Polyoxyalkylenes containing guanidine and method for the production thereof

1. A polymeric guanidine-group compound, comprising a structural element of general formula (Ia)

in at least one side-chain position,

wherein R 1 , R 2 , R 3 and R 4 are each independently a linear, cyclic or branched, aliphatic saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, or an aromatic hydrocarbon radical having 6 to 30 carbon atoms, which optionally comprise heteroatoms.

2. The compound according to claim 1 which has a structure of general formula (I)

wherein T 1 , T 2 , T 3 and T 4 are each independently hydrogen or linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 1 to 12 carbon atoms which optionally comprise halogen atoms, with the proviso that M3 is not the same as M1 or M2, and wherein two radicals selected from T 1 , T 2 , T 3 and T 4 together may form a three- to eight-membered ring,

wherein Y is independently a linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, which optionally comprise heteroatoms

wherein G is a guanidine radical of the formula,

wherein

R 1 , R 2 , R 3 and R 4 are each independently a linear, cyclic or branched, aliphatic saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, or an aromatic hydrocarbon radical having 6 to 30 carbon atoms, which optionally comprise heteroatoms,

i is 1 to 10,

m1, m2, m3, m4 and m5 are each independently 0 to 500,

m6 is 1 to 100,

wherein the sum of m1 and m2 is at least 3,

X is independently O, NH, N-alkyl, N-aryl or S,

Z is independently an i-functional linear, cyclic or branched, aliphatic saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, an aromatic hydrocarbon radical having 6 to 30 carbon atoms, and

J is independently is hydrogen, a linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, a carboxylic acid radical having 1 to 30 carbon atoms or a heteroatom-substituted, functional, organic, saturated or unsaturated radical.

3. The compound according to claim 2 , wherein

i is 1 to 2,

m1 is 0 to 30,

m2 is 3 to 500,

m3 is 0 to 20,

m4 is 0 to 20,

m5 is 0 to 10,

m6 is 1 to 30, and

J is hydrogen,

X is oxygen,

Y is an allyl radical,

R 1 , R 2 , R 3 and R 4 are each independently a linear or branched hydrocarbon having 1 to 8 carbon atoms,

T 1 , T 2 , T 3 and T 4 are each independently hydrogen or linear or branched hydrocarbons having 2 to 8 carbon atoms, with the proviso that M3 is not the same as M1 or M2, and

Z is independently a mono- or divalent linear or branched saturated or unsaturated hydrocarbon radical having 2 to 18 carbon atoms.

4. The compound according to claim 2 , wherein

i is 1 to 2,

m1 is 0 to 30,

m2 is 5 to 200,

m3 is 0 to 10,

m4 is 0 to 10,

m5 is 0 to 3,

m6 is 1 to 20, and

J is hydrogen,

X is oxygen,

R 1 , R 2 , R 3 and R 4 are methyl groups, and

Z is independently an allyl or butyl group.

5. A process for the preparation of the polymeric guanidine-group compound according to claim 1 , the method comprising:

reacting a compound of the general formula (II)

Z—(OH) i   (II)

wherein

Z is independently an i-functional linear, cyclic or branched, aliphatic saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, or an aromatic hydrocarbon radical having 6 to 30 carbon atoms, and

i is 1 to 10,

in the presence of a double metal cyanide catalyst with epichlorohydrin and one or more alkylene oxides thereby forming a chlorine-containing polyether, and

reacting the chlorine-containing polyether with a guanidine compound of the general formula (III)

wherein

R 1 , R 2 , R 3 and R 4 are each independently a linear, cyclic or branched, aliphatic saturated or unsaturated hydrocarbon radical having 1 to 30 carbon atoms, or an aromatic hydrocarbon radical having 6 to 30 carbon atoms, which optionally comprise heteroatoms,

thereby forming the polymeric guanidine-group compound.

6. The process according to claim 5 , wherein the guanidine compound of the general formula (III) is tetramethylguanidine,

wherein the molar ratio of tetramethylguanidine to the chlorine-containing polyether is 1:1 to 3:1,

wherein the reacting of the chlorine-containing polyether with the guanidine compound of the general formula (III) is performed at a temperature of 90° C. to 160° C. over a time period of 8 to 30 hours, and

wherein by-product guanidinium chloride is filtered off, and excess tetramethylguanidine is distilled off at a temperature of 100° C. and a pressure of 1.5 mbar.

7. The process according to claim 5 , further comprising

reacting the polymeric guanidine-group compound to obtain at least one guanidinium group, thereby forming a quaternary compound.

8. A composition comprising the polymeric guanidine-group compound according to claim 1 comprising the structural element of general formula (Ia).

9. A method, comprising:

adding the polymeric guanidine-group compound according to claim 1 comprising the structural element of general formula (Ia) to a formulation

wherein polyurethanes are obtained from the formulation and the polymer guanidine-group compound is a catalyst, or

the formulation is an epoxide resin and the polymer guanidine-group compound is a curing agent, or

the formulation is an alkoxysilyl-group-carrying system.

10. A method, comprising:

adding the polymeric guanidine-group compound according to claim 1 comprising the structural element of general formula (Ia) to a material as a dispersion additive,

wherein the material is at least one selected from the group consisting of coatings, paints, coating compositions and pigment pastes.

11. A composition comprising the polymeric guanidine-group compound according to claim 2 which has a structure of general formula (I).

12. The compound according to claim 2 , wherein T 1 , T 2 , T 3 and T 4 are each independently hydrogen or linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radicals having 2 to 8 carbon atoms which optionally comprise halogen atoms.

13. The compound according to claim 2 , wherein Y is independently a linear, cyclic or branched, aliphatic or aromatic, saturated or unsaturated hydrocarbon radical having 2 to 15 carbon atoms which optionally comprise heteroatoms.

14. The compound according to claim 2 , wherein i is 1 to 3.

15. The compound according to claim 2 , wherein m6 is 2 to 30.

16. The compound according to claim 2 , wherein X is independently oxygen.

17. The compound according to claim 2 , wherein Z is independently an i-functional linear, cyclic or branched, aliphatic saturated or unsaturated hydrocarbon radical having 4 to 15 carbon atoms or Z is an aromatic hydrocarbon radical having 8 to 12 carbon atoms.

18. The composition according to claim 8 , wherein the composition is at least one selected from the group consisting of a coating, a paint, a coating composition, and a pigment paste.

19. The composition according to claim 11 , wherein the composition is at least one selected from the group consisting of a coating, a paint, a coating composition, and a pigment paste.

20. A formulation comprising the polymeric guanidine-group compound according to claim 1 comprising the structural element of general formula (Ia), wherein the formulation is basically catalyzable.