Functionalized thermosetting resin systems

• US 20060173142A1
• Filed: 02/01/2005
• Published: 08/03/2006
• Est. Priority Date: 02/01/2005
• Status: Abandoned Application

• Current Assignee: Reichhold Incorporated
• Original Assignee: Reichhold Incorporated
• Inventors: Nava, Hildeberto, Small, Aaron C.
• Application Number:
  US11/048,173
• Publication Number:
  US 20060173142A1
• Time in Patent Office: Days
• US Class Current: 525/540
• CPC Class Codes: C08F 2438/02 Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
• CPC Class Codes: C08F 257/02 on to polymers of styrene or alkyl-substituted styrenes
• CPC Class Codes: C08F 265/04 on to polymers of esters
• CPC Class Codes: C08F 290/00 Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
• CPC Class Codes: C08F 291/00 Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
• CPC Class Codes: C08F 293/00 Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule on to polymers modified by introduction of unsaturated end groups C08F290/02
• CPC Class Codes: C08F 293/005 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 51/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C08L51/04, C08L51/06 take precedence
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Abstract

The present invention provides a crosslinkable polymer system that can be crosslinked to form a wide variety of polymeric, copolymeric and oligomeric compounds. The crosslinkable system comprises a product Q formed from an aromatic ethylenically unsaturated moiety and a first reactive ethylenically unsaturated moiety, and a second reactive ethylenically unsaturated moiety at least partially reacted with the first reactive ethylenically unsaturated moiety, and a first terminal moiety comprising a covalently bonded nitroxide containing group.

Claims

1. A crosslinkable polymer system comprising

(a) a main portion comprising a product Q formed from an aromatic ethylenically unsaturated moiety and a first reactive ethylenically unsaturated moiety wherein product Q provides carbon-carbon linkages in the backbone of said crosslinkable polymer system and a second reactive ethylenically unsaturated moiety at least partially reacted with said first reactive ethylenically unsaturated moiety of product Q, and

(b) a first terminal moiety comprising a nitroxide containing group.

2. The crosslinkable polymer system according to claim 1, wherein the covalently bonded nitroxide free radical group is provided by a hindered nitroxide compound selected from the group consisting of compounds having the formula:

3. The crosslinkable polymer system according to claim 2 further including a second terminal moiety provided by a peroxide or azo group selected from the group consisting of diacyl peroxides, peroxydicarbonates, peroxyesters, dialkylperoxides, ketone peroxides, hydroperoxides, peroxyketals and azo type initiators, or provided by a radiation curing type initiator.

4. The crosslinkable polymer system according to claim 1, wherein the first reactive ethylenically unsaturated monomer has the formula

5. The crosslinkable polymer system according to claim 1, wherein the second reactive ethylenically unsaturated moiety is selected from the group consisting of (meth)acrylates, polyfunctional acrylates, vinyl aromatics, vinyl heterocyclyl, vinyl halides, vinyl esters of carboxylic acids, and methyl(allylic) monomers.

6. The crosslinkable polymer system of claim 1, further comprising one or more additives selected from the group consisting of antioxidants, solvents, polymerization inhibitors, chain transfer agents, polymerization accelerators, and UV stabilizers.

7. The crosslinkable polymer system according to claim 1, further comprising a thermosetable moiety, a thermoplastic moiety or monomer wherein said thermosetable moiety, thermoplastic moiety or monomer is crosslinkable with said first or second reactive ethylenically unsaturated moiety or both.

8. The crosslinkable polymer system according to claim 3, further comprising a thermosetable moiety, a thermoplastic moiety or monomer wherein said thermosetable moiety, thermoplastic moiety or monomer is crosslinkable with said first or second reactive ethylenically unsaturated moiety or both.

9. A polymer comprising the cured crosslinkable polymer system of claim 1.

10. The polymer according to claim 9 further including an additive selected from the group consisting of fiber reinforcements, fillers, thickening agents, flow agents, lubricants, air release agents, wetting agents, UV stabilizers, compatibilizers, shrink reducing agents, waxes, and mold release agents.

