirring, 29.7 g of the polyamide solution AM1 prepared (corresponding to 20.79 g (0.01 mol) of polyamide), heated to around 60° C., are metered in by dropping funnel. The temperature is raised to 60° C. and maintained for 3 hours. The product obtained is amber in color and liquid (the number average M.sub.n determined by gel permeation chromatography is 2190 g/mol).

Example B16

(70) In a four-neck flask with stirrer, condenser, and thermometer, 646.8 g of N-ethylpyrrolidone, and 297.0 g of the polyamide solution AM1 prepared (corresponding to 207.9 g (0.1 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 37.4 g (0.01 mol) of the synthesized isocyanatourethane AD1, heated to around 50° C., are metered in with a pipette. The temperature is raised to 60° C. and maintained for 2.5 hours. The reaction mixture is subsequently admixed with 0.5 wt % of lithium chloride and homogenized at 80° C. over a period of an hour. The product obtained is amber in color and liquid.

Example B17

(71) In a four-neck flask with stirrer, condenser, and thermometer, 72.46 g of N-ethylpyrrolidone, and 30.82 g of the polyamide solution AM12 prepared (corresponding to 15.41 g (0.01 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 13.88 g (0.01 mol) of the synthesized uretdione-urethane AD7, heated to around 50° C., are metered in with a pipette in a period of 5 minutes. The temperature is raised to 80° C. and maintained for 3 hours. The product obtained is yellow and viscous (the number average M.sub.n determined by gel permeation chromatography is 3709 g/mol).

Example B18

(72) In a four-neck flask with stirrer, condenser, and thermometer, 66.41 g of N-ethylpyrrolidone and 28.84 g of the polyamide solution AM11 prepared (corresponding to 20.19 g (0.008 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 4.83 g (0.008 mol) of the synthesized isocyanatourethane AD2 are metered in by means of a pipette in a period of 5 minutes. The temperature is raised to 60° C. and maintained for 2 hours. The product obtained is amber in color and viscous (the number average M.sub.n determined by gel permeation chromatography is 2839 g/mol).

Example B19

(73) In a four-neck flask with stirrer, condenser, and thermometer, 65.72 g of N-ethylpyrrolidone and 23.43 g of the polyamide solution AM11 prepared (corresponding to 16.40 g (0.0065 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 7.85 g (0.013 mol) of the synthesized isocyanatourethane AD2 are metered in by means of a pipette in a period of 5 minutes. The temperature is raised to 60° C. and maintained for 2 hours. The product obtained is amber in color and viscous.

Example B20

(74) In a four-neck flask with stirrer, condenser, and thermometer, 67.52 g of N-ethylpyrrolidone and 20.4 g of the polyamide solution AM11 prepared (corresponding to 14.28 g (0.0056 mol) of polyamide) are heated to 40° C. and the apparatus is inertized with nitrogen. With stirring, 10.27 g (0.017 mol) of the synthesized isocyanatourethane AD2 are metered in by means of a pipette in a period of 5 minutes. The temperature is raised to 60° C. and maintained for 2 hours. The product obtained is amber in color and viscous.

Example B21

(75) The product of 37.0 g of the above-prepared polyamide solution AM13 (corresponding to 25.9 g (0.012 mol) of polyamide) and 8.00 g (0.012 mol) of the synthesized uretdione-urethane described in patent DE 10 2006 010 721 A1 under example 1 is prepared in accordance with patent specification DE 10 2006 010 721 A1. The product obtained is cloudy and viscous (the number average M.sub.n determined by gel permeation chromatography is 3924 g/mol).

