Chlorofluoropolymer coated substrates and methods for producing the same

Abstract

Disclosed is a coated substrate, which includes a substrate comprising a cellulosic fiber material and a copolymer coated in a thin film on at least one surface of the substrate. The copolymer has at least two comonomer units of the formula: CX 2 CYA, wherein each X is independently selected from the group consisting of H, Cl and F; Y is selected from the group consisting of H, Cl, F, O(CZ 2 ) n CZ 3 , (CZ 2 ) n CZ 3 , (OCZ 2 CZ 2 ) n CZ 3 and (O(CZ 2 ) n ) n CZ 3 , wherein each n is independently from about 1 to about 12 and each Z is independently selected from the group consisting of H, Cl and F; and A is selected from the group consisting of H, Cl and F; provided that for at least one comonomer unit, at least one of A, Y, and either X or any Z is Cl.

1 . A coated substrate comprising:
 a substrate comprising a cellulosic fiber material; and   a copolymer applied on at least one surface of the substrate, the copolymer having at least two comonomer units of the formula:
   CX 2 CYA 
   
       wherein each X is independently selected from the group consisting of H, Cl and F; Y is selected from the group consisting of H, Cl, F, O(CZ 2 ) n CZ 3 , (CZ 2 ) n CZ 3 , (OCZ 2 CZ 2 ) n CZ 3  and (O(CZ 2 ) n ) n CZ 3 , wherein each n is independently from about 1 to about 12 and each Z is independently selected from the group consisting of H, Cl and F; and A is selected from the group consisting of H, Cl and F; provided that for at least one comonomer unit, at least one of A, Y, and either X or any Z is Cl. 
     
     
         2 . The coated substrate of  claim 1 , wherein the cellulosic fiber material comprises a cellulosic fiber pulp. 
     
     
         3 . The coated substrate of  claim 1 , wherein the celluslosic fiber material comprises a wood product. 
     
     
         4 . The coated substrate of  claim 1 , wherein the copolymer comprises at least one comonomer selected from the group consisting of chlorotrifluoroethylene, fluorotrichloroethylene, 1,1-dichlorodifluoroethylene, cis and trans isomers of 1,2-dichlorodifluoroethylene, 1-chloro-1-fluoroethylene, 1-chloro-2,2-difluoroethylene, vinylidene chloride, vinyl chloride, trichloroethylene, perchlorofluoroethers, perchlorofluorodioxoles, and mixtures thereof. 
     
     
         5 . The coated substrate of  claim 4 , wherein the copolymer comprises chlorotrifluoroethylene. 
     
     
         6 . The coated substrate of  claim 5 , wherein the copolymer comprises a chlorofluoro-olefin copolymerized with at least one fluorinated monomer. 
     
     
         7 . The coated substrate of  claim 6 , wherein the fluorinated monomer is selected from the group consisting of vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, vinylfluoride, trifluoroethylene, fluorinated alkylvinylethers, perfluorinated alkylvinylethers, 1,2-difluoroethylene, fluorinated alpha-olefins, perfluorodioxoles, and mixtures thereof. 
     
     
         8 . The coated substrate of  claim 7 , wherein the copolymer comprises chlorotrifluoroethylene copolymerized with a fluorinated monomer selected from the group consisting of vinylidene fluoride, hexafluoropropylene, tetrafluoroethylene, vinylfluoride, trifluoroethylene, fluorinated alkyl vinyl ethers, perfluorinated alkyl vinyl ethers, and mixtures thereof. 
     
     
         9 . The coated substrate of  claim 6 , wherein the copolymer comprises chlorotrifluoroethylene copolymerized with vinylidene fluoride. 
     
     
         10 . The coated substrate of  claim 6 , wherein the copolymer further comprises a fluorinated alpha olefin. 
     
     
         11 . The coated substrate of  claim 5 , wherein the copolymer further comprises a monomer selected from the group consisting of vinyl esters, acids and their sulfur analogs and non-halogenated alpha-olefins and mixtures thereof. 
     
     
         12 . The coated substrate of  claim 11 , the copolymer comprises a chloro-olefin copolymerized with at least one fluoro-olefin and at least one alkylvinylester. 
     
     
         13 . The coated substrate of  claim 12 , wherein the alkylvinylester is selected from the group consisting of vinylpropionate, vinylacetate, vinylbutyrate, vinylisobutyrate, vinylhexanoate, vinylstearate, neononanoate ethenyl ester, versatic acid vinylester, valeric acid vinylester, caproic acid vinylester, lauric acid vinylester, isovaleric acid vinylester, 2-ethylhexanoic vinylester, 2,2-dimethyloctanoic acid vinylester, 2-methyl-2propyl-pentanoic acid vinylester, 4-methyl-4-butylhexanoic acid vinyl ester and vinylesters of neo acids, and mixtures thereof. 
     
     
         14 . The coated substrate of  claim 13 , wherein the chlorofluoro-olefin is chlorotrifluoroethylene, said fluoro-olefin is vinylidene fluoride, and said vinylester is vinylpropionate. 
     
     
         15 . The coated substrate of  claim 11 , wherein the acid is acrylic, methacrylic acids and their esters, and mixtures thereof. 
     
     
         16 . The coated substrate of  claim 1 , wherein the copolymer has a weight-average molecular weight between about 2,000,000 and about 20,000,000 Daltons. 
     
     
         17 . The coated substrate of  claim 16 , wherein the copolymer has a weight-average molecular weight of about 8,000,000 Daltons. 
     
     
         18 . A method of coating a substrate comprising:
 contacting at least one surface of a substrate comprising a cellulosic fiber material with an aqueous dispersion of a copolymer, the copolymer having at least two comonomer units of the formula:
   CX 2 CYA 
   
       wherein each X is independently selected from the group consisting of H, Cl and F; Y is selected from the group consisting of H, Cl, F, O(CZ 2 ) n CZ 3 , (CZ 2 ) n CZ 3 , (OCZ 2 CZ 2 ) n CZ 3  and (O(CZ 2 ) n ) n CZ 3 , wherein each n is independently from about 1 to about 12 and each Z is independently selected from the group consisting of H, Cl and F; and A is selected from the group consisting of H, Cl and F; provided that for at least one comonomer unit, at least one of A, Y, and either X or any Z is Cl. 
     
     
         19 . The method of  claim 18 , wherein contacting is performed at a temperature from about 20° C. to about 120° C. 
     
     
         20 . The method of  claim 18 , wherein contacting is performed for a period of time from about 60 seconds to about 1 hour. 
     
     
         21 . The method of  claim 18 , further comprising removing the substrate from the aqueous dispersion and drying the substrate. 
     
     
         22 . The method of  claim 21 , wherein drying is performed at a temperature from about 20° C. and about 120° C. and for a period of time from about 60 seconds to about 1 hour. 
     
     
         23 . The method of  claim 21 , further comprising re-contacting the at least one surface of the substrate with the aqueous dispersion.