US 11,453,750 B2 · Urea-group- and/or urethane-group-containing amides as and in rheology control agents, their preparation and their use

(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)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 ORe or halide, or Y and Y′ are connected to one another and together as Y—Y′ are an oxygen atom, and wherein Re is hydrogen or is Rd, wherein Rd is a protecting group for a carboxyl group, are reacted with one or more diamines of the general formula (VII)

H2N—R5-NH2 (VII)

optionally in the presence of one or more species of the general formula (VIII)

(HX)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]m′]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 COORd 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)

H2C═C(Rf)-E′ (X)

wherein Rf 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-NH2 (IXa)

and/or

HOOC—R5-NH2 (IXb)

are reacted in a polycondensation reaction in the presence of one or more species of the general formula (VIII)

(HX)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]m′]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 COORd 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)

H2C═C(Rf)-E′ (X)

wherein Rf 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)

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)k—R3-COOH (XII)

or

(b) in the presence of one or more species of the general formula

(HX)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]m′]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 COORd 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)

H2C═C(Rf)-E′ (X)

wherein Rf 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 COORd, the protective group Rd 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 Ra—[O—(C═O)uRb]v, in which

Ra 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 CH2—O—(C═O)wRc, in which w is 0 or 1 and Rc is an organic radical having 2 to 24 carbon atoms;

and the radicals Rb,

if u=1, are linear or branched alkylene radicals having 3 to 8 carbon atoms;

and

in the radicals [O—(C═O)uRb] 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⊖Z⊕, wherein Z⊕ is selected from the group consisting of alkali metal cations, alkaline earth metal cations, NH4⊕, heterocyclic cations, and mono- to tetra-organically substituted ammonium ions, wherein when Z⊕ is an alkaline earth metal cation, Z⊕ is ½ Z2≠,

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)

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 Ra—[O—(C═O)uRb]v, in which

Ra 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 Rb 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 CH2—O—(C═O)wRc, in which w is 0 or 1 and Rc is an organic radical having 2 to 24 carbon atoms;

and the radicals Rb,

if u=1, are linear or branched alkylene radicals having 3 to 8 carbon atoms;

and

in the radicals [O—(C═O)uRb] 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⊖Z⊕, wherein Z⊕ is selected from the group consisting of alkali metal cations, alkaline earth metal cations, NH4⊕, heterocyclic cations, and mono- to tetra-organically substituted ammonium ions,

wherein when Z⊕ is an alkaline earth metal cation, Z⊕ is ½ Z2⊕,

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⊕ in that case is absent;

m is 1 to 5;

n is 1 to 12;

and

k is 1 to 5.

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

Life of this patent

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

Life of this patent

Abstract

Claims15