(76) TABLE-US-00002 TABLE 2 Comparative examples according to the prior art Active Comparative substance example Name in % Manufacturer Description VB1 Rheovis AS 1130 30.0 BASF acrylate copolymer, emulsion in water VB2 Rheovis PU 1214 40.0 BASF nonionic polyurethane-based associative thickener VB3 Disparlon AQ-610 15.0 Kusumoto polyamide-based rheology additive VB4 Disparlon AQ-870 15.0 Kusumoto liquid polyamide-based rheology additive VB5 Acrysol RM 2020 20.0 Dow nonionic urethane-based rheology modifier VB6 Acrysol RM 895 23.5 Dow solvent-free HEUR rheology modifier VB7 BYK-7420 ES 40.0 BYK-Chemie solution of a modified urea VB8 Acrysol RM 8w 21.5 Dow nonionic urethane-based rheology modifier VB9 Borchigel LW44 47.0 Borchers nonionogenic polyurethane- based thickener VB10 Example 20 from 30 ./. ./. patent DE 10 2006 010 721 A1
Performance Testing of the Rheology Control Agents

(77) TABLE-US-00003 TABLE 3 Raw materials used Name Description Manufacturer Daotan VTW urethane acrylate hybrid Allnex S.á r.l. 6462 dispersion Isobutanol Overlack AG BYK-011 defoamer BYK-Chemie GmbH BYK-347 flow control additive BYK-Chemie GmbH DMEA dimethylaminoethanol Air Products and Chemicals Inc. STAPA IL aluminum effect pigment Eckart GmbH Hydrolan 2154 Butyl glycol ethylene glycol monobutyl Overlack AG ether Disperbyk-180 wetting and dispersing BYK-Chemie GmbH additive Bayhydrol A145 polyacrylate dispersion Covestro AG Disperbyk-194 wetting and dispersing BYK-Chemie GmbH additive Tronox RKB-4 titanium dioxide pigment Tronox Pigments BYK-345 flow control additive BYK-Chemie GmbH BYK-333 flow control additive BYK-Chemie GmbH Bayhydur 304 polyisocyanate Covestro AG Dowanol PMA 1,2-propanediol monoacetate Dow Chemical monomethyl ether Company Bayferrox 3920 yellow iron oxide pigment Lanxess GmbH BYK-1730 defoamer BYK-Chemie GmbH Acticide MBS microbiocide and algicide Thor GmbH Klarlack HS 2-component clearcoat BASF Coatings GmbH Racing Clear (Glasurit) VOC 923-135 Neocryl XK-205 acrylate styrene copolymer DSM Neoresins AMP-90 2-amino-2-methyl-1-propanol Dow Chemical Company BYK-024 defoamer BYK-Chemie GmbH BYK-346 flow control additive BYK-Chemie GmbH
Test System 1: Effect Pigment Orientation of an Aluminum Basecoat Material

(78) The effect pigment slurries are prepared according to the formulation specified in table 4. Subsequently the basecoat material is prepared according to the formulation specified in table 5. Then in each case 200 g of the basecoat material are weighed out into a 350 ml PE beaker and the respective rheology additive is incorporated with stirring using the Dispermat LV (from Getzmann) (5 min, 800 rpm, 5 cm paddle stirrer). The rheology additives are used in an added amount of 1.5% active substance, to obtain a minimum viscosity of 600 mPas for the coating system. If the minimum viscosity is not attained, the amount of the respective additive added is increased in line with the recommended amount in the technical datasheet. The basecoat materials are subsequently stored at RT overnight and then adjusted to a spray viscosity of 600-800 mPas with the Brookfield LV DV-I viscometer (from Brookfield, spindle 3 at 50 rpm) by addition of DI water. The basecoat material is applied using the APL 2.71 automatic applicator with a HVLP spray gun, 1.3 mm nozzle (from Oerter & Köhne GmbH & Co. KG) onto DIN A4 aluminum sheets (type: primed aluminum sheets, light gray on one side—285 mm×205 mm—rounded corners, manufacturer: Novelis Deutschland GmbH). After a drying time of 30 minutes at room temperature, a clearcoat material (2-component PU clearcoat HS Racing Clear VOC 923-135, from BASF Coatings) is applied manually by means of pneumatic spray application (spray gun: Sata Jet 4000 RP, 1.3 mm nozzle, from SATA GmbH & Co. KG) over the basecoat. The clearcoat is dried at RT overnight and then by forced drying for 20 minutes at 80° C. in a paint drying cabinet (FDL 115, from Binder). The orientation of the aluminum pigments was evaluated by measurement of the flop value using the BYK-mac i from BYK-Gardner. The higher the flop value, the more uniform the orientation of the aluminum pigment in the basecoat, and the more suitable the rheology additive in question for the orientation of effect pigments.

