Copolymers for barriers

Abstract

A polyvinylidene difluoride copolymer with a fluoroolefin selected from 2,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, 2-chloro-pentafluoropropene, hexafluoropropylene, trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoro-2-trifluoromethylpropene and a mixture thereof, wherein the stoichiometry of the co-monomers defines the barrier properties of the copolymer. Such polymers include moisture barrier copolymers and oxygen barrier copolymer. Processes for preparing such moisture barrier copolymers and oxygen barrier copolymers are also provided.

1 .- 11 . (canceled) 
     
     
         12 . A moisture barrier copolymer comprising: from about 0.1 wt % to about 50 wt % vinylidene fluoride; and from about 50 wt % to about 99.9 wt % a fluorinated comonomer; wherein said copolymer is substantially impermeable to moisture. 
     
     
         13 . The moisture barrier copolymer of  claim 12 , wherein said vinylidene fluoride is from about 5 wt % to about 30 wt % of the copolymer; and wherein said fluorinated comonomer is from about 70 wt % to about 95 wt % of the copolymer. 
     
     
         14 . The moisture barrier copolymer of  claim 12 , wherein said vinylidene fluoride is from about 5 wt % to about 15 wt % of the copolymer; and wherein said fluorinated comonomer is from about 85 wt % to about 95 wt % of the copolymer. 
     
     
         15 . The moisture barrier copolymer of  claim 12 , wherein said fluorinated comonomer is selected from the group consisting of: 2,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, 2-chloro-pentafluoropropene, hexafluoropropylene, trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoro-2-trifluoromethylpropene and a mixture thereof. 
     
     
         16 . The moisture barrier copolymer of  claim 12 , further comprising a non-fluorinated comonomer. 
     
     
         17 . The moisture barrier copolymer of  claim 16 , wherein said non-fluorinated comonomer is selected from the group consisting of: an alkene of 2-8 carbon atoms, acrylate or methacrylate ester of 4 to 24 carbon atoms, hydroxyethyl acrylate or methacrylate, hydroxypropyl acrylate or methacrylate, glycidyl acrylate or methacrylate, acrylonitrile, methacrylonitrile, vinyl ether of 4 to 24 carbon atoms optionally substituted by at least one hydroxy group, styrene, alpha-methylstyrene, paramethyl styrene, allyl alcohol, methallyl alcohol, vinyl acetate, vinyl carboxylate of 5-24 carbon atoms wherein the carboxylate is optionally substituted by at least one hydroxy group, methyl ethyl ketone, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, alkyl vinyl ether, and combinations thereof. 
     
     
         18 . A process for the preparation of a moisture barrier copolymer of  claim 12 , comprising the step of contacting in a reaction zone: vinylidene fluoride; a fluorinated comonomer; an initiator; and optionally a non-fluorinated comonomer; wherein said contacting is carried out at a temperature, pressure and length of time sufficient to produce a moisture barrier copolymer having a composition comprising from about 0.1 wt % to about 50 wt % vinylidene fluoride; and from about 50 wt % to about 99.9 wt % a fluorinated comonomer. 
     
     
         19 . The process of  claim 18 , wherein said reaction zone further comprises a solvent selected from the group consisting of: water, ethyl acetate, butyl acetate, toluene, xylene, methyl ethyl ketone, 2-heptanone, 1-methoxy-2-propanol acetate, 1,1,1-trichloroethane and mixtures thereof. 
     
     
         20 . The process of  claim 18 , wherein said fluorinated comonomer is selected from the group consisting of: 2,3,3,3-tetrafluoropropene, 1,1,3,3,3-pentafluoropropene, 2-chloro-pentafluoropropene, hexafluoropropylene, trifluoroethylene, chlorotrifluoroethylene, 3,3,3-trifluoro-2-trifluoromethylpropene and a mixture thereof. 
     
     
         21 . The process of  claim 18 , further comprising a non-fluorinated comonomer. 
     
     
         22 . The process of  claim 18 , wherein said non-fluorinated comonomer is selected from the group consisting of: an alkene of 2-8 carbon atoms, acrylate or methacrylate ester of 4 to 24 carbon atoms, hydroxyethyl acrylate or methacrylate, hydroxypropyl acrylate or methacrylate, glycidyl acrylate or methacrylate, acrylonitrile, methacrylonitrile, vinyl ether of 4 to 24 carbon atoms optionally substituted by at least one hydroxy group, styrene, alpha-methylstyrene, paramethyl styrene, allyl alcohol, methallyl alcohol, vinyl acetate, vinyl carboxylate of 5-24 carbon atoms wherein the carboxylate is optionally substituted by at least one hydroxy group, methyl ethyl ketone, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, alkyl vinyl ether, and combinations thereof. 
     
     
         23 . A moisture barrier copolymer, comprising: from about 90 wt % to about 99.9 wt % chlorotrifluoroethylene and from about 10 wt % to about 0.1 wt % of a fluoromonomer selected from the group consisting of CF 3 CF═CH 2 , CF 3 CF═CF 2 , CF 3 CH═CF 2 , CF 3 CF═CFH, cis-CF 3 CH═CFH, trans-CF 3 CH═CFH, CF 3 CH═CH 2 , and combinations thereof based on the total weight of the copolymer. 
     
     
         24 . The copolymer of  claim 23 , wherein the chlorotrifluoroethylene is present from about 93 wt % to about 99.9 wt %, wherein the fluoromonomer is present from about 7 wt % to about 0.1 wt %. 
     
     
         25 . The copolymer of  claim 23 , wherein the chlorotrifluoroethylene is present from about 96 wt % to about 99.9 wt %, wherein the fluoromonomer is present from about 4 wt % to about 0.1 wt %. 
     
     
         26 . The copolymer of  claim 23 , wherein the moisture permeability is about 0.25 gm-mil/(100 in 2 -day) or less. 
     
     
         27 . The copolymer of  claim 23 , wherein the moisture permeability is about 0.2 gm-mil/(100 in 2 -day) or less. 
     
     
         28 . The copolymer of  claim 23 , wherein the moisture permeability is about 0.1 to about 0.25 gm-mil/(100 in 2 -day) or less. 
     
     
         29 . The copolymer of  claim 23 , wherein the fluoromonomer is CF 3 CF═CH 2 . 
     
     
         30 . The copolymer of  claim 23 , further comprising a different fluorinated comonomer and/or a non-fluorinated comonomer. 
     
     
         31 . The copolymer of  claim 23 , wherein the copolymer is in the form of a film. 
     
     
         32 . A moisture barrier copolymer, comprising: from about 90 wt % to about 99.9 wt % chlorotrifluoroethylene and from about 10 wt % to about 0.1 wt % of a fluoromonomer based on the total weight of the copolymer, wherein the copolymer is substantially impermeable to moisture.