11. A crosslinkable polymer system comprising

(a) a main portion comprising a product Q formed from an aromatic ethylenically unsaturated moiety and a reactive ethylenically unsaturated moiety, said product Q providing carbon-carbon linkages in the backbone of said crosslinkable system, and a thermosetable moiety, a thermoplastic moiety or a monomer wherein said product Q and said thermosetable moiety, thermoplastic moiety or monomer is crosslinkable with said reactive moiety of product Q;

and

(b) a first terminal moiety comprising a nitroxide containing group.

12. The crosslinkable polymer system according to claim 11, wherein the covalently bonded nitroxide free radical group is provided by a hindered nitroxide compound selected from the group consisting of compounds having the formula:

13. The crosslinkable polymer system according to claim 12 further including a second terminal moiety provided by a peroxide or azo group selected from the group consisting of diacyl peroxides, peroxydicarbonates, peroxyesters, dialkylperoxides, ketone peroxides, hydroperoxides, peroxyketals, and azo type initiators, or provided by a radiation curing type initiator.

14. The crosslinkable polymer system according to claim 12, wherein the first reactive ethylenically unsaturated monomer has the formula

15. The crosslinkable polymer system according to claim 12, wherein the second reactive ethylenically unsaturated moiety is selected from the group consisting of (meth)acrylates, polyfunctional acrylates, vinyl aromatics, vinyl heterocyclyl, vinyl halides, vinyl esters of carboxylic acids, and methyl(allylic) monomers.

16. The crosslinkable polymer system of claim 12, further comprising one or more additives selected from the group consisting of antioxidants, solvents, polymerization inhibitors, chain transfer agents, polymerization accelerators, and UV stabilizers.

17. A polymer comprising the cured crosslinkable polymer system of claim 12.

18. The polymer according to claim 17 further including an additive selected from the group consisting of fiber reinforcements, fillers, thickening agents, flow agents, lubricants, air release agents, wetting agents, UV stabilizers, compatibilizers, shrink reducing agents waxes, and mold release agents.

19. A crosslinkable polymer having the formula:

20. A method of making a crosslinkable polymer system comprising the steps of:

(a) forming a main portion reaction mixture comprising an aromatic ethylenically unsaturated moiety and a first reactive ethylenically unsaturated moiety;

(b) adding a nitroxide containing group to the main portion reaction mixture to provide a first terminal moiety on the main portion reaction mixture; and

(c) polymerizing the product of (a) and (b).

21. The method according to claim 20, further comprising reacting a second reactive ethylenically unsaturated monomer with the polymerized product of step (c).

22. The method according to claim 21, further comprising reacting a thermosetable moiety, a thermoplastic moiety or a monomer crosslinkable with the first and/or second reactive ethylenically unsaturated monomer of the polymerized product of step (c).

23. The method according to claim 21, wherein the step (c) of polymerizing includes heating to a temperature of about 10°

to 200°

C. at a pressure of 0.10 MPa to 30 MPa.

24. The method according to claim 21, wherein the step of (c) polymerizing includes subjecting (a) and (b) to electromagnetic radiation.

25. A polymer, copolymer or oligomers in linear, block copolymer, graft, comb-like, star-like or hyperbranched form prepared by the method of claim 21.

26. A method of making a crosslinked polymer comprising:

(a) forming a main portion reaction mixture comprising an aromatic ethylenically unsaturated moiety and a first reactive ethylenically unsaturated moiety;

(b) adding a nitroxide containing group to the main portion reaction mixture to provide a first terminal moiety on the main portion reaction mixture;

(c) polymerizing the product of (a) and (b); and

(d) curing the polymerized product of step (c) to provide a crosslinked polymer.

27. The method according to claim 26, further comprising reacting a second reactive ethylenically unsaturated monomer with the polymerized product of step (c).

28. The method according to claim 26, further comprising reacting a thermosetable moiety, a thermoplastic moiety or a monomer crosslinkable with the first and/or second reactive ethylenically unsaturated monomer of the polymerized product of step (c).