Cyclic dynamic polyureas for polymeric urea processing

Patent metadata

Field	Value
Publication number	US-10428171-B2
Application number	US-201615547525-A
Country	US
Kind code	B2
Filing date	Feb 3, 2016
Priority date	Feb 3, 2015
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

The present invention relates to a one-component processing method and system for preparing polyurea materials. This method and system involves a polymerization process using cyclic oligomeric polyurea precursors. These cyclic oligomeric precursors have dynamic urea bonds such as hindered urea bonds (HUBs). These cyclic oligomeric precursors exhibit dynamic properties to reversibly dissociate in situ yielding isocyanate and amine components which polymerize to yield the polyureas, such as linear, branched or cross-linked polyureas. This method and system has advantages over conventional methods that utilize two-component systems. Such two-component systems require the segregation of the isocyanate and amine components to prevent premature or too rapid polymerization. The resulting polyureas are useful for a variety of applications including coatings.

First claim

What is claimed is:

1. A cyclic oligomer or polymer corresponding to formula (Ia) or (Ib)

wherein L and M are independently selected from aryl, (C 1 -C 20 )alkyl, (C 4 -C 10 )cyclolalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl(C 1 -C 20 )alkyl, (C 2 -C 20 )alkyl-PEG-(C 2 -C 20 )alkyl, —(C 1 -C 20 )alkylO(C 1 -C 20 )alkyl-, —(C 1 -C 20 )alkylS(C 1 -C 20 )alkyl-, —NR 4 —, ═N—, —C(R 5 ) 2 —, —NC(═O)(C 1 -C 20 )alkyl-, —C(═O)(C 1 -C 20 )alkyl-, —C(═O)—(NR 4 )—, —S(═O) 2 O—, —S(═O) 2 —(C 1 -C 20 )alkyl-, —OS(═O) 2 O(C 1 -C 20 )alkyl-, —S(═O) 2 NR 4 —, —S(═O)(C 1 -C 20 )alkyl-, —P(═O)(OR 4 )O—, —C(S)—(C 1 -C 20 )alkyl-, —C(O)O(C 1 -C 20 )alkyl-, —C(═O)O—, —C(═S)O(C 1 -C 20 )alkyl-, —C(═O)S(C 1 -C 20 )alkyl-, —C(═S)S(C 1 -C 20 )alkyl-, —C(O)NR 4 —(C 1 -C 20 )alkyl-, and —C(═NR 4 )NR 4 —;
each R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of aryl, (C 1 -C 20 )alkyl, (C 4 -C 10 )cyclolalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 2 -C 20 )alkyl-PEG-(C 2 -C 20 )alkyl, and H;
each R 5 is independently selected from F, Cl, Br, and I;
and x is an integer from about 2 to about 500.

2. A cyclic oligomer or polymer according to claim 1 wherein R 1 , R 2 , and R 3 are each methyl.

3. A cyclic oligomer or polymer according to claim 1 wherein M is

and L is —(CH 2 CH 2 )—.

4. A cyclic oligomer or polymer according to claim 1 wherein x is an integer from about 2 to about 50.

5. A hyperbranched cyclic oligomer or polymer corresponding to formula (IIa) or (IIb)

wherein P and Q are independently selected from functionalized branched linkers each having a total of three or more arms selected from aryl, (C 1 -C 20 )alkyl, (C 4 -C 10 )cyclolalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl(C 1 -C 20 )alkyl, and (C 2 -C 20 )alkyl-PEG-(C 2 -C 20 )alkyl, —(C 1 -C 20 )alkylO(C 1 -C 20 )alkyl-, —(C 1 -C 20 )alkylS(C 1 -C 20 )alkyl-, —NR 4 —, ═N—, —C(R 5 ) 2 —, —NC(═O)(C 1 -C 20 )alkyl-, —C(═O)(C 1 -C 20 )alkyl-, —C(═O)—(NR 4 )—, —S(═O) 2 O—, —S(═O) 2 —(C 1 -C 20 )alkyl-, —OS(═O) 2 O(C 1 -C 20 )alkyl-, —S(═O) 2 NR 4 —, —S(═O)(C 1 -C 20 )alkyl-, —P(═O)(OR 4 )O—, —C(S)—(C 1 -C 20 )alkyl-, —C(O)O(C 1 -C 20 )alkyl-, —C(═O)O—, —C(═S)O(C 1 -C 20 )alkyl-, —C(═O)S(C 1 -C 20 )alkyl-, —C(═S)S(C 1 -C 20 )alkyl-, —C(O)NR 4 —(C 1 -C 20 )alkyl-, and —C(═NR 4 )NR 4 —;
each R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of aryl, (C 1 -C 20 )alkyl, (C 4 -C 10 )cyclolalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 2 -C 20 )alkyl-PEG-(C 2 -C 20 )alkyl, and H;
each R 5 is independently selected from F, Cl, Br, and I;
and x is an integer from about 2 to about 500.

