Aqueous dispersions of polytetrafluoroethylene having a low amount of fluorinated surfactant

• US 7,041,728 B2
• Filed: 10/12/2004
• Issued: 05/09/2006
• Est. Priority Date: 11/17/2003
• Status: Expired due to Fees

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Hintzer, Klaus, Zipplies, Tilman, Loehr, Gernot, Dadalas, Michael C.
• Primary Examiner(s): Wu, David W.
• Assistant Examiner(s): Hu, Henry S.
• Application Number:
  US10/962,633
• Publication Number:
  US 20050107518A1
• Time in Patent Office: 574 Days
• Field of Search: 526/250, 526/242, 524/544, 524/545
• US Class Current: 524/544
• CPC Class Codes: C08F 214/26 Tetrafluoroethene
• CPC Class Codes: C08F 6/16 Purification
• CPC Class Codes: C08L 2666/02 Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 2666/22 Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
• CPC Class Codes: C08L 27/18 Homopolymers or copolymers or tetrafluoroethene
• CPC Class Codes: C08L 71/02 Polyalkylene oxides
• CPC Class Codes: C09D 127/18 Homopolymers or copolymers of tetrafluoroethene

Abstract

The present invention provides a method of making an aqueous dispersion of non-melt processible polytetrafluoroethylene, the method comprising:

(a) an aqueous emulsion polymerization of an amount of tetrafluoroethylene to produce a final amount of polytetrafluoroethylene solids and optionally up to 1% by weight based on the amount of tetrafluoroethylene of a perfluorinated comonomer, wherein said aqueous emulsion polymerization is initiated with a free radical initiator and the polymerization is carried out in the presence of a fluorinated surfactant, and wherein before completing the feeding of said amount of tetrafluoroethylene but after feeding at least 80% by weight of said amount of tetrafluoroethylene, free radicals capable of introducing ionic end groups or precursors thereof in the polytetrafluoroethylene polymer are caused to be formed at a rate that without counter measures would cause an increase in the polymerization rate of at least 20%;

(b) reducing the amount of fluorinated surfactant in the thus obtained aqueous dispersion to an amount of not more than 200 ppm, preferably not more than 100 ppm and more preferably not more than 50 ppm based on the amount of polytetrafluoroethylene solids. The invention further provides an aqueous dispersion of polytetrafluoroethylene particles and the use thereof in coating a substrate.

Claims

1. Method of making an aqueous dispersion of non-melt processible polytetrafluoroethylene, the method comprising:

(a) an aqueous emulsion polymerization of an amount of tetrafluoroethylene to produce a final amount of polytetrafluoroethylene solids and optionally up to 1% by weight based on the amount of tetrafluoroethylene of a perfluorinated comonomer, wherein said aqueous emulsion polymerization is initiated with a free radical initiator and the polymerization is carried out in the presence of a fluorinated surfactant, and wherein before completing the feeding of said amount of tetrafluoroethylene but after feeding at least 80% by weight of said amount of tetrafluoroethylene, free radicals capable of introducing ionic end groups or precursors thereof in the polytetrafluoroethylene polymer are caused to be formed at a rate that without counter measures would cause an increase in the polymerization rate of at least 20%;

(b) reducing the amount of fluorinated surfactant in the thus obtained aqueous dispersion to an amount of not more than 200 ppm based on the amount of polytetrafluoroethylene solids.

2. Method according to claim 1 wherein the amount of fluorinated surfactant is reduced by contacting the aqueous dispersion in the presence of a non-ionic surfactant with an anion exchange resin.

3. Method according to claim 1 wherein the formation of said free radicals capable of introducing ionic end groups or precursors thereof in the polytetrafluoroethylene polymer is caused by at least one of increasing the polymerization temperature, addition of an inorganic initiator and addition of one or more inorganic components of an initiator system.

4. Method according to claim 1 wherein said ionic groups are acid groups having a pK_a of not more than 3 or salts of said acid groups.

5. Method according to claim 1 wherein during formation of said ionic groups or precursors thereof, a perfluorinated comonomer is co-fed with tetrafluoroethylene to the polymerization.

6. Method according to claim 5 wherein said perfluorinated comonomer is selected from hexafluoropropylene, a perfluorovinyl ether or a perfluoroallyl ether.

7. Method according to claim 1 wherein the polymerization is conducted under conditions such that at least 90% by weight of polytetrafluoroethylene particles obtained after step (a) are spherical.

8. Method according to claim 1 wherein the method further comprises upconcentrating the resulting aqueous dispersion to a polytetrafluoroethylene solids amount between 30% and 70% by weight, said upconcentration being carried out in the presence of a non-ionic surfactant.

9. Method according to claim 1 wherein the aqueous emulsion polymerization is carried out under conditions so as to produce polytetrafluoroethylene particles having a volume average particle size between 50 nm and 350 nm.