Emulsion living-type free radical polymerization, methods and products of same

• US 20020065380A1
• Filed: 09/25/2001
• Published: 05/30/2002
• Est. Priority Date: 09/28/2000
• Status: Active Grant

• Current Assignee: Freeslate Inc. (Unchained Labs Inc.)
• Original Assignee: Symyx Technologies Incorporated (Dassault Systemes SA)
• Inventors: Li, Yunxiao, Charmot, Dominique, Chang, Han Ting, Huefner, Peter
• Granted Patent: US 6,518,364 B2
• Time in Patent Office: Days
• US Class Current: 526/219
• CPC Class Codes: C08F 2/38 Polymerisation using regulators, e.g. chain terminating agents , e.g. telomerisation
• CPC Class Codes: C08F 2438/03 Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]

Abstract

Heterogeneous (e.g., emulsion) polymerization systems include a control agent that has a nitrogen-nitrogen bond covalently bonded to a thiocarbonyl moiety for living-type free radical polymerization of a wide variety of monomers. These control agents provide superior properties for control of the polymerization and/or the properties of the polymers obtained and/or the monomers that may be polymerized. Multifunctional control agents provide the opportunity for a variety of structurally unique polymers, including block copolymers, stars and hyper-branched polymers.

Claims

1. A method of free radical polymerization comprising (1) forming a mixture of one or more monomers, water, optionally surfactant, at least one free radical source and a control agent and (2) subjecting said mixture to polymerization conditions, wherein said control agent is characterized by the general formula:

2. The method of claim 1, wherein R⁴ is selected from the group consisting of optionally substituted alkyl and optionally substituted aryl.

3. The method of claim 1, wherein R¹ is selected from the group consisting of optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted amino and optionally substituted polymer chains.

4. The method of claim 3, wherein R¹ is selected from the group consisting of—

CH₂Ph, —

CH(CH₃)CO₂CH₂CH₃,—

CH(CO₂CH₂CH₃)₂,—

C(CH₃)₂CN,—

CH(Ph)CN and—

C(CH₃) ₂Ph.

5. The method of claim 1, wherein R⁷ and R⁸ are each independently selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally substituted, aroyl, optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkylphosphonyl, optionally substituted arylsulfinyl, and optionally substituted arylphosphonyl.

6. The method of claim 1, wherein said polymerization conditions comprise a temperature in the range of from about 20°

C. to about 110°

C.

7. The method of claim 1, wherein two or more monomers are added to said polymerization mixture and said two or more monomers are added sequentially or simultaneously.

8. The method of claim 1, wherein said polymerization conditions comprise a continuous or semi-continuous addition of reagent to said mixture, wherein said addition of reagent comprises addition of said one or more monomers, surfactant, initiator and combinations thereof.

9. The method of claim 1, wherein said polymerization conditions comprise living kinetics.

10. A polymer formed by the method of claim 1.

11. The polymer of claim 10, wherein said copolymer is a block copolymer.

12. The polymer of claim 10, wherein said polymer is in an emulsion.

14. The method of claim 13, wherein R¹ is selected from the group consisting of optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted alkoxy, optionally substituted heterocyclyl, optionally substituted alkylthio, optionally substituted amino and optionally substituted polymer chains.

15. The method of claim 14, wherein the multi-functional control agent is not of formula III and R¹ is selected from the group consisting of—

CH₂Ph, CH(CH₃)CO₂CH₂CH₃,—

CH(CO₂CH₂CH₃)₂,—

C(CH₃)₂CN, —

CH(Ph)CN and C(CH₃)₂Ph.

16. The method of claim 13, wherein R⁷ and R⁸ are each independently selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl, optionally substituted alkenyl, optionally substituted acyl, optionally substituted, aroyl, optionally substituted alkoxy, optionally substituted heteroaryl, optionally substituted heterocyclyl, optionally substituted alkylsulfonyl, optionally substituted alkylsulfinyl, optionally substituted alkylphosphonyl, optionally substituted arylsulfinyl, and optionally substituted arylphosphonyl.

17. The method claim 13, wherein R⁴ is selected from the group consisting of hydrogen, optionally substituted alkyl, optionally substituted aryl, amino, thio, optionally substituted aryloxy and optionally substituted alkoxy.

18. The method of claim 13, wherein said polymerization conditions comprise a temperature in the range of from about 20°

C. to about 110°

C.

19. The method of claim 13, wherein two or more monomers are added to said heterogeneous polymerization mixture and said two or more monomers are added sequentially or simultaneously.

20. The method of claim 13, wherein said polymerization conditions comprise living kinetics.

21. A polymer formed by the method of claim 13.

22. The polymer of claim 21, wherein said copolymer is a block copolymer.

23. The polymer of claim 21, wherein said polymer is a star or hyperbranched polymer.

13. A method of method of heterogeneous free radical polymerization comprising (1) forming a heterogeneous mixture of one or more monomers, at least one free radical source, water, optionally surfactant and a multi-functional control agent and (2) subjecting said heterogeneous mixture to polymerization conditions, wherein said multi-functional control agent is selected from any of the following formulas:

24. A compound characterized by the general formula: