Radiation curable resins comprising hyperbranched polyesters

• US 5,834,118 A
• Filed: 05/09/1997
• Issued: 11/10/1998
• Est. Priority Date: 09/08/1994
• Status: Expired due to Fees

• Current Assignee: Neste Chemicals Oy (Fortum Oyj)
• Original Assignee: Neste Oy Of Keilaniemi
• Inventors: Wenfang, Shi, R.ang.nby, Bengt
• Primary Examiner(s): Acquah, Samuel A.
• Application Number:
  US08/793,611
• Time in Patent Office: 550 Days
• Field of Search: 528/272, 528/274, 528/283, 528/296, 528/297, 528/302, 528/306, 528/308, 525/437, 522/6, 428/480, 428/482
• US Class Current: 428/482
• CPC Class Codes: C08G 63/127 Acids containing aromatic rings
• CPC Class Codes: C08G 63/20 Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
• CPC Class Codes: C08G 63/21 in the presence of unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
• CPC Class Codes: C08G 63/58 Cyclic ethers C08G59/00 takes precedence; Cyclic carbonates; Cyclic sulfites ; Cyclic orthoesters
• CPC Class Codes: C08G 83/005 Hyperbranched macromolecules
• CPC Class Codes: Y10T 428/31786 Of polyester [e.g., alkyd, etc.]
• CPC Class Codes: Y10T 428/31794 Of cross-linked polyester

Abstract

Hyperbranched polyester of a polyol with 3 to 10 reactive hydroxyl groups, preferably of equivalent reactivity, and an aromatic polycarboxylic anhydride with 2 to 4 carboxyl groups, preferably 3 carboxyl groups, each hydroxyl group of the polyol forming an ester linkage with one anhydride group of the polycarboxylic anhydride, and further glycidyl (meth)acrylate or allyl glycidyl ether forming ester linkages with the remaining carboxyl groups of the anhydride and free hydroxyl groups. Further in the hyperbranched polyester (meth)acrylic anhydride and/or an aliphatic carboxylic anhydride form ester linkages with the free hydroxyl groups. The invention also comprises a process for the production of hyperbranched polyesters and such polyesters obtainable by the process. The hyperbranched polyesters can be used as resins, curable by UV irradiation, for the production of coatings, adhesives, laminates, foils and thin films and fibre-reinforced composites.

Claims

1. Hyperbranched polyester of a polyol with 3 to 10 reactive hydroxyl groups, and an aromatic polycarboxylic anhydride with 2 to 4 carboxyl groups,

each hydroxyl group of the polyol forming an ester linkage with one anhydride group of the polycarboxylic anhydride,

and further glycidyl (meth)acrylate or allyl glycidyl ether forming ester linkages with the remaining carboxyl groups of the anhydride and free hydroxyl groups.

8. The hyperbranched polyester of claim 1 wherein the reactive hydroxyl groups of the polyol have equivalent reactivity and the aromatic polycarboxylic anhydride has three carboxyl groups.

15. The hyperbranched polyester according to any one of claims 1 to 7, wherein the polyol is pentaerythritol and the aromatic polycarboxylic anhydride is 1,2,4-benzenetricarboxylic anhydride and the glycidyl (meth)acrylate is glycidyl acrylate.

16. The hyperbranched polyester according to any one of claims 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, wherein the hyperbranched polyester is a dendritic polyester or a crosslinked dendritic polyester.

30. The curable resin comprising the hyperbranched polyester of any one of claims 1 to 7.

31. The curable resin according to claim 30, further comprising a photofragmenting initiator.

32. The curable resin according to claim 31, further comprising a multifunctional monomer.

33. The curable resin according to claim 32 wherein the multifunctional monomer is trimethylolpropane triacrylate.

34. The curable resin according to claim 30 wherein the resin is curable with UV irradiation.

42. A coating, adhesive, laminate, foil, thin film, or fiber-reinforced composite comprising a cured product of the curable resin of claim 30.

2. Hyperbranched polyester of a polyol with 3 to 10 reactive hydroxyl groups and an aromatic polycarboxylic anhydride with 2 to 4 carboxyl groups,

each hydroxyl group of the polyol forming an ester linkage with one anhydride group of the polycarboxylic anhydride,

and glycidyl (meth)acrylate or allyl glycidyl ether forming ester linkages with the remaining carboxyl groups of the anhydride and free hydroxyl groups,

and further an anhydride selected from the group consisting of a (meth)acrylic anhydride, an aliphatic carboxylic anhydride, and blends thereof, forming ester linkages with the free hydroxyl groups.

9. The hyperbranched polyester of claim 2 wherein the reactive hydroxyl groups of the polyol have equivalent reactivity and the aromatic polycarboxylic anhydride has three carboxyl groups.