6. A hyperbranched cyclic oligomer or polymer according to claim 5 wherein R 1 , R 2 , and R 3 are each methyl.

7. A hyperbranched cyclic oligomer or polymer according to claim 5 wherein x is an integer from about 2 to about 50.

8. A cyclic oligomer or polymer comprising two or more hindered urea bond functional groups,
wherein the hindered urea bond functional groups correspond to formula (IIIa) or (IIIb)

wherein L and M are independently selected from aryl, (C 1 -C 20 )alkyl, (C 4 -C 10 )cyclolalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl(C 1 -C 20 )alkyl, and (C 2 -C 20 )alkyl-PEG-(C 2 -C 20 )alkyl, —(C 1 -C 20 )alkylO(C 1 -C 20 )alkyl-, —(C 1 -C 20 )alkylS(C 1 -C 20 )alkyl-, —NR 4 —, ═N—, —C(R 5 ) 2 —, —NC(═O)(C 1 -C 20 )alkyl-, —C(═O)(C 1 -C 20 )alkyl-, —C(═O)—(NR 4 )—, —S(═O) 2 O—, —S(═O) 2 —(C 1 -C 20 )alkyl-, —OS(═O) 2 O(C 1 -C 20 )alkyl-, —S(═O) 2 NR 4 —, —S(═O)(C 1 -C 20 )alkyl-, —P(═O)(OR 4 )O—, —C(S)—(C 1 -C 20 )alkyl-, —C(O)O(C 1 -C 20 )alkyl-, —C(═O)O—, —C(═S)O(C 1 -C 20 )alkyl-, —C(═O)S(C 1 -C 20 )alkyl-, —C(═S)S(C 1 -C 20 )alkyl-, —C(O)NR 4 —(C 1 -C 20 )alkyl-, and —C(═NR 4 )NR 4 —;
each R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of aryl, (C 1 -C 20 )alkyl, (C 4 -C 10 )cyclolalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 2 -C 20 )alkyl-PEG-(C 2 -C 20 )alkyl, and H;
and each R 5 is independently selected from F, Cl, Br, and I.

9. A cyclic oligomer or polymer according to claim 8 comprising from about 2 to about 500 hindered urea bond functional groups.

10. A cyclic oligomer or polymer according to claim 8 wherein R 1 , R 2 , and R 3 are each methyl.

11. A cyclic oligomer or polymer according to claim 8 wherein M is

and L is —(CH 2 CH 2 )—.

12. A cyclic hyperbranched oligomer or polymer comprising two or more hindered urea bond functional groups,
wherein the hindered urea bond functional groups correspond to formula (IVa) or (IVb)

wherein P and Q are independently selected from functionalized branched linkers each having a total of three or more arms selected from aryl, (C 1 -C 20 )alkyl, (C 4 -C 10 )cyclolalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl, (C 1 -C 20 )alkyl(C 6 -C 10 )aryl(C 1 -C 20 )alkyl, and (C 2 -C 20 )alkyl-PEG-(C 2 -C 20 )alkyl, —(C 1 -C 20 )alkylO(C 1 -C 20 )alkyl-, —(C 1 -C 20 )alkylS(C 1 -C 20 )alkyl-, —NR 4 —, ═N—, —C(R 5 ) 2 —, —NC(═O)(C 1 -C 20 )alkyl-, —C(═O)(C 1 -C 20 )alkyl-, —C(═O)—(NR 4 )—, —S(═O) 2 O—, —S(═O) 2 —(C 1 -C 20 )alkyl-, —OS(═O) 2 O(C 1 -C 20 )alkyl-, —S(═O) 2 NR 4 —, —S(═O)(C 1 -C 20 )alkyl-, —P(═O)(OR 4 )O—, —C(S)—(C 1 -C 20 )alkyl-, —C(O)O(C 1 -C 20 )alkyl-, —C(═O)O—, —C(═S)O(C 1 -C 20 )alkyl-, —C(═O)S(C 1 -C 20 )alkyl-, —C(═S)S(C 1 -C 20 )alkyl-, —C(O)NR 4 —(C 1 -C 20 )alkyl-, and —C(═NR 4 )NR 4 —;
each R 1 , R 2 , R 3 and R 4 are independently selected from the group consisting of aryl, (C 1 -C 20 )alkyl, (C 4 -C 10 )Cyclolalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl, (C 1 -C 20 )alkyl(C 4 -C 10 )cycloalkyl(C 1 -C 20 )alkyl, (C 2 -C 20 )alkyl-PEG-(C 2 -C 20 )alkyl, and H;
and each R 5 is independently selected from F, Cl, Br, and I.

13. A cyclic hyperbranched oligomer or polymer according to claim 12 comprising from about 2 to about 500 hindered urea bond functional groups.

14. A cyclic hyperbranched oligomer or polymer according to claim 12 wherein R 1 , R 2 , and R 3 are each methyl.

15. A cyclic oligomer or polymer according to claim 1 prepared from reacting a difunctional isocyante according to formula (V)

Assignees

• Univ Illinois

Inventors

• Cheng Jianjun
• Ying Hanze

Classifications

• C08G18/792

  formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates · CPC title

• C09D175/02

  Polyureas · CPC title

• C08G2150/20

  Compositions for powder coatings · CPC title

• C08G18/325

  containing secondary or tertiary amino groups (C08G18/3228, C08G18/3234, C08G18/3246 take precedence) · CPC title

• C08L75/02

  Polyureas · CPC title