(79) TABLE-US-00004 TABLE 4 Effect pigment slurry Butyl glycol 47.9 g DISPERBYK-180 1.5 g Dispermat LV, 10 min, 800 rpm, 5 cm paddle stirrer Hydrolan IL 2154 50.6 g Total 100.0 g

(80) TABLE-US-00005 TABLE 5 Effect pigment basecoat material Daotan VTW 6462 47.6 g  DI water 14.6 g  Isobutanol 2.3 g BYK-011 0.1 g BYK-347 0.3 g DMEA (10% in water) 1.7 g Effect pigment slurry 13.8 g  DI water 19.6 g  Total 100.0 g  Addition of the individual components with stirring, with further stirring for 10 minutes after addition of the last component, Dispermat LV, 5 cm paddle stirrer, 800 rpm

(81) TABLE-US-00006 TABLE 6 Amounts added and results Amount added of Spray viscosity Product active substance [%] 600 m-800 mPas Flop value Blank sample — * VB1 1.8 790 12.9 VB6 4  210** 12.7 VB4 0.8 (max. amount)  140** see below** VB7 2  480** see below** B3 1.5 605 17.1 B4 1.5 660 14.9 B2 1.5 750 13.4 B14 1.5 700 13.5 B10 1.8 765 14.5 B12 1.5 730 20.9 B17 1.5 600 17.1 B18 1.5 710 19.9 B19 1.5 691 15.9 B20 1.5 595 14.9 * a blank sample without rheology additive could not be used for coating, owing to its viscosity being much too low. **in spite of the use of the maximum amount as indicated in the technical datasheet, the application viscosity achieved was too low and so the flop could not be measured

(82) In table 6 it is evident that comparative examples VB4, VB6 and VB7, in spite of a higher amount deployed in some cases, do not achieve the required minimum viscosity for spray application, and/or this viscosity cannot be achieved even by increasing the amount added according to the datasheet.

(83) The coating results for comparative examples VB4 and VB7 are so poor that the flop value cannot be measured. Comparative example VB4 was added with the maximum amount as per the technical datasheet.

(84) All of the inventive examples can be adjusted to the required viscosity range for coating, and achieve higher flop values than comparative examples VB1 and VB6. The inventive examples are therefore more suitable than the comparative examples for improving the effect pigment orientation of basecoat materials.

(85) Test System 2: Storage Stability of an Effect Pigment Basecoat Material

(86) The effect pigment slurry and the basecoat material are prepared in accordance with the formulation specified in tables 7 and 8. Thereafter in each case 100 g of the basecoat material are weighed out into a 350 ml PE beaker and the respective rheology additive is incorporated with stirring using the Dispermat LV from Getzmann (5 min, 800 rpm, 5 cm paddle stirrer).

(87) The rheology additives are used in an added amount of 1.5% active substance in order to achieve a minimum viscosity of 600 mPas (spindle 3 at 50 rpm, Brookfield LV DV-I viscometer from Brookfield) for coating. If the minimum viscosity is not achieved, the amount of the respective additive added is increased in line with the recommended amount in the technical datasheet. The basecoat materials are subsequently stored at RT overnight and then adjusted to a spray viscosity of 600-800 mPas with the Brookfield LV DV-I viscometer from Brookfield (spindle 3 at 50 rpm) by addition of DI water. The basecoat material is dispensed into 100 ml glass tubes and stored at RT for 4 weeks. The storage stability of the effect pigment basecoat material is assessed by measuring the syneresis in percent in comparison to the total volume. The lower the value for the syneresis, the better the storage stability of the coating material and therefore the better the rheology activity of the rheology additive in question.

