Nucleophilic Acyl Substitution-based Polymerization Catalyzed by Oxometallic Complexes

• US 20070021585A1
• Filed: 07/20/2006
• Published: 01/25/2007
• Est. Priority Date: 07/22/2005
• Status: Abandoned Application

• Current Assignee: National Taiwan University (Government of The Republic of China)
• Original Assignee: National Taiwan University (Government of The Republic of China)
• Inventors: Chen, Chien-Tien
• Application Number:
  US11/459,003
• Publication Number:
  US 20070021585A1
• Time in Patent Office: Days
• US Class Current: 528/279
• CPC Class Codes: C08G 63/82 characterised by the catalyst used
• CPC Class Codes: C08G 69/00 Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule products obtained from isocyanates or isothiocyanates C08G18/00; polyamide-imides C08G73/14

Abstract

The present invention discloses a nucleophilic acyl substitution-based polymerization catalyzed by oxometalic complexes. In the first place, the first monomers with a plurality of carboxyl groups, and the second monomers with a plurality of protic nucleophilic groups are provided, wherein the protic nucleophilic groups comprise hydroxyl, amine, or thiol group. Next, catalyzed by the mentioned oxometallic complex, the first monomers and the second monomers are polymerized into the designed polymer. On the other hand, this invention discloses another nucleophilic acyl substitution-based polymerization catalyzed by oxometallic complexes. In the first place, monomers with at least one carboxyl (phosphonyl) group and at least one masked protic nucleophilic group are provided. Then, monomers are polymerized into the designed polymer, catalyzed by the mentioned oxometallic complexes.

Claims

1. A method of nucleophilic acyl substitution-based polymerization catalyzed by oxometallic complex, comprising:

providing the first monomer with a plurality of carboxyl groups or ester groups and a second monomer with a plurality of protic nucleophilic groups wherein said protic nucleophilic groups comprise hydroxyl, amine, or thiol group; and

,

catalyzing a polymerization between said first monomer and said second monomer by oxometalic complexes wherein said oxometallic complexes have the general formula MO_mL¹_yL²_z in which m and y are integers of greater than or equal to 1 and z is an integer of greater than or equal to zero, and said metal M of said oxometallic complexes comprise one selected from a group consisting of the following;

IVB, VB, VIB and actinide groups.

2. The method according to claim 1, wherein said first monomer has a plurality of ester groups and the carbon number of said ester groups is about from 1 to 5.

3. The method according to claim 1, wherein said L¹ comprises one selected from the group consisting of the following:

OTf, X, RC(O)CHC(O)R, OAc, OEt, O-iPr, butyl in which X comprises halogen elements.

4. The method according to claim 1, wherein said L² comprises one selected from the group consisting of the following:

H₂O, CH₃OH,

5. The method according to claim 1, wherein y=2 as said metal M comprises an IVB group transition metal element and m=1.

6. The method according to claim 5, wherein said metal M further comprises one selected from the group consisting of the following:

titanium (Ti), zirconium (Zr), and hafnium (Hf).

7. The method according to claim 1, wherein y=2, as said metal M comprises a VB group transition metal and m=1.

8. The method according to claim 7, wherein said metal M further comprises vanadium (V) or niobium (Nb)

9. The method according to claim 1, wherein y=3 as said metal M comprises a VB group transition metal and m=1.

10. The method according to claim 9, wherein said metal M further comprises vanadium (V) or niobium (Nb).

11. The method according to claim 1, wherein y=4 as said metal M comprises a VI B group transition metal and m=1.

12. The method according to claim 11, wherein said metal M further comprises molybdenum (Mo), tungsten (W), or chromium (Cr).

13. The method according to claim 1, wherein y=2 as said metal M comprises a VI B group transition metal and m=2.

14. The method according to claim 13, wherein said metal M further comprises molybdenum (Mo), tungsten (W), or chromium (Cr).

15. The method according to claim 1, wherein y=2 as said metal M comprises an actinide group transition metal and m=2.

16. The method according to claim 15, wherein said metal M further comprises uranium (U).

17. A method of nucleophilic acyl substitution-based polymerization catalyzed by oxometallic complexes:

providing a monomer with at least one carboxyl group or ester (phosphonates) group and at least one (masked) protic nucleophilic group wherein said protic nucleophilic group comprises hydroxyl, amine, or thiol group; and

,

catalyzing said monomer to polymerize with each other by oxometalic complexes wherein said oxometallic complexes have the general formula MO_mL¹_yL²_z in which m and y are integers of greater than or equal to 1 and z is an integer of greater than or equal to zero, and said metal M of said oxometalic complexes comprise one selected from a group consisting of the following;

IVB, VB, VIB and actinide groups.

18. The method according to claim 17, wherein the carbon number of said ester group is about from 1 to 5.

19. The method according to claim 17, wherein said L¹ comprises one selected from the group consisting of the following:

OTf, X, RC(O)CHC(O)R, OAc, OEt, O-iPr, butyl in which X comprises halogen elements.

20. The method according to claim 17, wherein said L² comprises one selected from the group consisting of the following:

H₂O, CH₃OH,

21. The method according to claim 17, wherein y=2 as said metal M comprises an IVB group transition metal element and m=1.

22. The method according to claim 21, wherein said metal M further comprises one selected from the group consisting of the following:

titanium (Ti), zirconium (Zr), and hafnium (Hf).

23. The method according to claim 17, wherein y=2 as said metal M comprises a VB group transition metal and m=1.

24. The method according to claim 23, wherein said metal M further comprises vanadium (V) or niobium (Nb).

25. The method according to claim 17, wherein y=3 as said metal M comprises a VB group transition metal and m=1.

26. The method according to claim 25, wherein said metal M further comprises vanadium (V) or niobium (Nb)

27. The method according to claim 17, wherein y=4 as said metal M comprises a VIB group transition metal and m=1.

28. The method according to claim 27, wherein said metal M further comprises molybdenum (Mo), tungsten (W), or chromium (Cr).

29. The method according to claim 17, wherein y=2 as said metal M comprises a VI B group transition metal and m=2.

30. The method according to claim 29, wherein said metal M further comprises molybdenum (Mo), tungsten (W), or chromium (Cr).

31. The method according to claim 17, wherein y=2 as said metal M comprises an actinide group transition metal and m=2.

32. The method according to claim 31, wherein said metal M further comprises uranium (U).