3. Hyperbranched polyester produced by a process comprising the following steps:

a) reacting an aromatic polycarboxylic anhydride with 2 to 4 carboxyl groups with a polyol with 3 to 10 reactive hydroxyl groups in the presence of an activating agent, the amount of anhydride being at least one mole of anhydride per hydroxyl group in the polyol,

b) reacting the product from a) with glycidyl (meth)acrylate or allyl glycidyl ether in an amount at least corresponding to one mole of glycidyl (meth)acrylate or allyl glycidyl ether per free carboxylic acid group of the product of a).

4. The hyperbranched polyester according to claim 3, wherein the activating agent is present in a catalytic amount.

5. The hyperbranched polyester according to claim 3, wherein the activating agent is SnCl₂.

6. The hyperbranched polyester of claim 3, the process further comprising c) reacting the product from step b) with (meth)acrylic anhydride in an amount sufficient to esterify at least a part of the free hydroxyl groups of the product from step b).

7. The hyperbranched polyester of claim 3, the process further comprising c) reacting the product from step b) with an aliphatic carboxylic anhydride in an amount sufficient to esterify at least a part of the remaining hydroxyl groups of the product.

10. The hyperbranched polyester of claim 3 wherein the reactive hydroxyl groups of the polyol have equivalent reactivity and the aromatic polycarboxylic anhydride has three carboxyl groups.

11. The hyperbranched polyester of claim 6, the process further comprising reacting the product from step c) with an aliphatic carboxylic anhydride in an amount sufficient to esterify at least a part of the remaining hydroxyl groups of the product.

12. The process of claim 11, wherein the aromatic polycarboxylic anhydride has three carboxyl groups and the reactive hydroxyl groups of the polyol have equivalent reactivity.

13. The process according to claim 12, further comprising the following step:

c) reacting the product from step b) with (meth)acrylic anhydride in an amount sufficiently to esterify at least a part of the free hydroxyl groups of the product from step b).

14. The hyperbranched polyester according to any one of claims 2, 6, 7, 9, or 11, wherein the (meth)acrylic anhydride is (meth)acrylic anhydride and the aliphatic carboxylic anhydride forming ester linkages with the free hydroxyl groups in acetic anhydride.

26. The process according to any one of claims 17, 24, 12, or 13, further comprising reacting the product from step b) or c) with an aliphatic carboxylic anhydride in an amount sufficient to esterify at least a part of the remaining hydroxyl groups of the product.

27. The process according to claim 26, wherein the aliphatic carboxylic anhydride is acetic anhydride.

35. The process according to claim 12, wherein the activating agent is present in a catalytic amount.

36. The process according to claim 12, wherein the activating agent is SnCl₂.

37. The process according to claim 12, wherein the reaction mixture of step a) is heated to a temperature below 100°

C.

38. The process according to claim 12, wherein the amount of anhydride in step a) is at least 1.2 moles per hydroxyl group and the amount of glycidyl (meth)acrylate or allyl glycidyl ether in step b) is at least 1.05 moles per free carboxylic acid group.

39. The process according to claim 12, wherein the reaction of step b) is carried out in the presence of a basic catalyst and an inhibitor for radical polymerization.

40. The process according to claim 39, wherein the basic catalyst is benzyldimethyldiamine.

41. The process according to claim 13, wherein the anhydride is methacrylic anhydride.

17. A process for the production of a hyperbranched polyester, said process comprising the steps of:

a) reacting an aromatic polycarboxylic anhydride with 2 to 4 carboxyl groups with a polyol with 3 to 10 reactive hydroxyl groups in the presence of an activating agent, the amount of anhydride being at least one mole of anhydride per hydroxyl group in the polyol,

b) reacting the product from a) with glycidyl (meth)acrylate or allyl glycidyl ether in an amount at least corresponding to one mole of glycidyl (meth)acrylate or allyl glycidyl ether per free carboxylic acid group of the product of a).

18. The process according to claim 17, wherein the activating agent is present in a catalytic amount.

19. The process according to claim 17, wherein the activating agent is SnCl₂.

20. The process according to claim 17, wherein the reaction mixture of step a) is heated to a temperature below 100°

C.

21. The process according to claim 17, wherein the amount of anhydride in step a) is at least 1.2 moles per hydroxyl group and the amount of glycidyl (meth)acrylate or allyl glycidyl ether in step b) is at least 1.05 moles per free carboxylic acid group.

22. The process according to claim 17, wherein the reaction of step b) is carried out in the presence of a basic catalyst and an inhibitor for radical polymerization.

23. The process according to claim 22, wherein the basic catalyst is benzyldimethyldiamine.

24. The process according to claim 17, further comprising the following step:

c) reacting the product from step b) with (meth)acrylic anhydride in an amount sufficient to esterify at least a part of the free hydroxyl groups of the product from step b).

25. The process according to claim 24, wherein the anhydride is methacrylic anhydride.

28. The process according to any one of claims 17 to 25, wherein the polyol is pentaerythritol and the aromatic polycarboxylic anhydride is 1,2,4-benzene-tricarboxylic anhydride and the glycidyl (meth)acrylate is glycidyl acrylate.

29. The process according to any one of claims 17 to 25, wherein the hyperbranched polyester is a dendritic polyester or a crosslinked dendritic polyester.