(88) TABLE-US-00007 TABLE 7 Effect pigment slurry Butyl glycol 47.9 g DISPERBYK-180  1.5 g Dispermat LV, 10 min, 800 rpm, 5 cm paddle stirrer Hydrolan IL 2154 50.6 g Total 100.0 g 

(89) TABLE-US-00008 TABLE 8 Effect pigment basecoat material Daotan VTW 6462 47.6 g  DI water 14.6 g  Isobutanol 2.3 g BYK-011 0.1 g BYK-347 0.3 g DMEA (10% in water) 1.7 g Effect pigment slurry 13.8 g  DI water 19.6 g  Total 100.0 g  Addition of the individual components with stirring, with further stirring for 10 minutes after addition of the last component, Dispermat LV, 5 cm paddle stirrer, 800 rpm

(90) TABLE-US-00009 TABLE 9 Results Amount added of Product active substance [%] Syneresis [%] Blank sample — 90 VB4  0.8** 38 VB6 4*  85 B1  2.4* 19 B2 1.5 28 B3 1.5 0 B4 1.5 24 B7  2.3* 16 B10  1.8* 0 *the amount had to be increased in order to achieve the required minimum viscosity of 600 mPas. **the amount could not be increased further beyond the maximum amount figure in the datasheet, owing to the excessively low active substance content

(91) In table 9 it can be seen that the products according to the invention lead to less syneresis by the effect pigment basecoat material, relative to the comparative examples. The inventive examples are therefore better suited than the comparative examples to improving the storage stability of the effect pigment basecoat material.

(92) Test System 3: Holdout in a 2K PU White Paint

(93) The white paint is produced in accordance with the formulation specified in table 10. Thereafter in each case 50 g of the white paint are weighed out into a 175 ml PE beaker and the respective rheology additive is incorporated with stirring using the Dispermat LV, with an added amount of 0.5% active substance (based on total paint) (5 min, 1000 rpm, 2.5 cm toothed disk). Comparative example VB3 requires incorporation during the production of the paint (for formula see table 10 in conjunction with table 11). The samples are then left to stand at RT for 1 day, after which the holdout test is conducted, as a measure of the rheology activity under application conditions.

(94) For this purpose, the curing agent solution is incorporated in the specified mixing ratio into the respective paint sample for 1 minute, with a spatula, and is then applied. Application takes place using a graduated doctor blade (model 421/I) from Erichsen at a wet film thickness of 30-300 μm using an automatic drawdown bench from BYK-Gardner with a speed of 5 cm/s onto BYK-Gardner contrast cards No. 2801. After application, the contrast cards are suspended directly horizontally for drying. After drying has taken place, a determination is made of the film thickness in μm (wet) at which the paint does not sag, meaning that no runs or ridging can be seen. The higher the value for the holdout when using the same active substance, the better the rheology activity of the additive. Besides the activity, the compatibility of the rheology additive also plays an important part in its suitability. The compatibility is evaluated by measuring the gloss at 20° using a Mikro-Trigloss from BYK-Gardner at a wet film thickness of 90 μm after overnight drying.

(95) The higher the gloss, the better the compatibility of the rheology additive in question. Only if a rheology additive improves the holdout without reducing the gloss relative to the blank sample is it suitable for use.

(96) TABLE-US-00010 TABLE 10 2K PU white paint Blank sample and AQ610 intermediate as Component A: other examples per table 11* Bayhydrol A 145 48.0 g  48.0 g  BYK-011 1.6 g 1.6 g DMEA (10% form) 4.2 g 4.2 g Disperbyk-194 2.1 g 2.1 g DI water 18.4 g  — AQ-610 intermediate (3% — 20.9 g  form) Tronox RKB-4 25.3 g  25.3 g  Dispermat CV, 30 min, 8500 rpm, 18 m/s, 1 mm glass beads (millbase:beads ratio = 1:1) BYK-345 0.3 g 0.3 g BYK-333 0.1 g 0.1 g Total 100.0 g  102.5 g  Bayhydur 304 20.5 g  20.5 g  MPA 4.5 g 4.5 g Total 25.0 g  25.0 g  Mixing ratio A:B 40:10 41:10 *datasheet for comparison product (AQ610) requires prior production as an intermediate before use in the paint, owing to the presentation form.

