Synthesis of chlorotrifluoroethylene-based block copolymers by iodine transfer polymerization

Patent metadata

Field	Value
Publication number	US-9394394-B2
Application number	US-201414448062-A
Country	US
Kind code	B2
Filing date	Jul 31, 2014
Priority date	Sep 30, 2013
Publication date	Jul 19, 2016
Grant date	Jul 19, 2016

Abstract

Methods for the synthesis of CTFE-based block copolymers through iodine transfer polymerization are disclosed. In an exemplary embodiment, a method includes reacting a fluoromonomer “M” with a chain transfer agent of the formula X—Y or Y—X—Y, wherein X represents a C 1 -C 3 hydrocarbon, a C 1 -C 6 hydrofluorocarbon, C 1 -C 6 hydrochlorofluorocarbon, or C 1 -C 6 fluorocarbon and Y represents iodine or bromine, in the presence of a radical initiator, to form a macro-initiator of the formula: X-poly(M)-Y or Y-poly(M)-X-poly(M)-Y, wherein poly(M) represents a polymer of the fluoromonomer. The method further includes reacting the macro-initiator with chlorotrifluoroethylene (CTFE) in the presence of a radical initiator to form a diblock or a triblock CTFE-based block copolymer of the formula: X-poly(M)-block-poly(CTFE) or PCTFE-block-poly(M)-X-poly(M)-block-PCTFE.

First claim

What is claimed is:

1. A method for the synthesis of CTFE-based block copolymers through iodine transfer polymerization, comprising:
reacting, in the presence of a radical initiator, a monomer “M” selected from the group consisting of: vinyl fluoride (VF), and vinylidene chloride (VDC) with a chain transfer agent of the formula:
X—Y or Y—X—Y,

wherein X represents a C 1 -C 3 hydrocarbon, a C 1 -C 6 hydrofluorocarbon, a C 1 -C 6 hydrochlorofluorocarbon, or a C 1 -C 6 fluorocarbon and Y represents iodine or bromine, thereby forming a macro-initiator of the formula:
X-poly(M)-Y or Y-poly(M)-X-poly(M)-Y,

wherein poly(M) represents a polymer of the monomer; and
reacting, in the presence of a radical initiator, the macro-initiator with chlorotrifluoroethylene (CTFE), thereby forming a diblock or a triblock CTFE-based block copolymer of the formula:
X-poly(M)-block-PCTFE or PCTFE-block-poly(M)-X-poly(M)-block-PCTFE.

2. The method of claim 1 , wherein reacting the monomer with the chain transfer agent comprises reacting the monomer with a chain transfer agent selected from the group consisting of: CF 3 (CF 2 ) n —Y and Y—(CF 2 ) n —Y, wherein n equals 0, 1, 2, 3, 4, 5, or 6.

3. The method of claim 1 , wherein reacting the monomer with the chain transfer agent in the presence of the radical initiator comprises reacting the monomer with a chain transfer agent in the presence of a radical initiator selected from the group consisting of: (NH 4 ) 2 S 2 O 8 , K 2 S 2 O 8 , Na 2 S 2 O 8 , Mn 2 (CO) 10 , tertbutyl peroxypivalate, dibenzoyl peroxide, and ditert-butyl peroxide.

4. The method of claim 1 , wherein reacting the monomer with the chain transfer agent comprises reacting the monomer with the chain transfer agent at a temperature of about 20° C. to about 130° C.

5. The method of claim 4 , wherein reacting the monomer with the chain transfer agent comprises reacting the monomer with the chain transfer agent at a temperature of about 60° C. to about 100° C.

6. The method of claim 1 , wherein reacting the monomer with the chain transfer agent comprises reacting the monomer with the chain transfer agent at a pressure of about 200 kPa to about 20,000 kPa.

7. The method of claim 6 , wherein reacting the monomer with the chain transfer agent comprises reacting the monomer with the chain transfer agent at a pressure of about 2,000 kPa to about 10,000 kPa.

8. The method of claim 1 , wherein reacting the monomer with the chain transfer agent comprises reacting the monomer with the chain transfer agent for a time period of about 1 to about 30 hours.

9. The method of claim 8 , wherein reacting the monomer with the chain transfer agent comprises reacting the monomer with the chain transfer agent for a time period of about 4 to about 20 hours.

10. The method of claim 1 , wherein reacting the macro-initiator with the CTFE in the presence of a radical initiator comprises reacting the macro-initiator with the CTFE in the presence of a radical initiator selected from the group consisting of: Mn 2 (CO) 10 and tert-butyl peroxy pivalate (TBPPi).

11. The method of claim 1 , wherein reacting the macro-initiator with the CTFE comprises reacting the macro-initiator with the CTFE at a temperature of about 20° C. to about 130° C.

12. The method of claim 11 , wherein reacting the macro-initiator with the CTFE comprises reacting the macro-initiator with the CTFE at a temperature of about 60° C. to about 100° C.

13. The method of claim 1 , wherein reacting the macro-initiator with the CTFE comprises reacting the macro-initiator with the CTFE at a pressure of about 200 kPa to about 20,000 kPa.

14. The method of claim 1 , wherein reacting the macro-initiator with the CTFE comprises reacting the macro-initiator with the CTFE for a time period of about 1 to about 30 hours.

15. The method of claim 1 , wherein reacting the monomer or the macro-initiator comprises reacting in a solvent selected from the group consisting of: esters of formula R—COOR′ where R and R′ are independently C 1-5 alkyl groups, ester OR″ where R″ is an alkyl containing 1 to 5 carbon atoms, and where R may also hydrogen, fluorinated solvents, 1,2-dichloroethane, isopropanol, tertiary butanol, acetonitrile, dimethyl carbonate, butyronitrile, and mixtures thereof.

16. The method of claim 15 , wherein reacting the monomer or the macro-initiator comprises reacting in a co-solvent selected from the group consisting of: acetonitrile, butyronitrile, alkyl ketones, cyclohexanone, and water.

17. The method of claim 1 , wherein the monomer “M” comprises vinyl fluoride (VF).

18. The method of claim 1 , wherein the monomer “M” comprises vinylidene chloride (VDC).

Assignees

• Honeywell Int Inc

Inventors

• Thenappan Alagappan
• Ameduri Bruno
• Lopez Gerald

Classifications

• C08F214/242 Primary

  with fluorinated vinyl ethers · CPC title

• C08F2438/00

  Living radical polymerisation · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F293/005

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title

• C08F214/24

  Trifluorochloroethene · CPC title