(97) TABLE-US-00011 TABLE 11 Intermediate AQ-610 DI water 80.0 g Dispermat CV, 20 min, 2000 rpm, 2.5 cm toothed disk VB3 20.0 g Total 100.0 g 

(98) TABLE-US-00012 TABLE 12 Results Product Holdout [μm] 20° Gloss Blank sample 90 50 VB2 90 69 VB3 210 9 VB5 120 65 VB6 150 67 B1 180 60 B2 180 65 B3 350 55 B4 180 65 B7 180 51 B12 180 62 B14 180 64 B15 180 64

(99) In table 12 it can be seen that relative to the blank sample, the inventive products on the one hand exhibit significantly improved holdout and on the other hand do not impair the gloss. In comparison to the inventive products, it is found that the comparative products only achieve either good holdout or good gloss, but not both properties in combination, as is possible with the inventive products.

(100) Test System 4: Holdout in an Acrylate Styrene Copolymer Clearcoat

(101) The clearcoat material is produced in accordance with the formulation specified in table 13. Thereafter in each case 50 g of the clearcoat material are weighed out into a 175 ml PE beaker and the respective rheology additive is incorporated with stirring using the Dispermat LV, with an added amount of 0.5% active substance (based on total paint) (5 min, 1000 rpm, 2.5 cm toothed disk). The samples are then left to stand at RT for 1 day, after which the holdout test is conducted, as a measure of the rheology activity under application conditions.

(102) For this purpose the sample is applied with a stepped doctor blade (model 421/I) from Erichsen at a wet film thickness of 30-300 μm using an automatic drawdown bench from BYK-Gardner with a speed of 5 cm/s onto BYK-Gardner contrast cards No. 2801. After application, the contrast cards are suspended directly horizontally for drying. After drying has taken place, a determination is made of the film thickness in μm (wet) at which the paint does not sag, meaning that no runs or ridging can be seen. The higher the value for the holdout when using the same active substance, the better the rheology activity.

(103) TABLE-US-00013 TABLE 13 Clearcoat based on acrylate-styrene copolymer Neocryl XK-205 75.0 g Butyl glycol 10.0 g DI water 13.4 g BYK-024  0.5 g BYK-346  1.0 g AMP-90  0.1 g* Dispermat LV, 5 min, 1000 rpm, 4 cm toothed disk Total 100.0 g  Preparation of the clearcoat material with stirring *adjustment of the pH with AMP-90 to pH 8.2-8.5

(104) TABLE-US-00014 TABLE 14 Results Product Holdout [μm] Visual evaluation Blank sample 30 satisfactory VB4 180 gel particles VB6 60 satisfactory VB8 90 satisfactory VB9 120 satisfactory VB10 200 nibs B2 300 satisfactory B3 350 satisfactory B4 300 satisfactory B14 300 satisfactory B17 210 satisfactory B18 180 satisfactory B19 210 satisfactory B20 240 satisfactory B21 250 satisfactory

(105) In table 14 it can be seen that the inventive products, relative to the comparative examples, lead to a much better holdout without any visual impairment. Comparative example VB4, while having a holdout comparable with that of example B9, nevertheless has adverse visual consequences in the dry coating film, since it shows gel particles. The processing properties or compatibility of comparative example VB4 are therefore poorer than those of the inventive examples. VB10 and B21 differ critically in the fact that, in contrast to B21, VB10 does not carry a COOH end group, being instead capped with tall oil fatty acid. In comparison to B21, VB10 possesses a lower holdout and an unacceptable appearance because of the formation of nibs.

(106) Test System 5: Storage Stability of a Yellow Iron Oxide Pigment Concentrate

(107) The pigment concentrate is prepared according to the formulation specified in table 15. Thereafter in each case 50 g of the pigment concentrate are weighed out into a 175 ml PE beaker and the respective rheology additive is incorporated with stirring using the Dispermat LV in an added amount of 0.5% active substance (based on total) (5 min, 1000 rpm, 2.5 cm toothed disk). Only the intermediate from VB3 had to be incorporated into the millbase, owing to the low active substance content. The pigment concentrates are subsequently dispensed into 50 ml tubes with snap-on lids, and are stored at 40° C. for 6 weeks. The storage stability of the pigment concentrate is assessed by measurement of the syneresis in percent in comparison to the total volume, and by visual assessment of the sediment by means of a metal spatula. The lower the value for the syneresis and for the sediment, the better the storage stability of the pigment concentrate and therefore the better the rheology activity of the rheology additive in question.

(108) TABLE-US-00015 TABLE 15 Yellow iron oxide pigment concentrate formulation AQ610 Blank sample and intermediate Component: other examples as per table 11* DI water 23.6 g  9.0 g Acticide MBS  0.1 g  0.1 g BYK-1730  0.5 g  0.5 g DISPERBYK-194 12.5 g 12.5 g AQ-610 intermediate — 16.6 g Bayferrox 3920 50.0 g 50.0 g Dispermat CV, 20 min, 8500 rpm, 4 cm toothed disk, 40° C. DI water 13.3 13.3 g Total 100.0 g  102.0 g 

(109) TABLE-US-00016 TABLE 16 Results Sample Syneresis/% Sediment, visual* Blank sample 45 4 VB1 38 3 VB3 40 3 VB4 35 3 B3 30 2 B11 28 2 B12 32 2-3 B13 26 2 B14 30 2 *sediment: 1: none/2: little/3: moderate/4: severe/5: very severe

(110) From table 16 it can be seen that the inventive products, relative to the blank sample and to the comparative examples, lead to relatively low syneresis and relatively low sediment. The inventive examples are therefore better suited than the comparative examples to improving the storage stability of the yellow iron oxide pigment concentrate.

(111) Test System 6: Antisettling in an Aqueous Basecoat

(112) The effect pigment slurry and the basecoat material are prepared according to the formulation specified in tables 17 and 18. Thereafter in each case 50 g of the basecoat material are weighed out into a 100 ml glass bottle and stored at RT for 4 days.

(113) The settling behavior of the effect pigment basecoat material is assessed by measurement of the syneresis in percent in comparison with the total volume.

(114) The lower the value for the syneresis, the better the antisettling properties and therefore the better the rheology activity of the rheology additive in question.

(115) TABLE-US-00017 TABLE 17 Effect pigment slurry Butyl glycol 47.9 g DISPERBYK-180  1.5 g Dispermat LV, 10 min, 800 rpm, 5 cm paddle stirrer Hydrolan IL 2154 50.6 g Total 100.0 g 

(116) TABLE-US-00018 TABLE 18 Effect pigment basecoat material Daotan VTW 6462 44.7 g  DI water 13.7 g  Isobutanol 2.2 g BYK-011 0.1 g BYK-347 0.3 g DMEA (10% in water) 1.6 g Effect pigment slurry 13.0 g  Rheology additive 25% form 4.0 g DI water 20.4 g  Total 100.0 g  Addition of the individual components with stirring, stirring continued for 10 minutes after addition of the last component, Dispermat LV, 5 cm paddle stirrer, 800 rpm

(117) TABLE-US-00019 TABLE 19 Results Product Syneresis [%] Blank sample 91 B17 35 B21 57 VB10 64

(118) From table 19 it can be seen that the inventive examples lead more effectively to lower syneresis than the respective comparative examples.

(119) The inventive examples are therefore better suited than the comparative examples to preventing settlement in the basecoat material.